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Book of Abstracts

NCC6 - The 6th Catalysis Conference April 27-30, 2016,

Bursa Technical University - Bursa / TURKEY

2 3NCC6 - The 6th Catalysis Conference April 27-30, 2016, Bursa Technical University

Organizing Institutions & Sponsors

Bursa Teknik Üniversitesi / NCC6 - The 6th Catalysis Conference

Editör / Prof. Dr. H. Levent Hoşgün

Görsel Tasarım / Yakup Şahiner

ISBN / 978-605-9332-00-2Basım Yılı ve Yeri / 1. Baskı; Nisan 2016, Star Matbaacılık / Bursa

Yapım / © 2016 Bursa Teknik Üniversitesi; Bu kitabın tüm yayın hakları Bursa Teknik Üniversitesi'ne aittir. Yazılı izin olmadan kısmen ya da tamamen yeniden basılamaz.

Dağıtım / Bursa Teknik Üniversitesi - 152 Evler Mahallesi Eğitim Caddesi 1.Damla Sok.No:2/10 16330 Yıldırım/BURSATel: + 90 224 300 32 32 Faks: + 90 224 300 32 09 [email protected] / www.btu.edu.tr


Table of Contents

LECTURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

ORAL PRESENTATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

TERRALAB POSTER PRESENTATIONS 28/04/2016 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

POSTER PRESENTATIONS 29/04/2016 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

Lectures (Abstracts) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

Support Effect in Oxide Catalysis: C-H Bond Activation on Vanadia/Ceria Compared to Vanadia/Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

Catalysis for bio-olefins production: from research to industrial application . . . . . . . . . . 37

Synthesis-Structure-Performance Relationships for Heterogeneous Catalysts . . . . . . . . 38

Hydrogenation and Hydrogenolysis Reactions Involved in Treatment of Water Contaminated with Chlorinated Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

Energy Intensified Reactor Design with Radio Frequency Heating . . . . . . . . . . . . . . . . . . 40

STRUCTURE-PERFORMANCE RELATIONSHIPS IN SUPPORTED METAL CATALYSTS WITH IONIC LIQUID LAYER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

Oral Presentations (Abstracts) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

Catalytic Role of Pyrite on Hydrodesulfurization of Lignite and Asphaltite . . . . . . . . . . . . 43

REDUCED GRAPHENE OXIDE (RGO) SUPPORTED Pt NANOPARTICLES: EFFECT OF DIFFERENT REDUCING AGENTS ON RGO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

Catalytic Tar Removal on Nickel-loaded Perovskites . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

Ultrasound assisted biodiesel production in presence of dolomite catalyst . . . . . . . . . . . 46

Ruthenium(0) nanoparticles supported on xonotlite nanowire: a long-lived catalyst for hydrolysis of ammonia-borane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

Synthesis of STA/SBA-15 Catalysts for Ethyl Acetate Production and Characterizations of Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

INVESTIGATION OF CATALYST, REACTION CONDITIONS AND PROCESS DESIGN FOR HYDROGEN PRODUCTION FROM STEAM REFORMING OF GLYCEROL . . . . . . . . . . . . . . . 49


Oxy-CO2 Reforming of Methane over Al2O3 Supported Nickel Catalysts prepared by Deposition-Precipitation with urea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

Production of 5-Hydroxymethylfurfural by Catalytic Dehydration of Fructose over SO4/La-TiO2-SiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

Catalytic performance of transition metal doped montmorillonite for biomass hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

Parametric investigation of glycerol reforming in a wall-coated microchannel reactor . . 54

BIODIESEL PRODUCTION FROM MODEL WASTE VEGETABLE OIL BY USING ZIRCONIUM SULFATE CATALYST . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

ESTERIFICATION OF CETYL ALCOHOL AND PALMITIC ACID OVER W AND Zr CONTAINING ACIDIC CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

DESIGN AND CHARACTERIZATION OF SELECTIVE CO2 ADSORBENTS . . . . . . . . . . . . . . . . 57

Novel Hybrid Perovskite Catalysts For DeNOx Applications . . . . . . . . . . . . . . . . . . . . . . . 58

NH3 Uptake Behavior of a Commercial Cu-Zeolite Monolithic Catalyst for the NH3-Selective Catalytic Reduction of NOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59

Sulfur-Tolerant BaO/ZrO2/TiO2/Al2O3 Quaternary Mixed Oxides for DeNOx Catalysis . . . . . 60

Development of CuOx/nr-TiO2 Catalysts for CO2 abatement . . . . . . . . . . . . . . . . . . . . . . 62

Carbon Aerogel Supported Platinum-Copper Nanoalloys Using Supercritical Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

Enviromental Friendly Latent Ruthenium Metathesis Catalysts for the Synthesis of Nano-ROMP Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

KINETIC AND MECHANISTIC FEATURES OF CARBON DIOXIDE REFORMING OF METHANE OVER Co–Ce/ZrO2 CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . 65

Computational (DFT) and Experimental (FTIR-DRIFT) Investigation of CO2 Activation on ZrO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

Performance test of monolithic Ni-based catalyts for carbon dioxide reforming of methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

Structure-performance relationships in supported nickel catalysts for hydrogen production from ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

The Effects of Reaction Parameters on Mn/Na2WO4/SiO2 Catalyst for Oxidative Coupling of Methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69


POSTER PRESENTATIONS (Abstracts) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

Schiff Base complexes on bleach catalyst for the real industrial applications . . . . . . . . . 70

CHARACTERIZATION OF CATALYTIC CONVERTER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

POLYANILINE COATING ON MODIFIED CARBON PASTE ELECTRODE TO CONSTRUCT AMPEROMETRIC GLUCOSE BIOSENSOR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

THE USE OF CYCLIC ENONES AS ORGANIC MOLECULES TO CONSTRUCT OF AMPEROMETRIC GLUCOSE BIOSENSORS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

IMPROVEMENT OF GLUCOSE BIOSENSOR BY CATALYTIC EFFICIENCY OF ZnFe2O4 NANOPARTICLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

GLUCOSE OXİDASE IMMOBILIZATION ON POLY(o-TOLUIDINE) COATED Pt ELECTRODE FOR AMPEROMETRIC BIOSENSOR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

Double Catalytic Centers: Potential Therepautic Applications for the Treatment of Oxidative Stress . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

RESPONSE SURFACE METHODOLOGY FOR OPTIMIZATION OF CONSTRUCTION OF AMPEROMETRIC GLUCOSE BIOSENSORS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

THE CO-IMMOBILIZED ENZYME SYSTEM FOR LACTOSE SENSITIVE BIOSENSOR . . . . . . . 79

CARBON PASTE ELECTRODE BASED SUCROSE BIOSENSOR . . . . . . . . . . . . . . . . . . . . . . 80

GLUCONIC ACID PRODUCTION BY co-IMMOBILIZED GLUCOSE OXIDASE-CATALASE ENZYME SYSTEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81

N,O-type Schiff base ligands and transition metal complexes containing functional groups: Structural Characterization and SOD Activity Studies . . . . 82

Catalytic Conversion of Superoxide by Porphyrine Based Metal Complexes . . . . . . . . . . 83

Porphyrine Based Mn(III) and Fe(III) Complexes as SOD Mimetics: Subsituent Effects on Catalytic Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84

Hydrolysis of microalgae oil Chlorella protothecoides via biocatalysis . . . . . . . . . . . . . . . 85

Immobilization and characterization of Candida rugosa lipase on magnetic nanoparticles through different spacer arms . . . . . . . . . . . . . . . . . . . . . . . . . . 87

Effect of Calcination Temperature on Production of DMN’s over Y Zeolite Catalyst . . . . . 88

Methylation of Naphthalene Oil Fraction of Coal Tar with Methanol on Metal/Bimetal Doped Beta Zeolite Catalysts . . . . . . . . . . . . . . . . . . . . . . . . 89

MODIFICATION OF ACTIVATED CARBON BASED ADSORBENTS FOR CO2 ADSORPTION . . 90

ENHANCING PHOTOCATALYTIC ACTIVITY OF ZnO NANOROD WITH HEAT TREATMENT . . 91


Low Platinum Loading Electrode for Formic Acid Fuel Cell Prepared by Ion-Beam Assisted Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92

Pt Catalyst Supported on Bi2O3 for Direct Formic Acid Fuel Cells . . . . . . . . . . . . . . . . . . 93

CATALYTIC GASIFICATION OF ÇAN LIGNITE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94

Ceria Incorporated Alumina Supported Nickel Catalysts for Steam Reforming Reaction of Diesel Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95

PtCu/C BIMETALLIC CATALYSTS FOR PEM FUEL CELLS . . . . . . . . . . . . . . . . . . . . . . . . . . 96

Effects of Synthesis Route and Calcination Temperature on Structural and Acidic Properties of Mesoporous -Al2O3 . . . . . . . . . . . . . . . . . . . . . . . . . . 97

Effect of Marl on the Production of Biodiesel as a Heterogeneous Catalyst . . . . . . . . . . 98

Hydrogen Production over Mesoporous Carbon Supported Iron Nanocatalysts using Microwave Reactor system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99

ELECTROCHEMICAL BEHAVIOUR OF HYBRID NANOSTRUCTURED MATERIALS FOR PEM FUEL CELL ELECTROCATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . 100

CARBON BLACK-GRAPHENE HYBRID SUPPORT MATERIALS FOR PEM FUEL CELL ELECTROCATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101

INFLUENCE OF TYPE OF CARBON SUPPORT ON THE REFORMING ACTIVITY AND SELECTIVITY OF SUPPORTED Pt CATALYSTS FOR APR OF GLUCOSE . . . . . . . . . . . . . . . 102

CoRh NANOPARTICLES: SYNTHESIS, CHARACTERIZATION, THEIR USE AS CATALYST IN THE HYDROLYSIS OF HYDRAZINE BORANE . . . . . . . . . . . . . 104

Ni(II) COMPLEX COVERED ZnO FILM OF PHOTOCATALYSTS FOR EFFICIENT HYDROGEN PRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105

Pt Catalyst Supported on High Surface Area MCM-41 and its Catalytic Activity for Formic Acid Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107

Development of Co-B/ Sepiolite Catalysts for Hydrogen Generation by Hydrolysis of Sodium Borohydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

Oxygen reduction and oxygen evolution reaction performances of PtNi/CuO catalyst for lithium-air batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

Preparation of Ni Catalyst on Co3O4 Support Material for H2 Production . . . . . . . . . . . . 110

Syntheses and Characterization of Ni Containing Silica Microspheres . . . . . . . . . . . . . 111

NEW DYE-SENSITIZIED Cu(I) COMPLEX PHOTOCATALYSTS BEHAVIOUR ON PHOTOELECTROLYSIS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112


THE CONVERSION OF CELLULOSE TO 5-HYDROXYMETHYL FURFURAL (HMF) WITH ZEOLITE CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

Oxidative Steam Reforming of Biogas by over NiCe/MgAl Hydrotalcite-like catalysts . . 114

Microwave Assisted COx-free Hydrogen Production over Mesoporous Carbon Supported Molybdenum Nanocatalysts . . . . . . . . . . . . . . . . . . . . . 115

HYDROGEN GENERATION FROM AMMONIA BORANE HYDROLYSIS CATALYZED BY CoPd NANOPARTICLES . . . . . . . . . . . . . . . . . . . . . . . . . . 116

EFFECT OF REACTION TEMPERATURE ON COKE FORMATION IN DRY REFORMING OF METHANE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

THE ROLE OF PRECIOUS METALS ON ADSORPTION/DESORPTION KINETICS OF OXYGEN OVER REDUCIBLE OXIDES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118

MODELING OF DATABASE CONSTRUCTED FROM PUBLISHED ARTICLES FOR WATER SPLITTING OVER PEROVSKITES . . . . . . . . . . . . . . . . . . . . . . . . 119

MORPHOLOGY OF PT-CU NANOPARTICLES BY USING GENETIC ALGORITHM AND DENSITY FUNCTIONAL THEORY . . . . . . . . . . . . . . . . . . . . . 120

TEMPERATURE EFFECT ON THE CARBON DIOXIDE SORPTION CAPACITY OF NATURAL MAGNESITE DERIVED SORBENT . . . . . . . . . . . . . . . . . . . . . . . 121

PREPARATION SUPPORTED PT AND RU CATALYSTS AND THEIR PERFORMANCES IN AVPR PROCESS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122

Investigation of Metal Loading Ratio Effect on Characteristics of Co/Al2O3 Catalysts and Utilization in Catalytic Pyrolysis . . . . . . . . . . . 123

AN EFFICIENT HETEROGENEOUS CR-ZEOLITE CATALYST FOR GLUCOSE TO 5-HYDROXYMETHYLFURFURAL CONVERSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124

N-HETEROCYCLIC CARBENE-BASED NICKEL(II) COMPLEXESIN KUMADA COUPLING . . . 125

Sorption Enhanced Steam Reforming of Ethanol Over Ni Impregnated SBA-15 Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126

ESTERIFICATION OF GLYCEROL WITH OLEIC ACID over Ti CONTAINING SULFATED SBA-15 CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127

Synthesis and Characterization of Perovskite Catalyst and Its Catalytic Activity in Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

EPOXIDATION OF METHYL OLEATE OVER SO4/TiO2-SiO2 AND WO3-ZrO2 CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129

THE EFFECT OF PEROXIDE ON BIOMASS HYDROLYSIS AND CATALYTIC GASIFICATION OF HYDROLYSATES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130


Palladium (0) Nanoparticles Supported on Amine-Functionalized Silica for the Catalytic Hexavalent Chromium Reduction . . . . . . . . . . . . . . . . . . . . . . . . 131

PALLADIUM NANOPARTICLES(Pd NPs) AS EFFICIENT CATALYSTS FOR SUZUKI-MIYAURA REACTION IN MILD CONDITIONS . . . . . . . . . . . . . . . . . . . . . . . . 132

Investigation of Isobutane Dehydrogenation in a Pd-membrane Reactor . . . . . . . . . . . . 133

PREPARATION OF NOVEL VIC-DIOXIME-Pd(II) COMPLEX FOR SUZUKI-MIYAURA REACTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134

POTENTIAL APPLICATIONS OF SOLID SUPPORT CATALYTIC MEDICAL MOLECULAR . . . 136

AMMONIA SYNTHESIS REACTION ON Ru NANOPARTICLES . . . . . . . . . . . . . . . . . . . . . 137

ARTIFICIAL HUMAN BLOOD and Antioxidant Enzyme Catalysis: Glutathione peroxidase, catalase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138

Ruthenium Nanoparticles Stabilized Hidrotalcite Catalyst for the Methanolysis of Ammonia-Borane under Mild Conditions . . . . . . . . . . . . . . . . . . . . . . . 139

Effect of Crystal Structure on the Catalytic Activity for Suzuki-Miyaura Coupling Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140

Sulfonic Acid Functionalized MIL-101 Metal Organic Framework Confined Palladium(0) Nanoparticles Catalyst for the Methanolysis of Ammonia-Borane under Mild Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141

IMMOBILIZATION OF GLUTAMATE DEHYDROGENASE ONTO AMINATED CARBON NANOTUBE AND INVESTIGATION OF CATALTIC ACTIVITY . . . . . . . . . . . . . . . . . 142

IMMOBILIZATION OF XANTHINE OXIDASE ONTO AMINATED CARBON NANOTUBE AND INVESTIGATION OF CATALTIC ACTIVITY AND STABILIZATION . . . . . . . . 143

THE INVESTIGATION OF DIMETHYGLOXIME LIGAND WHICH CAN BE USED FOR ACCUMULATION OF IRON IN THE BODY ON GLUTATATHIONE PEROXIDASE ENZYME . . . 144

THE INVESTIGATION OF DIMETHYGLOXIME LIGAND WHICH CAN BE USED FOR ACCUMULATION OF IRON IN THE BODY ON XANTHINE OXIDASE ENZYME . . . . . . . . . . 145

PREPARATION AND APPLICATION OF AlK(SO4)2 .12H2O LOADED CHITOSAN/ POLYVINYLPYRROLIDONE CATALYTIC MEMBRANE . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146

PHOSPHOTUNGSTIC ACID LOADED CELLULOSE MEMBRANE PREPARATION FOR CATALYTIC MEMBRANE REACTOR . . . . . . . . . . . . . . . . . . . . . . . . . 147

Palladium(II)-Schiff base complex supported on mwcnt for using as catalyst in the Suzuki-Miyaura reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149


Metal Organic Framework (MIL-101) Stabilized Ruthenium(0) Nanoparticles: Highly Efficient Catalytic Material for the Selective Hydrogenation of Phenol to Cyclohexanone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150

Trimetallic PdAuNi Alloy Nanoparticles Supported on Amine Functionalized Reduced Graphene Oxide for the Dehydrogenation of Formic Acid Under Mild Conditions . . . . . . 151

Synthesis and insitu catalytic aplication of 7-BER-NHC ligands on Suzuki reaction . . . . 152

Improvement of Sulfur Regenaration Ability of NSR Catalysts via Reducible Mixed Oxide Promoters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153

Selective CO2 adsorption studies on NaOH impregnated AC Adsorbents . . . . . . . . . . . . 155

Spectroscopic Investigation of NOx Storage and Reduction Pathways on Pt/K2O/ZrO2/TiO2/Al2O3 as NSR/LNT Catalysts . . . . . . . . . . . . . . . . . . . . . . 156

Removing of Synthetic Dyes from Aqueous Solutions By Using Photocatalysis and Adsorption Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158

ANODIC BEHAVIOR OF CARBON SUPPORTED Ni-Co, Ni AND Co ELECTROCATALYST IN DIRECT BOROHYDRIDE FUEL CELL . . . . . . . . . . . . . . . . . . . . . . 159

THE POLYANILINE FILMS on ZnNi PLATED COPPER ELECTRODE . . . . . . . . . . . . . . . . . 160

Mn3O4 BASED ELECTROCATALYST SYNTHESIS FOR VANADIUM REDOX FLOW BATTERIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161

Synthesis, Characterization and Photocatalytic Performance of Ag\ZnO in the Photodegradation of Methylene Blue under UV Irradiation . . . . . . . . . . . . . . . . . . . . . . 162

SYNTHESIS OF CNT-TiO2-SiO2 NANOCOMPOSITE THIN FILMS: THE EFFECT OF HEAT TREATMENT ON PHOTOCATALYTIC ACTIVITY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163

Determination of Reaction Kinetics for Electrochemical Oxidation of Tetracycline Antibiotic using Boron-Doped Diamond Anode . . . . . . . . . . . . . . . . . . . . . 164

THE ELECTROCATALYTIC BEHAVIOR OF COPOLYMER FILMS ON ZnFeCo DEPOSITED CARBON STEEL ELECTRODE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166

ELECTROCATALYTIC CONDUCTING POLYMER FILMS ON Zn DEPOSITED CARBON STEEL ELECTRODE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167

COBALT-BASED COORDINATION COMPOUNDS FOR ELECTROCATALYTIC WATER OXIDATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168

Determination of optimum Cu-CeO2 ANODE composition for direct methane solid oxide fuel cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169

Characterization of PAni-Fe Electrocatalyst Loaded on Multi-walled Carbon Nanotube Support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170


Benzene Oxidation as an Alternative Method for Assessing Photocatalytic Activity . . . . 171

Synthesis, Characterization and Catalytic Activityin The Direct Arylation Reactions . . . . 173

SYNTHESIS STUDIES OF THE PROMISING CATALIST; MIL-101 . . . . . . . . . . . . . . . . . . . . 174

Synthesis of Chiral Catalysts and Their Catalytic Activities in ScCO2 . . . . . . . . . . . . . . . 175

GREEN DEHYDROGENATION OF DIMETHYLAMINE-BORANE CATALYZED BY PVP, Al2O3AND PS-co-MASTABILIZED Ru NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176

Catalytic applications andsynthesis of Pd-PEPPSI N- Heterocyclic Carbene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177

Synthesis of poly(cyclooctene) derivatives bearing imidazole end group by ROMP Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178

Direct Arylation with Palladium-NHC Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179

Magnetic Nanoparticle Supported Latent Ruthenium Metathesis Catalysts for Olefin Metathesis Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180

Modification of Functional Polyesters by Metathesis Reactions in the Presence of Hoveyda-Grubbs Type Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181

Synthesis of Fe3O4@SiO2@RN(CH2PPh2)2PdCl2 Type Nanocomposite Catalystsfor Vitamin K3 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182

Modification of Poly(norbornenediester) Derivatives with Primary and Secondary Amine Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183

Reusability of nano-12-tungstophosporic acid cesium salt in alkylation of benzene with dec-1-ene reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184

Alumina Supported Mn-Ce Sorbents for High Temperature Desulfurization of Hydrogen Rich Gas Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185

Catalytic Wet Peroxide Oxidation of Bisphenol A in Water . . . . . . . . . . . . . . . . . . . . . . . 186

Graphene Supported Aminomethylphosphine-Pd(II) and Pt(II) Complexes: Highly Efficient Catalysts on Vitamin K3 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187

N-Alkylation Reaction with Functionalized Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . 189

The Coupling Reaction With Aryl Grignard Reagents in the Presence of Iron/NHC Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190

Palladium-NHC Complex Catalyzed Cross Coupling Reactions . . . . . . . . . . . . . . . . . . . 191

PHOTOCATALYTIC WATER SPLITTING OVER Au/SrTiO3CATALYST . . . . . . . . . . . . . . . . . . 192

IN SITU GENERATION COPPER(0) NPs AND CONCOMITANT GREEN DEHYDROGENATION OF DIMETHYLAMINE-BORANE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193


Synthesis of Palladium(II) Schiff Base Complex And it’s Catalytic Activities C-C Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194

HYDROBENZOIN TYPE LIGANDS FOR ASYMMETRIC CATALYSIS . . . . . . . . . . . . . . . . . . . 195

THE SYNTHESIS OF MAGNETIC NANOPARTICLES SUPPORTED AZOMETHINE-OXIME-PD COMPLEX AND ITS CATALYTIC ACTIVITY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196

N-Substitutedbenzimidazole-Ruthenium(II) Complexes and Their Catalytic Activity . . . 197

Determination of Radiation Absorption Properties of Gamma Irradiated Polyoxovanadate Based Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198

EFFECTS OF THE PREPARATION METHOD AND CALCINATION TEMPERATURE ON THE CHARACTERISTIC PROPERTIES OF NiO-Fe2O3-SiO2 CATALYSTS . . . . . . . . . . . . . . . . . . . 199

Modular Ligands Allowing Tunable Steric and Electronic Effects for Transition Metal Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200

Synthesis of Tungstophosphoric Acid Incorporated Mesoporous Alumina Catalysts for Methanol Dehydration in DME Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202

Production of 2,6-Dimethylnaphthalene with Methylation of Naphthalene over Au/Mordenite Zeolite Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203

CHARACTERIZATION OF Ni/ZrTiO4CATALYSTFOR THE PARTIAL OXIDATION of METHANE . 204

Characterization and Catalytic Performance of MnxOy-Na2WO4/SiO2 for the Oxidative Coupling of Methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205

The Effect of Metal Adding Sequence and Synthesis Media on the Properties of SnSBA-15 Catalysts at Low Metal Ratio . . . . . . . . . . . . . . . . . . . . . . . . . 206

Effect of Ti-Ce Contenton the Catalytic Activity of Alumina Supported Catalysts in Selective Oxidation of H2S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207

INVESTIGATION and CHARACTERIZATION of Ni/MgO CATALYST PREPARED BY ELECTROSPINNIG TECHNIQUE for the PARTIAL OXIDATION and DRY REFORMING of METHANE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209

THE CATALYTICACTIVITY OF AZO CONTAINING SCHIFF BASE COMPLEXES . . . . . . . . . . . 211

TRANSITION METAL COMPLEXES OF NOVEL CHROMONE SCHIFF BASES: SYNTHESIS, CHARACTERIZATION AND CATECHOLASE-LIKE ACTIVITY . . . . . . . . . . . . . . . . . . . . . . . . 212

Hydrothermal Synthesis and Characterization of Heterogeneous Catalysts for the Oxidation of the Thymol To Thymoquinone . . . . . . . . . . . . . . . . . . . . . 214

SUITABLE CATALYST OBTAINING FOR ALKANE OXIDATION AND ALKENE EPOXIDATION REACTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215

POLYMER SOLID SUPPORT CATALYSTS FOR ALKANE OXIDATION . . . . . . . . . . . . . . . . . 216


CATALYST DESIGN FOR ALKENE EPOXIDATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217

New Ferrocene Based Schiff Bases Metal Complexes: Synthesis and Investigation of Catalytic Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218

Oxidation of alkanes with hydrogen peroxide catalyzed by ferrocene . . . . . . . . . . . . . 220

Transition Metal Complexes of Ligand in a Liquid Crystal Properties: Investigation of the Catalytic Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221

Novel Gallic Esters: Its Synthesis, Structural Characterization, Photoluminescence, Electrochemical Properties And Alkene Epoxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . 222

Catalytic activity of Schiff Base Mn(III)/Co(III) complexes on bleach catalyst . . . . . . . . . 223

Catalytic Oxidation of Nitrogen Containing Compounds for Nitrogen Determination . . . 224

Catalytic Properties of ONO Type Salicylaldimine Copper(II) Complexes . . . . . . . . . . . . 225

Copper Complexes with Bidentate NO Ligands as Novel Catalysts for the Homogeneous Partial Oxidation of Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226

The comparison of catalytic activity of non-ionic and ionic Mn(III)/Co(II) Phthalocyanine complexes on bleach systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227

THE CATALYTIC ACTIVITY OF NOVEL, AZO-CONTAINING SCHIFF BASES AND THEIR METAL COMPLEXES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228

Investigation of Oxidation Reaction Pathways of Oxygenates on Au(111) Single CrystalDepending on the Behaviour of Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229

Effective Catalysts Derived from Carbazole for Alkene oxidation . . . . . . . . . . . . . . . . . . 230

Schiff base transition metal complexes with ceftazidime: Synthesis and Investigation of Alkane Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231

Drug metal complexes: Synthesis and Investigation of Alkane Oxidation . . . . . . . . . . . . 232

Synthesis and Characterization of MCM-41 Supported Ni Catalysts for Acetic Acid Steam Reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233

COMPARISON OF FRESH FCC CATALYSTS, E-CAT SAMPLES and FCC ADDITIVES FOR COMPREHENSION OF THE PROCESS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234

Hydrogen Adsorption on M2+-LTL Zeolite Clusters (M = Be, Mg and Ca) : A Density Functional Theory Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235

Investigation of Surface Acidity of Metal/Bimetal Modified Zeolite Catalysts using Pyridine Probe Molecule by FT-IR . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236

Synthesis and Characterization of CMK-3 and Activated Carbon Based Catalysts . . . . . 237

IMPACT OF HYDROCRACKING CATALYST CHARACTERISTICS ON THE


PERFORMANCE OF HYDROCRACKING UNIT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238

AMMONIA DECOMPOSITION REACTION OVER ZEOLITE Y SUPPORTED IRON CATALYSTS: EFFECT OF DEALUMINATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239

Palladium (II) Schiff Base Complexes: Precursor for the Deposition onto the mesoporous SBA-15 in scCO2 Media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240

Synthesis and Characterization of SBA15 Mesoporous Materials Functionalized with Boron Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241

Determination of ΔH°, ΔS° and ΔG° valuesof B-SBA15 Mesoporous Materials Using InverseGasCromatographyTechnique . . . . . . . . . . . . . . . . . . . . . . . . . . 242

Single Step Synthesis of HPA loaded Al-PILCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243

Zeolite Catalysis for Bio-oil Upgrading via Esterification . . . . . . . . . . . . . . . . . . . . . . . 244


Dear Colleagues of Universal Catalysis Community,

We are honored to welcome you to the NCC6-The 6th Catalysis Conference in Turkey. On behalf of the Organization Committee, it is my privilege to extend our regards to all our invited lecturers and the participants which will share their special scientific findings and high academic knowledge, in the ever expanding world of catalyst.

I would like to commence by quoting some specific numbers to give a broad picture of the status of the NCC6. The number of abstracts submitted, rose to about 184; approximately 27 oral presentations have been scheduled, together with 157 posters. We will have the opportunity to listen to about six Invited and Pleanary Talks in this meeting, including our world-renowned Plenary and Invited Speakers: Prof. Dr. Joachim Sauer (EFCATS Francois Gault Lecture, Humboldt University), Prof. Dr. Krjin De Jong (Utrecht University), Prof. Dr. Ümit Özkan (Ohio State Univeristy), Prof. Dr. Fabrizio Cavani (Bologna University), Volkan Değirmenci (University of Warwick) and Alper Uzun (Koç University)

The NCC6 acquired the efforts of many people and the support from a number of parties. The Chairs of NCC6 –Catalysis Society of Turkey, Organizing Committee, Scientific Committee and Reviewers – were involved in the organization and devoted their time and talent. I have only praise for their dedication to make the NCC6 a world-class event. To all of my fellows in this organization, our most sincere recognition and gratefulness.

The NCC6 has benefited from many sponsors. Their support of the congress as a whole is duly appreciated. Particularly, we would like to thank TUBITAK (The Scientific and Technological Research Council of Turkey), BTSO (Bursa Chamber of Commerce and Industry), Bursa Metropolitan Municipality and TUPRAS A.Ş for their great support.

I wish you all, a fruitful and rewarding experience at NCC6. We are in anticipation that NCC6 will provide a versatile platform for formal and informal discussions with colleagues both from academia and industry and foster new visions of collaborations.

On the Behalf of Organizing CommitteeProf. Dr. M. Ali GürkaynakChairman


Committes

Honorary BoardProf. Dr. Mahmut Ak Rector of İstanbul UniversityProf. Dr. Arif Karademir Rector of Bursa Technical UniversityProf. Dr. Timur Doğu Middle East Technical UniversityProf. Dr. Zeynep İlsen Önsan Middle East Technical UniversityRecep Altepe Mayor of Metropolitan Municipality

Scientific CommitteeProf. Dr. Mehmet Ali Gürkaynak İstanbul University, TurkeyProf. Dr. Mehmet Çopur Bursa Technical University, TurkeyProf. Dr. J W (Hans) Niemantsverdriet Director Syngaschem BV, BeijingProf. Dr. Jens Rostrup-Nielsen Haldor Topsøe A/S, DenmarkProf. Dr. Mahmut Bayramoğlu Gebze Technical University, TurkeyProf. Dr. Gülşen Doğu Gazi University, TurkeyProf. Dr. Xenophon Verykios University of Patras, GreeceProf. Dr. Deniz Üner Middle East Technical University, TurkeyProf. Dr. R.A. (Rutger) van Santen Eindhoven of University,NetherlandsProf. Dr. Can Erkey Koç University, TurkeyProf. Dr. Ramazan Yıldırım Boğaziçi University, TurkeyProf. Dr. Maria Flytzani-Stephanopoulos University of Tufts, USAProf. Dr. Enrique Iglesia University of California, Berkeley, USAProf. Dr. Bilgehan Güzel Çukurova University, TurkeyProf. Dr. Ayşe Nilgün Akın Kocaeli University, TurkeyProf. Dr. Ahmet Erhan Aksoylu Boğaziçi University, TurkeyProf. Dr. Martin Muhler Ruhr-Universitat Bochum, GermanyProf. Dr. Suna Balcı Gazi University, TurkeyProf. Dr. Süheyda Atalay Ege University, TurkeyProf. Dr. Selahattin Yılmaz İzmir High Technology Institute, TurkeyProf. Dr. Matthias Beller Leibniz-Institute for Catalysis, GermanyAssoc. Prof. Ahmet Kerim Avcı Boğaziçi University, TurkeyAssoc. Prof. M. Ali Faruk Öksüzömer İstanbul University, TurkeyAssoc. Prof. Serkan Naci Koç İstanbul University, TurkeyDr. Daniele Toffoli University of Trieste, Italy


Organizing CommitteeProf. Dr. Mehmet Ali Gürkaynak İstanbul UniversityProf. Dr. Mehmet Çopur Bursa Technical UniversityAssoc. Prof. Dr. M. Ali Faruk Öksüzömer İstanbul UniversityAssoc. Prof. Dr. Emrah Özensoy Bilkent UniversityAssoc. Prof. Dr. Mehmet Ferdi Fellah Bursa Technical UniversityAssist. Prof. Dr. Tuba Gürkaynak Altınçekiç İstanbul UniversityAssist. Prof. Dr. H. Levent Hoşgün Bursa Technical University

Catalysis Society of Turkey Executive BoardProf. Dr. Z. İlsen Önsan Boğaziçi UniversityCantaş Öğülmüş Damla KimyaProf. Dr. Deniz Üner Middle East Technical UniversityAssoc. Prof. Dr. Alper Tapan Gazi UniversityAssoc. Prof. Dr. Emrah Özensoy Bilkent UniversityAssist. Prof. Dr. Alper Uzun Koç UniversityProf. Dr. İsmail Özdemir İnönü University

ReviewersProf. Dr. Ahmet Erhan Aksoylu Boğaziçi UniversityProf. Dr. Can Erkey Koç UniversityProf. Dr. Deniz Üner Middle East Technical UniversityProf. Dr. Ayşe Nilgün Akın Kocaeli UniversityAssoc. Prof. Dr. Emrah Özensoy Bilkent UniversityAssoc. Prof. Dr. Ahmet Kerim Avcı Boğaziçi UniversityAssoc. Prof. Dr. M. Ali Faruk Öksüzömer İstanbul UniversityAssoc. Prof. Dr. Serkan Naci Koç İstanbul UniversityAssoc. Prof. Dr. Mehmet Ferdi Fellah Bursa Technical UniversityAssist. Prof. Dr. H. Levent Hoşgün Bursa Technical UniversityAssist. Prof. Dr. Solmaz Akmaz İstanbul University


LECTURES

TITLE AUTHOR(S)L1 Support Effect in Oxide Catalysis:C-H Bond

Activation on Vanadia/Ceria Compared to Vanadia/Silica

Prof . Dr . Joachim Sauer, (EFCATS Francois Gault Lecture)

Humboldt University, BerlinL2 Catalysis for bio-olefins production: from

research to industrial applicationProf . Dr . Fabrizio Cavani,

Bologna University ,Industrial Chemistry L3 S y n t h e s i s - S t r u c t u r e - Pe r f o r m a n c e

Relationships for Heterogeneous CatalystsProf . Dr . ir . K .P . (Krijn) de Jong,

Utrecht University, Inorganic Chemistry and Catalysis

L4 Hydrogenation and Hydrogenolysis Reactions Involved in Treatment of Water Contaminated with Chlorinated Hydrocarbons

Prof . Dr . Ümit Özkan,

Ohio State Univeristy , Chemical & Biomolecular Eng .

L5 Energy Intensified Reactor Design with Radio Frequency Heating

Dr . Volkan Değirmenci,

University of Warwick, School of Engineering

L6 Structure-Performance Relationships In Supported Metal Catalysts With Ionic Liquid Layer

Assist . Prof . Dr . Alper Uzun,

Koç University, Chemical & Biological Engineering


ORAL PRESENTATIONS

Catalysts for coal based chemicals

TITLE AUTHOR(S)

O-CBC1 Catalytic Role of Pyrite on Hydrodesulfurization of Lignite and Asphaltite

Veysi Halvaci, Arzu Kanca, Deniz Uner

Catalysts for sustainable energy and alternative fuels

TITLE AUTHOR(S)

O-SEAF1 REDUCED GRAPHENE OXIDE (RGO) SUPPORTED Pt NANOPARTICLES: EFFECT OF DIFFERENT REDUCING AGENTS ON RGO

Elif DAŞ, Ayşenur ÖZTÜRK, Ayşe BAYRAKÇEKEN YURTCAN

O-SEAF2 Catalytic Tar Removal on Nickel-loaded Perovskites

Basar Caglar, Taymaz Tabari, Deniz Üner

O-SEAF3 Ultrasound assisted biodiesel production in presence of dolomite catalyst

İbrahim Korkut, Mahmut Bayramoğlu

O-SEAF4 Ruthenium(0) nanoparticles supported on xonotlite nanowire: a long-lived catalyst for hydrolysis of ammonia-borane

Serdar Akbayrak, Saim Özkar

O-SEAF5 Synthesis of STA/SBA-15 Catalysts for Ethyl Acetate Production and Characterizations of Catalysts

Veli SIMSEK, Kirali MURTEZAOGLU

O-SEAF6 INVESTIGATION OF CATALYST, REACTION CONDITIONS AND PROCESS DESIGN FOR HYDROGEN PRODUCTION FROM STEAM REFORMING OF GLYCEROL

Öykü Parlar, M . Efgan Kibar, A . Nilgün Akın, Meltem Karaman

O-SEAF7 OXY-CO2 REFORMING OF METHANE OVER Al2O3 SUPPORTED NICKEL CATALYSTS PREPARED BY DEPOSITION-PRECIPITATION WITH UREA

Tuba Gürkaynak Altınçekiç, Tugay Pehlivan

Catalytic Conversion of renewable resources

TITLE AUTHOR(S)

O-CRS1 PRODUCTION OF 5-HYDROXYMETHYLFURFURAL BY CATALYTIC DEHYDRATION OF FRUCTOSE OVER SO4/La-TiO2-SiO2

Emre KILIÇ, Tjeerd Alexander NIJHUIS, Selahattin YILMAZ

O-CRS2 Catalytic performance of transition metal doped montmorillonite for biomass hydrolysis

Emir Zafer Hoşgün, Ebru Tunç, Halit Levent Hoşgün, Berrin Bozan


O-CRS3 Parametric investigation of glycerol reforming in a wall-coated microchannel reactor

Sinan Koc, Ahmet Kerim Avci

O-CRS4 BIODIESEL PRODUCTION FROM MODEL WASTE VEGETABLE OIL BY USING ZIRCONIUM SULFATE CATALYST

Melike İmge ŞENOYMAK, Oğuzhan İLGEN

O-CRS5 ESTERIFICATION OF CETYL ALCOHOL AND PALMITIC ACID OVER W AND Zr CONTAINING ACIDIC CATALYSTS

Vahide Nuran Mutlu, Selahattin YILMAZ

Catalytic methods for air water pollution control

TITLE AUTHOR(S)

O-AWPC1 DESIGN AND CHARACTERIZATION OF SELECTIVE CO2 ADSORBENT

Burcu Acar, Burcu Selen Çağlayan, A . Erhan Aksoylu

O-AWPC2 Novel Hybrid Perovskite Catalysts For DeNOx Applications

K .E . Ercan, Z . Say, E .I . Vovk, G . Pantaleo, L . Liotta, A . Venezia, and E . Ozensoy

O-AWPC3 NH3 Uptake Behavior of a Commercial Cu-Zeolite Monolithic Catalyst for the NH3-Selective Catalytic Reduction of NOx

Selmi Erim Bozbağ, Feyza Gökaliler, Gökhan Hisar, Can Erkey

O-AWPC4 Sulfur-Tolerant BaO/ZrO2/TiO2/Al2O3 Quaternary Mixed Oxides for DeNOX Catalysis

Z . Say, O . Mihai, M . Tohumeken, L . Olsson, E . Ozensoy

Electrochemical and photochemical catalysts

TITLE AUTHOR(S)

O-EPC1 Development of CuOx/nr-TiO2 Catalysts for CO2 abatement

Murat Efgan KİBAR, Gizem GÜRGÜR, Ayşe Nilgün AKIN

O-EPC2 Carbon Aerogel Supported Platinum-Copper Nanoalloys Using Supercritical Deposition

Şansım Bengisu BARIM, Ezgi Erdem, Selmi Erim Bozbağ, Rıza Kızılel, Mark Aindow, Haibo Yu, Can Erkey,

Environmentally friendly catalytic processes

TITLE AUTHOR(S)

O-EFCP1 Enviromental Friendly Latent Ruthenium Metathesis Catalysts for the Synthesis of Nano-ROMP Polymers

Bengi Özgün ÖZTÜRK, Solmaz KARABULUT ŞEHİTOĞLU

O-EFCP2 KINETIC AND MECHANISTIC FEATURES OF CARBON DIOXIDE REFORMING OF METHANE OVER Co–Ce/ZrO2 CATALYSTS

Aysun İpek Paksoy, Cansu Yassı Akdağ, Burcu Selen Çağlayan, A . Erhan Aksoylu

O-EFCP3 Computational (DFT) and Experimental (FTIR-DRIFT) Investigation of CO2 Activation on ZrO2

A . Uzun, A . İ . Paksoy, V . Çimenoğlu, A . E . Aksoylu


O-EFCP4 Performance test of monolithic Ni-based catalyts for carbon dioxide reforming of methane

Aybüke Leba, Ramazan Yıldırım

O-EFCP5 Structure-performance relationships in supported nickel catalysts for hydrogen production from ammonia

İbrahim Şahin, Alper Uzun

Oxidation catalysts

TITLE AUTHOR(S)

O-OXC1 The Effects of Reaction Parameters on Mn/Na2WO4/SiO2 Catalyst for Oxidative Coupling of Methane

Hasan Özdemir, M .A . Faruk Öksüzömer, M . Ali Gürkaynak

O-OXC2 Schiff Base complexes on bleach catalyst for the real industrial applications

Ertug Yildirim,S . Zeki Yildiz, Okan Yuzuak, Idil Yilmaz Yalinalp, Nihat Toslu

O-OXC3 CHARACTERIZATION OF CATALYTIC CONVERTER

Yiğit Türe, Emre Gürlek, Nurcan Çalış Açıkbaş, Şeref Soylu and Türker Güdü


TERRALAB POSTER PRESENTATIONS 28/04/2016

Biocatalysts

TITLE AUTHOR(S)

BC1 POLYANILINE COATING ON MODIFIED CARBON PASTE ELECTRODE TO CONSTRUCT AMPEROMETRIC GLUCOSE BIOSENSOR

A . Ebru AYDIN, Gul OZYILMAZ, Serbay BUCAK, Nureddin ÇOLAK, Ali Tuncay OZYILMAZ

BC2 THE USE OF CYCLIC ENONES AS ORGANIC MOLECULES TO CONSTRUCT OF AMPEROMETRIC GLUCOSE BIOSENSORS

Gul OZYILMAZ, A . Ebru AYDIN, Serbay Bucak, Seda AGCAM, Ali Tuncay OZYILMAZ

BC3 IMPROVEMENT OF GLUCOSE BIOSENSOR BY CATALYTIC EFFICIENCY OF ZnFe2O4 NANOPARTICLES

Ali Tuncay OZYILMAZ, Esiye İrem BAYRAM and Gul OZYILMAZ

BC4 GLUCOSE OXİDASE IMMOBILIZATION ON POLY(o-TOLUIDINE) COATED Pt ELECTRODE FOR AMPEROMETRIC BIOSENSOR


BC5 Double Catalytic Centers: Potential Therepautic Applications for the Treatment of Oxidative Stress

Ferhan Tümer, Songül Şahin, Mehmet Tümer, Muhammet Köse

BC6 RESPONSE SURFACE METHODOLOGY FOR OPTIMIZATION OF CONSTRUCTION OF AMPEROMETRIC GLUCOSE BIOSENSORS

Gul OZYILMAZ, Seda AGCAM and Ali Tuncay OZYILMAZ

BC7 THE CO-IMMOBILIZED ENZYME SYSTEM FOR LACTOSE SENSITIVE BIOSENSOR

Esra YAĞIZ, Gul OZYILMAZ and Ali Tuncay OZYILMAZ

BC8 CARBON PASTE ELECTRODE BASED SUCROSE BIOSENSOR

Esra YAĞIZ, Gul OZYILMAZ, and Ali Tuncay OZYILMAZ

BC9 GLUCONIC ACID PRODUCTION BY co-IMMOBILIZED GLUCOSE OXIDASE-CATALASE ENZYME SYSTEM

Gul OZYILMAZ

BC10 N,O-type Schiff base ligands and transition metal complexes containing functional groups: Structural Characterization and SOD Activity Studies

İlyas GÖNÜL, Muhammet KÖSE, Selahattin SERİN

BC11 Catalytic Conversion of Superoxide by Porphyrine Based Metal Complexes

Muhammet Köse, Ferhan Tümer, Mehmet Tümer


BC12 Porphyrine Based Mn(III) and Fe(III) Complexes as SOD Mimetics: Subsituent Effects on Catalytic Activity

Mehmet Tümer, Ferhan Tümer, Muhammet Köse

BC13 Hydrolysis of microalgae oil Chlorella protothecoides via biocatalysis

Togayhan Kutluk, Nurcan Kapucu

BC14 Immobilization and characterization of Candida rugosa lipase on magnetic nanoparticles through different spacer arms

Muge SENGUL, Leman BEYKAN, Deniz YILDIRIM, Guzide YUCEBILGIC

Catalysts for coal based chemicals

TITLE AUTHOR(S)

CBC1 Effect of Calcination Temperature on Production of DMN’s over Y Zeolite Catalyst

Aysel Niftaliyeva, Ali Karaduman

CBC2 Methylation of Naphthalene Oil Fraction of Coal Tar with Methanol on Metal/Bimetal Doped Beta Zeolite Catalysts

Aysun Özen, Fatih Güleç, Aysel Niftaliyeva, Ali Karaduman

CBC3 MODIFICATION OF ACTIVATED CARBON BASED ADSORBENTS FOR CO2 ADSORPTION

Melek Selcen BAŞAR, Burcu SELEN ÇAĞLAYAN, Ahmet Erhan AKSOYLU

Catalysts for sustainable energy and alternative fuels

TITLE AUTHOR(S)

SEAF1 ENHANCING PHOTOCATALYTIC ACTIVITY OF ZnO NANOROD WITH HEAT TREATMENT

Fatih TEZCAN, Gülfeza KARDAŞ

SEAF2 Low Platinum Loading Electrode for Formic Acid Fuel Cell Prepared by Ion-Beam Assisted Deposition

M . Selim ÇÖGENLİ, Sanjeev MUKERJEE, Ayşe BAYRAKÇEKEN YURTCAN

SEAF3 Pt Catalyst Supported on Bi2O3 for Direct Formic Acid Fuel Cells

M . Selim ÇÖGENLİ, Ayşe BAYRAKÇEKEN YURTCAN

SEAF4 CATALYTIC GASIFICATION OF ÇAN LIGNITE Açelya Seçer Ateş, Arif Hasanoğlu

SEAF5 Ceria Incorporated Alumina Supported Nickel Catalysts for Steam Reforming Reaction of Diesel Fuel

Arzu Arslan, Arife Derya Deniz Kaynar, Naime Aslı Sezgi, Timur Doğu

SEAF6 PtCu/C BIMETALLIC CATALYSTS FOR PEM FUEL CELLS

Ayşenur ÖZTÜRK, Elif DAŞ, Gamze BOZKURT, Ayşe BAYRAKÇEKEN YURTCAN

SEAF7 Effects of Synthesis Route and Calcination Temperature on Structural and Acidic Properties of Mesoporous γ-Al2O3

D . Erkal, B . Pekmezci, N . Oktar, G . Doğu, N .A . Sezgi, T . Doğu

SEAF8 Effect of Marl on the Production of Biodiesel as a Heterogeneous Catalyst

Bakhtiyar NAJAFOV, Niyazi Alper TAPAN


SEAF9 Hydrogen Production over Mesoporous Carbon Supported Iron Nanocatalysts using Microwave Reactor system

C .Korkusuz, D .Varışlı, T .Doğu

SEAF10 ELECTROCHEMICAL BEHAVIOUR OF HYBRID NANOSTRUCTURED MATERIALS FOR PEM FUEL CELL ELECTROCATALYSTS

Elif DAŞ, Selmiye ALKAN GÜRSEL, Lale IŞIKEL ŞANLI, Ayşe BAYRAKÇEKEN YURTCAN

SEAF11 CARBON BLACK-GRAPHENE HYBRID SUPPORT MATERIALS FOR PEM FUEL CELL ELECTROCATALYSTS

Elif DAŞ, Selmiye ALKAN GÜRSEL, Lale IŞIKEL ŞANLI, Ayşe BAYRAKÇEKEN YURTCAN

SEAF12 INFLUENCE OF TYPE OF CARBON SUPPORT ON THE REFORMING ACTIVITY AND SELECTIVITY OF SUPPORTED Pt CATALYSTS FOR APR OF GLUCOSE

Burçak Kaya Özsel, Bahar Meryemoğlu, Mehtap Kurtuluş, Arif Hasanoğlu, Sibel Irmak

SEAF13 CoRh NANOPARTICLES: SYNTHESIS, CHARACTERIZATION, THEIR USE AS CATALYST IN THE HYDROLYSIS OF HYDRAZINE BORANE

Bayram Abay, Nihat Tunç, Murat Rakap

SEAF14 Ni(II) COMPLEX COVERED ZnO FILM OF PHOTOCATALYSTS FOR EFFICIENT HYDROGEN PRODUCTION

Eylül Büşra HEREYTANİ, Fatih TEZCAN, Bilgehan GÜZEL, Gülfeza KARDAŞ, Osman SERİNDAĞ

SEAF15 Pt Catalyst Supported on High Surface Area MCM-41 and its Catalytic Activity for Formic Acid Oxidation

Niyazi ÖZÇELİK, M . Selim ÇÖGENLİ, Ayşe BAYRAKÇEKEN YURTCAN

SEAF16 Development of Co-B/ Sepiolite Catalysts for Hydrogen Generation by Hydrolysis of Sodium Borohydride

Seda EROL, Mine ÖZDEMİR

SEAF17 Oxygen reduction and oxygen evolution reaction performances of PtNi/CuO catalyst for lithium-air batteries

Gamze BOZKURT, Tansel ŞENER, Dino TONTI, A . Kadir ÖZER, Ayşe BAYRAKÇEKEN YURTCAN

SEAF18 Preparation of Ni Catalyst on Co3O4 Support Material for H2 Production

Gamze BOZKURT, Ayşe BAYRAKÇEKEN YURTCAN, A . Kadir ÖZER

SEAF19 Syntheses and Characterization of Ni Containing Silica Microspheres

Gamze Gunduz Meric, Levent Degirmenci

SEAF20 NEW DYE-SENSITIZIED Cu(I) COMPLEX PHOTOCATALYSTS BEHAVIOUR ON PHOTOELECTROLYSIS

Gurbet YERLİKAYA, Fatih TEZCAN, Gülfeza KARDAŞ, Osman SERİNDAĞ

SEAF21 THE CONVERSION OF CELLULOSE TO 5-HYDROXYMETHYL FURFURAL (HMF) WITH ZEOLITE CATALYSTS

Esra Sezgin, Merve Esen, Solmaz Akmaz, Serkan Naci Koç, M . Ali Gürkaynak

SEAF22 Oxidative Steam Reforming of Biogas by over NiCe/MgAl Hydrotalcite-like catalysts

Merve Doğan, Orhan Özcan, Murat Efgan Kibar, Ayşe Nilgün Akın


SEAF23 Microwave Assisted COx-free Hydrogen Production over Mesoporous Carbon Supported Molybdenum Nanocatalysts

Melih GÜLER, Dilek VARIŞLI, Timur DOĞU

SEAF24 HYDROGEN GENERATION FROM AMMONIA BORANE HYDROLYSIS CATALYZED BY CoPd NANOPARTICLES

Nihat Tunç, Bayram Abay, Murat Rakap

SEAF25 EFFECT OF REACTION TEMPERATURE ON COKE FORMATION IN DRY REFORMING OF METHANE

Hüseyin Arbağ, Sena Yaşyerli, Nail Yaşyerli, Gülşen Doğu, Timur Doğu

SEAF26 THE ROLE OF PRECIOUS METALS ON ADSORPTION/DESORPTION KINETICS OF OXYGEN OVER REDUCIBLE OXIDES

Deniz Kaya, Dheerendra Singh, Deniz Üner

SEAF27 MODELING OF DATABASE CONSTRUCTED FROM PUBLISHED ARTICLES FOR WATER SPLITTING OVER PEROVSKITES

Elif Can, Ramazan Yıldırım,

SEAF28 MORPHOLOGY OF PT-CU NANOPARTICLES BY USING GENETIC ALGORITHM AND DENSITY FUNCTIONAL THEORY

Ezgi ERDEM, Rıza KIZILEL, Can ERKEY

Catalytic Conversion of renewable resources

TITLE AUTHOR(S)

CRS1 TEMPERATURE EFFECT ON THE CARBON DIOXIDE SORPTION CAPACITY OF NATURAL MAGNESITE DERIVED SORBENT

Dilsad Dolunay Eslek Koyuncu, Sena Yasyerli, Nail Yasyerli

CRS2 PREPARATION SUPPORTED PT AND RU CATALYASTS AND THEIR PERFORMANCES IN AVPR PROCESS

Bahar Meryemoglu, Mehtap Kurtulus, Arif Hasanoglu, Sibel Irmak

CRS3 Investigation of Metal Loading Ratio Effect on Characteristics of Co/Al2O3 Catalysts and Utilization in Catalytic Pyrolysis

Nurgül ÖZBAY, Pınar BAŞ, Adife Şeyda YARGIÇ

CRS4 AN EFFICIENT HETEROGENEOUS CR-ZEOLITE CATALYST FOR GLUCOSE TO 5-HYDROXYMETHYLFURFURAL CONVERSION

Merve Esen, Esra Sezgin, Solmaz Akmaz, Serkan Naci Koç, M . Ali Gürkaynak

CRS5 N-HETEROCYCLIC CARBENE-BASED NICKEL(II) COMPLEXES IN KUMADA COUPLING

Deniz DEMİR ATLI, Şebnem E . SÖZERLİ

CRS6 Sorption Enhanced Steam Reforming of Ethanol Over Ni Impregnated SBA-15 Catalyst

Merve Sarıyer, Arzu Arslan, Naime Aslı Sezgi, Timur Doğu


CRS7 ESTERIFICATION OF GLYCEROL WITH OLEIC ACID OVER Ti CONTAINING SULFATED SBA-15 CATALYSTS

Gamze AY, Giray MUTLU, Emre KILIÇ, Hasan ÖRTÜN, Selahattin YILMAZ

CRS8 Synthesis and Characterization of Perovskite Catalyst and Its Catalytic Activity in Pyrolysis

Nurgül ÖZBAY, Rahmiye Zerrin YARBAY ŞAHİN

CRS9 EPOXIDATION OF METHYL OLEATE OVER SO4/TiO2-SiO2 AND WO3-ZrO2 CATALYSTS

Vahide Nuran Mutlu, Canan TAŞ, Selahattin YILMAZa

CRS10 THE EFFECT OF PEROXIDE ON BIOMASS HYDROLYSIS AND CATALYTIC GASIFICATION OF HYDROLYSATES

Mehtap Kurtulus, Bahar Meryemoglu, Arif Hasanoglu, Sibel Irmak

Catalytic membranes and nanostructured catalysts

TITLE AUTHOR(S)

MNC1 Palladium(0) Nanoparticles Supported on Amine-Functionalized Silica for the Catalytic Hexavalent Chromium Reduction

Metin Celebi, Mehmet Yurderi, Ahmet Bulut, Murat Kaya, Mehmet Zahmakiran

MNC2 PALLADIUM NANOPARTICLES(Pd NPs) AS EFFICIENT CATALYSTS FOR SUZUKI-MIYAURA REACTION IN MILD CONDITIONS

Burcu DARENDELİ, Fatma Ulusal, Bilgehan GÜZEL

MNC3 Investigation of Isobutane Dehydrogenation in a Pd-membrane Reactor

Saliha Çetinyokuş Kılıçarslan, Meltem Doğan, Timur Doğu

MNC4 PREPARATION OF NOVEL VIC-DIOXIME-Pd(II) COMPLEX FOR SUZUKI-MIYAURA REACTIONS

Özge Atış, Fatma Ulusal, Bilgehan Güzel

MNC5 POTENTIAL APPLICATIONS OF SOLID SUPPORT CATALYTIC MEDICAL MOLECULAR

Ümit YAŞAR, Fatma ULUSAL, Bilgehan GÜZEL, Pınar Yılgör HURİ, Nurten DİKMEN

MNC6 AMMONIA SYNTHESIS REACTION ON Ru NANOPARTICLES

M .Y .Aslan, S . Akbayrak, S . Özkar, D . Üner

MNC7 ARTIFICIAL HUMAN BLOOD AND ANTIOXIDANT ENZYME CATALYSIS: GLUTATHIONE PEROXIDASE, CATALASE

Ümit YAŞAR, Fatma ULUSAL, Bilgehan GÜZEL, Pınar Yılgör HURİ, Nurten DİKMEN

MNC8 Ruthenium Nanoparticles Stabilized Hidrotalcite Catalyst for the Methanolysis of Ammonia-Borane under Mild Conditions

Yaşar Karataş, Ahmet Bulut, Mehmet Yurderi, Mehmet Gülcan, Mehmet Zahmakıran

MNC9 EFFECT OF CRYSTAL STRUCTURE ON THE CATALYTIC ACTIVITY FOR SUZUKI-MIYAURA COUPLING REACTION

Fatma Ulusal, Burcu Darendeli, Özge Atış, Mustafa Kemal Yılmaz, Bilgehan Güzel


MNC10 Sulfonic Acid Functionalized MIL-101 Metal Organic Framework Confined Palladium(0) Nanoparticles Catalyst for the Methanolysis of Ammonia-Borane under Mild Conditions

Nurdan Caner, Ahmet Bulut, Mehmet Yurderi, Mehmet Zahmakıran

MNC11 IMMOBILIZATION OF GLUTAMATE DEHYDROGENASE ONTO AMİNATED CARBON NANOTUBE AND INVESTIGATION OF CATALTIC ACTIVITY

Yusuf Döğüş, Gülüzar Özbolat, Hasan Ulusal, Nevin Yılmaz, Abdullah Tuli

MNC12 IMMOBILIZATION OF XANTHINE OXIDASE ONTO AMINATED CARBON NANOTUBE AND INVESTIGATION OF CATALTIC ACTIVITY AND STABILIZATION

Yusuf Döğüş, Gülüzar Özbolat, Hasan Ulusal, Nevin Yılmaz, Abdullah Tuli

MNC13 THE INVESTIGATION OF DIMETHYGLOXIME LIGAND WHICH CAN BE USED FOR ACCUMULATION OF IRON IN THE BODY ON GLUTATATHIONE PEROXIDASE ENZYME

Gülüzar Özbolat, Hasan Ulusal ,Yusuf Döğüş, Abdullah Tuli

MNC14 THE INVESTIGATION OF DIMETHYGLOXIME LIGAND WHICH CAN BE USED FOR ACCUMULATION OF IRON IN THE BODY ON XANTHINE OXIDASE ENZYME

Gülüzar Özbolat, Hasan Ulusal ,Yusuf Döğüş, Abdullah Tuli

MNC15 PREPARATION AND APPLICATION OF AlK(SO4)2 .12H2O LOADED CHITOSAN/ POLYVINYLPYRROLIDONE CATALYTIC MEMBRANE

Derya Unlu, Aynur Hacıoglu, Nilufer Hilmioglu

MNC16 PHOSPHOTUNGSTIC ACID LOADED CELLULOSE MEMBRANE PREPARATION FOR CATALYTIC MEMBRANE REACTOR

Filiz Ugur Nigiz, Nilufer Durmaz Hilmioglu

MNC17 PALLADIUM(II)-SCHIFF BASE COMPLEX SUPPORTED ON MWCNT FOR USING AS CATALYST IN THE SUZUKI-MIYAURA REACTION

Ayşen Berna Tekin, Bilgehan Güzel

MNC18 Metal Organic Framework (MIL-101) Stabilized Ruthenium(0) Nanoparticles: Highly Efficient Catalytic Material for the Selective Hydrogenation of Phenol to Cyclohexanone

Ilknur Efecan Ertas, Mehmet Gulcan, Ahmet Bulut, Mehmet Yurderi, Mehmet Zahmakiran

MNC19 Trimetallic PdAuNi Alloy Nanoparticles Supported on Amine Functionalized Reduced Graphene Oxide for the Dehydrogenation of Formic Acid Under Mild Conditions

Mehmet Yurderi, Metin Çelebi, Ahmet Bulut, Mehmet Zahmakıran


Catalytic methods for air water pollution control

TITLE AUTHOR(S)

AWPC1 Synthesis and insitu catalytic aplication of 7-BER-NHC ligands on Suzuki reaction

Sedat YAŞAR, Emine Özge KARACA, Nevin GÜRBÜZ,İsmail ÖZDEMİR

AWPC2 Improvement of Sulfur Regenaration Ability of NSR Catalysts via Reducible Mixed Oxide Promoters

Z . Aybegum Samast, Emrah Ozensoy

AWPC3 Selective CO2 adsorption studies on NaOH impregnated AC Adsorbents

B . M . Eropak, B . S . Çağlayan, A . E . Aksoylu

AWPC4 Spectroscopic Investigation of NOx Storage and Reduction Pathways on Pt/K2O/ZrO2/TiO2/Al2O3 as NSR/LNT Catalysts

Merve Tohumeken, Zafer Say, Emrah Ozensoy

AWPC5 Removing of Synthetic Dyes from Aqueous Solutions By Using Photocatalysis and Adsorption Methods

Ali Kara, A .Çiğdem Karaerkek


POSTER PRESENTATIONS 29/04/2016

Electrochemical and photochemical catalysts

TITLE AUTHOR(S)

EPC1 ANODIC BEHAVIOR OF CARBON SUPPORTED Ni-Co, Ni AND Co ELECTROCATALYST IN DIRECT BOROHYDRIDE FUEL CELL

Alpay ŞAHİN, İrfan AR,

EPC2 THE POLYANILINE FILMS on ZnNi PLATED COPPER ELECTRODE

Nureddin Colak, A .Tuncay Ozyilmaz, Ibrahim Filazi

EPC3 Mn3O4 BASED ELECTROCATALYST SYNTHESIS FOR VANADIUM REDOX FLOW BATTERIES

Büşranur DUMAN, Berker FIÇICILAR

EPC4 Synthesis, Characterization and Photocatalytic Performance of Ag\ZnO in the Photodegradation of Methylene Blue under UV Irradiation

Kadir KARAKAŞ, Metin ÇELEBİ, Mehmet ZAHMAKIRAN

EPC5 SYNTHESIS OF CNT-TiO2-SiO2 NANOCOMPOSITE THIN FILMS: THE EFFECT OF HEAT TREATMENT ON PHOTOCATALYTIC ACTIVITY

Tuğçe Kırbaş, Gürkan Karakaş

EPC6 Determination of Reaction Kinetics for Electrochemical Oxidation of Tetracycline Antibiotic using Boron-Doped Diamond Anode

Bahadır K . KÖRBAHTİ, Selin ALACA

EPC7 THE ELECTROCATALYTIC BEHAVIOR OF COPOLYMER FILMS ON ZnFeCo DEPOSITED CARBON STEEL ELECTRODE

A .Tuncay Ozyilmaz, Gul Ozyilmaz, İ .Hakkı Karahan

EPC8 ELECTROCATALYTIC CONDUCTING POLYMER FILMS ON Zn DEPOSITED CARBON STEEL ELECTRODE

A .Tuncay Ozyilmaz, Gul Ozyilmaz, İ .Hakkı Karahan

EPC9 COBALT-BASED COORDINATION COMPOUNDS FOR ELECTROCATALYTIC WATER OXIDATION

Emine Ülker, Aysun Tekin , Satya Vijaya Kumar Nune, Ferdi Karadaş

EPC10 DETERMINATION OF OPTIMUM Cu-CeO2 ANODE COMPOSITION FOR DIRECT METHANE SOLID OXIDE FUEL CELL

Vedat Sarıboğa, M .A . Faruk Öksüzömer

EPC11 Characterization of PAni-Fe Electrocatalyst Loaded on Multi-walled Carbon Nanotube Support

Göknur Dönmez, Merve Deniz, Hüseyin Deligöz,


EPC12 Benzene Oxidation as an Alternative Method for Assessing Photocatalytic Activity

M .M . Oymak, T . Tabari D . Uner

Environmentally friendly catalytic processes

TITLE AUTHOR(S)

EFCP1 Pd-PEPPSI-Type N-Heterocyclic Carbene Complexes: Synthesis, Characterization and Catalytic Activity in The Direct Arylation Reactions

Murat Kaloğlu, İsmail Özdemir, Henri Doucet, Christian Bruneau

EFCP2 SYNTHESIS STUDIES OF THE PROMISING CATALIST; MIL-101

Emine EKİNCİ

EFCP3 Synthesis of Chiral Catalysts and Their Catalytic Activities in ScCO2

Aysen DEMİR, Burcu DARENDELİ, Bilgehan GÜZEL

EFCP4 GREEN DEHYDROGENATION OF DIMETHYLAMINE-BORANE CATALYZED BY PVP, Al2O3 AND PS-co-MA STABILIZED Ru NPs

BERİVAN BUKAN, Sibel DUMAN

EFCP5 Catalytic applications and synthesis of Pd-PEPPSI N- Heterocyclic Carbene Complexes

Nazan Kaloğlu, İsmail Özdemir, Henri Doucet, Christian Bruneau

EFCP6 Synthesis of poly(cyclooctene) derivatives bearing imidazole end group by ROMP Reactions

Gülşah ÇALIŞGAN, Bengi Özgün ÖZTÜRK, Solmaz KARABULUT ŞEHİTOĞLU

EFCP7 Direct Arylation with Palladium-NHC Complexes

Emine Özge KARACA, Nevin GÜRBÜZ, Sedat YAŞAR, İsmail ÖZDEMİR

EFCP8 Magnetic Nanoparticle Supported Latent Ruthenium Metathesis Catalysts for Olefin Metathesis Reactions

Bengi Özgün ÖZTÜRK, Solmaz KARABULUT ŞEHİTOĞLU

EFCP9 Modification of Functional Polyesters by Metathesis Reactions in the Presence of Hoveyda-Grubbs Type Catalysts

Didem OKUR, Bengi Özgün ÖZTÜRK, Solmaz KARABULUT ŞEHİTOĞLU

EFCP10 Synthesis of Fe3O4@SiO2@RN(CH2PPh2)2PdCl2 Type Nanocomposite Catalysts for Vitamin K3 Synthesis

Serhan Uruş

EFCP11 Modification of Poly(norbornenediester) Derivatives with Primary and Secondary Amine Groups

Elif Ak, Elif Yakut, Bengi Özgün ÖZTÜRK, Solmaz KARABULUT ŞEHİTOĞLU

EFCP12 Reusability of nano-12-tungstophosporic acid cesium salt in alkylation of benzene with dec-1-ene reaction

Elif AKBAY, Gülberk DEMİR


EFCP13 Alumina Supported Mn-Ce Sorbents for High Temperature Desulfurization of Hydrogen Rich Gas Mixtures

Melike Kucuker, Sena Yasyerli, A . Derya Deniz Kaynar

EFCP14 Catalytic Wet Peroxide Oxidation of Bisphenol A in Water

Fatma TOMUL

EFCP15 Graphene Supported Aminomethylphosphine-Pd(II) and Pt(II) Complexes: Highly Efficient Catalysts on Vitamin K3 Synthesis

Serhan Uruş, Mahmut Çaylar, İbrahim Karteri

EFCP16 N-Alkylation Reaction with Functionalized Ionic Liquids

Nevin GÜRBÜZ, Emine Özge KARACA, Sedat YAŞAR, İsmail ÖZDEMİR

EFCP17 The Coupling Reaction With Aryl Grignard Reagents in the Presence of Iron/NHC Catalyst

İsmail Özdemir, Serpil Demir Düşünceli, Nevin Gürbüz

EFCP18 Palladium-NHC Complex Catalyzed Cross Coupling Reactions

Serpil Demir Düşünceli, Rukiye Zengin Yaman, İsmail Özdemir

EFPC19 PHOTOCATALYTIC WATER SPLITTING OVER Au/SrTiO3 CATALYST

Ramazan Yıldırım, Dilara Saadetnejad

EFCP20 IN SITU GENERATION COPPER(0) NPs AND CONCOMITANT GREEN DEHYDROGENATION OF DIMETHYLAMINE-BORANE

Sibel DUMAN

EFCP21 Synthesis of Palladium(II) Schiff Base Complex And it’s Catalytic Activities C-C Coupling Reactions

Sinan SEVEN, Figen KOÇAK, Bilgehan GÜZEL

Hydrogenation catalysts

TITLE AUTHOR(S)

HYD1 HYDROBENZOIN TYPE LIGANDS FOR ASYMMETRIC CATALYSIS

Seda KILIÇARSLAN, Halil Zeki GÖK, İlker Ümit KARAYİĞİT, Yaşar GÖK

HYD2 THE SYNTHESIS OF MAGNETIC NANOPARTICLES SUPPORTED AZOMETHINE-OXIME-PD COMPLEX AND ITS CATALYTIC ACTIVITY

Eylül Büşra Hereytani, Fatma Ulusal, Bilgehan Güzel

HYD3 N - S u b s t i t u t e d b e n z i m i d a z o l e -Ruthenium(II) Complexes and Their Catalytic Activity

Kenan Buldurun, Nevin Gürbüz, İsmail Özdemir

HYD4 Determination of Radiation Absorption Properties of Gamma Irradiated Polyoxovanadate Based Catalysts

A .Çiğdem Karaerkek, Faruk Demir, Ali Kara


HYD5 EFFECTS OF THE PREPARATION METHOD AND CALCINATION TEMPERATURE ON THE CHARACTERISTIC PROPERTIES OF NiO-Fe2O3-SiO2 CATALYSTS

Filiz BALIKÇI DEREKAYA

HYD6 MODULAR LIGANDS ALLOWING TUNABLE STERIC AND ELECTRONIC EFFECTS FOR TRANSITION METAL CATALYSIS

Yaşar GÖK, Seda KILIÇARSLAN, Halil Zeki GÖK, İlker Ümit KARAYİĞİT

New catalytic approaches to oil refining and petrochemistry

TITLE AUTHOR(S)

ORP1 Synthesis of Tungstophosphoric Acid Incorporated Mesoporous Alumina Catalysts for Methanol Dehydration in DME Synthesis

M . İlker Şener, Naime Aslı Sezgi, Timur Doğu, Gülşen Doğu, Nuray Oktar

ORP2 Production of 2,6-Dimethylnaphthalene with Methylation of Naphthalene over Au/Mordenite Zeolite Catalysts

Eda Karayılan, Aysun Özen, Fatih Güleç, Ali Karaduman

Oxidation catalysts

TITLE AUTHOR(S)

OXC2 CHARACTERIZATION OF Ni/ZrTiO4 CATALYST FOR THE PARTIAL OXIDATION of METHANE

Burcu Aygün, Hasan Özdemir, M .A . Faruk Öksüzömer, Serkan Naci Koç

OXC3 Characterization and Catalytic Performance of MnxOy-Na2WO4/SiO2 for the Oxidative Coupling of Methane

Mahmut Yildiz, Reinhard Schomaecker

OXC4 The Effect of Metal Adding Sequence and Synthesis Media on the Properties of SnSBA-15 Catalysts at Low Metal Ratio

Filiz AKTI, Suna BALCI, Timur DOĞU

OXC5 Effect of Ti-Ce Content on the Catalytic Activity of Alumina Supported Catalysts in Selective Oxidation of H2S

H .Mehmet Tasdemir, Yavuz Yagizatli, Sena Yasyerli, Nail Yasyerli, Gulsen Dogu

OXC6 INVESTIGATION AND CHARACTERIZATION OF Ni/MgO CATALYST PREPARED BY ELECTROSPINNIG TECHNIQUE FOR THE PARTIAL OXIDATION AND DRY REFORMING OF METHANE

Burcu Aygün, Hasan Özdemir, M .A . Faruk Öksüzömer, M . Ali Gürkaynak

OXC7 THE CATALYTIC ACTIVITY OF AZO CONTAINING SCHIFF BASE COMPLEXES

Mesut İKİZ, Esin İSPİR

OXC8 TRANSITION METAL COMPLEXES OF NOVEL CHROMONE SCHIFF BASES: SYNTHESIS, CHARACTERIZATION AND CATECHOLASE-LIKE ACTIVITY

Cahit Demetgül, Neslihan Beyazıt


OXC9 Hydrothermal Synthesis and Characterization of Heterogeneous Catalysts for the Oxidation of the Thymol To Thymoquinone

Burak AY, Emel YILDIZ

OXC10 SUITABLE CATALYST OBTAINING FOR ALKANE OXIDATION AND ALKENE EPOXIDATION REACTIONS

Mehmet TÜMER, Muhammet KÖSE, Ferhan TÜMER

OXC11 POLYMER SOLID SUPPORT CATALYSTS FOR ALKANE OXIDATION


OXC12 CATALYST DESIGN FOR ALKENE EPOXIDATION


OXC13 New Ferrocene Based Schiff Bases Metal Complexes: Synthesis and Investigation of Catalytic Activities

Gökhan CEYHAN

OXC14 Oxidation of alkanes with hydrogen peroxide catalyzed by ferrocene

Gökhan CEYHAN

OXC15 Transition Metal Complexes of Ligand in a Liquid Crystal Properties: Investigation of the Catalytic Activity

Gökhan Ceyhan, Savaş Purtaş

OXC16 Novel Gallic Esters: Its Synthesis, Structural Characterization, Photoluminescence, Electrochemical Properties And Alkene Epoxidation

Gökhan Ceyhan, Savaş Purtaş

OXC17 Catalytic activity of Schiff Base Mn(III)/Co(III) complexes on bleach catalyst

Büşra GENÇOĞLU, Pınar Şen, Salih Zeki Yıldız

OXC18 Catalytic Oxidation of Nitrogen Containing Compounds for Nitrogen Determination

Alper SEVİNÇ, Gürkan KARAKAŞ, İ . Bülent ATAMER

OXC19 Catalytic Properties of ONO Type Salicylaldimine Copper(II) Complexes

Gökhan Ceyhan, Münire Sarıgül, Muhammet Köse, and Mukerrem Kurtoglu

OXC20 Copper Complexes with Bidentate NO Ligands as Novel Catalysts for the Homogeneous Partial Oxidation of Alkanes

Gökhan Ceyhan, Sevgi Kahraman, Muhammet Köse, and Mukerrem Kurtoglu

OXC21 The comparison of catalytic activity of non-ionic and ionic Mn(III)/Co(II) Phthalocyanine complexes on bleach systems

Pınar ŞEN, Salih Zeki YILDIZ

OXC22 THE CATALYTIC ACTIVITY OF NOVEL, AZO-CONTAINING SCHIFF BASES AND THEIR METAL COMPLEXES

Ayşe İNAN, Mesut İKİZ, Esin İSPİR


OXC23 Investigation of Oxidation Reaction Pathways of Oxygenates on Au(111) Single Crystal Depending on the Behaviour of Oxygen

Mustafa Karatok, Evgeny Vovk, Asad A . Shah, Emrah Ozensoy

OXC24 Effective Catalysts Derived from Carbazole for Alkene oxidation

Selma Bal

OXC25 Schiff base transition metal complexes with ceftazidime: Synthesis and Investigation of Alkane Oxidation

Ozge Eren, Harun Muslu, Gökhan Ceyhan, Mehmet Tumer and Aysegul Golcu

OXC26 Drug metal complexes: Synthesis and Investigation of Alkane Oxidation

Ozge Eren, Derya Kılıcaslan, Gökhan Ceyhan, Mehmet Tumer and Aysegul Golcu

Zeolites and mesoporous catalytic materials

TITLE AUTHOR(S)

ZMC1 Synthesis and Characterization of MCM-41 Supported Ni Catalysts for Acetic Acid Steam Reforming

Nurbanu Çakıryılmaz, H . Arbağ, N . Oktar, G . Doğu, T . Doğu

ZMC2 COMPARISON OF FRESH FCC CATALYSTS, E-CAT SAMPLES and FCC ADDITIVES FOR COMPREHENSION OF THE PROCESS

Deniz Onay Atmaca, Melek Bardakcı Türkmen, Burcu Yüzüak, Ayşegül Bayat, Ersen Ertaş

ZMC3 Hydrogen Adsorption on M2+-LTL Zeolite Clusters (M = Be, Mg and Ca): A Density Functional Theory Study

Mehmet Ferdi FELLAH

ZMC4 Investigation of Surface Acidity of Metal/Bimetal Modified Zeolite Catalysts using Pyridine Probe Molecule by FT-IR

Hülya MADENCİOĞLU and Ali KARADUMAN

ZMC5 Synthesis and Characterization of CMK-3 and Activated Carbon Based Catalysts

Gülce ÇAKMAN , Nahide NARİN, Feza GEYİKÇİ

ZMC6 IMPACT OF HYDROCRACKING CATALYST CHARACTERISTICS ON THE PERFORMANCE OF HYDROCRACKING UNIT

Melek Bardakcı Türkmen, Burcu Yüzüak, Ayşegül Bayat, Deniz Onay Atmaca, Ersen Ertaş

ZMC7 AMMONIA DECOMPOSITION REACTION OVER ZEOLITE Y SUPPORTED IRON CATALYSTS: EFFECT OF DEALUMINATION

Yeliz DURAK-ÇETİN, Şerife SARIOĞLAN, Alper SARIOĞLAN, Hasancan OKUTAN

ZMC8 Palladium (II) Schiff Base Complexes: Precursor for the Deposition onto the mesoporous SBA-15 in scCO2 Media

Asım Eğitmen, Bilgehan Güzel

ZMC9 Synthesis and Characterization of SBA15 Mesoporous Materials Functionalized with Boron Metal

Taner Tuncer, Gizem Akbıyık, Tuğba Candaş, Alime Çıtak


ZMC10 Determination of ΔH°, ΔS° and ΔG° values of B-SBA15 Mesoporous Materials Using Inverse Gas Chromatography Technique

Sercan Koç, Tuğçe Güner, Alime Çıtak

ZMC11 Single Step Synthesis of HPA loaded Al-PILCs

Suna BALCI, M .Candan KARAEYVAZ, Gulce ACIL, Funda TURGUT BASOGLU

ZMC12 Zeolite Catalysis for Bio-oil Upgrading via Esterification

Ayşenur Yeşilyurt, Ayşe Gül Türe, H . Levent Hoşgün


Lectures(Abstracts)


Support Effect in Oxide Catalysis: C-H Bond Activation on Vanadia/Ceria Compared to Vanadia/Silica

Joachim Sauer

Institut für Chemie, Humboldt-Universität zu Berlin, Unter den Linden 6, 10099 Berlin, Germany

Density functional theory is used for periodic models of monomeric vanadia species deposited on the CeO

2(111) surface to study dissociative adsorption of methanol and

its subsequent dehydrogenation to formaldehyde.1 Dissociative adsorption of methanol at different sites on VO

2·CeO

2(111) is highly exothermic with adsorption energies

of 1.8 to 1.9 eV. Two relevant pathways for desorption of formaldehyde are found with intrinsic barriers for the redox step of 1.0 and 1.4 eV. The calculated desorption temperatures (370 and 495 K) explain the peaks observed in temperature-programmed desorption experiments. Different sites of the supported catalyst system are involved in the two pathways: (i) methanol can chemisorb on the CeO

2 surface filling a so-

called pseudovacancy and the H atom is transferred to an V–O–Ce interphase bond or (ii) CH

3OH may chemisorb at the V–O–Ce interphase bond and forms a V–OCH

3

species from which H is transferred to the ceria surface, providing evidence for true cooperativity.

Compared to the vanadia-silica system,2 the vanadia –ceria system is a more active catalyst both because methanol binds more strongly on the surface and the intrinsic barriers for the hydrogen transfer step are lower. The reason is the direct participation of ceria in the redox process. On non-reducible supports like silica vanadia is reduced, whereas ceria as support stabilizes vanadium in its highest oxidation state.

References1. Kropp, T.; Paier, J.; Sauer, J., Support Effect in Oxide Catalysis: Methanol Oxidation on Vanadia/

Ceria. J. Am. Chem. Soc. 2014, 136, 14616-14625.2. Döbler, J.; Pritzsche, M.; Sauer, J., Oxidation of Methanol to Formaldehyde on Supported

Vanadium Oxide Catalysts Compared to Gas Phase Molecules. J. Am. Chem. Soc. 2005, 127, 10861-10868.


Catalysis for bio-olefins production: from research to industrial application

Fabrizio Cavani

Dipartimento di Chimica Industriale “Toso Montanari”, Università di Bologna, Viale Risorgimento 4, 40136 Bologna, Italy

In the context of a more sustainable chemical industry, the invention of new (or reconsidered) processes for the synthesis of C

2-C

4 olefins from renewables is of crucial

importance, since these molecules are fundamental building blocks for the production of polymers and intermediates. For example, butadiene is an important monomer for the production of synthetic rubber (principally for making tires and automobiles components). In this lecture the production of C

4 olefins from renewable sources is

discussed, highlighting the technologies involved and the best performing catalysts. Among the viable options, particular focus is given to the more environmentally benign and sustainable routes, that are the syntheses involving the least possible number of steps and relatively mild reaction conditions. One important example is the process for the production of butadiene from bio-ethanol. This technology was implemented at an industrial level in several countries, such as Russia, USA, Poland and Italy, during the years 1930-1950, because of the urgent need to develop an autarchic production of strategic chemicals for the 2nd World War. After the end of the war, the interest for the use of ethanol for chemicals production declined rapidly, because of the advent of the economically more convenient production from oil. Nowadays, because of both the advent of bio-ethanol production from lignocellulosic biomasses, and the scarcity of butadiene due to the shift of several cracker units from naphtha to ethane feedstock, several chemical companies have decided to investigate again old technologies for the on-purpose production of butadiene. We have investigated the mechanism of the transformation of ethanol into butadiene on bifunctional acid-base catalysts, by combining reactivity experiments, DFT calculations and in-situ DRIFT spectroscopy measurements [1,2].

References[1] A. Chieregato, J. Velasquez Ochoa, C. Bandinelli, G. Fornasari, F. Cavani, M. Mella,

ChemSusChem 8 (2015) 377.[2] J. Velasquez Ochoa, C. Bandinelli, O. Vozniuk, A. Chieregato, A. Malmusi, C. Recchi, Fabrizio

Cavani, Green Chem. 18 (2016) 1653.


Synthesis-Structure-Performance Relationships for Heterogeneous Catalysts

Krijn P. de Jong

Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science Utrecht University, The Netherlands

Supported metal catalysts are widely used for the production of transportation fuels and chemicals as well as in environmental catalysis. The metal nanoparticles are typically 1-10 nm in size and often suffer from growth during catalysis. First results on the relationship between synthesis, structure and performance for the conversion of synthesis gas (a mixture of CO and H

2) will be addressed for supported Co, Cu, Ni and

Fe catalysts. Second, control over the nanoscale distribution of Pt in alumina-zeolite composite catalysts will be related to the performance for hydrocracking of alkanes.


Hydrogenation and Hydrogenolysis Reactions Involved in Treatment of Water Contaminated with Chlorinated

Hydrocarbons

Umit. S. Ozkan

The Ohio State University, Columbus, Ohio – USA

Contamination of ground water by chlorinated hydrocarbons such as carbon tetrachloride (CTC), tetrachloroethene (PCE), trichloroethene (TCE) and 1,1,1-trichloroethane (TCA) is a growing environmental concern. The current methods to treat water contaminated with chlorinated hydrocarbons are expensive, due to high energy requirements and media replacement costs, and serve only to transfer contaminants from one phase to another, such as from water to air or from water to landfills. While elimination of these contaminants by catalytic hydrogenation and hydrodehalogenation offers a treatment strategy, there are challenges, such as the need to run these reactions at low temperatures as well as the very low concentrations of the contaminants in water. An equally important challenge is the poisoning of the catalysts by sulfides and nitrates.

Catalytic systems developed by using swellable organosilicates as catalyst scaffold have the potential to meet the challenges involved in catalytic hydrogenation and hydrogenolysis of water contaminants. Swellable organically modified silicates (SOMS) offer unique characteristics such as high affinity for absorbing organics while repelling water due to their hydrophobicity. The swelling capability of these materials allows active metals (precious metals, transition metals) dissolved in organic solvents to be deposited inside the pores, thus forming active sites “protected” in a hydrophobic matrix. This property also allows concentration of organic contaminants inside the pores, near the active sites, hence accelerating the kinetics. The presentation will discuss the use of swellable organosilica materials as a catalyst scaffold for precious and transition metals and examine their use in water treatment strategies. Characterization results from different techniques such as NMR, laser Raman spectroscopy, TEM, XPS, and infrared spectroscopy will also be presented.


Energy Intensified Reactor Design with Radio Frequency Heating

Volkan Değirmenci

University of Warwick, School of Engineering

In a conventional heating system in chemical reactors the heat is generated externally and transferred through the reaction medium. In our novel reactor design the magnetic catalyst bodies generate heat by the use of an external magnetic field through radio frequency (RF) heating. Local heat generation at the catalyst body prevents heat transfer limitations and the formation of overheated hot zones in the reactor. The precise control of temperature provides a more selective and thus a greener synthesis platform for fine chemicals. Furthermore, cascade reactions are performed in single pass continuous flow reactor with dual temperature and catalyst zones, which is a fine example of process intensification.


STRUCTURE-PERFORMANCE RELATIONSHIPS IN SUPPORTED METAL CATALYSTS WITH IONIC LIQUID LAYER

Alper Uzun

Koç University, Department of Chemical and Biological Engineering, Sariyer, 34450, Istanbul

Tuning the electronic environment on metal sites can help to control the selectivity performance of supported metal catalysts. For this purpose, coating supported metal catalysts with an ionic liquid (IL) layer offers tremendous potential. The tunable physiochemical properties of ILs play a role in controlling selectivity by not only determining the electronic environment of active sites (ligand effect), but also in controlling the active concentrations of reactants and intermediates (filter effect). In this talk, recent results on the structure-performance relationships in supported metal catalysts with IL layer will be presented. The first part of the talk will illustrate the performance improvements of a commercial supported nickel catalyst for an industrially relevant reaction, partial hydrogenation of 1,3-butadiene. Data show that upon coating the nickel catalyst with ILs, the selectivity to butenes increases from less than 1 % to values exceeding 96 % irrespective of conversion. XPS results indicate that this increase in selectivity is associated with electron donation from ILs to nickel sites. Density functional theory calculations confirm that the ILs strongly influence the electronic environment over the nickel sites. This change in electronic environment results in a strong decrease in the binding energies of butenes over the active sites. Thus, the results confirm that butene molecules formed in the first step of 1,3-butadiene hydrogenation cannot stay over the active sites, and they are replaced 1,3-butadiene molecules which can bond more strongly, as a result of electron donation from ILs to the metal sites. In the second part of the talk, the effects of ILs on metal sites will be further illustrated at the atomic level. Highly uniform and site-isolated iridium complexes supported on various metal oxides were coated with almost 40 different ILs. Infrared spectra of these samples illustrate that IL structure can be adjusted to tune the electronic environment on the metal sites. These results offer opportunities for the rational design of supported metal catalysts with IL layer for superior selectivity towards desired products for various reactions.

This study is supported by TUBITAK under 3501 Program (113M552). A.U. acknowledges the BAGEP Award of the Science Academy, Turkey.


Oral Presentations(Abstracts)


Catalytic Role of Pyrite on Hydrodesulfurization of Lignite and Asphaltite

Veysi Halvacia, Arzu Kancab, Deniz Unera

a Chemical Engineering Department, Middle East Technical University, 06800 Ankara, TURKEYb Chemical Engineering Department, Ataturk University, 25240 Erzurum, TURKEY

Pyrite, FeS2, naturally present in solid fuels can act as catalysts during hydrogenation

processes. In general, metal sulfide catalysts are used as hydrogenation and hydrodesulfurization processes of petroleum fractions. The defects in crystal lattice were considered as the responsible parts of catalytic activity. Therefore, the presence of metal sulfide active sites in the structure increases the process efficiency. Since pyrite is a metal sulfide present in the coal structure, Guin et al. reported a higher reaction rate in the presence of pyrite during hydrogenation process [1].

In this study, catalytic effect of pyrite has been investigated by hydrogenation of a high sulfur Turkish lignite and asphaltite at atmospheric pressure. The first results of hydrogenation experiments for Tuncbilek lignite with high pyrite content (2.6% in weight) revealed that H

2 reduction decreases the sulfur contents considerably. Additionally, the

amount of residual carbon decreased as observed from the decrease in CO2 formation

rate of hydrogenation residue during TPO. These effects are interpreted for the catalytic effect of pyrite [2]. Hydrodesulfurization of Şırnak asphaltite with 1.59% pyrite, is carried out under 100 sccm flow of 10% H

2 and balance N

2. Gas and liquid product analysis

indicated that hydrogenation of asphaltite results in a significant decrease in total sulfur while producing nearly 20% liquid fuel, which contains organics from C

6 to C

26.

AcknowledgementsThe authors kindly acknowledge Atalay Calisan for his assistance during experiments and METU

PAL for detailed hydrocarbon analysis.

Reference[1] J.A. Guin, A.R. Tarrer, J.W. Prather, D.R. Johnson, J.M. Lee, Effects of Coal Minerals on

Hydrogenation, Desulfurization, and Solvent-Extraction of Coal, Industrial & Engineering Chemistry Process Design and Development, 17 (1978) 118-126.

[2] A. Kanca, D. Matthew, J.A. Reimer, D. Uner, Following The Structure and Reactivity of Tuncbilek Lignite During Pyrolysis and Hydrogenation, Fuel Processing Technology, Submitted for publication. (2016).


REDUCED GRAPHENE OXIDE (RGO) SUPPORTED Pt NANOPARTICLES: EFFECT OF DIFFERENT REDUCING AGENTS ON

RGO

Elif DAŞa, Ayşenur ÖZTÜRKb, Ayşe BAYRAKÇEKEN YURTCANa,b

a Department of Nanoscience and Nanoengineering, Atatürk University, 25240, Erzurumb Department of Chemical Engineering, Atatürk University, 25240, Erzurum

Proton exchange membrane fuel cell (PEMFC) is a potential power source with high efficiency and an attractive solution to global energy demand. However, one of the most challenging problems that needs to be overcome is development of cost-effective and durable electrocatalysts [1]. Carbon supported platinum (Pt/C) is a well accepted catalyst on PEMFC and shows high electrochemical performance, but the corrosion of carbon leads to the detachment of platinum nanoparticles from the support materials and the aggregation of these particles causes the decrease of active surface area. Recently, various carbon support materials with different nanostructures have been used as the electrocatalyst support in PEMFCs.

Graphene, a monolayer of carbon atom in a crystal lattice, has received great attention as a support material for PEMFC applications due to its basal plane structure with high surface area and high conductivity.

In this study, graphene oxide (GO) was synthesized from natural graphite powder by the method of Hummers and Offeman [2]. GO can be readily reduced by different reduction processes and using different reducing agents. In this study, two different reducing agents (hydrazine [3] and DMF [4]) were used. Pt nanoparticles were decorated on reduced GO by using microwave irradiation technique. The properties were analyzed by SEM, EDS, BET, TGA, FTIR, TEM and cyclic voltammetry (CV) techniques.

References[1] F. Memioğlu, A. Bayrakçeken, T. Öznülüer, M. Ak, International Journal of Hydrogen Energy, 37

(2012) 16673-16679 .[2] W.S. Hummers, R.E. Offeman J Am Chem Soc, 1958;80:1339-40[3] Ö. Metin, E. Kayhan, S. Özkar, J.J. Schneider, International Journal of Hydrogen Energy, 37

(2012) 8161-8169. [4] Ö. Metin, Ş. Aydoğan, K. Meral, Journal of Alloys and Compounds, 585 (2014) 681-688.


Catalytic Tar Removal on Nickel-loaded Perovskites

Basar Caglara, Taymaz Tabaria, Deniz Ünera,a Middle East Technical University, Chemical Engineering Department, 06531, Ankara, Turkey

Dry reforming of tar compounds has been studied on Ni loaded perovskites to gain insight into conversion of tar compounds (produced by biomass gasification) into synthesis gas. Nickel is a highly active hydrocarbon decomposition and water-gas shift (WGS) catalyst suffering from coke deposition and sintering. Perovskite materials (e.g. LaCoO

3 and LaFeO

3) are used to compensate the problems related to stability of nickel

catalyst by sintering and coke formation. Perovskites exhibit high thermal stability, high oxygen storage/release capacity and high tar removal activity [1-3]. For this study, we choose benzene as a model compound for tars. We have investigated dry reforming of benzene on Ni/LaCoO

3 at various Ni loadings, CO

2 to benzene ratios and temperatures.

The conventional Ni/Al2O

3 catalyst was also used as a reference material to determine

the relative activity of Ni/LaCoO3. Several techniques were used to characterize catalyst

materials: XRD to determine crystal structure, BET to determine surface area, pore structure and volume of catalysts, Temperature Programmed Reduction (TPR) to determine the reducibility of materials, XPS to detect the oxidation state and chemical composition of the catalyst surface, TGA to determine the amount of carbon deposited after reaction. We found that the reducibility of Ni/LaCoO

3 catalyst is 4 times higher

than that of Ni/Al2O

3 catalyst and the surface concentration of nickel is 4 times more

on Ni/LaCoO3 catalyst than that on Ni/Al

2O

3 catalyst. Due to its high surface nickel

concentration and reducibility, Ni/LaCoO3 catalyst shows two times higher benzene

conversion and H2 yield and less carbon formation than than the conventional Ni/Al

2O

3

catalyst.

References[1] J. Suntivich, K.J. May, H.A. Gasteiger, J.B. Goodenough, Y. Shao-Horn, Science, 334 (2011)

1383-1385.[2] R.J.H. Voorhoeve, D.W. Johnson, J.P. Remeika, P.K. Gallagher, Science 195 (1977) 827-833. [3] P. Ammendola, L. Lisi, B. Piriou, G. Ruoppolo, Chemical Engineering Journal, 154 (2009) 361-

368.


Ultrasound assisted biodiesel production in presence of dolomite catalyst

İbrahim Korkuta, Mahmut Bayramoğlua

a Gebze Technical University, Chemical Eng. Department, 41400 Kocaeli, Turkey

Ultrasound (US) assisted transesterification of canola oil in presence of dolomite catalyst. An US generator (200 W, 20 kHz) equipped with an horn type probe (19 mm) as shown in Figure 1, was used to study the effect of catalyst amount (3-7 % wt. of oil), methanol/oil molar ratio(4/1-15/1), ultrasound power (30-50 W), temperature (25 - 60° C) and time (60-120 min.) on US assisted biodiesel synthesis. As seen in Figure 2, biodiesel yield reached over 97.4% for dolomite at the end of 90 min. According to the results, US improved the transesterification reaction by reducing necessary time for high biodiesel yield, using dolomite as heterogeneous catalyst.

Figure 1. Scheme of experimental setup

Figure 2. Effect of ultrasound irradiation time on the biodiesel yield (Transesterification conditions; catalyst amount: 5% wt. of oil, methanol/oil molar ratio: 9/1, US power: 45 W, temperature: 60 °C)


Ruthenium(0) nanoparticles supported on xonotlite nanowire: a long-lived catalyst for hydrolysis of ammonia-borane

Serdar Akbayrak, Saim Özkar

Department of Chemistry, Middle East Technical University, 06800 Ankara.

Ruthenium(0) nanoparticles supported on xonotlite nanowire (Ru(0)@X-NW) were prepared by the ion exchange of Ru3+ ions with Ca2+ ions in the lattice of xonotlite nanowire followed by their reduction with sodium borohydride in aqueous solution at room temperature. Ru(0)@X-NW were characterized by a combination of advanced analytical techniques. The results show that (i) highly dispersed ruthenium(0) nanoparticles of 4.4 ± 0.4 nm size were formed on the surface of xonotlite nanowire, (ii) Ru(0)@X-NW show high catalytic activity in hydrogen generation from the hydrolytic dehydrogenation of ammonia borane with a turnover frequency value up to 135 min−1 at 25.0 ± 0.1 ºC. (iii) They provide unprecedented catalytic life time (TTO = 134,100) for hydrogen generation from the hydrolysis of ammonia borane at 25.0 ± 0.1 ºC (Fig.1). (iv) The results of a kinetic study on the hydrogen generation from the hydrolysis of ammonia borane were also reported including the activation energy of 77 ± 2 kJ mol−1 for this reaction [1].

Figure 1. The variation in turnover number (TON) and turnover frequency (TOF) during the catalytic lifetime experiment performed at 25.0 ± 0.1 °C.

References[1] Serdar Akbayrak, Saim Özkar Dalton Trans., 2014, 43,1797.


Synthesis of STA/SBA-15 Catalysts for Ethyl Acetate Production and Characterizations of Catalysts

Veli SIMSEKª, Kirali MURTEZAOGLUb

a Bilecik Seyh Edebali University, Chemical and Process Engineering Department, 11100, Gulumbe Campus, Bilecik.

b.Gazi Universty, Chemical Engineering Department,06570, Maltepe Ankara.

Silicate structured mesoporous materials with larger surface areas, narrow pore size distributions and high thermal stability are a good candidate for some application fields and as support materials in the catalytic synthesis[1,2]. Although application of SBA-15 as catalyst is unlikely due to it’s weak Lewis acidity and absence of Bronsted acid sites, Bronsted acidity should be enhanced by impregnation and other methods[3]. For instance, the hydrothermal method has also been used for STA/SBA-15 catalysts by Simsek et al[2,4]. Ethyl esters have long been attracted alternatives to biodisel additives[5].

In the present study, STA was loaded by dry impregnation method after TEOS on SBA-15 support material. SBA-15 and STA (Silicotungstic acid) were used to support and active material respectively. The loading amount of silicotungstic acid were determined as 1.25, 2.5, 5% (W/Si; w/w ratio). Actually this loading ratios are very low for the impregnation method. But catalysts were succesfully synthesized by appyling impregnation method. Ethanol/acetic acid molar ratio, temperature and catalyst amount were determined as 1/1, 343 K and 0.4g respectively. The catalytic activities of STA/SBA-15 (2.5 and 5%) catalysts were investigated in ethyl acetate reaction. The results showed that the activity of catalysts increased with increasing active material(STA) in the catalyst. The physical properties of the catalysts were determined with XRD, DRIFT, BET, SEM/EDX and MAPPING analysis methods. The low angle XRD results of the catalysts revealed characteristic peaks (100),(110) and (200) reflections. In order to determine Lewis and Bronsted sites of the catalysts were used to pyridine and then analyzed FT-IR. The results indicated that the catalysts had Lewis and Bronsted sites.

References[1] Obalı, Z. Doğu, T. Chem. Eng. J. (2008) 138:548-555.[2] Şimşek, V. Değirmenci L. Mürtezaoğlu K., Turk J. Chem.(2015) 39:683-696[3] Ghiaci, M. Aghabarari, B. Chinese Journal of Catalysts (2010) 31: 759-764[4] Şimşek, V. Değirmenci L. Mürtezaoğlu K., Reac Kinet Mech Cat.(2015) in press.[5] Merchant, S. Q. Almohammad, K. A. Bassam, A. A. M. Ali, S. H. Fuel (2013) 111: 140-147


INVESTIGATION OF CATALYST, REACTION CONDITIONS AND PROCESS DESIGN FOR HYDROGEN PRODUCTION FROM STEAM

REFORMING OF GLYCEROL

Öykü Parlar, M. Efgan Kibar, A. Nilgün Akın, Meltem Karaman

Kocaeli University, Chemical Engineering Department, 41380, İzmit, Kocaeli

There is an increasing energy demand, due to the limitation of fossil oil reserves. In search of alternative energies, many scientists, pay more attention on the renewable energy sources because of less pollution, reliability and long-term profit. Fuel cell technology is an attractive alternative lately for producing electricity. The growth in fuel cell technology has improved the demand for hydrogen (H

2), which is the simplest

and most abundant element [1]. Hydrogen production process and technology, has been improving and changing but, currently hydrogen is mostly produced from natural gas and oil fractions, which are still abundant and economically feasible. Nevertheless, hydrogen production by these methods, produces high amount of carbon monoxide. Glycerol, which is the by-product of biodiesel production, is non-toxic, non-volatile and has high energy density. Theoretically, after the transesterification process, 10 kg biodiesel and as by-product, 1 kg glycerol can be produced [2]. Increasing energy demand will cause the need for clean energy technologies, like biodiesel, and this will effect glycerol production. By using glycerol for hydrogen production, more effective and clean energy can be produced. In this study, a reaction prosess is designed and built in Kocaeli University Chemical Engineering Department Catalyst Investigation and Development Laboratory (KARGEL) and proper catalyst and reaction conditions are investigated. With using nickel based catalysts, the most favorable support is found as CeO

2 with % 15 (wt) nickel loading. Besides that, some reaction conditions, like water /

glycerol ratio is also investigated and hydrogen yield is increased with increasing water/ glycerol ratio. The highest hydrogen yield is found as 4,82, with % 15 Ni/ CeO

2 catalyst,

water / glycerol ratio of 15 and 650°C.

REFERENCES[1] Johnston, Technovation, 25 (2005) 569.[2] Wang, Fuel Processing Technology, 91 (2010) 1812.


Oxy-CO2 Reforming of Methane over Al2O3 Supported Nickel Catalysts prepared by Deposition-Precipitation with urea

Tuba Gürkaynak Altınçekiça, Tugay Pehlivana

a Chemical Engineering Department, İstanbul University,34320,Istanbul,Turkey

One of the most attractive chemical approaches for the utilization of carbon dioxide (CO

2) and methane (CH

4), which are the main components of some natural gas

resources including coal bed gases, could be the catalytic oxy-CO2 reforming of

methane to produce syngas [1]. Noble metal based catalysts exhibit high activities and stabilities, their limited availabilities and high costs confine their wide spread application in industry. So nickel (Ni)-based catalyst became commercially more attractive for the methane reforming processes. But the carbon deposition which causes rapid deactivation on the Ni based catalysts is one of the important problems associated with the methane reforming processes. This problem could be minimized by modification of the catalysts. The oxy-CO

2 reforming of methane to produce syngas were tested over

Ni/Al2O

3, Ni/ZrO

2, Ni/CeO

2 and Ni/MgAl

2O

4 catalysts with various Ni loadings which

were prepared via deposition-precipitation method using precursor of nickel nitrate and urea [2]. The catalysts were characterized by X-ray powder diffraction analysis (XRD), H

2-temperature-programmed reduction (H

2-TPR) and Brunauer Emmett Teller

(BET) analysis techniques. The reforming reactions were carried out using a gas mixture with a feed ratio of (CH

4/CO

2/O

2/N

2=3/1/1/4) and reaction temperatures in the range

700–800 ºC. The activity and stability of the catalyst, carbon deposition, and synthesis gas (H

2/CO) ratio were determined. Among the catalysts evaluated, catalyst with 15

wt.% Nickel content Ni/Al2O

3 catalysts revealed the most active catalytic performance

toward combined reforming reactions. In addition, catalyst with 15 wt.% nickel loading was employed in long term stability test and has shown stable catalytic performance up to 10 h time on stream without any decrease in methane conversion in the process.

Fig.1 HRTEM micrograph of 15 wt.% Ni/Al2O

3 catalysts Fig.2 Activity Results of Ni/Al

2O

3 catalysts


AcknowledgementThis study was supported by The Scientific and Technological Research Council of Turkey,

Engineering Research Grant Committee (MAG), through project No: 213M381 and by Istanbul University Research Fund through project No: 49082

References[1] Hu, Y.H., Ruckenstein, E., 2004, Catalytic conversion of methane to synthesis gas by partial

oxidation and CO2 reforming, Advances in Catalysis, 48, 297-345[2] Wiley, J., 2009, Synthesis of Solid Catalysts, ISBN: 9783527320400, 111-112


Production of 5-Hydroxymethylfurfural by Catalytic Dehydration of Fructose over SO4/La-TiO2-SiO2

Emre KILIÇ1, Tjeerd Alexander NIJHUIS2, Selahattin YILMAZ1

1 Department of Chemical Engineering, Izmir Institute of Technology, Izmir, Turkey2 SABIC T&I Chemical, Geleen, The Netherlands

5-hydroxymethylfurfural (HMF) is a valuable intermediate for fine chemicals, pharmaceuticals and furan-based polymers. It can be produced by acid-catalyzed dehydration of fructose. In the present study, acidic mesoporous SO

4/La-TiO

2-SiO

2 catalyst prepared by sol-gel method was developed for this reaction. Its titanium and La content was 6 and 1 wt. %, respectively. The catalyst was sulfated by ammonium sulfate. With La addition, the sulfur captured by the catalyst increased and thereby its acidity increased magnificently. Reaction tests were carried out in water-methylisobutylketone at three different temperatures (110, 160, 200 oC). Different fructose/catalyst weight ratios (W

Fr/W

cat= 0.5, 1.0 and 2.0) were also applied.

Activity results showed that SO4/La-TiO

2-SiO

2 catalyst was very active and fructose was

completely converted in 3 h at 160 and 200 oC. HMF selectivity of 96 % was achieved at 160 oC. At higher temperature of 200 oC, the selectivity dropped to some extent due to the secondary decomposition of HMF. Fructose conversion and HMF selectivity was also affected significantly by fructose/catalyst weight ratio. A complete conversion (100 %) was observed for W

Fr/W

cat 0.5 and 1. However, activity dropped significantly (from 99

% to 69 %) when WFr/W

cat increased from 1 to 2. This was attributed to the reaction of

fructose with side products instead of adsorption to the catalyst acid sites. In addition, selectivity to HMF decreased slightly (from 99 to 93% at about 90 % conversion).


Catalytic performance of transition metal doped montmorillonite for biomass hydrolysis

Emir Zafer Hoşgüna, Ebru Tunça, Halit Levent Hoşgünb, Berrin Bozana

a Anadolu University, Engineering Faculty, Chemical Engineering Department, Eskisehir.b Bursa Technical University, Engineering Faculty, Chemical Engineering Department, Bursa.

In recent years, hydrolysis of cellulose with solid catalysts has taken attention by many researchers. This process is an environmentally friendly technology with overcomes problems associated with less-environmentally friendly chemicals and product purification.Montmorillonite is one of the most common 2:1 type clays. It is widely dispersed on the earth’s surface which has high hydrothermal stability and large surface area [1]. In this study, hazelnut shells were used as biomass transition metals doped montmorillonite used as heterogeneous catalyst. The doped montmorillonite catalyst were prepared by impregnation methods using Cr(NO

3)

3, CuNO

3, Fe(NO

3)

3, Co(NO

3)

2

and Zn(NO3)

2. Metal nitrates (10 wt%) were dissolved in an ethanol-water mixture (50-

50%) and montmorillonite was added into the solution and mixed for 24 h. Collected clay was washed with DI water and dried under vacuum at 40°C. Catalytic hydrolysis were carried out in a high temperature-high pressure stainless steel reactor (Parr, USA) reactor. Reaction conditions were 180°C, 2 hr and 1/100 catalyze/biomass ratio. The solution was kept liquid under N

2 atmosphere (10 bar). At the end of the treatment,

the treated slurry was collected and filtered using filter paper to separate the solid and liquid fractions for further analysis. Compositions of liquid products were analyzed by high-performance liquid chromatography (HPLC) [2].All the catalysts synthesized in this study were effective on the furfural and HMF yield and selectivity from the biomass. Cr-MMT was the most effective one, followed by Cu-MMT, Zn-MMT and Fe-MMT. 30.38 mg furfural and 1.96 mg HMF was produced per gram of the biomass in the presence of the Cr-MMT catalyst.

AcknowledgementThis study was supported by Anadolu University Scientific Research Projects Commission under the

grant no: 1502F065

References[1] Tong, D. S., Xia, X., Luo, X. P., Wu, L. M., Lin, C. X., Yu, W. H., & Zhong, Z. K. (2013).

Catalytic hydrolysis of cellulose to reducing sugar over acid-activated montmorillonite catalysts. Applied Clay Science, 74, 147-153.

[2] Sluiter, A., Hames, B., Ruiz, R., Scarlata, C., Sluiter, J. ve Templeton, D. (2006), “Determination of sugars, byproducts, and degradation products in liquid fraction process samples,” National Renewable Energy Laboratory, Golden, CO.


Parametric investigation of glycerol reforming in a wall-coated microchannel reactor

Sinan Koc, Ahmet Kerim Avci

Department of Chemical Engineering, Bogazici University, Bebek 34342 Istanbul/Turkey

Conventional production of biodiesel via transesterification of animal-based or vegetable oils is known to cause an oversupply of glycerol as a byproduct. A possible solution for removing excess glycerol involves efficient conversion of glycerol to H

2.

This conversion requires high temperatures and external energy demand, both of which depend strongly on the catalyst type and reactor geometry. Microchannel reactors are known to enable high heat transfer rates, and fast and homogeneous distribution of external heat to the catalyst bed, favoring its efficient utilization.

The work is aimed to investigate non-oxidative (GSR) and oxidative glycerol steam reforming (OGSR) over Ni-based catalysts in a microchannel reactor. The effects of reaction temperature (773-873 K), molar inlet steam-to-carbon (S/C=3-6) and carbon-to-oxygen (C/O=0.75-2.25) ratios are studied. The reactor is composed of a Ni coated FeCrAlY plate that is inserted into a µ-EDM machined cylindrical steel housing to give a single microchannel (0.75x4x20 mm). Coated FeCrAlY plate is obtained by first preparing powdered catalyst (5 and 10% Ni/Al

2O

3) and then by mixing it with deionized

water to form slurry, which is coated on oxidized FeCrAlY. Product analysis is done via two on-line GCs on MS-5A and Porapak Q columns.

Results show that glycerol conversions and product yields obtained in OGSR are notably higher than those of GSR. Decreasing C/O ratio improves conversion, but decrease H

2 yield. Changing S/C ratio affects product distribution via water-gas shift. H

2

yield is improved S/C, which is found to be optimal between 4 and 5; higher values lead to lower conversions due to possible Ni sintering and/or reoxidation of Ni sites. In all cases, coking is detected, but found to be much less severe in OGSR. Increasing metal loading gives only a minor increase in conversion due to better Ni dispersion in the 5% case, as observed from SEM-EDX analysis.


BIODIESEL PRODUCTION FROM MODEL WASTE VEGETABLE OIL BY USING ZIRCONIUM SULFATE CATALYST

Melike İmge ŞENOYMAKa, Oğuzhan İLGEN a,b

a Chemical Engineering Department, Kocaeli University, 41380, Kocaeli, Turkeyb Alternative Fuels R&D Center, Kocaeli University, 41040 Kocaeli, Turkey

Biodiesel is defined as mono-alkyl-esters of long chain fatty acids derived from renewable and natural resources like vegetable oils and animal fats [1, 2]. In biodiesel production process, the most important disadvantage is high cost of feedstock oils. For this reason, many studies have been done for using cheaper feedstocks such as non-edible oils, animal oils or waste cooking oils [3]. Since the cheaper oil sources contain high free fatty acid, acid catalysts that catalyzed transesterification and esterification reactions simultaneously are more suitable [4]. In this study, zirconium sulfate was used as a heterogeneous acid catalyst because of its high catalytic activity, low toxicity, low cost and easy handling [5]. Waste vegetable oil was modeled by adding 6 wt.% of oleic acid as free fatty acids into sunflower oil. In the course of biodiesel production, effects of some reaction parameters such as reaction time, reaction temperature and reusability of catalyst were investigated. The highest fatty acid methyl ester (FAME) yield of 86 % was obtained under reaction conditions of 115°C reaction temperature, 4 h reaction time, 9:1 methanol/oil molar ratio and 3 wt.% catalyst amount.

References[1] Mohapatra S.B., Das P., Swain D., Satapathy S., Sahu S. R., A Review on Rejuvenated Techniques

in Biodiesel Production from Vegetable Oils, International Journal of Current Engineering and Technology 6 (2016) 100-111.

[2] Sirisomboonchai S., Abuduwayiti M., Guan G.,Samart C., Abliz S., Hao X., Kusakabe K., Abudula A., Biodiesel production from waste cooking oil using calcined scallop shell as catalyst, Energy Conversion and Management 95 (2015) 242-247.

[3] Z. Wen, X. Yu, S. Tu, J. Yan, E. Dahlquist, Biodiesel production from waste cooking oil catalyzed by TiO2–MgO mixed oxides, Bioresource Technology 101 (2010) 9570–9576.

[4] O. Ilgen, Investigation of reaction parameters, kinetics and mechanism of oleic acid esterification with methanol by using Amberlyst 46 as a catalyst, Fuel Processing Technology 124 (2014) 134-139.

[5] Juan J., Zhang J., Yarmo M., Study of catalysts comprising zirconium sulfate supported on a mesoporous molecular sieve HMS for esterification of fatty acids under solvent-free condition, Applied Catalysis A, 347 (2008) 133-141.


ESTERIFICATION OF CETYL ALCOHOL AND PALMITIC ACID OVER W AND Zr CONTAINING ACIDIC CATALYSTS

Vahide Nuran Mutlua, Selahattin YILMAZa

a Izmir Institute of Technology, Chemical Engineering, Izmir Instıtute of Technology Chemical Eng. Department Urla, Izmir Turkey

Esters of fatty acids and alcohols are used as raw materials for emulsifiers, oiling agents and surfactants in different industrial areas. Cetyl palmitate is one of the most important cetyl esters for cosmetics industry. In the present study, it was aimed to develop active, selective and reusable heterogeneous catalysts for esterification of cetyl alcohol by palmitic acid. For this purpose, Zr incorporated SBA-15 was prepared by hydrothermal synthesis. Silylation of Zr-SBA-15 was performed to see the effect of hydrophobicity of the catalyst. WO

3 loading onto the Zr-SBA-15 was also performed by incipient wetness

impregnation. Moreover, WO3-ZrO

2 catalyst was prepared by co-precipitation with two

different contents of WO3 (15 wt% and 20 wt%). The catalysts were characterized by

XRD, Raman, BET, NH3-TPD and FTIR. The reaction tests were carried out in mesitylene

under reflux conditions within 6 h reaction time. Zr-SBA-15 catalyst which had the highest amount of Brønsted acid sites gave maximum cetyl palmitate yield (See Table 1). This catalyst retained its activity up to 3 reuse cycles without significant loss of activity.

Table 1 Initial rate of disappearance and conversion of cetyl alcohol and yield of cetyl palmitate over different catalysts

* r0/TA

is defined as r0x105 per total acidity

This study was founded by TUBITAK as project number 112M701. Their support is gratefully acknowledged.

References[1] K. Mantri, K. Komura, Y. Sugi, Green Chemistry 7, (2005), 677-682[2] A. Sakthivel, K. Komura, Y. Sugi, Ind.Eng.Chem.Res. 47, (2008) 2538-2544


DESIGN AND CHARACTERIZATION OF SELECTIVE CO2 ADSORBENTS

Burcu Acara, Burcu Selen Çağlayana,b, A. Erhan Aksoylu,a

a Boğaziçi University, Department of Chemical Engineering, 34342, Istanbul, Turkeyb Advanced Technologies R&D Center, Boğaziçi University, 34342, Istanbul, Turkey

Nearly 40% of CO2 in the atmosphere is emitted by fossil fuel based power production

plants (coal, oil, gas). In abatement of CO2 emission to the atmosphere originating

from these units, carbon capture and sequestration technologies (CCS) have a high potential. As CCS currently is an expensive process, cost effective CCS options need to be developed. Adsorption is taught as one of the most promising approach due to the low energy requirement, cost advantage, and ease of applicability over a relatively wide range of temperatures and pressures [1].

The aim of this study is to design and develop AC-based CO2 adsorbent(s) having both

high and stable CO2 adsorption capacity, and ability to adsorb CO

2 selectively from CO

2-

CH4 mixture. In this context, a commercial activated carbon, Norit ROX, was oxidized

by air and HNO3, and two series of adsorbents, AC8 and AC9 series, respectively, were

prepared on those oxidized ACs by K2CO

3 impregnation followed by calcination at

various temperatures. Adsorption/selective adsorption tests were conducted for 0-1000 mbar pressure range under 50 ml/min gas flow rate at room temperature (RT), 120 °C and 200 °C for pure CO

2, pure CH

4 and their mixtures, 50% CO

2-50% CH

4 and

10% CO2-90% CH

4. Adsorbent with the best CO

2/CH

4 selectivity results was further

tested for 0-5000 mbar pressure range at RT. While pressure icrease had a positive effect on adsorption, temperature increase had a negative effect on adsorbed CO

2 and

CH4 amounts.The experimental adsorption isotherm data were fitted to Langmuir,

Freundlich and Dubinin-Radushkevich (D-R) models and D-R model was found to be the most successful one in explaining CO

2 and CH

4 adsorption behaviors of AC samples.

Pseudo-first order and pseudo-second order kinetic models are fitted to kinetic data. Pseudo-first order kinetic model was more successful in explaining both CO

2 and CH

4

adsorption kinetics at RT.

References[1] B. S. Caglayan, A. E Aksoylu, Journal of Hazardous Materials 252-253 (2013) 19-28.


Novel Hybrid Perovskite Catalysts For DeNOx Applications

K.E. Ercana, Z. Saya, E.I. Vovka,b, G. Pantaleoc, L. Liottac, A. Veneziac, and E. Ozensoy*c

aDepartment of Chemistry, Bilkent University, 06800 Ankara, TurkeybBoreskov Institute of Catalysis, 630090, Novosibirsk, Russian Federation

cCNR-Institute for the Study of Nanostructured Materials (ISMN), 90146, Palermo, Italy

Air pollution due to the emission of toxic gases is a serious threat for human health. Recently, it was reported that perovskite based De-NO

x catalysts can be used as an

alternative to the high-cost Pt oxidation catalysts [1,2]. In this work, a new generation of hybrid perovskites were designed in the form of LaCo

xMn

1-xO

3 by varying Co and

Mn loadings (x=0.1-0.9) in an attempt to fine-tune the thermal stability and catalytic activity of the catalysts as shown in Figure 1. NO

x adsorption and release properties

of hybrid perovskites were analyzed via TPD. Figure 2 shows the NO(g) desorption channels of the investigated materials during nitrate decomposition indicating that NO desorption characteristics are strongly influenced by Mn/Co ratio in the catalytic formulation. Co-rich hybrid perovskites can store and release a significantly higher amount of NO

x where LaCo

0.8Mn

0.2O

3 catalyst has the greatest amount of NO

x storage

as compared to all other perovskites.

Figure 1: Material design strategy for the Figure 2: NO(g) TPD profiles of H2 pre-treated perovskites

synthesis of hybrid perovskites.

References:[1] C. Kim, G. Qi, K. Dahlberg, W. Li, Science (2010) 1624–1627,327 (2010)[2] Z. Say, M. Dogac, E.I. Vovk, Y.E. Kalay, C.H. Kim, W. Li, E. Ozensoy, Appl. Catal. B: Environ.

154-155, 51 (2014)


NH3 Uptake Behavior of a Commercial Cu-Zeolite Monolithic Catalyst for the NH3-Selective Catalytic Reduction of NOx

Selmi Erim Bozbağa, Feyza Gökalilerb, Gökhan Hisarb, Can Erkeya,c

a Koç University, Chemical and Biological Engineering Department, 34450, Sarıyer, Istanbul, Turkey.

b Ford-Otosan Sancaktepe Engineering Center, Akpınar Mh. Hasan Basri Cd. No:2 34885 Sancaktepe, İstanbul, Turkey

c Koç University TÜPRAŞ Energy Center (KUTEM), Koç¸ University, 34450 Sarıyer, Istanbul, Turkey.

Selective Catalytic Reduction of NOx with NH3 is a widely used technology for the

engine aftertreatment of diesel vehicles in the presence of excess oxygen and water. Cu ion-exhanged zeolites with chabazite (CHA) structure have recently become the catalyst of choice because of its high NOx conversion performance at a relatively large temperature range and good hydrothermal stability [1, 2]. The recent and most consistent reaction scheme for NH

3-SCR of NOx on Cu/CHA suggests the reaction of

the adsorbed NH3 with adsorbed N=O or adsorbed nitrite species on Cu+ and Cu2+ sites,

respectively [3]. Therefore, the fundamental understanding of NH3 adsorption on the

catalyst is the first and a very important step towards elucidating the reaction kinetics for the development of a reactor model. In this study, we used the synthetic gas bench heterogeneous catalysis setup we have installed in Koç University and investigated the adsorption of NH

3 on Cu/CHA using the Temperature Programmed Desorption

of NH3 (TPD-NH

3) in the absence and presence of O

2 and H

2O at a NH

3 saturation

temperature range of 150-400 oC. TPD curves indicated three desorption sites at 343, 471 and 560 oC associated with NH

3 chemisorption when the adsorption was carried

out at 150 oC in the absence of O2 and H

2O. The peak at the 343 oC gradually degraded

as the saturation temperature increased or when O2/H

2O was present in the saturation

stream. The amount of chemisorbed NH3 stored in the catalyst decreased when the

saturation temperature increased from 150 to 400 oC, respectively. The presence of 8% O

2 and 5% H

2O in the NH

3 saturation stream caused a decrease in the NH

3 uptake from

6 to 100% when the saturation temperature increased from 150 to 400 oC, respectively, due to the oxidation of NH

3.

References[1] J. H. Kwak et al., J. of Catalysis 275 (2010) 187.[2] Supriyanto et al., Applied Catalysis B: Environmental 163 (2015) 382.[3] T. V. W. Janssens et al., ACS Catalysis 5 (2015) 2832.


Sulfur-Tolerant BaO/ZrO2/TiO2/Al2O3 Quaternary Mixed Oxides for DeNOx Catalysis

Z. Say[a,c], O. Mihai[b], M. Tohumeken[a], L. Olsson[b], E. Ozensoy[a

[a] Department of Chemistry, Bilkent University, 06800 Ankara, Turkey[b] Chemical Reaction Engineering and Competence Centre for Catalysis, Chalmers University of

Technology, SE-412 96 Göteborg, Sweden[c] Chemistry Laboratory Directorate, Turkish Standardization Institute, 06800 Ankara, Turkey

Advanced quaternary mixed oxide materials in the form of BaO/Al2O

3/ZrO

2/TiO

2 which were functionalized with Pt active sites (i.e. Pt/BaO/AZT) were synthesized and structurally characterized via XRD and BET in comparison to a conventional Pt/20BaO/Al benchmark NSR/LNT catalyst. Interaction of these catalyst surfaces with SOx and NOx gases were monitored via spectroscopic techniques such as in-situ FTIR and TPD. There exists a delicate trade-off between NO

x Storage Capacity (NSC) and sulfur

uptake/poisoning which is strongly governed by the BaO loading/dispersion as well as the surface structure and acidity of the support material. Flow reactor measurements performed under realistic catalytic conditions show high NOx activity for Pt/8BaO/AZT and Pt/20BaO/AZT catalysts at 473 and 573 K. After sulfur poisoning and subsequent regeneration at 773 and 973 K, Pt/8BaO/AZT and Pt/20BaO/AZT surpassed NOx catalytic performances of all other investigated materials including the conventional Pt/20BaO/Al benchmark catalyst at 473 and 573 K [1-9].

Figure 1: FTIR spectra related to SOx release properties of sulfur-poisoned (a) Pt/AZT, (b) Pt/8Ba/AZT,

(c) Pt/20Ba/AZT and (d) Pt/20Ba/Al in the presence of H2(g).

References[1] Z. Say, E.I. Vovk, V.I. Bukhtiyarov, E. Ozensoy, Topics in Catalysis 56 (2013) 950.[2] Z. Say, E.I. Vovk, V.I. Bukhtiyarov, E. Ozensoy, Appl. Catal. B: Environ. 142-143 (2013) 89. [3] Z. Say, M. Tohumeken, E. Ozensoy, Catalysis Today 231 (2014) 135. [4] Z. Say, M. Dogac, Y.E. Kalay, C.H. Kim, W. Li, E. Ozensoy, Appl. Catal. B: Environ.154-155


(2014) 51.[5] Z. Say, M. Tohumeken, E. Ozensoy, Catalysis Today Catalysis Today 10.1016/j.

cattod.2015.12.013[6] G.S. Senturk, E.I. Vovk, Z. Say, A.M. Soylu, V.I. Bukhtiyarov, E. Ozensoy, Catalysis Today 184,

54 (2012). [7] Z. Say, O. Mihai, M. Tohumeken, K.E. Ercan, L. Olsson, E. Ozensoy, ChemSusChem (2016)

submitted [8] M. Dogac, Z. Say, E.I. Vovk, C.H. Kim, E. Ozensoy, Topics in Catalysis (2016) submitted. [9] Z. Say, O. Mihai, M. Tohumeken, K.E. Ercan, L. Olsson, E. Ozensoy, ChemSusChem (2016)

submitted


Development of CuOx/nr-TiO2 Catalysts for CO2 abatement

Murat Efgan KİBARa,b, Gizem GÜRGÜRa,b, Ayşe Nilgün AKINa,b

a Kocaeli University, Department of Chemical Engineering, 41380, Kocaelib Kocaeli University, Alternative Fuels Research and Development Center, 41040, Kocaeli

The amount of greenhouse gases has been increasing with the energy consumption. Uncontrolled CO

2 release is the first actor of global warming. Therefore the reduction of

CO2 emission supports to produce more efficient energy systems. CO

2 can be used and/

or reduced by storage, artificial photosynthesis, active reactant, catalytic CO2 reactions

and etc. Photocatalytic reactions exhibit more moderate reaction conditions with respect to thermal reactions [1,2]. In the present study, the catalytic reaction conditions are investigated between sodium metaborate solutions and CO

2. Nano rod (nr) titania

(TiO2) are synthesized from commercial TiO

2 as a support material and the activities

of the cupper are investigated for the photocatalytic reactions. The conversions were calculated due to the online observation of feed and output stream concentrations. The reactions performed in a semi-batch quartz reactor with the constant flow rate of CO2 and also with 5% and 10% CuO

x/nr-TiO

2 catalysts. The catalysts were charecterised

with the analytical tecniques of BET, x-ray powder diffraction and transmission electron microscopy. Nano rod formation is given in Figure 1. According to the results, CuOx/nr-TiO

2 has been found as an active catalyst for CO

2 abatement with sodium metaborate

solution.

Figure 1. TEM image of CuOx/nr-TiO

2 catalyst

References[1] Tahir, M., NorAishah S. A., Renewable and Sustainable Energy Reviews, 25 (2013) 560-579.[2] Jeyalokshmi,V., Rajalokshmi, K., Res Chem Intermed., 39 (2013) 2565-2602.


Carbon Aerogel Supported Platinum-Copper Nanoalloys Using Supercritical Deposition

Şansım Bengisu BARIMª, Ezgi Erdemª, Selmi Erim Bozbağª, Rıza Kızılelb, Mark Aindowc, Haibo Yuc, Can Erkeya,b

a Department of Chemical and Biological Engineering, Koç University, 34450, Sarıyer, Istanbul,b Koç University Tüpraş Energy Center (KUTEM), Koç University, 34450, Sariyer, Istanbul

c Department of Materials Science and Engineering, Institute of Materials Science, University of Connecticut, 06269, United States

Supercritical deposition method is attracting increasing attention for preparation of supported bimetallic nanoalloys because it provides good control of metal loading, particle size and homogeneous distribution of bimetallic nanoparticles on the substrate surface. The technique involves dissolution of organometallic compounds in the supercritical fluid and exposure of a porous substrate into this mixture followed by the adsorption of metallic precursors onto the substrate. Precursors on the surface are then converted to their metal forms via different routes. Carbon supported Pt is the commercial catalyst for polymer electrolyte membrane fuel cell (PEMFC) electrodes, however; its high cost constitutes a big obstacle for the commercialization of PEMFCs. Therefore, research efforts are directed to reduce the amount of platinum while maintaining the activity by developing alloys of Pt with cheap metals. In this study, the applicability of supercritical deposition was investigated for preparation of carbon aerogel (CA) supported Pt-Cu- nanoalloys for use as electrocatalysts for PEMFCs. For this purpose, dimethyl(1,5-cyclooctadiene) platinum(II) (Pt(cod)me

2) was used as the

platinum precursor and copper(II)trifluoroacetylacetonate (Cu(tfa)2) was used as the

copper precursor. Single adsorption isotherms of both precursors were determined and from single adsorption isotherms binary adsorption isotherms of Pt(cod)me

2-

Cu(tfa)2-CA system were determined using Ideal Adsorbed Solution Theory (IAST).

Reduction of adsorbed precursors were done at 200 oC under flowing hydrogen. Catalysts were then annealed at 600 oC. STEM images and XRD data showed that Pt-Cu nanoparticles were alloys and the average size of the particles was around 3-4 nm with a narrow particle size distribution. Electrochemical activity of the prepared catalysts were investigated using cyclic voltammetry which were conducted in a conventional three electrode electrochemical cell assembly containing 0.1 M HClO

4 as electrolyte.


Enviromental Friendly Latent Ruthenium Metathesis Catalysts for the Synthesis of Nano-ROMP Polymers

Bengi Özgün ÖZTÜRKa, Solmaz KARABULUT ŞEHİTOĞLUa

a Hacettepe University, Department of Chemistry, 06800, Beytepe, ANKARA

Scheme 1. Ruthenium indenylidene complexes bearing protonable side groups

Olefin metathesis is a useful synthetic method to prepare complex molecular structures in an efficient manner[1]. Due to the tremendous interest in olefin metathesis, recent studies focus on the development of latent and more environmentally friendly metathesis catalysts [2]. Latent catalysts are of great importance in polymer chemistry, since the latency of the catalyst allows the efficient mixing of the catalyst in monomer without any polymerization reaction occurring at ambient temperatures [3].

In this study, we developed two novel ruthenium indenylidene Schiff base catalysts, bearing morpholine (Ru-1) and tertiary amine (Ru-2) functionality (Scheme 1). Ru-1 and Ru-2 are latent and inactive towards olefin metathesis reactions under normal conditions and can be activated on demand by introduction of HCl to the reaction media. Emulsion ring opening metathesis polymerization (ROMP) reactions were carried out in aqueous media using non-ionic surfactants and nano-sized polymeric particles (25-75 nm) were obtained. Molecular weights (M

n) of ROMP polymers

were controlled between 90-280 kDa by varying HCl/Ru (mol/mol) ratio during the activation step. In addition, both catalysts exhibit high silica gel affinity. The metal concentration of the final product can be reduced to 2 ppm from 500 ppm by simple silica gel filtration.

References [1] T.M. Trnka, R.H. Grubbs, Acc Chem Res, 34 (1) (2001), 18–29[2] A. Szadkowska, K. Grela, Curr Org Synth, 12 (2008), 1631–1647[3] A. Leitgeb, M. Abbas, A. Poater, L. Cavallo, C. Slugovc, Catal Sci Technol, 2 (2012), 1640–1643


KINETIC AND MECHANISTIC FEATURES OF CARBON DIOXIDE REFORMING OF METHANE OVER Co–Ce/ZrO2 CATALYSTS

Aysun İpek Paksoyª, Cansu Yassı Akdağª, Burcu Selen Çağlayanb,ª. Erhan Aksoyluªa Bogazici University, Department of Chemical Engineering, 34342, Istanbul, TURKEY

b Bogazici University, Research and Development Center, 34342, Istanbul, TURKEY

Carbon dioxide reforming of methane (CDRM) is an environmentally friendly catalytic process since it utilizes two thermodynamically stable greenhouse gasses, CO

2 and CH

4,

to produce synthesis gas. The low H2/CO product ratio is also preferable for further

processes like Fischer-Tropsch synthesis. However, highly endothermic nature of CDRM imposes high reaction temperatures and this may cause coking and/or metal sintering. [1] It is also reported that this is a slow reaction involving long residence times [2]. Therefore, to compete with the other reforming routes in commercial production, the economical impediments of the process should also be overcome. Thus, mechanistic features of the reaction need to be revealed.

The previous studies have shown that Ce-doped Co/ZrO2 catalysts perform high

activity and have a very limited activity loss [1]. This study aims to determine the kinetic behavior of CDRM over 5%Co-2%Ce/ZrO

2 and 10%Co-2%Ce/ZrO

2 catalysts

as a function of temperature and partial pressures of CH4, CO

2, CO and H

2. In this

context, power-law type rate expressions were obtained for both catalysts. Then, the experimental data were fit to mechanistic rate expressions, and the model parameters were determined. The reaction orders with respect to CH

4 were estimated to be higher

than that for CO2 in the power type rate laws of both catalysts. An inhibitory effect of

H2 introduction to the feed was also noted. The model that best fitted to the CDRM

kinetics on 5%Co-2%Ce/ZrO2 catalyst was expressed as the one based on an Eley-Rideal

type mechanism with the reaction of adsorbed CO2 with CH

4 in the gas phase as rate

determining step. For 10%Co-2%Ce/ZrO2 catalyst, the model derived from Langmuir-

Hinshelwood type mechanism with CH4 dissociation as the rate determining step gave

the lowest squared error.

References: [1] A. I. Paksoy, B. Selen Caglayan, A. E. Aksoylu, Applied Catalysis B: Environmental, 168 (2015)

164-174. [2] Y. Kathiraser, U. Oemar, E. T. Saw, Z. Li, S. Kawi, Chemical Engineering Journal, 278 (2015)

62–78.


Computational (DFT) and Experimental (FTIR-DRIFT) Investigation of CO2 Activation on ZrO2

A. Uzuna, A. İ. Paksoya, V. Çimenoğlub, A. E. Aksoylu*,a

aBoğaziçi University, Department of Chemical Engineering, 34342, Istanbul, TurkeybSiemens Healthcare, Kartal, Istanbul, Turkey

Carbon dioxide reforming of methane (CDRM) consumes carbon dioxide and methane, two thermodynamically stable greenhouse gasses, and produces synthesis gas. CO

2 utilization makes dry reforming in attractive way to avoid global warming. CDRM process has been attracted widespread attention of many researchers considering the fact that its product has H

2/CO=1, which is suitable for production of valuable hydrocarbons

and oxygenated compounds through following reactions such as Fischer-Tropsch process. Supports like ZrO

2 play a crucial role in stable activity of CDRM catalysts by

activating CO2 to yield surface oxygen which is responsible for cleaning surface carbon

forms during reaction [1]. Though oxygen formation and transfer mechanism has been used in many research papers for explaining CDRM process, there has been less work merely focus on CO

2 activation on ZrO

2.

In the current study, computational and experimental findings were used in a combined fashion to understand the details of the CO

2-ZrO

2 interaction. In the experimental

part, CO2 adsorption on ZrO

2 was analyzed by FTIR-DRIFT, and the results confirmed

ZrO2-CO

2 interaction via detection of CO as a product when CO

2 adsorption on

ZrO2 was conducted. Additionally, formation of different surface groups was noted.

In computational part, the adsorption of CO2, CO and O on the stoichiometric

m-ZrO2(11) was explored using DFT calculations on periodic models. DFT simulations

clearly showed that CO2 interacts with stoichiometric m-ZrO

2(11), but this does not

yield C-O bond breakage, and there is weak CO adsorption on surface sites of the ordered m-ZrO

2(11). As the DFT results eliminated the surface oxygen production

on ordered m-ZrO2(11) sites, the evaluation of experimental and computational

results indicated that CO2 activation yielding surface oxygen occurs on defect sites of

m-ZrO2. DFT results on O adsorption also revealed that oxygen mobility is possible on

m-ZrO2(11) surface.

References:[1] A. I. Paksoy, B. Selen Caglayan, A. E. Aksoylu, Applied Catalysis B: Environmental, 168 (2015)

164-174.


Performance test of monolithic Ni-based catalyts for carbon dioxide reforming of methane

Aybüke Lebaa, Ramazan Yıldırıma

a Department of Chemical Engineering, Boğazici University, 34342 İstanbul, TURKEY

The utilization of carbon dioxide and methane together as a reforming process to synthesis gas has been received a great attention for a few decades since it has been considered as a promising solution for global warming. From the industrial point of view, the demand of an effective and economic catalyst is still a crucial issue. Ni-based catalysts have been seemed to be a good alternative for the process as having low cost and remarkable activity; however, stability is still a major problem [1]. Therefore, great efforts to diminish the deactivation and to extend its industrial application are ongoing.

In this study, Ni-based catalysts were evaluated in the monolithic form which is believed to provide excellent heat transfer [2]. The cordierite monoliths were wash-coated with various supports such as MgO, SiO

2 and CeO

2 to see support effect on this form; and

then were co-impregnated with Ni and Co active metals. The performance test of the catalyst was conducted in a fixed bed quartz reactor (I.D.=10.00mm) at the temperature interval of 873–1173 K and at 1 atm. A gas hour space velocity (GHSV) of 42,000mL/hg-catalyst was used with CH

4/CO

2 feed ratios of 1 to obtain a product H

2/CO ratio of

1. N2 was also used as an internal standard. The results showed that monolithic form of

the catalyst has a positive effect on the performance of the catalyst, such as in the case of MgO, where CH

4 conversion and CO

2 conversion at 800°C were increased from 83%

and 90% to 90% and 94%, respectively, comparing with the granule form.

References[1] C. Li et al., Fuel Processing Technology, 140 (2015) 39-45.[2] M.P. Kohn et al., Applied Catalysis B, 94 (2010) 125-133.


Structure-performance relationships in supported nickel catalysts for hydrogen production from ammonia

İbrahim Şahina, Alper Uzuna

aDepartment of Chemical and Biological Engineering, Koç University, 34450 Sariyer, Istanbul, Turkey

Hydrogen can be produced in on-board applications via ammonia decomposition with no CO

x emissions. Ruthenium based supported catalysts were initially studied for this

reaction because of their superior performance; however, there is a need for a cheaper alternative due to high price and limited availability of ruthenium. Thus, in this study, we focus on nickel based catalysts as cheap alternatives. We have elucidated the structure-performance relationships of on these cheap counterparts for hydrogen production by ammonia decomposition. These relationships were studied by changing nickel nanoparticle size systematically on various metal-oxides, such as SiO

2, Al

2O

3, MgO, TiO

2,

CeO2, La

2O

3, SBA-15, and MCM-41 covering a variety of surface electronic structures

ranging from a point of zero charge of pH = 2 to 11.

Figure 1. Arrhenius plots for the reaction rates of tested catalysts measured at differential conversion.

Data show that hydrogen production rate is controlled by metal nanoparticle size; but the support’s surface acidity is the dominant factor. As the surface basicity increases, the rate of hydrogen production increases significantly. Results offer valuable information towards the design of Ni-based catalysts as cheap alternatives to Ru-based counterparts.

This study is supported by TUBITAK under 1003 Program (Project number: 213M028). A.U. acknowledges the BAGEP Award of the Science Academy, Turkey.


The Effects of Reaction Parameters on Mn/Na2WO4/SiO2 Catalyst for Oxidative Coupling of Methane

Hasan Özdemira, M.A. Faruk Öksüzömera, M. Ali Gürkaynaka

a Department of Chemical Engineering, Istanbul University, Avcilar/Istanbul, 34320, Turkey

Oxidative coupling of methane (OCM), which produces ethane and ethylene from methane directly, attracted considerable attention over decades [1]. However, it has not been possible to design a catalyst that could provide higher C

2 yields than 27%

for the commercialization of this process because of the thermodynamic and kinetic constraints [2]. Many catalysts have been developed for OCM reaction and amongst them, Na

2WO

4/MnO

2/SiO

2 is the most investigated catalyst in the literature and its

OCM activity and selectivity is quite remarkable. However, there are few reports that examined the influence of reaction conditions on Na

2WO

4/MnO

2/SiO

2 catalyst and

there is no work about the influence of N2O as an oxidant.

Considering these facts, it was aimed to investigate the influence of reaction parameters such as oxidant type, CH

4/O ratio, GHSV and temperature on 2(wt%)Mn/5(wt%)

Na2WO

4/SiO

2 catalyst for OCM reaction. Activity tests showed that high C

2 yields

could be obtained at low CH4/O ratios and contact time independent of the oxidant

type (O2 or N

2O) and reaction medium within the selected range of the parameters.

Continuous increase in temperature enhanced the C2 yield especially when N

2O was

used for the gas phase reactions. However, the highest C2 yield (16.4%) was obtained

with the catalyst at CH4/O=1, 7500 L kg-1 h-1 and 780°C using O

2 as an oxidant and

11.5% at 820°C with the use of N2O. Thus, the optimum temperature depends on

the type of oxidant and catalyst use. Obtained results also indicated that, the catalyst activity towards O

2 dissociation is well but not for N

2O decomposition. O

2 is more

efficient than N2O but the latter is more selective than the former. 2Mn/5Na

2WO

4/SiO

2

was found to be quite stable during the stability tests performed with both oxidants under the optimum conditions.

References [1] J.H. Lunsford, Catal Today, 63 (2000) 165-174.[2] R. Ghose, H.T. Hwang, A. Varma, Appl Catal a-Gen, 472 (2014) 39-46.


Schiff Base complexes on bleach catalyst for the real industrial applications

Ertug Yildirima,S. Zeki Yildiza, Okan Yuzuakb, Idil Yilmaz Yalinalpb, Nihat Toslub

aSakarya University, Faculty of Arts and Sciences, Department of Chemistry, 54187, SAKARYA-TURKEY

bHayat Holding, Hayat Road, No:2, 41000, KOCAELI-TURKEY

Schiff base chemistry is played an important role in the development of coordination chemistry due to forming complexes with most transitions metals having wide applications in chemical industry as catalysts [1]. One of the most important approaches in the chemical industry concerning with the oxidation reactions is the bleaching process [2]. Oxidative bleach processes are great importance for the pulp and paper production, textile pre-treatment, waste water treatment and industrial and domestic laundry processes [3]. Oxidation catalysis is used to increase the performance of hydrogen peroxide in laundry bleach applications [4].

Bleach activator systems, such as N,N,N’,N’-tetraacetylethylenediamine (TAED), have been developed and are applied in many laundry detergents. However, bleach catalyst provide cost-effective, energy saving and environmentally friendly bleach systems recently [5].

So, in this study the preparation of manganese and cobalt complexes was performed by using MnCl

2. 4H

2O and CoCl

2.6H

2O salts in basic condition for bleach catalysis. FT-IR,

UV–vis spectra were applied to characterize the prepared compounds. The degradation of Morin dye characterizes the wine stains. The degradation progress in the detergent characteristic has been examined using online spectrophotometric method (OSM). It was found that the prepared catalysts exhibited better bleaching performance at 25 °C than to that of TAED.

References:[1] Z. Liang, Z. Liu, L. Jiang, Y. Gao, Tetrahedron Lett. 48 (2007) 1629.[2] J.I. Kroschwitz, M. Howe-Grant Kirk-Othmer, Encyclopedia of Chemical Technology, 4th ed.,

Wiley, New York, 1991. [3] H. Offermanns, G. Dittrich, N. Steiner, Chemie in Unserer Zeit 34 (2000) 150.[4] Ranold Hage, Achim Lienke, Angew. Chem. Int. Ed. 45 (2006) 206–222.[5] G. Reinhardt, M.Loeffler, Tenside Surfact. Deterg. 34, 1997,404.


CHARACTERIZATION OF CATALYTIC CONVERTER

Yiğit Türea, Emre Gürlekb, Nurcan Çalış Açıkbaşa, Şeref Soylub and Türker Güdüc

a Bilecik Şeyh Edebali University, Metallurgical and Materials Science Engineering Department, 11230, Bilecik

b Bilecik Şeyh Edebali University, Mechanical and Manufacturing Engineering Department, 11230, Bilecik

c TOFAŞ Türk Otomobil Fabrikası A.Ş., 16369, Bursa

In this study, the analyses of a commercially available oxidation catalyst (two way catalytic converter) which was obtained from TOFAŞ A.Ş., were conducted in order to determine manufacturing process, chemical composition and phase analysis by several characterization methods, mainly optical microscopy, scanning electron microscopy (SEM) and x-ray diffraction (XRD). Macrostructural observations by optical microscopy showed that structure type was honeycomb and dimensions of cells and frame thickness were 1011x997.4 µm and 116.35 µm, respectively and shaping technique was extrusion. SEM (SEM-SE-EDX) was used for elemental analysis and size measurements of coating materials. The results showed that three layers of coating material existed and included carbon, oxygen, aluminium, silicon, titanium and cerium. The average thickness of each of layer was 25 µm. XRD analysis showed that the main phase was Cordierite.


POSTERPRESENTATIONS

(Abstracts)


POLYANILINE COATING ON MODIFIED CARBON PASTE ELECTRODE TO CONSTRUCT AMPEROMETRIC GLUCOSE BIOSENSOR

A.Ebru AYDIN, Gul OZYILMAZ, Serbay BUCAK, Nureddin ÇOLAK, Ali Tuncay OZYILMAZ

Mustafa Kemal University Faculty of Art and Science, Department of Chemistry,31000, Hatay, Turkey

Carbon paste electrode (CPE) has been shown a convenient type of working electrode/substrate for such electropolymerization and many studies regarding electropolymerization on the surface of CPE were done [1]. In this study, amperometric biosensor construction was carried out by immobilization of glucose oxidase (GOD) enzyme on CPE coated by polyaniline (PANI) which was synthesized by cyclic voltammetry technique. CPE was prepared by mixing 875 mg graphite powder and 375 µl mineral oil and after homogenization, the mixture was packed into the piston-driven CPE holder with a surface diameter of 4.5 mm [2]. An organic molecule, 2-hydroxy-3-methylcyclohex-2-enone (HMCE) (Fig.1(A)), was added to CPE to modify glucose biosensor. Also, PANI film was synthesized in two different electrolyte as oxalic acid and p-toluenesulfonic acid. The first cyclic curves are given in Figure 1(B) and Figure 1(C) for oxalic acid and p-toluenesulfonic acid, respectively.

Figure 1. The structure of 2-hydroxy-3-methylcyclohex-2-enone (HMCE) (A) and The Cyclic voltammograms of modified carbon paste electrode (blue) (HMCE-CPE) and unmodified carbon paste electrode (red) in oxalic acid medium (B) and in p-toluenesulfonic acid medium (C)

As seen in Figure 1 (B) and (C), modified carbon pasta electrode with HMCE showed an increase in the current for both oxalic acid and p-toluenesulfonic acid mediums when comparing with unmodified CPE.

References [1] Stoces, M., Kalcher, K., Svancara, I., Vytras, K., Int.l J Electrochem Sci 6 (2011) 6 1917-1926[2] Yağız, E., Preparation And Characterization of Carbon Paste Electrode Modified By Different

Ways Using Response Surface Methodology and Use in Biosensor Applications (2015), PhD Thesis, Mustafa Kemal University.


THE USE OF CYCLIC ENONES AS ORGANIC MOLECULES TO CONSTRUCT OF AMPEROMETRIC GLUCOSE BIOSENSORS

Gul OZYILMAZ, A. Ebru AYDIN, Serbay Bucak, Seda AGCAM, Ali Tuncay OZYILMAZ

Mustafa Kemal University, Department of Chemistry,31000, Hatay, Turkey

A glucose sensitive amperometric biosensor was constructed by immobilizing glucose oxidase (GOD) onto Pt electrode coated double layers of conductive polymers. First layer, polypyrrole (PPy), was synthesized in pyrrole, LiClO

4, cyclic enones as

organic molecule (6-hydroxy-2-methoxy-3-methyl-cyclohex-2-enone or 2-hydroxy-3-methylcyclohex-2-enone) containing acetonitrile medium by cyclic voltammetry technique. Then, second layer, polianiline (PANI), was synthesized using aniline and HCl containing aqueous medium onto PPy coating. GOD was immobilized onto conductive film layered Pt electrode via chitosan and glutaraldehyde. Organic molecules used in study and electrode scheme was given in Figure 1. α-Hydroxy and α’-hydoxy-α-methoxy cyclic enones were synthesized according to literature procedures [1].

Figure 1. Organic molecules used in PPy layer and schematic representation of obtained electrode.

GOD catalyzes the oxidation of glucose in presence of molecular oxygen by forming gluconic acid and H

2O

2 [2]. The current value which was measured by oxidation of

formed H2O

2 was proportional by glucose concentration. (Fig.2).

Figure 2. Principle of the amperometric glucose biosensor

References [1] Demir, A.S., Caliskan, Z., Aydin A.E., Bicer, I., Tetrahedron-Asymmetry 17 (2006) 786-791.[2] Ozyilmaz, G., Ozyilmaz, A.T., Can F., Applied Biochemistry and Microbiology 47 (2011) 196-

205.


IMPROVEMENT OF GLUCOSE BIOSENSOR BY CATALYTIC EFFICIENCY OF ZnFe2O4 NANOPARTICLES


Mustafa Kemal University, Department of Chemistry,31000, Hatay

ZnFe2O

4 nanoparticle was used to improve the glucose sensitivity of glucose oxidase

(GOD) electrode. GOD electrode was constructed using three steps. Poly(o-anisidine) (POA) was synthesized onto Pt electrode by using cyclic voltammogram technique in sodium oxalate electrolyte at first. Secondly, GOD was immobilized on POA surface with chitosan and ZnFe

2O

4 nanoparticles. Finally, surface was reacted with glutaraldehyde

solution. GOD electrode was used in glucose solution by chronoamperometric technique to obtain current value proportioned with glucose concentration (Figure 1).

Figure 1. Enzymatic reaction occurred on GOD electrode

Imax

values of nanoparticle-free and ZnFe2O

4 nanoparticle containing GOD electrode

were 6.02 and 11.95 µA, respectively. There were similar results in the literature [1,2]. It was observed that residual activities at the end of the 20 repeated uses of nanoparticle-free and ZnFe

2O

4 nanoparticle containing GOD electrodes were 92 % and 93 %,

respectively.

AcknowledgementThe authors wish to thank the Mustafa Kemal University department of Scientific Research Projects

for supporting the this study (Project no:8681)

References[1] Ren, J., Shi, W., Li, K., Ma, Z., Sensors and Actuators B, 163 (2012) 115-120.[2] Luo, X., Xu, J., Du, Y., Chen, H., Analytical Biochemistry, 334 (2004) 284-289.


GLUCOSE OXİDASE IMMOBILIZATION ON POLY(o-TOLUIDINE) COATED Pt ELECTRODE FOR AMPEROMETRIC BIOSENSOR


Mustafa Kemal University, Department of Chemistry,31000, Hatay

A glucose sensitive amperometric biosensor was developed by immobilizing glucose oxidase (GOD) enzyme on poly(o-toluidine) (POT) coated Pt electrode. Firstly, POT synthesis was carried out in sodium oxalate (NaOx) medium using cyclic voltammetry technique on the Pt electrode surface and doped with HCl solution. Then, A thin layer was constructed by dipping polymer coated electrode in GOD enzyme and ZnFe

2O

4 nanoparticle containing chitosan solution. Finally immobilization of enzyme on the surface was carried out via crosslinking by reacting with glutaraldehyde (GAL) solution (Figure 1).

Figure 1. Schematic representation of enzyme electrode construction.

The current value which was measured by oxidation of forming H2O

2 which was

produced enzymatic catalysis. Optimal electrode construction parameters were determined for segment number, scan rate, monomer, chitosan, glutaraldehyde, GOD and nanoparticle concentrations. It was observed that, current values measured for nanoparticle containing electrodes were higher than those of non-containing counterparts. This result is supported by the literature [1,2]. It was concluded that, ZnFe

2O

4 nanoparticles showed catalytic activity on H

2O

2 decomposition.

AcknowledgementThe authors wish to thank the Mustafa Kemal University department of Scientific Research Projects


References[1] Ren, J., Shi, W., Li, K., Ma, Z., Sensors and Actuators B, 163 (2012) 115-120.[2] Luo, X., Xu, J., Du, Y., Chen, H., Analytical Biochemistry, 334 (2004) 284-289.


Double Catalytic Centers: Potential Therepautic Applications for the Treatment of Oxidative Stress

Ferhan Tümer, Songül Şahin, Mehmet Tümer, Muhammet Köse

Chemistry Department, Kahramanmaraş Sütçü Imam University, 46100, Turkey

Porphyrins in natural systems play an important role in biological systems such as in oxygen transportation (hemoglobin), photosynthesis (chlorophyll) and enzymatic catalysis (Cytochrome) [1]. The main advantage of utilizing porphyrins as catalysts is to control of modification of the structures and ease of following structure-catalytic activity correlation. Catalytic activity is thought to link to the substitute groups on p-phenyl positions [2] as well as central metal atoms. Schiff bases are considered as an important class of biological model compounds and their metal complexes are in use as biomimetic catalysts. Counts all these advantages make the important of the Schiff bases in bioinorganic chemistry, catalyst, encapsulation, transportation, seperation and magnetochemistry [3]. These knowledge about porphyrins and Schiff base compounds have led us to combine these two different class into a new class “Porp-Schiff” type compound for possible treatment of oxidative stress caused by mainly superoxide. A new porphyrin- Schiff base ligands and their transition metal complexes were synthesised and characterised by spectroscopic and analytical methods. The catalytic performance of the for the dismutation of superoxide (Figure 1) were then evaluated and their potential usage as metolo-drugs were invetigated.

Figure 1: Dismutation of superoxide by Porphyrin based metal complexes.

AcknowledgmentsWe are grateful to The Scientific & Technological Research Council of Turkey (TUBITAK) (Project

number: 113Z907) for the support of this research.

References[1] S. Aronoff, J. Phys. Chem. 62 (1958) 428–431.[2] G. De Luca, A. Romeo, L.M. Scolaro, G. Ricciardi, A. Rosa, Inorg. Chem. 46 (2007)5979–5988.[3] A.J. Atkins, D. Black, A.J. Blake, A. Marin-Bocerra, S. Parsons, L. Ramirez, , M. Schroder. Chem.

Commun. (1996) 457-458.


RESPONSE SURFACE METHODOLOGY FOR OPTIMIZATION OF CONSTRUCTION OF AMPEROMETRIC GLUCOSE BIOSENSORS

Gul OZYILMAZ, Seda AGCAM and Ali Tuncay OZYILMAZ

Mustafa Kemal University, Department of Chemistry, 31040, Hatay

Pt electrode was coated by poly(N-methylpyrrole) (PNMP) by cyclic voltammetry technique in 10 mM monomer (N-methyl pyrrole) containing sodium oxalate solution. Glucose sensitive electrode was constituted by immersing PNMP coated Pt electrode into Glucose Oxidase (GOD) containing chitosan (Chi) solution and then glutaraldehyde (GAL) solution, respectively. The optimization of concentrations of Chi (0.25-1.00 mM), GOD (1-4 mg/ml) and GAL (0.025-0.10%) were carried out by Response Surface Methodology (RSM) using Box-Behnken design. Current values were measured in presence of glucose and results were evaluated by State Ease Design Expert 8.0.7.1 software programme (Serial No: 0021-6578) to get ANOVA analysis, 3D surface, contour and predicted-actual values graphics. The changing of current values by investigated parameters in presence of glucose were given in Figure 1 (a-b-c-d) as 3D surface graphics and predicted values vs actual values.

Figure 1. Current values in presence of glucose depending on investigated parameters (a, b and c), and predicted vs actual value (d)

AcknowledgementThe authors wish to thank the TUBITAK (Project no: 113Z424) and Mustafa Kemal University

department of Scientific Research Projects for supporting the this study (Project no:13781)


THE CO-IMMOBILIZED ENZYME SYSTEM FOR LACTOSE SENSITIVE BIOSENSOR

Esra YAĞIZ, Gul OZYILMAZ and Ali Tuncay OZYILMAZ

Mustafa Kemal University,Department of Chemistry,31000, Hatay

A new lactose sensitive amperometric biosensor was developed using β-galactosidase (β-GAL) and glucose oxidase (GOx). β-GAL catalyzes the hydrolysis of lactose into galactose and glucose; afterwards GOx catalyzes the oxidation of glucose by forming gluconic acid and H

2O

2 (Ferreira et al., 2004). The current value which was measured

by oxidation of forming H2O

2 was proportional by glucose thereby by lactose

concentration. In this study, polyaniline (PANI) was synthesized by two sequential step onto CPE and modified CPE with 1-(2-cyanoethy)pyrole (CNEP) (Fig 1 a, a'). Biosensor was constructed by co-immobilization of β-GAL and GOx via glutaraldehyde onto PANI.

Figure 1. PANI synthesis curves obtained from first (a) and second (a') step; impedance analsis for CPE/PANI/GOx+β-GAL in buffer (--) and in lactose (-) (b); and for CPE-CNEP/PANI/GOx+β-GAL in buffer (-) and lactose (-) solution (b')

As seen in Fig. 2 (b) and (b’), charge transfer resistance values which corresponding to first loop observed at high frequencies were lower in presence of lactose. This means that biosensor is sensitive to lactose. Besides, charge transfer resistance of modified CPE were significantly low than that of unmodified CPE. This was concluded by increasing electron transfer rate in terms of CNEP molecule. Also, K

M and I

MAX values were obtained

for CPE/PANI/GOD+β-GAL as 1.9 mM and 2.7 µA, respectively; and for CPE-CNEP/PANI/GOD+β-GAL as 1.23 mM and 4.6 µA, respectively. AcknowledgementThe authors wish to thank the Mustafa Kemal University Department of Scientific Research Projects


References [1] Ferreira, L., S., Trierweiler, J. O., De Souza Jr, M. B., Folly, R. O. M., Brazilian Journal of

Chemical Engineering, 21 (2004).


CARBON PASTE ELECTRODE BASED SUCROSE BIOSENSOR

Esra YAĞIZ, Gul OZYILMAZ, and Ali Tuncay OZYILMAZ


Recently, carbon paste electrodes (CPE) have been used extensively due to having many advantages such as low cost, easily preparation and modification [1,2]. A co-immobilized enzyme system based biosensor for sucrose was constructed using CPE modified by 1-(2-cyanoethyl) pyrrole (CNEP). CPE was prepared by graphite:mineral oil:CNEP at 1.75:0.38:0.25 weight ratio. Polyaniline (PANI) was synthezed onto modified CPE by cyclic voltammetry technique in aniline monomer containing sodium oxalate medium. Invertase and glucose oxidase were immobilized onto PANI film by crosslinking via glutaraldehyde to obtained sucrose biosensor.The effect of CNEP was investigated by cyclic voltammograms obtained in buffer and glucose containing buffer solution (Fig.1-a). As seen in Fig 1-a, current values for modified electrode were significantly higher than those of unmodified counterpart. Also for both electrodes, it was clearly seen that, current values were higher in sucrose containing buffer solution. Similarly, as seen in Fig.1-b, current values depending on sucrose concentration for modified electrodes were at least three times higher than those of unmodified electrode.

Figure 1. Cyclic voltammogram of unmodified CPE in buffer (-) and in sucrose (-) solution and cyclic voltammogram of modified CPE in buffer (--) and sucrose (-) solutions (a); Current values depending on sucrose concentration, (¢):modified and (£): unmodified CPE (b)

KM

and IMAX

values for unmodified electrodes were 1.86 mM and 0.98 µA, respectively and 0.65 mM and 2.7 µA for modified electrodes, respectively.

AcknowledgementThe authors wish to thank the Mustafa Kemal University Department of Scientific Research Projects

for supporting the this study (Project no:12980)References [1]Boujita, M. Boitard M., El Murr N., Biosensorsand Bioelectronics, 14 (1999) 545-553.[2]Comba, F. N., Rubianes, M. D., Herrasti, P., Rivas, G. A., Sensors and Actuators B:Chemical. 149

(2010) 306–309.


GLUCONIC ACID PRODUCTION BY co-IMMOBILIZED GLUCOSE OXIDASE-CATALASE ENZYME SYSTEM

Gul OZYILMAZ

Mustafa Kemal University, Department of Chemistry 31040, Hatay

Glucose oxidase (GOD) catalyzes the oxidation of glucose in presence of O2 by

producing gluconic acid and H2O

2, while, catalase (CAT) decomposes H

2O

2 to H

2O

and O2

[1]. In this study, GOD and CAT enzymes were co-immobilized in calcium

alginate gel (Ca-ALG) by dripping sodium alginate (Na-Alg) and enzyme mixture into CaCl

2 solution at 4 °C. Co-immobilization parameters were optimized and results were

given in Table 1.

Table 1. Optimization of co-immobilization parameters

Co-immobilized GOD-CAT enzyme system was used to produce gluconic acid from glucose in batch reactor, recycled packed bed column reactor and continuous column reactor

Figure 1. Recycled packed bed column reactor (A) and continuous column reactor (B) which were used to gluconic acid production.

The effect of glucose concentration, flow rate and reaction time on gluconic acid yield was investigated in detail.

AcknowledgementThe author wish to thank the TUBITAK for supporting the this study (Project no:105T514)

References [1] Ozyilmaz G., Tukel S.S., Journal of Microbiology and Biotechnology, 17(6) (2007): 960-967


N,O-type Schiff base ligands and transition metal complexes containing functional groups: Structural Characterization and

SOD Activity Studies

İlyas GÖNÜLa, Muhammet KÖSEb, Selahattin SERİNa

aDepartment of Chemistry, Arts and Science Faculty, Cukurova University, 01330, Adana, TurkeybDepartment of Chemistry, Kahramanmaraş Sütçüimam University, K. Maras 46100, Turkey

Azomethine group (–C=N–) containing compounds typically known as Schiff bases have been synthesized by the condensation of primary amines with active carbonyls [1]. Schiff base metal complexes are among the most explored types of compounds in coordination chemistry and play an important role in catalysis (including enantioselective synthesis), materials science, and biochemistry [2]. Oxidative stress results from an imbalance between the generation of reactive oxygen and nitrogen species (RONS) and antioxidant defense mechanisms. A great deal of interest has been shown in the development of therapeutic SOD mimetics for the detoxification of RONS in conditions associated with oxidative stress [3]. In this study, transition metal complexes of Co(II), Ni(II) and Cu(II) of 2,4-dimethoxy-N-(2-hydroxy-3-methoxy benzylidene)benzenamine (HL1) and 2,4-dimethoxy-N-(2-hydroxynaphthalidene) benzenamine (HL2) derived N,O-type Schiff base ligands were prepared and characterised by FT-IR, 1H,13C-NMR, TG/DTA, elemental analysis and X-ray diffraction techniques. Additionally, catalytic activity for the dismutation of superoxide into dioxygen and hydrogen peroxide by the Schiff base metal complexes were evaluated by a modified indirect chemical method.

References[1] Pradhan, A., Kumar, A., Chemical and Process Engineering Research, Vol.35, 2015.[2] Aleksanyan, D. V., Nelyubina, Y. V., Dmitrienko, A.O., Bushmarinov, I. S., Klemenkova, Z. S.,

and Kozlov, V. A. Polyhedron 85:295–301, 2015.[3] A.E.O. Fisher, D.P. Naughton / Biomedicine & Pharmacotherapy 59, 158–162, 2005.


Catalytic Conversion of Superoxide by Porphyrine Based Metal Complexes

Muhammet Köse, Ferhan Tümer, Mehmet Tümer


Superoxide is a free radical and believed as a contributing cause of many neurological disorders such as Parkinson`s and Alzheimer`s diseases [1]. Moreover, some types of cancer are thought to be associated with superoxide. Healthy cells can defense themselves against ROS damage through the use of superoxide dismutases enzymes (SODs) which control the level of superoxide at low levels [2]. Natural SOD enzymes have shown promising therapeutic properties yet suffer as drug candidates due to some drawbacks. Considerable efforts have been made to obtain stable, non-toxic, and inexpensive low molecular weight biomimetic molecules which are capable of catalyzing superoxide dismutation and therefore to provide important therapeutic applications. Mn(III)porphyrinato complexes also have been found to possess SOD-like activity based on indirect analysis [3]. In this project, new porphyrin based Schiff base ligands and their transition metal complexes were prepared and characterised by spectroscopic and analytical methods (Figure 1). The catalytic conversion of superoxide into hydrogen peroxide and molecular oxygen was investigated by an indirect method.

Figure 1: Proposed structures of the complexes used in the catalytic conversion of superoxide.AcknowledgmentsWe are grateful to The Scientific & Technological Research Council of Turkey (TUBITAK) (Project


References[1] A. Bruce, B. Malfroy and M. Baudry, Proc. Natl. Acad. Sci. U. S. A., 93 (1996) 2312-2316. [2] J. S. Valentine, in Biological Inorganic Chemistry Structure and Reactivity, Eds. I. Bertini, H. B.

Gray, E. I. Stiefel and J. S. Valentine, University Science Books, California, (2007) 319-353.[3] R. F. Pasternack, A. Banth, J. M. Pasternack and C. S. Johnson, J. Inorg. Biochem., 15 (1981)

261-267.


Porphyrine Based Mn(III) and Fe(III) Complexes as SOD Mimetics: Subsituent Effects on Catalytic Activity

Mehmet Tümer, Ferhan Tümer, Muhammet Köse


The oxidant and reductant properties of superoxide can be converted to other dangerous reactive species including hydrogen peroxide, hydroxyl radicals, hypochloride ions and peroxynitriles which are all harmfull for mamalian cells [1]. Oxidative stress is mainly due to the overproduction of these reactive oxygen species (ROS) [2]. A biochemical defence system via enzymes such as superoxide dismutase and catalase is then required to control the level of superoxide and reactive oxygen species in the living cells. Many synthetic transition metal complexes have been prepared, displaying a superoxide scavenger activity and proposed as SOD models for therapeutic applications. Metal complexes of Cu, Mn, Fe and Ni have been found to disproportionate the superoxide to molecular oxygen and hydrogen peroxide. Among these, manganese complexes have received special attention due to lower toxicity of manganese ions [3]. In this study, porphyrin-Schiff base ligands and their Mn(III) and Fe(III) complexes were prepared (Figure 1) and the subsituent effect on the catalytic performance for superoxide scavenging were examined in detail.

Figure 1: Proposed structures of the complexes.

AcknowledgementsWe are grateful to The Scientific & Technological Research Council of Turkey (TUBITAK) (Project


References[1] I. Fridovich, J. Biol. Chem. 264 (1989) 7761-7764.[2] R. H. Weiss, D. P. Riley, Drugs of the Future, 21 (1996) 383-389.[3] D. Riley, Chem. Rev. 99 (1999) 2573-2587.


Hydrolysis of microalgae oil Chlorella protothecoides via biocatalysis

Togayhan Kutluka,b, Nurcan Kapucua,b

a Department of Chemical Engineering, Kocaeli University, 41380 Kocaeli, Turkeyb Alternative Fuels R&D Center, Kocaeli University, 41040 Kocaeli, Turkey

The hydrolysis of oils and fats is a significant industrial operation: world wide 1.6 × 106 tons of fatty acids are produced every year. The fatty acids synthesised by the hydrolysis of natural oils and fats from naturally produced renewable raw materials. These products include oils from corn, rapeseed, sunflower, palm, coconut, olives and rice bran, and a wide range of animal fats such as cattle and sheep. A large number of high-value products need fatty acids in their manufactures. These include coatings, adhesives, specially lubricating oils, shampoos and other cosmetic products [1]. In recent years microalgae oils are able to replace with traditional raw materials. Microalgaes appear to be the promising source of fatty acids that their competitive advantages such as oil contents can climb over 80% by weight of dry biomass and needs to be small harvesting areas than oil seeds [2]. There are three main processes existing used for the hydrolysis of fats and oils; high pressure steam splitting, alkaline hydrolysis and enzymatic hydrolysis. The high temperature and pressure (typically 250°C, 70 bar) necessary for steam splitting make this process inconvenient for splitting sensitive free fatty acids,this may expose thermal degradation, and occurs polyunsaturated oils with high iodine number called polymerize. At the same time alkaline hydrolysis has strains such as an high energy costs and the need to acidify the soaps formed, to produce the fatty acid products. Enzymatic hydrolysis of oils may be executes at soft processes conditions (typically 35°C and atmospheric pressure), making it energy efficient and more environmentally in contrast to the steam splitting and alkaline process [3]. Therefore in this study we were investigated that biocatalyst ( Lipozyme TL IM) loading and oil:water mass ratio effect on hydroysis of microalgae oil. Reactions were implement that 100 ml flasks with oil:water mass ratio of 1:20 at 50°C 600 rpm 24 hours and different biocatalyst amount. Fatty acids analyses was performed that NaOH titration according to the ASTM-D5555-95 standard. As a result of experimental studies, maximum fatty acids content of 99% was reached with 100 mg biocatalyst. This study clearly shows microalge oils are useful as a raw material for production of fatty acids with environmentally friendly enzymatic processes rather than alkaline catalysts.

AcknowledgementWe wish to thank Novo Nordisk and Soley Instute for presenting Lipozyme TL 100L and microalgae

oil from Chlorella protothecoides.


References1. Murfy V. R., Bhaf J. , Muniswanas P. K. A. , Hydrolysis Of Oils By Using Immobilized Lipase

Enzyme : A Review, Biotechnology Bioprocess Engineering, 7, 2002, 57-66. 2. Melis A., Green alga hydrogen production: progress, challenges and prospects. International

Journal of Hydrogen Energy 27, 2002, 1217–28, 3. Pronk, W., P. J. A. Kerkhof, C. van Helden, and K. Van’t Reit The hydrolysis of triglycerides by

immobilized lipase in a hydrophilic membrane reactor. Biotechnology and Bioengineering. 32, 1988, 512-518.


Immobilization and characterization of Candida rugosa lipase on magnetic nanoparticles through different spacer arms

Muge SENGULa, Leman BEYKAN*a, Deniz YILDIRIMb, Guzide YUCEBILGICa

aUniversity of Cukurova, Faculty of Science and Letters, Department of Chemistry, 01330 Adana, TURKEY

bUniversity of Cukurova, Vocational School of Ceyhan, Adana, TURKEY

In recent years, much attention has been paid toward synthesis of magnetic nano-sized particles and their use for immobilization of enzyme [1,2]. In this study, magnetic nano-sized Fe

3O

4 particles were synthesized and characterized by using FT-IR, SEM

and XRD techniques. The size of prepared nanoparticles was found as 158.2 nm. The magnetic nanoparticles were functionalized with glutaraldehyde and epichlorohydrin to covalently immobilize Candida rugosa lipase. The optimum pH and temperature were determined as 7.0 and 40 °C, respectively for all the lipase preparation. The K

m, V

max, k

cat and k

cat/K

m values were determined as 0.48 mM, 420.7 U/mg protein, 2.82x104 min-1,

58.8x103 min-1 mM-1, respectively for the free lipase. The corresponding values were 1.3 mM, 33.6 U/mg protein, 2.25x103 min-1, 1.73x103 min-1mM-1 for the lipase immobilized on Fe

3O

4 through glutaraldehyde spacer arm. For the lipase immobilized on Fe

3O

4

through epichlorohydrin spacer arm, these values were found as 9.4 mM, 51.7 U/mg protein, 3.47x103 min-1, 0.37x103 min-1 mM-1. After 20 reuses, the residual activities were found as 71 and 63% of their initial activities, respectively for the lipases immobilized on Fe

3O

4 through glutaraldehyde and epichlorohydrin spacer arms.

References[1] A.K. Johnson, A.M. Zawadzka, L.A. Deobald, R.L. Crawford, A.J. Paszczynski, Journal of

Nanoparticle Research, 10 (2008) 1009–1025.[2] M.Cao, Z.Li, J.Wang, W.Ge, T.Yue, R.Li, V.L. Colvin, W.W. Yu, Trends in Food Science and

Technology, 27 (2012) 47–56.


Effect of Calcination Temperature on Production of DMN’s over Y Zeolite Catalyst

Aysel Niftaliyevaa, Ali Karadumanb

ª Selçuk University Faculty of Engineering, Dept. of Chemical Eng. 42075 Konya, TÜRKİYEb Ankara University Faculty of Engineering, Dept. of Chemical Eng. 06100 Ankara, TÜRKİYE

Polyethylene naphthalate (PEN) is a relatively new family between polyesters that is getting a lot of attention currently [1]. PEN shows better properties than polyethylene terephthalate (PET) such as lower oxygen permeability, thermal shrinkage, youngs modulus, glass transition temperature, oligomer extraction and higher resistance to radiation, etc [2-3]. 2,6-dimethylnaphthalene is an important compound for producing 2,6-naphthalene dicarboxylic acid (2,6-NDA), which is significant monomer of the polyethylene naphthalate (PEN) [4]. One of the 2,6-DMN production method is the methylation of 2-methylnaphthalene (2-MN) which is the most preferred method. There are lots of works in the literature related to production of 2,6-DMN [5]. In this study, the effect of calcination temperature to the synthesis of dymethylnaphthalenes over Y zeolite are intended. For this purpose, Y zeolite which were available from Zeolyst (USA) company and 10% La metals doped Y zeolite and calcined at 550°C and 750°C temperature and tested in the methylation of 2-MN. For all experiments carried out over Y zeolite catalysis in a continuous flow fixed-bed reactor and molar ratio of 1:5:5 2-MN, methanol and mesytylene was fed into the reactor. In reactor the quantity of catalyst was 2cm3, temperature ranging from 400oC to 500oC and weight hourly space velocity (WHSV) ranging from 1 to 3 h-1. The liquid products were analyzed using the available ThermoFinnagan DSQ250 GC-MS. As a result, the effect of calcination temperature over 2-MN conversion, 2,6-DMN yield, 2,6-DMN selectivity and 2,6-DMN/2,7-DMN ratio was examined. In the all prepared catalysts, increasing the calcination temperature was decreased the conversion of 2-MN. But the yield of 2,6-DMN was increased by the increasing of calcination temperature from 550°C to 750°C. Also, the 2,6-DMN/2,7-DMN ratio and the selectivity of 2,6-DMN was increased by increasing the calcination temperature to 750°C. AcknowledgementsWe are thankful and greatfully appreciate The Scientific and Thechnological Research Council of Turkey (TÜBİTAK) for the support of this work. (Project No:112M297)

References[1]. Wenyu, T; Weilan, X; Zuoxiang, Z; Ji, Sh. C. J. Chem. Eng.17, (2009), 72-77.[2]. J. Park,J.Wang,C.Lee,Park,S.Bull.Korean Chem.Soc.23, (2002),1011-1013.[3]. L.Zhao,X.Guo,M.Liu,X.Wang,Song,C.C.J.Am.Chem.Eng.18,(2010),742-749.[4]. J. Park,J.Wang,S.Hong,C.W.Lee, Appl. Cata.,292, (2005), 68-75.[5]. J.Lijun, F.Yunming, H.Haoquan, Catalysis Com.,7, (2006), 255-259.


Methylation of Naphthalene Oil Fraction of Coal Tar with Methanol on Metal/Bimetal Doped Beta Zeolite Catalysts

Aysun Özen¹, Fatih Güleç¹, Aysel Niftaliyeva2, Ali Karaduman¹

¹Ankara University Faculty of Engineering, Dept. of Chemical Eng. 06100 Ankara, TÜRKİYE

²Selçuk University Faculty of Engineering, Dept. of Chemical Eng. 42075 Konya, TÜRKİY

Coal tar naphthalene oil fraction (CTNOF) is composed of many substances such as significant naphthalene derivatives which are 1-Methylnaphtalene (1-MN), 2-Methylnaphtalene (2-MN) and Dimethylnaphtalenes (DMNs). Due to methylation of CTNOF, many reaction products including 2-MN and 2,6-dimethylnaphthalene (2,6 DMN) can be produced [1,2]. 2-MN and 2,6-DMN are desirable products in terms of used in synthesis of polyethylene naphthalate (PEN) .When compared with polyethylene terephthalate (PET), PEN has widespread application area due to improved features such as gas barrier, high tensile strength, heat resistance etc.[3-5]. In this study synthesis of 2-MN and 2,6-DMN by methylation of CTNOF over Fe/Beta, Au-Fe/Beta and Pd-Fe/Beta zeolite catalysts was investigated. Metals were doped on Beta by using wet impregnation method. The experiments were investigated in a fixed bed reactor using mixture of CTNOF, methanol (methylation agent) and xylene (solvent) with 1:5:5 mass composition as a feedstock. The reactor temperature and weight hourly space velocity (WHSV) were ranged from 300°C to 400°C and 1h-1 to 3h-1, respectively. The reaction products were analyzed with using GC-MS which has 60 meter capiler column. Conversion of Naphthalene, ratio of 2-MN/1-MN and 2,6-DMN/2,7-DMN, selectivity of 2-MN, 2,6-DMN and DMNs were calculated. The modified catalysts were characterized by XRF, SEM, FTIR and BET techniques. In conclusion, conversion of Naphthalene increased with temperature and diminished with whsv. The selectivity of 2,6-DMN and 2-MN was enhanced with using Au and Pd doped Beta zeolite. Generally, ratio of and 2-MN/1-MN was above 5.0, 2,6-DMN/2,7-DMN fluctuated around 1.0.

Acknowledgement

We are thankful and greatfully appreciate Ankara University Scientific Research Projects (AÜ-BAP) for the support of this work. (Project No: 15B0443009)

References[1] Azpiroz M.D.G., Balanco, C.G., Banciella M.D.C., Fuel Processing Technology, 89,( 2008), 111-117.[2] Tang, W., Fang, M., Wang, H., Yu, P., Wang, Q., Luo Z., Chemical Engineering Journal, 236,(

2014),529-537.[3] Wu,W., Wu,W., Kikhtyanin,O.V., Lingfei,L., Toktarev, A.V., Ayupov,A.B., Khabibulin,J.F.,

Echevsky,G.V., Huang,J., Applied Catalysis A: General, 375, (2010), 279-288.[4] Niftaliyeva, A., Güleç,F., Şimşek,E,H., Güllü,M., Karaduman,A., Anadolu University Journal of Science

and Technology,16, (2015),167-178.[5] Zhao,L., Guo,X., Liu,M., Wang,X., Song, C., Chinese Journal of Chemical Engineering 18 ,(2010), 742-

749.


MODIFICATION OF ACTIVATED CARBON BASED ADSORBENTS FOR CO2 ADSORPTION

Melek Selcen BAŞARa, Burcu SELEN ÇAĞLAYANa,b, Ahmet Erhan AKSOYLUa

a Boğaziçi University, Department of Chemical Engineering, 34342, Bebek, Istanbulb Boğaziçi University, Advanced Technologies R&D Center, 34342, Bebek, Istanbul

Carbon dioxide is the primary greenhouse gas, which is responsible for global warming and climate change. Main emissions arise from the release as one of the flue gases from the combustion of fossil fuels such as coal, natural gas, and oil and as a by-product from industrial processes such as cement, iron, and steel [1]. Adsorption is an attractive technique in CO

2 removal in terms of its cost advantage, low energy requirement,

ease of applicability and regeneration over a relatively wide range of temperatures and pressures. An ideal adsorbent for effective CO

2 capture should possess the following

characteristics; (i) high surface area, (ii) big pore volume, (iii) high selectivity for CO2,

(iv) adequate adsorption/desorption kinetics and (v) stable adsorption capacity and high mechanical strength after repeated adsorption and desorption cycles. Since the adsorption performance of a solid sorbent, e.g. activated carbon (AC), depends on its porous structure and surface chemistry, modification of AC-based adsorbents through different thermal and chemical pretreatments enhanced effectiveness of ACs by changing the surface functional groups in capture of CO

2 [2,3].

In the present work, the aim is to introduce basic N-containing groups to the carbon surface through different ammonia treatment methods and to observe the contribution of the treatment effects on the adsorption properties of modified ACs towards acid agents like CO

2. More specifically, the effect of liquid ammonia (wet-amination),

gaseous ammonia (amination) and ammonia-oxygen (ammoxidation) treatment at different temperature and flow compositions to produce highly CO

2-selective AC-

based adsorbents are studied.

References[1] Shafeeyan, M.S., Daud, W.M.A.W., Houshmand, A., Arami-Niya A., Fuel, 94 (2012) 465-472.[2] Adelodun, A.A., Lim, Y.-H., Jo, Y.-M., Journal of Analytical and Applied Pyrolysis, 105 (2014)

191-198.[3] Selen Caglayan, B., Aksoylu, A.E., Journal of Hazardous Materials, 252-253 (2013) 19-28.


ENHANCING PHOTOCATALYTIC ACTIVITY OF ZnO NANOROD WITH HEAT TREATMENT

Fatih TEZCANa, Gülfeza KARDAŞa

aÇukurova University, Science and Literature Faculty Chemistry Department, 01330, Adana

Enhancing energy demands of human have accelerated the investigation of the photovoltaic application for photoelectrochemical(PEC) water splitting under solar light irradiation[1, 2]. Among the semiconductor materials, ZnO has been abundantly examined as photoanode for PEC water splitting in order to the appropriate band gap of ZnO can transform water to H

2 via photoelectrolysis, low-cost and environmental

friendly. On the other hand, efficiency of ZnO is not adequate for PEC cells. Different heat treatments have been enhanced photoanode the PEC. For this reason our study, the electrochemically sensitized ZnO nanorods were calcinated at 350°C. Surface of ZnO nano material was characterized Scanning Electron Microscopy(SEM). Photoluminescence (PL) properties were carried out Flurorescence Spectrometer LS55. PEC measurements were examined in a convenient three-electrodes cell, an electrochemical analyzer Gamry (interface 1000) and a 300W Xe lamp solar simulator (100 mW/cm2). The calcinated ZnO nanorod has higher photocurrent density and PL properties than uncalcinated ZnO nanorod. Therewithal, SEM images of ZnO nanorod change with deposition potential.

Figure 1. SEM imagine of -0.7 V(a), -0.8 V(b) and -0.9 V(c) ZnO nanorod using electrochemical deposition method

The authors are greatly thankful to Scientific Research Project of Çukurova University (Project No: FDK-2014-3488)

References[1] K.Y. Guo, Z.F. Liu, Y. Wang, Y.F. Zhao, Y.C. Xiao, J.H. Han, Y.J. Li, B. Wang, T. Cui,

International Journal of Hydrogen Energy, 39 (2014) 13408-13414.[2] C. Wang, Y.J. Feng, L. Cai, X.Y. Yang, J.F. He, W.S. Yan, Q.H. Liu, Z.H. Sun, F.C. Hu, Z. Xie, T.

Yao, S.Q. Wei, Journal of Power Sources, 269 (2014) 24-30.


Low Platinum Loading Electrode for Formic Acid Fuel Cell Prepared by Ion-Beam Assisted Deposition

M. Selim ÇÖGENLİa, Sanjeev MUKERJEEb, Ayşe BAYRAKÇEKEN YURTCANa,c

a Nanoscience and Nanoengineering Department, Atatürk University, Erzurum 25240, Turkeyb Department of Chemistry and Chemical Biology, Northeastern University, Boston-MA 02115,

USAc Faculty of Engineering, Department of Chemical Engineering, Ataturk University, Erzurum

25240, Turkey

Formic acid has a high open cell potential (OCP), and the fact that it is liquid at room temperature and non-toxic in diluted solutions makes it an attractive fuel candidate [1]. Direct formic acid fuel cells (DFAFCs) are promising alternatives to hydrogen proton exchange membrane fuel cells (PEMFC) for electronic applications.

Ion-beam assisted deposition (IBAD) is a vacuum-deposition process that combines physical vapor deposition (PVD) with ion-beam bombardment. Vapor of coating atoms are generated with an electron-beam evaporator and deposited on a substrate [2]. In this study, anode electrode is prepared with the IBAD method with 0.08mgPt/cm2 loading and cathode electrode is prepared with painting method with 4mgPt/cm2

loading. Structural properties of IBAD electrode were determined by using SEM images and EDS (Figure 1). Prepared electrode by direct coating (via IBAD) of un-catalyzed carbon cloth, at first will be used at anode electrode side for DFAFCs then will be compared with other studies in the literature.

Figure1. SEM image and EDS result of ibad electrode

References[1]Yu X, Pickup P G. J Power Sources. 2008;182:124–132.[2] M.S. Saha et al. / Electrochimica Acta 51 (2006) 4680–4692.


Pt Catalyst Supported on Bi2O3 for Direct Formic Acid Fuel Cells

M. Selim ÇÖGENLİa, Ayşe BAYRAKÇEKEN YURTCANa,b

a Nanoscience and Nanoengineering Department, Atatürk University, Erzurum 25240, Turkeyb Faculty of Engineering, Department of Chemical Engineering, Ataturk University, Erzurum 25240,

Turkey

In recent years, formic acid has been used as an important fuel either without reformation (in direct formic acid fuel cells, DFAFCs). Platinum (Pt) is the most common catalyst in both anode and cathode fuel cell reactions. When formic acid is used as the fuel, the catalyst can be poisoned Because of formic acid oxidized by Pt to CO and CO

2. This can

cause significant problems for the fuel cells.

Carbon has traditionally been the most common material of choice for fuel cell electrocatalyst supports. In this study, Bi

2O

3 was used for support material because

of some advantages. Geng et al. reported that Pt/Bi2O

3 catalyst are tolerant to CO

poisoning and have higher electrocatalytic activity for CO oxidation [1]. At another study, PtRu/Bi

2O

3 showed high selectivity towards dehydrogenation and the rate of

hydrogen generation is determined [2].

In this study, Bi2O

3 supported Pt catalyst was prepared by using microwave irradiation

technique. Firstly, required amounts of Bi2O

3 and aqueous solution of H

2PtCl

6 added in

ethylene glycol and then stirred for 30 min. Then the resulting mixture was reduced in microwave oven. The structural properties of the Bi

2O

3 and Pt/Bi

2O

3 catalyst were

characterized by SEM (Figure 1). Other physicochemical characterizations will also be made. Electrocatalytic activity of Pt/Bi

2O

3 catalyst for formic acid oxidation will be

tested with CV measurements.

Figure 1. SEM images of a) Bi2O

3 b) Pt/Bi

2O

3

References[1] J. Geng et al. Catal Lett (2010) 135:114–119[2] Tsang Kwok-ying, HKU Theses Online, The University of Hong Kong, 2007.


CATALYTIC GASIFICATION OF ÇAN LIGNITE

Açelya Seçer Ateş, Arif Hasanoğlu

Çukurova University,Chemistry Department, Adana

The majority of the world’s energy requirement is provided by fossil fuels. The direct burning of fossil fuels causes serious environmental problems by effecting atmosphere, water sources etc. The current reserves of the fossil fuels ,production coasts, usage amounts and the extrapolation of the these statistics to future indicates that, the fossil fuels will be major for providing worlds energy requirements in the future. Furthermore, coal, probably, will be the most dominant energy source in the first half of 22th century. Therefore, research on coal and coal derivatives are getting more important for improving the alternative usage of coal, such as production of hydrogen from coal. Catalytic hydrogen production from coal is an important way to produce high yiled hydrogen gas from coal. Steam is used as gasification agent in traditional methods of production of hydrogen from coal and the process temperatures are over 1000 °C. Also, A steam generator is used to produce steam, and carrier gases are used in these traditional methods. In this study, a new method, which will be called as atmospheric pressure vapor phase reforming (AVPR), in which water is directly vaporized in the gasification reactor instead of producing steam with steam generator, is used to produce hydrogen from coal. For this aim, Çan lignite, a Turkish coal with a % 4,6 S content, is gasificated for hydrogen production with AVPR method by using different catalysts. Coal samples including catalysts were prepared with Na

2CO

3,K

2CO

3,CdSO

4,FeSO

4,FeCl

3,CaNO

3, NiCl

2

salts by impregnation. Gasification experiments were performed at , 700°C with a 0,5ml/min flow rate. Maximum gasification volume and hydrogen yield were obtained with Na

2CO

3 catalyst with a volume of 1053,5 ±30,4 ml/h and %74,7±1,0 H

2.

References: [1] Yeboah,D.Y., Xu, H., Sheth,A., Agrawal,P., Catalytic Gasification of Coal using Eutectic Salt

Mixtures , 2001.


Ceria Incorporated Alumina Supported Nickel Catalysts for Steam Reforming Reaction of Diesel Fuel

Arzu Arslana, Arife Derya Deniz Kaynarb, Naime Aslı Sezgia, Timur Doğua

a Middle East Technical University, 06800, Ankara, Turkeyb Vestel Defense Industry, 06800, Ankara, Turkey

Increase in energy demand with developing technology introduces a need for synthesis of alternative fuels. Hydrogen is considered as the energy carrier of the future in fuel-cell applications. Hydrogen production from diesel through steam reforming reaction (DSR) is an attractive route, due to its easy accessibility and very high hydrogen content (70-80% in volume base) [1]. Alumina supported nickel catalysts are generally used in steam reforming of hydrocarbons due to their high catalytic activity, availability and low cost. However, they are also active towards side reactions and carbon deposition. An ideal catalyst support should possess a strong interaction with nickel clusters, strong oxygen storage-release capacity, such as CeO

2. In this study, effect of catalyst support structure

and composition on its catalytic performance in DSR was investigated. Alumina was synthesized by following the evaporation-induced-self-assembly method (Al

2O

3-EISA)

[2]. Procedure was modified to synthesize ceria-alumina with a ceria incorporation amount of 20 wt.% (CeO

2-Al

2O

3-EISA). In order to analyze the effect of synthesis

method, commercial Al2O

3 (Al

2O

3-COM) and 20 wt.% ceria impregnated commercial

alumina (CeO2@Al

2O

3-COM) were also characterized and tested in DSR. According

to N2 physisorption analysis, BET surface areas of Al

2O

3-EISA Al

2O

3-COM CeO

2-Al

2O

3-

EISA, and CeO2@Al

2O

3-COM materials were found to be 265, 190, 81, and 168 m2/g,

respectively. It can be deduced that ceria addition to the synthesis solution significantly altered the mesoporous structure. However, impregnation of ceria on commercial alumina reduced surface area and pore volume of the material by plugging the pores. Activity test results showed that ceria incorporation enhanced hydrogen production by minimizing side product formation. Results proved that CeO

2-Al

2O

3 material was a

promising candidate as a catalyst support for steam reforming applications.

AcknowledgementFinancial supports of Tübitak through project number 213M027, Vestel Defence Industry and

İbrahim Pamuk are gratefully acknowledged.

References[1] A. D. Deniz, D. Dogu, and N. Yasyerli, Fuel Process. Technol., 140 (2015.), 96–103.[2] S. Gunduz and T. Dogu, Ind Eng Chem, 51, 26 (2012), 8796–8805.


PtCu/C BIMETALLIC CATALYSTS FOR PEM FUEL CELLS

Ayşenur ÖZTÜRKa, Elif DAŞb, Gamze BOZKURTa,b, Ayşe BAYRAKÇEKEN YURTCANa,b

a Department of Chemical Engineering, Atatürk University, 25240, Erzurumb Department of Nanoscience and Nanoengineering, Atatürk University, 25240, Erzurum

PEM fuel cell is a good alternative as power generator and Pt based catalysts are the most common materials to improve sluggish oxygen reduction reaction (ORR) rate in these systems. However, it is confronted with two major problems regarding Pt catalysts. One of them is using hydrogen gas that contains CO as reactant in fuel cell, leads to Pt metal poisoning because strongly adsorption of CO on Pt. The other one is expensiveness and inability of Pt metal. Novel cheaper catalysts that are comparable with Pt attract great attention. Therefore, Pt-containing binary and ternary alloys have been investigated in literature as catalyst in PEM fuel cell.

Synergy of platinum and other transition metals in alloy form provides higher catalytic activity for the ORR than pure platinum catalyst [1]. This improvement can be attributed to modified binding of surface reaction intermediates and delicate catalytic reactivity control over the metal surface. The studies that are relevant to Pt-Pd, Pt-Ni, Pt-Co binary catalysts have been mostly encountered over the past decade [2].

In the scope of this study, Cu was used as transition metal that is less prevalent in literature and PtCu bimetallic catalyst on carbon support was prepared by microwave-irradiation technique. This method includes reduction step in order to dope metal particles on the support material. Additionally in an attempt to facilitate liquid water transport in catalyst layer, hydrophobic polymer was included in catalyst ink with different loadings [3]. Polydimethylsiloxane (PDMS) polymer was preferred for this purpose due to its high hydrophobic property and chemical stability [4]. Physicochemical and electrochemical characterizations of prepared catalysts were performed.

References[1] A. Seo, J. Lee, K. Han, H. Kim, Electrochimica Acta, 52 (2006) 1603-1611.[2] P. Mani, R. Srivastava, P. Strasser, The Journal of Physical Chemistry, 112 (2008) 2770-2778.[3] G. S. Avcıoğlu, B. Fıçıcılar, A. Bayrakçeken, İ. Eroğlu, International Journal of Hydrogen Energy,

40 (2015) 7720-7731 . [4] Q. Ke, W. Fu, H. Jin, L. Zhang, T. Tang, J. Zhang, Surface & Coatings Technology, 205 (2011)

4910-4914.


Effects of Synthesis Route and Calcination Temperature on Structural and Acidic Properties of Mesoporous -Al2O3

D. Erkal1, B. Pekmezci1, N. Oktar1, G. Doğu1, N.A. Sezgi2, T. Doğu2 1GaziUniversity, Department of Chemical Engineering, 06570 Ankara, Turkey;

2Middle East Technical University, Department of Chemical Engineering, Ankara, Turkey.

Due to their high surface area and low diffusion resistance, mesoporous materials with ordered pore structures have been considered as potential catalyst support materials [1]. Among these materials, mesoporous alumina has attracted great interest because of its high thermal stability and its acidic properties. These materials have tunable pore size between 2-10 nm, large surface area, narrow pore-size distribution and moderate Lewis acidity [2]. In this study, effects of synthesis procedure and the calcination temperature on the structure of mesoporous alumina were examined. Hydrothermal and sol-jel processes have been followed as synthesis routes and these materials were calcinated at different temperatures in the range of 750-950 oC. XRD results revealed that, γ-Al

2O

3 was succesfully formed and crystal size was increased with an increase in calcination temperature. Nitrogen adsorption/desorption analysis indicated some decrease of BET surface area of the materials with an increase in temperature. In the case of the material which was synthesized following the hydrothermal route, the highest surface area (235 m²/g) was obtained at a calcination temperature of 750oC. Surface area of the material which was synthesized by the sol-gel route was 206.6 m2/g. The average pore diameter of this material was about 9.8 nm. Surface acidities of these materials were evaluated by the DRIFTS analysis of pyridine adsorbed samples. Bronsted acidities of these materials were further increased by incorporation of heteropoly acids into their structure for use as solid acid catalysts in dehydration of methanol to produce dimethyl ether.

AcknowledgementFinancial support of TUBITAK 115M377 was gratefully acknowledged

Reference[1] Yuan Q., Yin A.-X., Luo C., Sun L.-D., Zhang Y.-W., Duan W.-T., Liu H.-C., Yan C.-H., Facile

Synthesis for Ordered Mesoporous gamma-Aluminas with High Thermal Stability, Journal of the American Chemical Society, 130: 3465–3472, 2008.

[2] Márquez-Alvarez C., Žilková N., Pérez-Pariente J., Čejka J., Synthesis, Characterization and Catalytic Applications of Organized Mesoporous Aluminas, Catalysis Reviews Science and Engineering, 50: 222–286, 2008.


Effect of Marl on the Production of Biodiesel as a Heterogeneous Catalyst

Bakhtiyar NAJAFOVa, Niyazi Alper TAPANa

a Gazi Üniversity, Engineering Faculty, Chemical Engineering Department, Maltepe, 06570, ANKARA

Biodiesel which is alkyl esters of fatty acids, is an alternative to diesel fuel due to its equivalent engine performance and low emissions to the environment. The aim of this study is to examine reaction variables such as the effect of marl catalyst ratio, reaction time and determine optimum conditions for biodiesel production. After transesterification of domestic waste vegetable oil, product samples were analyzed by the amount of glycerol produced and viscosity, density, flash point, acidity, refractive index of biodiesel. The results of this study indicate that optimum conditions for 99.35% biodiesel yield are 55oC reaction temperature, (6:1) alcohol to oil ratio, 1% NaOH , 1%

marl catalyst by weight and 30 min reaction time.


Hydrogen Production over Mesoporous Carbon Supported Iron Nanocatalysts using Microwave Reactor system

C.Korkusuz1 D.Varışlı1 T.Doğu2

1Gazi University, Department of Chemical Engineering, 06570, Ankara Turkey2Middle East Technical University, Department of Chemical Engineering, 06500,Ankara, Turkey.

Ammonia is an important raw material for hydrogen due to its superior properties suc as CO

x free hydrogen, which is necessary for fuel cell applications, can be produced by

its decomposition reaction. Nowadays, alternative heat sources such as microwave has gained great attention. Higher conversion values can be obtained at a lower reaction temperature in the microwave assisted system in comparison to the conventional systems due to the efficient heating of active sites present in the structure of the catalyst by means of microwave heating [1]. In the literature, it can be seen that alternative heating systems have been applied to hydrogen production from different sources such as methane, biomass, however, any studies related with the microwave application to ammonia decomposition reaction cannot be found.

In this work, Iron (Fe) incorporated Mesoporous Carbon (MC) supported catalysts were prepared by impregnation procedure and the synthesized catalysts were characterized with different techniques such as TGA-DTA, TPA, XRD, Nitrogen Physisorption, SEM-EDX, HRTEM and they were tested in both Microwave Reactor System and Conventional Heating system. Results of experiments show that higher conversion values were achieved at lower reaction temperatures in microwave system. Ammonia conversion value of 55% was obtained at 350oC and total conversion was achieved at 450oC in the experiments that were carried out in Microwave Reactor system with GHSV

NH3 of 36,000 ml/hg

cat while negligible conversion of ammonia was seen in conventional

heating systems at these reaction temperatures. Total conversion could be achieved at 600oC in conventional heating system.

AcknowledgementFinancial support of TUBITAK 214M148 was gratefully acknowledged.

Reference1- S.Gündüz, T. Dogu, Applied Catalysis B: Applied Catalysis B: Environmental 168-169 (2015)

497–5082- H. Zhang, Y. Alhamed, Y. Kojima, A.Zahrani, H. Miyaoka, L. Petrov, İnternational Journal of

Hydrogen Energy 39 (2014) 277-287 3-X. Duan, G. Qian,J. Zhou,X. Zhou, Catalysis Today 186 (2012) 48– 53


ELECTROCHEMICAL BEHAVIOUR OF HYBRID NANOSTRUCTURED MATERIALS FOR PEM FUEL CELL ELECTROCATALYSTS

Elif DAŞa, Selmiye ALKAN GÜRSELb, Lale IŞIKEL ŞANLIb, Ayşe BAYRAKÇEKEN YURTCANa,c

a Department of Nanoscience and Nanoengineering, Atatürk University, 25240, Erzurumb Faculty of Engineering & Natural Sciences, Nanotechnology Research & Application Center

(Sunum), Sabancı University, Istanbul 34956, Turkeyc Department of Chemical Engineering, Atatürk University, 25240, Erzurum

Graphene based hybrid materials has recieved enormous attention which seek to combine the attractive features of the two dimensional lattice with some additional functionality afforded by a second component such as metal or semiconductor nanoparticles, polymers or organic molecules [1]. These hybrid structures have shown promise for use as catalysts and electrodes for fuel cells, supercapacitors and batteries. In this study, carbon black-graphene (CB-G) hybrid composite support materials are prepared by mixing CB with G. Pt nanoparticles on hybrid materials are obtained by using superciritical carbon dioxide deposition (scCO

2) technique. A certain amount of

precursor is firstly dissolved in scCO2 (at 35˚C and 12 MPa) and then adsorbed on the

hybrid materials and the catalysts were obtained via thermal conversion of the adsorbed precursor molecule to Pt metal. Pt loading over the hybrid materials were determined by using TGA analysis. Electrochemical characterizations of all prepared catalysts are made. According to polarization curve of the catalysts, the hybrid composite ratio of 50:50 shows the best PEM fuel cell performance as shown in Figure 1.

Figure 1. Polarization curve of electrocatalystsAcknowledgementsThe authors are greatfully acknowledge the financial support of TÜBİTAK with grant numbers of

114F029 and 114F506.

References[1] Tepeli Y, Anik U. Comparison of performances of bioanodes modified with graphene oxide and

graphene–platinum hybrid nanoparticles. Electrochemistry Communications. 2015;57:31-4


CARBON BLACK-GRAPHENE HYBRID SUPPORT MATERIALS FOR PEM FUEL CELL ELECTROCATALYSTS

Elif DAŞa, Selmiye ALKAN GÜRSELb, Lale IŞIKEL ŞANLIb, Ayşe BAYRAKÇEKEN YURTCANa,c,a Department of Nanoscience and Nanoengineering, Atatürk University, 25240, Erzurum

b Faculty of Engineering & Natural Sciences, Nanotechnology Research & Application Center (Sunum), Sabancı University, Istanbul 34956, Turkey

c Department of Chemical Engineering, Atatürk University, 25240, Erzurum

Proton exchange membrane fuel cell (PEMFC) technology has recieved significant attention as a potential alternative source of power generation thanks to high efficiency, high power density, low operating temperature. However, long-term durability still needs to be improved. Platinum (Pt) catalysts supported carbon blacks (CB) have been widely used as electrocatalysts for PEMFCs, but CB can be easily oxidized at the potential of oxygen reduction reaction [1]. The oxidation of CB can cause agglomeration and loss of Pt nanoparticles, resulting in a decrease of the electrochemical surface area and activity of the electrocatalysts. Up to now, many attempts have been made to solve the durability problem by introducing robust materials as a catalyst support and graphene (G) also is one of them which exhibits highly ordered graphitic structure.

In present study, we report hybrid material supported Pt catalysts (Pt/CB-G). Firstly, CB-G hybrid support materials are prepared by mixing CB with G at 50, 60, 70, 80, 90 and 100 wt% percentages of G. Pt nanoparticles over hybrid materials are obtained by using superciritical carbon dioxide deposition (scCO

2) technique which is facile and effective.

1,5-dimethyl platinum cyclooctadien (Me2PtCOD) is used as the Pt organometallic

precursor. A certain amount of precursor is firstly dissolved in scCO2 (at 35˚C and 12

MPa) and then adsorbed on the hybrid materials. The precursor is decomposed to metallic Pt form with heat treatment at 400˚C for 4 h in nitrogen atmosphere. Surface areas of the hybrid materials are determined by using BET analysis. All prepared catalysts are characterized by using TEM and XRD techniques.

AcknowledgementsThe authors are greatfully acknowledge the financial support of TÜBİTAK with grant numbers of

114F029 and 114F506.

References[1] J. Jung, M. Kwon, H.-R. Kim, J. Kim, International Journal of Hydrogen Energy, 39 (2014)

966-973.


INFLUENCE OF TYPE OF CARBON SUPPORT ON THE REFORMING ACTIVITY AND SELECTIVITY OF SUPPORTED Pt CATALYSTS FOR

APR OF GLUCOSE

Burçak Kaya Özsela*, Bahar Meryemoğlub, Mehtap Kurtuluşb, Arif Hasanoğlub, Sibel Irmakc

aDepartment of Chemistry, Bursa Technical University, 16190 Bursa, TURKEYbDepartment of Chemistry, University of Cukurova, 01330 Adana, TURKEY

c Biological Systems Engineering, University of Nebraska, Lincoln, NE, 68583-0726, USA

In recent years, due to the reduction of fossil fuel resources and increasing emissions of greenhouse gases, the interest on the production of alternative energy from renewable and eco-friendly sources such as biomass which is cheap and abundant has increased considerably. Aqueous Phase Reforming (APR) of real biomass or suitable model compounds (glycerol, glucose etc.) is an alternative process to convert biomass material into hydrogen energy and hydrogen thus produced can be used in fuel cells to generate electricity or can be used as a fuel directly instead of fossil fuels [1-3] . One of the biggest challenges for hydrogen production by aqueous- phase reforming of biomass compounds is catalyst development for improving the conversion. In this study, we aimed to see the influences of different commercial activated carbon support materials on the activity and selectivity of Aqueous Phase Reforming catalysts. Activated carbon (Sigma-Aldrich), Elorit, Superdarco and Norit-rox 0.8 (Norit Inc.) were tested as supportive materials for nano-sized and uniform Pt metal deposition. Pt was doped as the only active metal to different activated carbon supports so as to differentiate the reforming performance of various carbon supported Pt catalysts. We have used wetness impregnation method to load the metal precursor on activated carbon support, followed by two sequential reduction methods; reduction with NaBH

4

solution and termal reduction [4]. The structural characterization of the supported catalysts were investigated by using X-Ray diffraction and TEM. Surface area and pore size distribution were measured by N

2 adsorption–desorption at 77 K using a

Quantachrome Autosorb-6 Analyzer. The APR experiments are carried out in batch using a 100 mL Parr micro bench reactor equipped with magnetic drive stirrer heated to 250 °C for two hours. All gaseous products were analyzed by a dual-channel gas chromatograph (GC) system equipped with two thermal conductivity detectors. It was observed that the overall catalytic activities of these reforming catalysts when used in the APR of glucose for hydrogen production decreased in the following order: Pt-elorit > Pt-activated carbon > Pt-superdarco > Pt-norit-rox0.8. The results show that the type of support material has a direct influence on the kinetic behavior and affects the reforming peformance of catalysts for aqueous phase reforming of glucose solution.


Elorit, a steam activated carbon, exhibited better catalytic activity compared to other activated carbon supports.

References[1] G.W. Huber, J.W. Shabaker, S.T. Evans, J.A. Dumesic, Applied Catalysis B 62 (2006) 226-35.[2] B. Kaya, S. Irmak, A. Hesenov, O. Erbatur, Bioresource Technology 37 (2012) 17844-17852. [3] B. Meryemoglu, S. Irmak, A. Hesenov, O. Erbatur, Int. J. Hydrogen Energy 37 (2012) 17844-

17852.[4] B. Meryemoglu, S. Irmak, B. Kaya Ozsel, A. Hasanoglu, O. Erbatur, Int. J. Hydrogen Energy 40

(2015) 14826-14832.


CoRh NANOPARTICLES: SYNTHESIS, CHARACTERIZATION, THEIR USE AS CATALYST IN THE HYDROLYSIS OF HYDRAZINE BORANE

Bayram Abaya, Nihat Tunça, Murat Rakapb,a Yuzuncu Yil University, Department of Chemistry, 65080, Van

b Yuzuncu Yil University, Maritime Faculty, 65080, Van

Lightweight boron containing hydride compounds are very useful hydrogen storage materials due to their outstanding properties like high stability, high hydrogen content, safe storage, easy catalytic hydrogen release at room temperature and environmentally benign side products formation [1]. Among these storage materials, one of the mostly used materials is hydrazine borane (N

2H

4BH

3, HB). HB has 15.4 wt% of hydrogen and

can easily be synthesized from the reaction of hydrazine hemisulfate and sodium borohydride in dioxane at room temperature [2]. Hydrazine borane releases 3 moles of hydrogen gas upon hydrolysis in the presence of appropriate metal catalysts in aqueous solution.

In this study, PVP-stabilized cobalt-rhodium nanoparticles was synthesized and characterized by UV-VIS spectroscopy, TEM, XRD, and XPS techniques. Catalytic activity of CoRh@PVP nanoparticles in the hydrolysis of hydrazine borane was investigated and related kinetic data were obtained.

References[1] Eberle, U., Felderhoff, M., Schueth, F. Angew. Chem. Int. Ed. 48 (2009) 6608-6630. [2] Hannauer, J., Akdim, O., Demirci, U.B., Geantet, C., Herrmann, J.M., Mielec, P., Xu, Q. Energ.

Env. Sci. 4 (2011) 3355–3358.


Ni(II) COMPLEX COVERED ZnO FILM OF PHOTOCATALYSTS FOR EFFICIENT HYDROGEN PRODUCTION

Eylül Büşra HEREYTANİa, Fatih TEZCANa, Bilgehan GÜZELa, Gülfeza KARDAŞa, Osman SERİNDAĞb

aÇukurova University, Faculty of Science and Letters Department of Chemistry, AdanabKanuni University, Institute of Science and Technology, Adana

ZnO semiconductor photo electrochemical (PEC) water splitting systems are promised as a renewable-energy resources using with solarlight [1,2]. The only drawback of ZnO semiconductor is that it absorbs a small portion of the solar spectrum in the UV region. Therefore, enhancing to utilize of solar energy is essential to shift absorption of the visible light region. Dye-sensitized organic molecules are demonstrated to be one of the possible methods for dealing with this issue[3]. Aminomethlydiphospine Ni(II) has been synthesized by our group in order to its investigate photoluminescence and photo catalytic properties to generate H

2 from water. Photo electrochemical (PEC)

measurements were carried out in a convenient three-electrodes cell which bare ZnO and Ni complex film covered ZnO as working electrodes, an Ag/AgCl electrode was used as the reference electrode and platinum plate was used as the counter electrode at 0.5 M Na

2SO

4 as the electrolyte. Photoluminescence (PL) property of the electrode

was investigated with Fluorescence Spectrometer LS 55. When Ni complex film was covered ZnO surface, the photocurrent density and photoluminescence intensity enhanced according to bare ZnO.

Figure 1. PL spectra of Aminomethlydiphospine Ni(II) [Ni(dppab)] covered ZnO film and bare ZnO film

The authors are greatly thankful to Scientific Research Project of Çukurova University (Project No: FYL-2015-5201)


References[1] C.H. Hsu, D.H. Chen, International Journal of Hydrogen Energy, 36 (2011) 15538-15547.[2] Y.K. Hsu, S.Y. Fu, M.H. Chen, Y.C. Chen, Y.G. Lin, Electrochimica Acta, 120 (2014) 1-5.[3] T.A.M. Devens Gust, and Ana L. Moore, Accounts of Chemical Research, 42 (2009) 1890-1898.


Pt Catalyst Supported on High Surface Area MCM-41 and its Catalytic Activity for Formic Acid Oxidation

Niyazi ÖZÇELİKa, M. Selim ÇÖGENLİa, Ayşe BAYRAKÇEKEN YURTCANa,b

a Nanoscience and Nanoengineering Department, Atatürk University, Erzurum 25240, Turkeyb Faculty of Engineering, Department of Chemical Engineering, Ataturk University, Erzurum 25240,

Turkey

Direct formic acid fuel cells (DFAFCs) have been reported as an alternative for green energy. We report here the comparative studies of high surface area support materials and their influence on catalytic activities towards the electrochemical oxidation of formic acid. MCM-41 has been used in various areas including drug delivery, electronic, column seperation and catalysts because of its high surface area and mesoporous pore size distribution ranging from 2 nm to 50 nm [1].

MCM-41 with high surface area was prepared by sol-gel method [2]. MCM-41 supported Pt catalyst was prepared by using microwave irradiation technique. Firstly, required amounts of MCM-41 and aqueous solution of H

2PtCl

6 added in ethylene glycol and

then stirred for 30 min. Then the resulting mixture was reduced in microwave oven. MCM-41 had a BET surface area of 1057 m2/g this value is significantly higher than Vulcan carbon (250 m2/g). The characteristic peaks for fcc Pt is clearly seen from XRD (Figure 1). In this study, MCM-41 and carbon supported Pt catalysts will be tested for formic acid oxidation by CV measurements.

Figure 1: XRD result of MCM-41 supported Pt catalyst

References[1] Taguchi A. and Schüth F. Microporous and mesoporous materials 77 (2005) 1-45[2] Hu et al. Microporous and mesoporous materials 147 (2012) 94-101


Development of Co-B/ Sepiolite Catalysts for Hydrogen Generation by Hydrolysis of Sodium Borohydride

Seda EROL, Mine ÖZDEMİR

Eskisehir Osmangazi University, Faculty of Engineering, Department of Chemical Engineering, 26480, Eskisehir

Hydrogen is considered to be an efficient energy carrier for the future due to increasing demand of energy along with depletion of conventional fossil fuel reserves. Borohydrides are the most promising source to produce clean H

2 gas with very high

rate at room temperature. Among the chemical borohydrides, sodium borohydride (NaBH

4) is more favorable due to its advantages of high hydrogen density (10.8 %) and

stability in alkaline solution [1]. To increase and control the H2 generation rate through

hydrolysis of borohydrides an efficient and durable catalysts are necessary, made up of elements that are abundant in our earth. Interest in Co-based catalysts, mainly cobalt boride (Co-B), arises by their special features that make them potential catalyst for H

2

production [2].

In this study, CoB catalysts were synthesized on the sepiolite by impregnation using cobalt (II) chloride solution and then were reducted by sodium borohydride solution. The Co loadings in catalysts used in this study were 10wt. % and 15wt. %. The hydrogen generation activity of Co-B/sepiolite catalysts was tested through hydrolysis of sodium borohydride alkaline solution. Effects of NaBH

4 concentration and reaction temperature

on hydrogen generation rate were investigated. As the NaBH4 concentration increases

from 0.13 M to 0.33 M the hydrogen generation rate rises 3007.9 to 5863.2 mL/min g

CoB and 4013.67 to 10981.5 mL/min g

CoB for catalysts containing 10wt % and 15wt %

Co, respectively. The hydrogen generation rate increases from 1438 to 5863 mL/min g

CoB and 3152 to 10982 mL/min g

CoB for catalysts containing 10wt % and 15wt % Co,

respectively, with increasing reaction temperature from 30 °C to 50 °C.

References

[1]. Patel, N., Antonio, M., Progress in Co-B related catalyst for hydrogen production by hydrolysis of boron-hydrides: A review and the perspectives to substitute noble metals, International Journal of Hydrogen Energy, 2015, 1429-1464.

[2]. Özdemir, E., Enhanced catalytic activity of Co-B/glassy carbon and Co-B/graphite catalysts for hydrolysis of sodium borohydride, International Journal of Hydrogen Energy, 2015, 14045-14051.


Oxygen reduction and oxygen evolution reaction performances of PtNi/CuO catalyst for lithium-air batteries

Gamze BOZKURTa,b, Tansel ŞENERb, Dino TONTIc, A. Kadir ÖZERa,d, Ayşe BAYRAKÇEKEN YURTCANa,d

a Atatürk University, Nanoscience and Nanoengineering Department, 25200, Erzurum,Turkeyb TUBITAK, Marmara Research Center, Energy Institute, 41470, Kocaeli, Turkey

c The Spanish National Research Council (CSIC), 28006, Serrano, Madrid, Spaind Atatürk University, Chemical Engineering Department, 25200, Erzurum, Turkey

Energy is a very important part of both the universe and our daily lives. Especially, clean and high energy have a place in modern automotive industries. Therefore metal-air batteries have been promising such as Al–air, Li–air, Mg–air, Fe–air, and Zn–air. One of these types of batteries Li-air batteries have high energy potential for commercial applications [1]. In recent years, various catalysts have been developed for Li-air batteries. In this context, literature studies have focused on bifunctional catalysts that are cheap and abundant transition metals for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in Li-air batteries [2].

In this study, CuO supported PtNi catalyst was prepared by using microwave irradiation technique. In order to synthesize PtM (M;metal) on the supporting material various methods such as impregnation, polyol, solverthermal, sputtering and nanocapsule have been investigated. One of these methods microwave-irradiation technique is used in this study for catalyst preparation. In the studies carried out in the literature, it was observed that PtNi catalyst is effective for ORR and CuO catalyst is effective for OER [3]. In this context, preparation of PtNi catalyst on CuO support material is achieved by microwave irradiation. This catalyst is tested for charge and discharge capacity in Li-air battery. The cycle-life tests will be also done to check the impact of the catalyst. Physicochemical and electrochemical characterizations of the prepared catalysts were performed.

AcknowledgementsThe authors are gratefully acknowledge the financial support of Scientific Research Projects

Committee of Atatürk University with grant number of 2012/114.

References[1] Akhtar N., Akhtar W., Int. J. Energy Res., 39 (2015) 303–316.[2] Jung K., Riaz A., Lee S., Lim T., J. Power Sources, 244 (2013) 328-335.[3] Hyun K., Lee J.H., Yoon C.H., Kwon Y., Int. J. Electrochem. Sci., 8 (2013) 11752 - 11767.


Preparation of Ni Catalyst on Co3O4 Support Material for H2 Production

Gamze BOZKURTa,b, Ayşe BAYRAKÇEKEN YURTCANa,b, A. Kadir ÖZERa,b,a Atatürk University, Nanoscience and Nanoengineering Department, 25200, Erzurum,Turkey

b Atatürk University, Chemical Engineering Department, 25200, Erzurum, Turkey

The drawbacks of fossil fuels to the environment and human health have led to the quest of cleaner fuels. For this reason, hydrogen (H

2) as a renewable energy source and

environmentally friendly fuel has been gained increasing importance. H2 has the highest

energy content per unit mass at known fuels. At systems using hydrogen as fuel released only water and water vapour to the atmosphere. Therefore, the hydrogen production is quite important and a strategic issue [1].

Catalyst preparation is an important study area for H2 production from sodium

borohydride (NaBH4) which is safe and highly productive. Metallic catalysts that

transfer electrons to the molecular H2O to generate hydrogen are used for this purpose.

Behaviour of catalysts such as cobalt (Co) and nickel (Ni) are investigated for BH4

- hydrolysis. BH

4- adsorption on the catalyst (M=Co, Ni) was observed [2].

Various methods have been used such as dip coating, impregnation, electroplating, hydrogel, electroless plating etc. for catalysts preparation in the literature. One of these methods microwave-irradiation technique is both efficient and time saving. Co

3O

4 prepared with microwave-irradiation technique can be used as support material for metals as well as it is an effective catalyst for H

2 generation [3]. In this study, Ni catalyst

on Co3O

4 support material was synthesized by using microwave-irradiation technique

for H2 production from NaBH

4 and physicochemical characterizations were performed

for the synthesized catalysts in order to determine the properties of the catalysts.

AcknowledgementsThe authors are gratefully acknowledge the financial support of Scientific Research Projects

Committee of Atatürk University with grant number of 2015/360.

References[1] Dutta S., J. Ind. Eng. Chem. 20 (2014) 1148–1156.[2] Liu B.H,. Li Z.P., J. Power Sources, 187 (2009) 527–534.[3] Hung T.F., Kuo H.C., Tsai C.W., J. Mater. Chem., 21 (2011) 11754-11759.


Syntheses and Characterization of Ni Containing Silica Microspheres

Gamze Gunduz Meric, Levent Degirmenci

Bilecik Seyh Edebali University, Chemical and Process Engineering Department, 11100, Gulumbe Campus, Bilecik.

Ni-based catalysts have long been investigated for their potential use in industry. However, the sintering of Ni particles and carbon deposition are major problems preventing their utilization [1]. Studies in recent years to develop highly active and stable catalysts are of vital importance [2]. Noble metal bases catalysts, such as Rh, Ru, Pt, Pd have good catalytic activity at the expense of high price [3]. As an alternative, Fe-, Co- and Ni-based catalysts have drawn attention due to their high activity [4]. Ni-based catalysts are the most promising because of their low cost, high selectivity and good activity.

In this study, we investigate core-shell Ni containing microspheres prepared by a modified sol- gel method. Initially varying amounts of Ni (10, 5, 1.25, 1 and 0.75 wt. %) were dispersed into 20 ml deionized water, ultrasonicate for 15 min, and then homogeneously dispersed in a mixture of 50 ml ethanol, 10 ml 25 wt. % ammonia aqueous solution. 5 ml of TEOS was added to this solution. After stirring at room temperature for 6 h, the product was washed with ethanol and deionized water for 3 times, centrifuged and dried at room temperature for 24 h. The structure of the samples was characterized by X- ray diffraction (XRD), scanning electronic microscopy (SEM). Surface area of the samples were determined using Brunauer-Emmett-Teller (BET) method. Pore volume and pore size of the catalysts were derived using Barrett- Joyner-Halanda (BJH) method. Finally, metal loading of Ni was determined using an Inductively Coupled Plasma (ICP) Method.

References[1] J. Liu, H. Peng, W. Liu, X. Xu, X. Wang, C. Li, W. Zhou, P. YYuan, X. Chen, W. Zhang, HH.

Zhan, ChemCatChem 6 (2014), 2095- 2104.[2] Odedairo T, Chen J, Zhu Z. Catal Commun (2013) 31:25- 31.[3] A. Erdöhelyi, J. Cserenyi, F. Solymosi, J. Catal. 141 (1993) 287–299.[4] Yu M, Zhu Y-A, Lu Y, Tong G, Zhu K, Zhou X. Appl Catal B (2015)165:43- 56.


NEW DYE-SENSITIZIED Cu(I) COMPLEX PHOTOCATALYSTS BEHAVIOUR ON PHOTOELECTROLYSIS

Gurbet YERLİKAYAa, Fatih TEZCANa, Gülfeza KARDAŞa, Osman SERİNDAĞb

aÇukurova University, Science and Literature Faculty Chemistry Department, 01330, AdanabKanuni University, Institute of Science and Technology, 01170, Adana,

Increasing of energy necessity all over the world has motivated to researchers who new clean and renewable energy application systems. Photoelectrochemical(PEC) water splitting using with ZnO semiconductor has been extremely interested because of environmentally produce H

2 from water utilizing abundant plenty solar energy[1, 2]. On

the other hand, ZnO nano materials have need to improve in order to H2 production at the lower bias potential for water photoelectrolysis. Within this framework our study aim, photoluminescence(PL) of ZnO nanorods has been enhanced firstly using 4,4’,6,6’-terakis(N,N-ethlyaminostril)-[2,2’]bipyrimidineCu(I)aminomethlydiphospine as organic dye-sensitized. Photoelectrochemical (PEC) measurements were carried out in a convenient three-electrodes cell, an electrochemical analyser Gamry (interface 1000) and a 300W Xe lamp solar simulator (100 mW/cm2). PL properties of ZnO films and dye-sensitizied ZnO films have been examined with Flurorescence Spectrometer LS 55. Dye-sensitizied ZnO nanorods are higher photocurrent density and emission intensity than bare ZnO nanorods.

Figure 1. Molecule structureofa)4,4’,6,6’-terakis(N,N-ethlyaminostril)[2,2’]bipyrimidineCu(I)aminomethlydiphospine b) PL spectra of Cu(I) complex covered ZnO film and bare ZnO filmThe authors are greatly thankful to The Scientific and Technical Research Council of Turkey(TUBITAK) for financial support (Project No. 114R023).References[1] R. Lv, T. Wang, F.L. Su, P. Zhang, C.J. Li, J.L. Gong, Nano Energy, 7 (2014) 143-150.[2] M.F. Shao, F.Y. Ning, M. Wei, D.G. Evans, X. Duan, Advanced Functional Materials, 24 (2014)

580-586.


THE CONVERSION OF CELLULOSE TO 5-HYDROXYMETHYL FURFURAL (HMF) WITH ZEOLITE CATALYSTS

Esra Sezgin, Merve Esen, Solmaz Akmaz, Serkan Naci Koç, M. Ali Gürkaynak

Istanbul University, Engineering Faculty, Chemical Engineering Department, 34320 Avcılar, İstanbul

Fossil fuel resources are limited and depletion concern of resources in recent years has increased interest in alternative energy production. Cellulose is known as the most extensive renewable carbon-containing feedstock on earth. Therefore cellulose has the potential to be source for the manufacture of many chemicals. The implementation of new techniques and the development of catalytic processes made cellulose an important source for production of a variety of chemicals, especially fuel production, so the interest in studies on the production of alternative fuels from cellulose has increased [1].

5-hydroxymethylfurfural (HMF) is one of the most important intermediate products that lead cellulosic materials to fuel chemicals. From a commercial point of view, a multifunctional compound HMF, among other biomass-derived materials, has attracted attention due to being a major building block for the pharmaceuticals, plastics and fuels since the last years of the 19th century [2,3].

The proposed work aims the design of solid acid catalysts which will be effective for the conversion of cellulose to HMF, will not require the use of dissolved catalyst in the reaction mixture. Support material was used as the porous structures such as zeolite. The metal amounts of catalysts and phase structures were determined with ICP-MS and X-Ray Diffraction (XRD), respectively. XPS and NH

3-TPD techniques are also used

for characterization. The conversion of HMF from cellulose was studied at different temperatures and time in the solvent medium. HMF was analyzed at High-Performance Liquid Chromatography (HPLC) instrument.

The production of any type fuel additives as an alternative to fossil fuels having limited resources, will contribute economically.

AcknowledgmentsThis study was supported by The Scientific and Technological Research Council of Turkey

(TUBITAK), project No: 214M149

References[1] Yabushita M., Kobayashia, H., Fukuoka A. Applied Catalysis B: Environmental, 145, (2014) 1– 9 [2] Tong, X., Ma, Y., Li, Y. Applied Catalysis A: General, 385, (2010) 1–13.[3] Hu, L., Zhao, G., Hao, W., Tang, X., Sun, Y., Lin L., Liu S. RSC Advances, 2, (2012) 11184–

11206


Oxidative Steam Reforming of Biogas by over NiCe/MgAl Hydrotalcite-like catalysts

a Merve Doğan, a,b Orhan Özcan, a,b Murat Efgan Kibar, a,b Ayşe Nilgün Akına Kocaeli University, Department of Chemical Engineering, 41380, Kocaeli,

b AYARGEM, Alternative Fuels R&D Center, Kocaeli University, 41040, Kocaeli,

In the future, energy systems will need to be cleaner, more reliable, much efficient and sustainable. Hydrogen is a promising energy carrier and considered to be one of the best candidates to use instead of fossil fuels. Nowadays, methane is the main source for the production of hydrogen. Methane is usually supplied from natural gas. In recent years, biogas pointed out as alternative source of methane to produce hydrogen [1]. In hydrogen production processes, tri-reforming process offers the most important potential for economical and efficient conversion of biogas to hydrogen, due to the high conversion, high selectivity and adjustable H

2/CO molar ratio [2].

In this study, NiCe/MgAl Hydrotalcite-like catalysts (Ni content: 10 wt.% and Ce contents: 2.5/5/7.5/10 wt.%) were prepared by wet impregnation and coprecipitation methods and tested in tri-reforming reaction of model biogas to produce hydrogen. XRD and BET technologies were conducted to characterize the catalysts. The reactions were performed in a fixed-bed quartz reactor at 800 oC under atmospheric pressure. The catalysts were studied under the reaction conditions of the feed gas molar ratios of CH

4/CO

2/O

2/H

2O = 1/0.67/0.1/0.3. The reactor was inserted in an insulated electric

furnace, controlled by a programmable temperature controller. A K-type thermocouple was placed into the middle of the catalyst bed to control the bed temperature. The gaseous feed was controlled by mass flow controllers and steam was supplied to the gaseous feed by using an isocratic pump. The products of the reactions analyzed by a gas chromatograph equipped with FID and TCD. The results show that NiCe/MgAl Hydrotalcite-like catalyst is a promising catalyst to obtain high H

2 yield.

References[1] U. Izquierdo ., V.L. Barrio., J. Requies., J.F. Cambra., M.B. Güemez., P.L. Arias., International

Journal of Hydrogen Energy, 7623-7631 (2013) 38.[2] Pino L., Vita A., Lagana M., Recupero V., Applied Catalysis B: Environmental, 91-105 (2014)

148-149.


Microwave Assisted COx-free Hydrogen Production over Mesoporous Carbon Supported Molybdenum Nanocatalysts

Melih GÜLER1 Dilek VARIŞLI1 Timur DOĞU2

1GaziUniversity, Department of Chemical Engineering, 06570 Ankara, Turkey2Middle East Technical University, Department of Chemical Engineering, 06500, Ankara, Turkey.

In recent years, utilization of hydrogen as an alternative energy source by means of fuel cell increases steadily, due to its energy content and its clean fuel properties [1]. Ammonia is regarded as a prospective hydrogen carrier because of its favorable properties for on-site hydrogen generation and its decomposition produce only nitrogen as a by-product [2]. Nowadays, microwave heating has gained great attention in reaction systems [3] due to the efficient heating of active sites present in the catalyst which resulted in higher conversion at lower reaction temperatures.

In this work, microwave assisted ammonia decomposition reaction was carried out over mesoporous carbon (MC) supported Molybdenum(Mo) incorporated catalysts. Carbon, is selected as a supporting material due to its good dielectric properties andMolybdenum (Mo) was loaded at 5-15 wt % onto this support by following impregnation procedure. Synthesized catalysts in their calcined, reduced and used form were characterized with different techniques. Results of experiments that were carried out in Microwave reactor system with GHSV

NH3of 36,000 ml/hg

cat showed that

32% ammonia conversion could be seen at 350oC and total conversion was achieved at 400oC. In the literature, application of microwave heating on hydrogen production from ammonia decomposition reaction cannot be found, and studies that include conventional heating indicate higher temperatures, over 600oC, to obtain total conversion over Mo incorporated mono-bi metallic supported catalysts [4,5].


References[1] A. Kirubakaran, S. Jain, R.K. Nema, Renew. Sustain. Energy Rev. 13 (2009) 2430.[2] Kaname Okura, Takeou Okanishi, Applied Catalysis A: General 505 (2015) 77–85[3] S. Gündüz, T. Dogu , Applied Catalysis B: Environmental 168-169 (2015) 497–508[4] B. Lorenzut, T. Montini, M. Bevilacqua, P.Fornasiero, Applied Catalysis B: Env. 125 (2012) 409–

417[5] X. Duan, G. Qian, X. Zhou, D. Chen, W. Yuan,Chemical Engineering Journal 207–208 (2012)

103–108


HYDROGEN GENERATION FROM AMMONIA BORANE HYDROLYSIS CATALYZED BY CoPd NANOPARTICLES

Nihat Tunça, Bayram Abaya, Murat Rakapb,a Yuzuncu Yil University, Department of Chemistry, 65080, Van

b Yuzuncu Yil University, Maritime Faculty, 65080, Van

Ammonia borane (NH3BH

3, AB) has extensively been employed as solid hydrogen

storage material over the last ten years due to its features like quite high hydrogen content (19.6 wt%), high solubility in water, and high stability of its aqueous solution [1]. AB releases 3 moles of hydrogen gas upon hydrolysis in the presence of suitable metal catalsysts in aqueous solution. Up to date, a vast number of catalyst systems have been used for the hydrolysis of ammonia borane, and more recently especially bimetallic catalysts are focused on. With the addition of second element to the catalyst structure, catalytic activity increases drastically [2].

In this study, PVP-stabilized cobalt-palladium nanoparticles were synthesized and characterized by UV-VIS spectroscopy, TEM, XRD, and XPS techniques. The catalytic activity of CoPd@PVP nanoparticles in the hydrolysis of ammonia borane was investigated.

References[1] Xu, Q., Chandra, M. J. Power Sources 163 (2006) 364-370.[2] Chen, G., Desinan, S., Nechache, R., Rosei, R., Rosei, F., Ma, D. Chem. Commun. 47 (2011)

6308-6310.


EFFECT OF REACTION TEMPERATURE ON COKE FORMATION IN DRY REFORMING OF METHANE

Hüseyin Arbağa, Sena Yaşyerlia, Nail Yaşyerlia, Gülşen Doğua, Timur Doğub

a Department of Chemical Engineering, Gazi University, 06570 Ankara, Turkey b Department of Chemical Engineering, METU, 06800 Ankara, Turkey

Production of syngas from biogas through dry reforming of methane attracts researchers due to its reducing effect of CO

2 and CH

4 emissions. Syngas may then be converted into

various fuels and chemicals. Research on dry reforming mainly focus on developing highly active and stable catalysts with low coke formation. In our earlier studies it was observed that modification of Ni catalysts by Rh, Ru and W improved coke resistance of the catalyst [1-4]. In the present study, effect of reaction temperature on coke formation on the surface of %8 wt Ni on mesoporous alumina catalysts (8Ni@SGA) was investigated. Synthesized material had type IV adsorption-desorption isotherms. In the XRD pattern of 8Ni@SGA, peaks which belong to -alumina and metallic Ni were observed. The reactions were carried out in a fixed bed flow reactor at a space time of 0.1 s.g.cm-3 at different reaction temperatures, namely at 600oC and 750oC. The catalysts showed stable performance during reaction time of four hours at both temperatures. Increase of the reaction temperature from 600oC to 750oC increased the fractional conversion of methane (0.26 at 600oC and 0.75 at 750oC) and carbon dioxide (0.38 at 600oC and 0.85 at 750oC). Higher fractional conversion of carbon dioxide than the fractional conversion of methane obtained was due to the occurrence of reverse water gas shift reaction together with dry reforming of methane. TGA analysis of used catalysts also showed that weight loss (%33) at reaction temperature of 600oC was much higher than weight loss (%12) at reaction temperature of 750oC, indicating significant decrease in coke formation with an increase in reaction temperature. This result is also supported by XRD patterns of the used catalysts.

References[1] H. Arbag, S.Yasyerli, N. Yasyerli, G. Dogu, T. Dogu, I. G. O. Črnivec, A. Pintar, Ind. Eng. Chem.

Res., 54 (2015) 2290−2301.[2] H. Arbag, S. Yasyerli, N. Yasyerli, T. Dogu, G. Dogu, Topics in Catalysis 56 (2013) 1695-1707. [3] S. Yasyerli, S. Filizgok, H. Arbag, N. Yasyerli, G. Dogu, Int. J. Hydrogen Energy 36 (2011) 4863-

4874. [4] H. Arbag, S.Yasyerli, N. Yasyerli, G. Dogu, Int. J. Hydrogen Energy 35 (2010) 2296-2304.


THE ROLE OF PRECIOUS METALS ON ADSORPTION/DESORPTION KINETICS OF OXYGEN OVER REDUCIBLE OXIDES

Deniz Kayaa, Dheerendra Singha, Deniz Üner*,a

a Middle East Technical University, Chemical Engineering, 06800, Ankara, TURKEY

In this study, 1 wt. % Pd/CeO2-Al

2O

3 oxides with CeO

2:Al

2O

3 wt:wt ratios of 10:90, 15:85

and 20:80 were synthesized by sequential impregnation of CeO2 and Pd. Temperature

programmed reduction (TPR), temperature programmed oxidation (TPO) and temperature programmed thermal decomposition (TPtD) experiments were performed by using Micromeritics Chemisorb 2720 TPR experiments revealed that for CeO

2 coated alumina samples with 10 % and 15 % CeO

2 loading, surface reduction

peak of ceria was observed nearly at 600 °C, however bulk reduction peak of ceria could not be observed. TPtD experiments performed upto 950 °C did not reveal any thermal dissociation resulting in oxygen release over CeO

2-Al

2O

3.TPR of the mixed oxides

indicated the absence of the reduction characteristic peak from the bulk ceria, while the intensity of the surface related peaks starting at 300 °C increased with increasing ceria amount. The amount of the oxygen released during TPtD did not change with ceria loading much.

Figure 1. TPR (left) and TPtD (right) spectrum of 1 % Pd/CeO2-Al

2O

3 samples at 20 °C/

min heating rate

Heat of adsorption of oxygen was measured using a Setaram C-80 Tian-Calvet microcalorimeter. Heat of adsorption at the saturation coverage of 2.41 μmole O

2/g

cat. and 1.93 μmole H

2/g

cat. for 1 wt. % Pd/CeO

2 was 478 and 154 kJ/mol respectively.

AcknowledgementThis project is financially supported by TÜBİTAK 213M006 project under the leadership of Assoc.

Prof. Serkan Kıncal.


MODELING OF DATABASE CONSTRUCTED FROM PUBLISHED ARTICLES FOR WATER SPLITTING OVER PEROVSKITES

Elif Cana, Ramazan Yıldırımb,a Boğaziçi University, Department of Chemical Engineering, 34342 Bebek, Istanbulb Boğaziçi University, Department of Chemical Engineering, 34342 Bebek, Istanbul

The aim of this work was to extract useful knowledge from published articles for photocatalytic water splitting over perovskite-type catalysts, then to examine whether the result of an unperformed experiment can be estimated, or whether the best conditions for the future works can be determined in advance. For this purpose, the articles published from 2005 to 2014 about PWS in the literature were studied. A comprehensive database involving 2704 instances was constructed from those articles available in online libraries. The hydrogen production rate (µmol/g-cat/h) was selected as output variable, and it was tried to be estimated by using input variables related to catalytic or operational variables. During the generation of the database, it was observed that the interest on PWS studies has been aroused since 2000s as it is evident from Figure 1. Different data mining tools and models were developed and utilized in “R” environment. The data for ABO

3 and ABS

3 type perovskites were modelled separately,

and the best predictions were obtained with “random forest” technique. The plot of predicted vs. observed hydrogen production rate for ABO

3 perovskites is given in Figure

2 as example.

Figure 1. Number of Published Articles Figure 2. Results of Best Performed Model on PWS vs. Years

Analysis was indicated that the operational variables seem to be more influential for hydrogen evolution. Nb (as B site of perovskite) and K (as A site of perovskite) were determined as relatively more effective compare to the other elements.


MORPHOLOGY OF PT-CU NANOPARTICLES BY USING GENETIC ALGORITHM AND DENSITY FUNCTIONAL THEORY

Ezgi ERDEMa, Rıza KIZILELb, Can ERKEYa,b

a Koç University, Chemical and Biological Engineering Department, Sarıyer 34450, Istanbulb Koç University, Koç University Tupraş Energy Center (KUTEM), Sarıyer, 34450, Istanbul

Supported bimetallic nanoparticles can provide enhanced activity and selectivity compared to their pure counterparts in many reactions catalyzed by heterogeneous catalysts. The morphology of these nanoparticles plays a very important role in how a particular catalytic cycle proceeds. Carbon supported Pt-Cu nanoparticles show promise for use as electrocatalysts in polymer electrolyte membrane fuel cells. In this study, we investigated the morphology of Pt-Cu clusters by computational chemistry methods. One of the most effective optimization approaches for finding the structure of a cluster with the minimum energy level is Density Functional Theory (DFT) which allows a close connection between theory and experiment and often leads to important clues about the geometric, electronic and spectroscopic properties of the systems being studied. Essential part of working under DFT environment is the identifying initial structure of cluster qualitatively, because of feeding locally optimized structures rather than randomly arranged structures to DFT, reduces processing time and provides energetically stable clusters at global minima. In this study, the locally optimized structures of Pt-Cu bimetallic clusters (1:1 composition for N=10-40 atoms) were searched using Genetic Algorithm (GA) by using Gupta potential which is based on second moment approximation to tight binding theory. GA was used to solve a series of attractive and repulsive potential energy equations and find which morphology gives a minimum potential. The energy scaling parameters for Gupta potential which are A, 𝜉, p and q describing heteronuclear Pt-Cu interactions, were obtained by taking weighted averages of these parameters for pure bulk Pt and Cu metals. Then, the lowest energy structures which were found empirically were reoptimised at the ab-initio DFT level (first principles). DFT calculations were carried out using Gaussian 09 quantum chemistry simulation package within a LANL2DZ basis, and B3PW91 exchange correlational function (Becke Three Parameters Hybrid Function). The structural motifs calculated by Gupta potential, as a function of composition and weighted parameters, were similar with structures obtained by DFT but the distances and places of certain atoms were different. The structures predicted by combination of GA and DFT are randomly chemically disordered structures as minimum energy states with no apparent segregation of a particular species either to the core or to the surface.


TEMPERATURE EFFECT ON THE CARBON DIOXIDE SORPTION CAPACITY OF NATURAL MAGNESITE DERIVED SORBENT

Dilsad Dolunay Eslek Koyuncua, Sena Yasyerlia,Nail Yasyerlia,aChemical Engineering Department,Gazi University, 06570, Ankara

Due to the significant increase in atmospheric CO2 concentration, the removal of CO

2

has become an important global issue in the field of energy and environment [1]. Natural minerals (such as dolomite and limestone) have been used conventionally because of its availability and low cost, high CO

2 capture capacity and suitable

reaction kinetics [2, 3]. The aim of this study is to investigate the CO2 sorption capacity

of natural magnesite mineral as sorbent due to its high MgO content and availability in Turkey.

XRF results showed the presence of nearly 80 wt % MgO in the raw mineral structure. It is expected that MgO is mainly active phase for CO

2 sorption at low temperatures.

MgCO3-magnesite and CaMg(CO

3)

2-dolomite phases were detected in the XRD

patterns of natural magnesite mineral.In the TGA-DTA analysis, decomposition of carbonate species were observed within the following ranges of 500-670 0C and 670-830 0C, respectively.At the end of characterization studies magnesite mineral was calcined at 900 0C (3 0C/min, 3 h).Before calcination step natural magnesite mineral was finely ground to obtain powder (< 0.7 mm).Surface area of the calcined sorbent was found to be 23 m2/g and MgO and small amount of CaO phases were detected by XRD. CO

2 capture tests were performed in a fixed bed reactor system using feed

stream containing 4% CO2 in He with a GHSV of 3600 cm3h-1g-1 at temperature range

of 35-400 0C.CO2 sorption capacity of the magnesite mineral sorbent was decreased

by increase in sorption temperature. The highest CO2 sorption capacity of magnesite

derived sorbent was found as 0.18 mmol CO2/g sorbent at 35 0C using breakthrough

analysis.

References[1] Zhang, Z., Xu, M., Wang, H., Li, Z., Chemical Engineering Journal, 160 (2010) 571-577.[2] Wang, K., Zhao, P., Guo, X., Han, D., Chao, Y.,Energy Conversion and Management, 86 (2014)

1147-1153.[3] Mastin, J., Aranda, A., Meyer, J.,Energy Procedia, 4 (2011) 1184–1191.


PREPARATION SUPPORTED PT AND RU CATALYSTS AND THEIR PERFORMANCES IN AVPR PROCESS

Bahar Meryemoglua, Mehtap Kurtulusa,Arif Hasanoglua, Sibel Irmakb

aCukurova University,Chemistry, 01330, AdanabUniversity of Nebraska-Lincoln, Biological Systems Engineering, 68583, Lincoln, USA

Precious metal catalysts are widely used in the supported form on porous materials such as activated carbon, alumina, silica, silica-alumina, various organic polymers, and so forth, with a variety of properties (e.g., particle size, surface area, pore volume and size, mechanical strength and resistance to attrition, thermal stability, etc.) [1].In this study, alumina, silica and activated carbon (AC) supported Pt and Ru catalysts were prepared and the effect of support material and metals investigated in atmospheric pressure catalytic vapor phase reforming (AVPR) for lignocellulosic biomass. The characterization of catalysts were investigated with XRD, BET, TEM and the structure of samples were also investigated using FTIR, GC-TCD and GC-MS. The BET surfaces of supported materials showed differences.

Activated carbon has the highest BET surfaces area (951 m2/g), while alümina has the lowest (190 m2/g). TEM analysis results that Pt and Ru particles loaded uniformly on support material and there was no sintering. However, it was observed that Pt and Ru particles loaded on silica dispersed as a stack. The gas volume of supported catalysts were 30.0, 25.0 and 15.0 ml for activated carbon, alumina and silica, respectively. The order of gasification effiency and hydrogen yield was as AC > Alumina > Silica. The activity of AC supported catalysts (Pt-AC and Ru-AC) were most efficent because of that activated carbon support had the highest surface area among the other supports. The 13.4 ml H

2/g catalyst was produced when Ru-AC was used as catalyst in AVPR.

Alumina support with the lowest BET surface area produced high hydrogen selectivity 13.7 ml H

2/g catalyst as much as activated carbon. Silica supported catalysts showed

the lowest performance in gasification.

AcknowledgementFinancial support from Scientific and Technical Research Council of Turkey (TUBITAK) is gratefully

acknowledged (The project number: 114M146).

References:[1]Kaya B, Irmak S, Hesenov A, Erbatur O, Erkey C. Bioresour Technol 2012;123:723–6.


Investigation of Metal Loading Ratio Effect on Characteristics of Co/Al2O3 Catalysts and Utilization in Catalytic Pyrolysis

Nurgül ÖZBAYa, Pınar BAŞa, Adife Şeyda YARGIÇa

aBilecikŞeyhEdebali University, Faculty of Engineering, Chemical and Process Engineering Department, 11210 Bilecik

Supported Co catalysts are often used for many catalytic reactions such as Fischer Tropsch synthesis, pyrolysis, oxidation reactions, etc. due to their good activity and selectivity[1-3].Catalytic pyrolysis is a promising method for the direct conversion of solid biomass into fuel andvaluable chemical feedstocks [4]. Catalytic pyrolysis process provides to obtain desired product yields and improve the bio-oil quality. Besides, catalytic effect of additives can reduce the initial devolatilization temperature and the char formation.A variety of catalysts have been studied for the catalytic pyrolysis of biomass, such as ZSM-sulfated metal oxides, Al-MCM-41, SBA-15, and noble metal catalysts. Among these catalyts, cobalt-based catalysts have potential to use in catalytic pyrolysis reactions [2].

In this study, catalysts with different cobalt loading ratio (5 and 10 wt. %) were prepared by the co-precipitation method. The catalysts were characterized by SEM, XRD, and BET method. The prepared Co/Al

2O

3 catalysts were used in tomato waste pyrolysis

at 500 °C and non-catalytic and catalytic pyrolysis product yields were compared.The chemical compositions of liquid products were determined by GC–MS, FT-IR and Elemental Analysis.

References:[1] Visconti, C. G., Lietti, L., Tronconi, E., Forzatti, P., Zennaro, R., Finocchio, E. Applied Catalysis

A: General, 355(1) (2009), 61-68.[2] Le, T. A., Ly, H. V., Kim, J. Energy Sources, Part A: Recovery, Utilization, and Environmental

Effects, 36(21) (2014), 2392-2400.[3] Zhang, X. W., Shen, S. C., Hidajat, K., Kawi, S., Liya, E. Y., Ng, K. S. Catalysis Letters, 96(1-2)

(2004), 87-96.[4] Carlson, T. R. (2010). Catalytic fast pyrolysis of biomass for the production of fuels and

chemicals.


AN EFFICIENT HETEROGENEOUS CR-ZEOLITE CATALYST FOR GLUCOSE TO 5-HYDROXYMETHYLFURFURAL CONVERSION

Merve Esen, Esra Sezgin, Solmaz Akmaz, Serkan Naci Koç, M. Ali Gürkaynak

İstanbul Üniversitesi, Mühendislik Fakültesi, Kimya Mühendisliği Bölümü, 34320 Avcılar, İstanbul

Cellulose as a polysaccharide is the most abundant biomaterial in the world and its bio-based products are considered to be one of the alternatives to many petroleum products. The conversion of cellulose and glucose to valuable biorefinery products has gained great importance in recent years [1-3].

The dehydration product of glucose and/or fructose is 5-hydroxymethyl furfural (HMF). Five-membered ring compound HMF is one of the most important bio-based so-called platform chemicals. The ring structure of glucose is more stable than that of fructose and hence higher HMF yields are obtained from fructose with homogeneous or heterogeneous acid catalysts. HMF is an important chemical that can be easily converted to valuable furan derivatives, such as, high octane 2,5-dimethylfuran biofuel compound [4].

In this study, CrCI3, H-zeolite and calcined Cr-zeolites were studied in the liquid phase

heterogeneous catalytic conversion of glucose to HMF in ionic liquids. Characterization of catalysts were done in XPS, XRD and NH

3-TPD. The prepared catalysts were tested

for the conversion of HMF from glucose at different temperatures and time in the solvent medium. At the end of the reactions, the liquid product was analyzed at High-Performance Liquid Chromatography (HPLC) instrument. A Little decrease in both glucose conversion and HMF yield was observed with the addition of chromium (III) chloride impregnated zeolite catalysts when compared to homogeneous CrCI

3-[BMIM]

CI system. High glucose and HMF yields were obtained with heterogeneous calcined Cr-zeolite. Best HMF yield achieved was 58.8%.

AcknowledgmentsThis study was supported by The Scientific and Technological Research Council of Turkey

(TUBITAK), project No: 214M149

References[1] Hu, S.; Zhang, Z.; Song, J.; Zhou, Y.; Han, B. Green Chem., 2009, 11, 1746-1749[2] Takeuchi, Y.; Jin, F.; Tohji, K.; Enomoto, H. J Mater. Sci. 2008, 43, 2472-2475[3] Hu, L.; Zhao, G.; Tang, X.; Wu, Z.; Xu, J.; Lin, L.; Liu, S. Bioresource Technol. 2013, 148, 501-

507[4] Román-Leshkov, Y.; Barrett, C. J.; Liu, Z. Y.; Dumesic, J. A. Nature 2007, 447, 982-985


N-HETEROCYCLIC CARBENE-BASED NICKEL(II) COMPLEXESIN KUMADA COUPLING

Deniz DEMİR ATLI, Şebnem E. SÖZERLİ

Celal Bayar University, Faculty of Arts and Sciences, Department of Chemistry, 45050, Manisa

Kumada cross coupling reaction has been widely used in organic synthesis to construct biaryl compounds, which are important building blocks of functional materials, natural products and medicines [1-3]. N-heterocyclic carbene nickel(II) complexes efficiently catalyze these reactions [4-7].

In this study, threenew neutral N-heterocyclic carbene nickel(II) complexes of the formula [(NHC)CpNiX] (X = Br, Cl) were synthesized by the reaction of nickelocene with corresponding ester-functionalized benzimidazolium salts. The complexeswere characterized by 1H NMR,13C NMR, FT-IR and elemental analysis methods.It was found that nickel(II) complexes exhibited high catalytic activities in the cross-coupling reactions of aryl chlorides and bromides with phenylmagnesium bromide at room temperature.

References[1] K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc., 94 (1972) 4374-4376.[2] R.J.P. Corriu, J.P. Masse, J. Chem. Soc., Chem. Commun., (1972) 144.[3] M. Kumada, Pure Appl. Chem., 52 (1980) 669-679.[4] Z. Xi, B. Liu, W. Chen, J. Org. Chem., 73 (2008) 3954-3957.[5] H.V. Huynh, R. Jothibasu, Eur. J. Inorg. Chem., (2009) 1926-1931.[6] J. Berding, T.F. Dijkman, M. Lutz, A.L. Spek, E. Bouwman, Dalton Trans., (2009) 6948-6955.[7] W. Guo, Z. Wang, J. Org. Chem., 78 (2013) 1054-1061.


Sorption Enhanced Steam Reforming of Ethanol Over Ni Impregnated SBA-15 Catalyst

Merve Sarıyer, Arzu Arslan, Naime Aslı Sezgi, Timur Doğu

Chemical Engineering Department,Middle East Technical University, 06800, Ankara

Environmental concerns and fast depletion of fossil resources accelerated the research and development activities for the production of alternative fuels and energy carriers. Hydrogen has been considered as one of the most promising energy carriers for fuel-cell-derived cars. Bio-ethanol is one of the most promising non-fossil resources for the production of hydrogen [1, 2]. Thermodynamic limitations of steam reforming reaction of ethanol cause reduction in hydrogen yield, in this process. In the present work, ethanol reforming was performed in a sorption enhanced process, to increase hydrogen yield by in-situ removal of produced CO

2, using CaO as a sorbent. Ni impregnated SBA-15

was used as the reforming catalyst in this system. SBA-15 is a promising catalyst support due to its ordered mesoporous silicate structure, high surface area and moderate hydrothermal stability, while Ni has been shown to give high activity in reforming reactions. Characterization results of synthesized materials showed that this catalyst had a surface area of 856 m2/g and exhibited Type IV nitrogen adsorption/desorption isotherm with H1 hysteresis loops, indicating mesoporous structure with ordered pores. Comparison of the activity test results obtained in the presence and absence of CaO sorbent revealed significant increase of hydrogen yield in the sorption enhanced reforming test. Mole fractions of CO

2 and CO in the product stream decreased from

0.12 to 0.2 and from 0.14 to 0.4, respectively, as a result of in-situ removal of CO2 in

the sorption enhanced process. Results proved the advantages of sorption enhanced process for the production of high purity hydrogen from ethanol.

References[1] Gunduz, S., & Dogu, T. (2012). Sorption-enhanced reforming of ethanol over Ni- and Co-

incorporated MCM 41 type catalysts. Industrial and Engineering Chemistry Research, 51(26), 8796–8805.

[2] Arslan, A., Gunduz, S., & Dogu, T. (2014). Steam reforming of ethanol with zirconia incorporated mesoporous silicate supported catalysts. International Journal of Hydrogen Energy, 39(32), 18264–18272.


ESTERIFICATION OF GLYCEROL WITH OLEIC ACID over Ti CONTAINING SULFATED SBA-15 CATALYSTS

Gamze AY, Giray MUTLU, Emre KILIÇ, Hasan ÖRTÜN, Selahattin YILMAZ

Department of Chemical Engineering, Izmir Institute of Technology, Izmir, Turkey

Production of biodiesel is based on the trans-esterification of vegetable oil and short chain alcohol. Being a renewable resource, its use is increasing steadily. During this process, glycerol is formed as a byproduct in large quantities. Also there is glycerol formation in soap production. Glycerol formed can be converted to valuable product glycerol monoesters (monoglycerides) which can be used as emulsifiers in food, pharmaceutical and cosmetic industries. The aim of this study is to develop active and selective heterogeneous catalyst for esterification of glycerol and oleic acid to obtain monoglyceride. This reaction requires acidic catalysts.

In this study, titania containing sulfated SBA-15 catalysts with different Ti loadings (2% and 6%) were prepared (SO

4/TiSBA-2 and SO

4/TiSBA-6). Sulfation process was carried

out by using ammonium sulfate solution. Esterification reaction was performed under nitrogen flow in three necked glass reactor at 160 oC without using a solvent. Effect of glycerol/oleic acid mole ratio (3 and 6) was also investigated.

The catalysts prepared were mesoporous and had high acidity. Higher titania loading provided more sulfur bonding and improved the total and Brønsted acidity. The main products were found as mono, -di, and triglycerides. The highest monoglyceride yield was obtained over SO

4/TSBA-6 catalyst as 49 % when conversion of oleic acid was 62

% after 5 h reaction time. It was found that catalyst with high acidity and Brønsted acid sites were more active in esterification reaction and gave higher yield to monoglycerides. Glycerol/oleic acid ratio affected the monoglyceride yield significantly. It was improved from 49 % to 65 % by rising the glycerol/oleic acid mole ratio from 3 to 6. When excess amount of glycerol was used, oleic acid reacts with unreacted glycerol instead of monoglyceride, also equilibrium shifts towards the products. Thus, yield was improved.


Synthesis and Characterization of Perovskite Catalyst and Its Catalytic Activity in Pyrolysis

Nurgül ÖZBAYa, Rahmiye Zerrin YARBAY ŞAHİNa

a Bilecik Şeyh Edebali University, Faculty of Engineering, Chemical and Process Engineering Department, 11210 Bilecik

Biomass has taken great attention as a clean and alternative energy source which has advantages such as being renewable, emitting relatively low CO

2 levels, and having

negligible amount of sulfur. Pyrolysis is thermal decomposition of biomass in the absence of oxygen to achieve liquid (bio-oil), gas and char products[1-3]. Addition of catalyst into the pyrolysis is one of the common upgrading method in order to improve the bio-oil quality.

In this study, mandarin peel was used as a biomass source and pyrolysis was performed to achieve bio-oil, gas and char products at the temperature of 550°C using 100°C/min of constant heating rate and 100 ml/min of constant nitrogen gas (N

2) flow rate. The

effect of catalyst (LaMnO3)on the product yields was investigated. The crystal structures

of catalysts were determined X-Ray Diffraction (XRD), morphology of the samples were analyzed by Scanning Electron Microscope (SEM), and the specific surface area of the samples were determined by nitrogen adsorption desorption isotherms (BET) measurements.The chemical compositions of liquid products were determined by GC–MS, FT-IR and Elemental Analysis.

References:[1] Aysu T., Durak H., Güner S., Bengü A.Ş., Esim N., Bioresource Technology, http://dx.doi.

org/10.1016/j.biortech.2016.01.015[2] Li, S., Zhu, J., Chen, M., Xin, W., Yang, Z., Kong, L., Int J Hyd Energ., 39 (2014),13128-35.[3] Li, S., Xu, S., Liu, S., Yang, C., Lu, Q., Fuel Process Technol., 85 (2004), 1201-11


EPOXIDATION OF METHYL OLEATE OVER SO4/TiO2-SiO2 AND WO3-ZrO2 CATALYSTS

Vahide Nuran Mutlua, Canan TAŞa, Selahattin YILMAZa

a Izmir Institute of Technology, Chemical Engineering, Izmir Instıtute of Technology Chemical Eng. Department Urla, Izmir Turkey

Diminishing petroleum resources increased the demand on development of alternative and renewable sources. Epoxidized fatty acid esters are one of the key raw materials for a wide variety of products. They are used for many commercial applications, as plasticizers and stabilizers, as additives in lubricants, as components in thermosetting plastics and in cosmetics and pharmaceutical formulations [1]. Industrially, epoxidized fatty acids produced by the homogeneous peracid process.However, to fulfill the environmental concerns, it is preferred to carry out these epoxidation reactions by heterogeneous catalysts instead of homogeneous catalysts.In this work, methyl oleate was produced byesterification of methanol and oleic acid using sulfuric acid as catalyst. Methyl oleate produced was then epoxidized with hydrogen peroxide over SO

4/TiO

2-

SiO2 and WO

3-ZrO

2catalysts in ethyl acetate at 80oC. TiO

2-SiO

2 catalyst was prepared by

sol-gel and sulphated. WO3-ZrO

2 was prepared by co-precipitation method. Catalysts

were characterized using BET, XRD and NH3-TPD methods. Characterization studies

showed that while WO3-ZrO

2 smallersurface area and pore size compared to SO

4/

TiO2-SiO

2. Surface acidity studies showed thatWO

3-ZrO

2 possessed medium strength

acid sites while SO4/TiO

2-SiO

2had peaks at both weak andstrong acid sites. The methyl

oleate conversion obtained over SO4/TiO

2-SiO

2(35%) than WO

3-ZrO

2(24%). When the

results obtained over two catalysts were compared, it can be said that the acidity of the catalyst is important for the activity.

References[1] A. Campanella, M. A. Baltanás M. C. Capel-Sánchez, J. M. Campos-Martín J. L. G. Fierro,Green

Chemistry, 6 (2003) 330 – 334 [2] J. Sepulveda, S. Teixeria, U. Schuchardt, Applied Catalysis A: Gen. 318 (2007) 213 – 217


THE EFFECT OF PEROXIDE ON BIOMASS HYDROLYSIS AND CATALYTIC GASIFICATION OF HYDROLYSATES

Mehtap Kurtulusa, Bahar Meryemoglua, Arif Hasanoglua, Sibel Irmakb

a Cukurova University,Chemistry, 01330, Adanab University of Nebraska-Lincoln, Biological Systems Engineering, 68583, Lincoln, USA

The present study was designed to produce hydrogen gasin AVPR of lignocellulosic biomass hydrolysates using peroxide. In this study, lignocellulosic biomass was hydrolyzed in subcritical water condition in the absence and presence of peroxide and was gasified with Raney Ni catalyst. The gaseous products were analyzed with GC-TCD and liquid products were analyzed GC-MS.

The 88,5 ml gas volume of hydrolysate without peroxide obtained in AVPR. The hydrogen yield of this hydrolysate was 5,7 ml H

2 / g catalyst (Table 1). The total gas

volume and gas composition changed with the use of peroxide in hydrolysis. When biomass hydrolysates were gasified by AVPR, hydrolysate with %0,5 H

2O

2 produced the

highest gas yield with high hydrogen selectivity (110,0 ml; 6,9 ml H2 /g catalyst). It was

observed that the gas volume and hydrogen yield of hydrolysate used in the AVPR for hydrogen production decreased with increasing amount of peroxide in hydrolysis process. This could be attributed to gasification of organic molecules during hydrolysis in the presence of peroxide.

Table 1. Gasification of hydrolysates with different percentage peroxide using Raney Ni catalyst

AcknowledgementFinancial support from Scientific and Technical Research Council of Turkey (TUBITAK) is gratefully

acknowledged (The project number: 114M146).


Palladium (0) Nanoparticles Supported on Amine-Functionalized Silica for the Catalytic Hexavalent Chromium Reduction

Metin Celebia, Mehmet Yurderia, Ahmet Buluta, Murat Kayab, Mehmet Zahmakirana,*

a Nanomaterials and Catalysis (NanoMatCat) Research Laboratory, Department of Chemistry, Yüzüncü Yıl University, 65080 Van, Turkey

b Department of Chemical Engineering and Applied Chemistry, Atilim University, 06836 Ankara, Turkey

Hexavalent chromium (Cr(VI)) is commonly identified acutely toxic, a proven mutagen and carcinogen heavy metal polluant in the aquatic environment, whereas Cr(III) is believed to be essential element. In the present study, we show that palladium(0) nanoparticles supported on 3-aminopropyltriethoxysilane (APTS) funtionalized silica (Pd@SiO

2-NH

2) effectively catalyze te reduction of Cr(VI) to Cr(III) by using formic acid

(HCOOH) as reducing agent under mild conditions (at room temperature under air). Pd@SiO

2-NH

2 catalyst was reproducibly prepared by deposition-reduction technique

and characterized by the combination of various spectroscopic tools including ICO-OES, P-XRD, DR/UV-vis, XPS, BFTEM, HRTEM and TEM-EDX techniques. The sum of their results is indicative of the formation of well-dispersed palladium(0) nanoparticles (d

mean= 3.7 nm) on the surface of APTS-functionalized SiO

2. The catalytic performance of

the resulting palladium(0) nanoparticles in terms of activity and stability was evaluated by the catalytic reduction of Cr(VI) to Cr(III) in aqueous solution in the presence of formic acid as a reducing agent. Our results reveal that Pd@siO

2-NH

2 catalyst displays

unprecedented activity (TOF=258 mol Cr2O

72- / mol Pd min) and reusability (<85% at

5th reuse) forthe reduction of Cr(VI) to Cr(III) at room temperature.

Figure 1.The photographs of the reaction solution for Pd@SiO2–NH

2 catalyzed reduction of Cr(VI) to

Cr(III) by using formic acid (HCOOH) and formation of green hexahydroxochromate via addition of excess NaOH.


PALLADIUM NANOPARTICLES(Pd NPs) AS EFFICIENT CATALYSTS FOR SUZUKI-MIYAURA REACTION IN MILD CONDITIONS

Burcu DARENDELİa, Fatma Ulusala, Bilgehan GÜZELa

a Chemistry Departmant, University of Cukurova, 01330 Adana, TURKEY

Recently, there has been great interest on the use of metal nanoparticles (NPs) for nanocatalysis[1]. Palladium NPs have become of increasing scientific interest as catalysts for carbon–carbon bond-forming reactions, such as Suzuki–Miyaura cross-coupling reactions, which are among the most powerful methods in organic synthesis.These reactions are typically performed under heating or at reflux [1,2]. Much less is known about the room temperature Suzuki–Miyaura cross-coupling reaction catalyzed by PdNPs. In this work, Suzuki-Miyaura cross-coupling reaction is performed at room temperature and the conversion yields were nearly as same as the typical reaction results. Performing the reaction under lower temperature is a huge advantage for industrial processes cause of saving energy.

Figure 1. XRD pattern of Pd NPs

Pd NPs were prepared chemical impregnation method and the metal loading was determined by ICP analysis. XRD and SEM analysis were used for characterization of the prepared PdNPs (Fig.1.). The catalytic activities were performed in Suzuki-Miyaura cross coupling reactions and the reactant/product ratio was determined with gas chromotography (GC).

References:[1] D. Astruc, Nanoparticles and Catalysis, Wiley-VCH, Weinheim, 2008. [2] J. Tsuji, Palladium Reagents and Catalysts, Wiley, New York, 2004.


Investigation of Isobutane Dehydrogenation in a Pd-membrane Reactor

Saliha Çetinyokuş Kılıçarslanª, Meltem Doğanb, TimurDoğuc,

ª Republic of Turkey Disaster and Emergency Management Authority, Department of Planning and Mitigation,06530 Ankara, Turkey

b Gazi University, Chemical Engineering Department, 06570 Ankara, Turkeyc Middle East Technical University, Chemical Engineering Department, 06800 Ankara, Turkey

Isobutane dehydrogenation is an endothermic equilibrium-limited reaction. In order to overcome equilibrium limitations, produced hydrogen can be removed from the reaction medium[1,2,3]. In this work, isobutane dehydrogenation was achieved in a commercial Pd-membrane reactor system. Reaction was performed under fixed–bed conditions using aCr/MCM-41 catalyst [4] (surface area: 990m2/g, averagepore diameter: 2nm, containing 3% of Cr by mass), which was synthesized following a hydrothermal route. Experimental studies were performed at different temperatures (T=723K, 773K, 823K), using a pure isobutane feed stream (50ml/min, WHSV=28h-1).Isobutane dehydrogenation was performed at a pressure difference of 70kPa across the membrane. Isobutane conversion value of 25% was determined at873K. No side reaction products (propane, propene, methane) were observed at 773K and 823K in the membrane reactor. However, isobutenes electivity decreased to about 55% at 873 K, because of the occurrence of side reactions.All of the side reaction products were observed in the experiment carried out in 873K and without catalyst. Experiments performed in the membrane reactor without the Cr/MCM-41 catalyst showed that Pd membrane itself was also a highly active catalyst for the occurrence of isobutane dehydrogenation, as well as side reactions, especially at a high temperature (873 K). Results proved that produced hydrogen was first used in reduction of Cr6+and significant information was obtained about the reaction mechanism. References[1] Sahebdelfar, S., MoghimpourBijani, P., Saeedizad, M., TahririZangeneh, F. and Ganji, K., Appl.

Catal., A, 395, 2011,107–113.[2] Farsi, M., Jahanmiri, A., Rahimpour, M.R., J. Ind. Eng. Chem., 18, 2012, 1676–1682.[3] Çetinyokuş Kılıçarslan, S., Doğan, M., Doğu, T., Int. J. Chem. Reactor Eng., DOI 10.1515/

ijcre-2015-0031, 2015.[4]Kılıçarslan, S., Doğan, M., Doğu, T., Ind. Eng. Chem. Res.,52(10), 2013, 3674–3682.


PREPARATION OF NOVEL VIC-DIOXIME-Pd(II) COMPLEX FOR SUZUKI-MIYAURA REACTIONS

Özge Atışa, Fatma Ulusala, Bilgehan Güzela

a Çukurova University, Science and Literature Faculty Chemistry Department, 01330, Adana

In the past two decades, a great number of coordination compounds were synthesized for catalytic application onSuzuki-Miyaura and Heck reaction, hydrogenation,hydroformylationof unsaturated substrates. Organophosphine compounds are generally used as homogenous catalysis in Suzuki-Miyaura cross coupling reaction. But usage of these compounds are limited for having environmental damages.Pd(II) complexes of vic-dioxime can be used for Suzuki-Miyaura as an alternative to organophosphine owing to non-toxicity and high activity. In this work, novel vic-dioxime ligand (2-fluoroaniline-amphi-vic-dioxime) and Pd(II) complex were synthesized and characaterized. Catalytic activities of the synthesized Pd complex were investigated in Suzuki-Miyaura reaction of bromobenzene and phenilboronic acid.

Fig.1.Suzuki Miyaura reaction

Fig.2.Per cent conversion ratio of reaction

Suzuki-Miyaura experiments were carried out-at room temperature. The conversion ratio was determinated by gas chromatography. In this experiments which has 1/1000 catalyst ratio,conversion close up to %100 has been observed in 45 minutes. We can say, Pd(II) complexes of vic-dioxime can be used as catalyst in Suzuki-Miyaura reactions according to these results.

This study have been supported by the The Scıentıfıc And Technologıcal Research


Councıl of Turkey (TÜBİTAK) (project no:214Z097).

References:[1] Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483 [1]. [2] Suzuki, A. Diederich,F., Stang, P. J., Eds.; Wiley-VCH: Weinheim, 1998.


POTENTIAL APPLICATIONS OF SOLID SUPPORT CATALYTIC MEDICAL MOLECULAR

Ümit YAŞARa, Fatma ULUSALb, Bilgehan GÜZELb, Pınar Yılgör HURİc, Nurten DİKMENa

a Çukurova University, Faculty of Medicine Department of Biochemistry, 01330, Adanab Çukurova University, Science and Literature Faculty Chemistry Department, 01330, Adanac Ankara University,Engineering, Biomedical Faculty, Engineering Department,06100 Ankara

Hemoglobin (Hb) is a molecule that can act as a peroxidase in the presence of H2O

2.

Recently, the spectrophotometric methods have been used to determine the peroxidase activity of the hemoglobin molecule in human plasma fluid in the studies and Hb levels have been reported with positive correlations.The immobilization studies of enzymes onto support forstabilization,prolong the shelf life and resistance to harsh conditions in sectors such as the food, medicine, medical, enzyme have been continued.In this study, the immobilization of Hb on the solid support was investigated. The functional and structural characterization of this material was performed. The effect of material on endothelial cell superoxide dismutase (SOD) that is the antioxidant enzyme was assayed. The Hbmolecules has been immobilized on tartaric acid-coated magnetic nanoparticles, construction was analyzed by FT-IR, elemental analysis, SEM-EDX, XRD, TEM spectrometry. Oxygen-carbon dioxide transportation capability of immobilized Hb was investigated by CV.We can say that SOD antioxidant catalase activity did not show a statistically significant difference compared to control (p> 0.05).These results showed the natural conformation and function of hemoglobin are preserved. It is suggested that obtained material isbiocompatible according to these results.

References: [1]Kapralov A1, Vlasova II, Feng W, Maeda A, Walson K, Tyurin VA, Huang Z, Aneja RK,

Carcillo J, Bayir H, Kagan VE. Peroxidase activity of hemoglobin-haptoglobin complexes: covalent aggregation and oxidative stress in plasma and macrophages. J Biol Chem. 2009 Oct 30;284(44):30395-407.

[2] Grigorieva DV1, Gorudko IV, Sokolov AV, Kosmachevskaya OV, Topunov AF, Buko IV, Konstantinova EE, Cherenkevich SN, Panasenko OM. Measurement of plasma hemoglobin peroxidase activity. Bull Exp Biol Med. 2013 May;155(1):118-21.


AMMONIA SYNTHESIS REACTION ON Ru NANOPARTICLES

M.Y.Aslan1, S. Akbayrak2, S. Özkar2, D. Üner1

1 Department of Chemical Engineering, Middle East Technical University, 06800 Ankara/Turkey2 Department of Chemistry, Middle East Technical University, 06800 Ankara/Turkey

Our previous studies revealed that it is possible to synthesize ammonia at room temperature using hydrogen spilled over on the support [1]. In the present study, Ru(0)/zeolite-Y catalysts with different Ru loadings were prepared via ion exchange method[2] to investigate the role of zeolite in accommodating spilled over hydrogen and ammonia synthesis reaction under mild conditions. Ru(0)-zeolite-Y catalysts, were characterized by H

2 chemisorption, H

2 and CO adsorption microcalorimetry. H

2

chemisorption result of 2wt. % Ru(0)/zeolite-Y catalyst indicated high hydrogen uptakes with very high initial heats of adsorption, confirming the small particles (in Figure 1). Experiments are in progress demonstrating the role of zeolite and large number of defect sites in N

2 activation.

Figure 1: H2 microcalorimetry measurement of 2wt.% Ru(0)/Zeolite-Y

References:[1] D. Uner and M.Y. Aslan, Using spilled over hydrogen in NH3 synthesis over supported Ru

catalysts, Catalysis Today (doi:10.1016/j.cattod.2015.11.038)[2] M. Zahmakıran and S. Özkar, Langmuir, 25 (2009), 2667-2678


ARTIFICIAL HUMAN BLOOD and Antioxidant Enzyme Catalysis: Glutathione peroxidase, catalase

Ümit YAŞARa, Fatma ULUSALb, Bilgehan GÜZELb, Pınar Yılgör HURİc, Nurten DİKMENa

a Çukurova University, Faculty of Medicine Department of Biochemistry, 01330, Adanab Çukurova University, Science and Literature Faculty Chemistry Department, 01330, Adanac Ankara University, Engineering, Biomedical Faculty, Engineering Department,06100 Ankara

Artificial blood studiesbasically aims to improve the oxygen-carrying compound.The main objective of this study will be blood substitute, which may carry blood and oxygen absence lifesaving targeted promoter, it targeted improve biological material. The effect of this solution on the enzyme activity that is antioxidant in vitro against the controls in human endothelial cells was investigated.

Figure 1.Immobilization of hemoglobine

We immobilized ultra-pure hemoglobin molecule on the 3-(aminopropyl)trimetoxysilan-glutalaldehyde coated magnetic nanoparticles using various techniques. Construction was analyzed by FT-IR, elemental analysis, SEM-EDX, XRD, TEM spectrometry. The effect of material on endothelial cell glutathione peroxidase (GPx) and catalase (CAT) was assayed. Oxygen-carbon dioxide transportation capability of immobilized Hb was investigated by CV. We can say that CAT and GPx activities did not show a statistically significant difference compared to control (p> 0.05).These results showed the natural conformation and function of hemoglobin are preserved. It is suggested that obtained material isbiocompatible according to these results.

References: [1]Kapralov A1, Vlasova II, Feng W, Maeda A, Walson K, Tyurin VA, Huang Z, Aneja RK,

Carcillo J, Bayir H, Kagan VE. Peroxidase activity of hemoglobin-haptoglobin complexes: covalent aggregation and oxidative stress in plasma and macrophages. J Biol Chem. 2009 Oct 30;284(44):30395-407.


Ruthenium Nanoparticles Stabilized Hidrotalcite Catalyst for the Methanolysis of Ammonia-Borane under Mild Conditions

Yaşar Karataş, a,b Ahmet Bulut,a Mehmet Yurderi,aMehmet Gülcan,a Mehmet Zahmakıran,a,*


b Muradiye Vocational School,Yüzüncü Yıl University, 65080, Van

Ruthenium(0) nanoparticles stabilized by hydrotalcite (HTaL) were prepared, for the first time, by using a direct anionic exchange approach and subsequent reduction with sodium borohydride at room temperature. The characterization of the resulting Ru@HTaL material was done by using multi pronged analyses including ICP-OES, EA, P-XRD, XPS,DR-UV–vis, BFTEM, HRTEM, STEM-EDX and N-adsorption–desorptiontechnique, which revealed that the formation of ruthenium(0) nanoparticles (2.95 ± 0.9 nm) stabilized by the hydrotalcite. The catalytic performance of Ru@HTaL interms of activity, selectivity and stability was demonstrated in the methanolysis of ammonia-borane (NH

3BH

3) under mild conditions (at 25 .C). We found that Ru@HTaL catalyst

catalyzes the methanolysis of ammonia-borane at almost complete conversion (> 95%). Moreover, the resulting ruthenium nanoparticleswere found to be highly stable against leaching and sintering, which makes Ru@HTaLa reusable heterogeneous catalyst without losing of significant activity and selectivity.


Effect of Crystal Structure on the Catalytic Activity for Suzuki-Miyaura Coupling Reaction

Fatma Ulusala,Burcu Darendelia, Özge Atışa, Mustafa Kemal Yılmazb, Bilgehan Güzela

a Çukurova University, Science and Literature Faculty Chemistry Department, 01330, Adanab Mersin University, Silifke Vocational College, 33343, MERSİN

The structure, geometry and surface morphology of the heterogeneous catalyst affect the catalytic activity in the catalyst.This effect shows that it is possible to the selection of the physical properties of the catalyst according to the desired product. Based on this study, obtaining of desired geometry nanoparticles is gradually accelerated. It was determined that catalytic activity is affected from the location of atoms in crystal lattice and almost every atoms at different positions catalyzed different reactions.

Figure 1.Suzuki-Miyaura cross-coupling reaction results of various Pd(0) nanoparticles

In this study,the catalytic activity ofcarbon nanotube supported palladium nanoparticles in Suzuki-Miyaura cross-coupling reaction was investigated. These nanoparticles have various geometriesobtained by various deposition methods. Particle sizes of nanoparticleswere selected approximately similar and for all of them the Pd/substrate ratio was the same.InvestigatedPd(0) nanoparticles are in octahedral, cubic and cuboctahedral geometry. Accordingly, while the cubic nanoparticles catalyzed Suzuki-Miyaura reaction in a good yield,octahedral nanoparticles did not catalyze at all.

This study was supported by the Management Unit of Scientific Research Projects of Çukurova University (BAP project no: FDK-2015-3668 under thesis).

References: [1]Gillian Collins, Michael Schmidt, Colm O’Dwyer, Justin D. Holmes andGerard P.

McGlacken,Angew. Chem. Int. Ed., 53,2014, 4142 –4145.


Sulfonic Acid Functionalized MIL-101 Metal Organic Framework Confined Palladium(0) Nanoparticles Catalyst for the

Methanolysis of Ammonia-Borane under Mild Conditions

Nurdan Caner,a Ahmet Bulut,a Mehmet Yurderi,a Mehmet Zahmakıran,a,

aNanomaterials and Catalysis (NanoMatCat) Research Laboratory, Department of Chemistry, Yüzüncü Yıl University, 65080 Van, Turkey

Palladium(0) nanoparticles stabilized by sulfonic acid functionalized metal-organic framework (Pd@SMIL-101)were prepared, for the first time, by using a direct cationic exchange approach and subsequent reduction with sodium borohydride at room temperature. The characterization of the resulting Pd@S-MIL-101 material was done by using multi pronged analyses including ICP-OES, EA, P-XRD, XPS,DR-UV–vis, BFTEM, HRTEM, STEM-EDX and N-adsorption–desorption technique, which revealed that the formation of palladium(0) nanoparticles (2.95 ± 0.9 nm) stabilized by the framework of S-MIL-101by keeping the host framework intact (Pd@S-MIL-101). The catalytic performance of Pd@S-MIL-101 interms of activity, selectivity and stability was demonstrated in the methanolysis of ammonia-borane (NH

3BH

3) under mild

conditions (at 25 oC). We found that Pd@S-MIL-101 catalyst catalyzes the methanolysis of ammonia-borane at almost complete conversion (> 95%). Moreover, the resulting palladium nanoparticleswere found to be highly stable against leaching and sintering, which makes Pd@S-MIL-101 reusable heterogeneous catalyst without losing of significant activity and selectivity.

Figure 1: The network and pore structure of MIL-101metal-organic framework.

References:[1] Ferey, G., Draznieks, C. M., Serre, C., Millange, F., Dutour, J., Surble, S., Margiloski, I. 2005.

“A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area”, Science, 309, 2040-2042.


IMMOBILIZATION OF GLUTAMATE DEHYDROGENASE ONTO AMINATED CARBON NANOTUBE AND INVESTIGATION OF CATALTIC

ACTIVITY

Yusuf Döğüşa, Gülüzar Özbolata, Hasan Ulusalb, Nevin Yılmaza, Abdullah Tulia

a Cukurova University, Faculty of Medicine Department of Biochemistry, 01330 Adana, TurkeybGaziantep University, Faculty of Medicine Department of Biochemistry, 27070 Gaziantep, Turkey

Enzymes which occuring within the cell, constitute life itself, regulate speed and specificity of thousands of chemical reactions is very important for the body. As one of the thousands of enzymes in our bodies can even lead to a fatal disease which shows us how are they important. Such important structures to be stored in vitro environment is quite important. Immobilized enzyme are becoming resistant to changes in ambient conditions. And this allows that both conservation and use the enzyme in the more temperate conditions. Enzyme immobilization has begun to attract increasing attention since it has several advantages such as reusing enzyme, stabilization and long term use. Carbon nanotubes, magnetic nanoparticles and support materials such as chitosan are widely used in immobilization. Creation of appropriate groups are necessary for immobilization of support material. Generally, intermediate arms which using groups such as carboxylic acid and aldehyde are the most preferred materials in the immobilization. In our study enzyme immobilization onto aminated carbon nanotubes has been carried by means of glutaraldehyde intermediate arm.

In this study, glutamate dehydrogenase enzyme are bonded to aminated carbon nanotube by forming imine bond with epichlorohydrin intermediate arm. The resulting carbon nanotubes supported glutamate dehydrogenase enzyme activity was examined. It was observed that there was improvement in shelf-life and storage conditions.

References: [1]Atieh MA. Effect of Functionalize Carbon Nanotubes with Amine Functional Group on the

Mechanical and Thermal Properties of Styrene Butadiene Rubber. Journal of Thermoplastic Composite Materials, 2011; 24- 613.


IMMOBILIZATION OF XANTHINE OXIDASE ONTO AMINATED CARBON NANOTUBE AND INVESTIGATION OF CATALTIC ACTIVITY

AND STABILIZATION

Yusuf Döğüşa, Gülüzar Özbolata, Hasan Ulusalb, Nevin Yılmaza, Abdullah Tulia

a Cukurova University, Faculty of Medicine Department of Biochemistry, 01330 Adana, TurkeybGaziantep University, Faculty of Medicine Department of Biochemistry, 27070 Gaziantep, Turkey

Recently, enzyme immobilization has been begun to take place among the most attractive subjects by the scientists. Immobilized enzyme are becoming resistant to changes in ambient conditions. And this allows that both conservation and use the enzyme in the more temperate conditions. Immobilized enzymes has advantages such as resistance to high temperature and very low and high pH, long shelf life and repeated use. Many support materials may be used for this purpose. Carbon nanotubes constitutes a disadvantage in terms of the inability to digest by the body. But, the functionalization of carbon nanotube by amination provides it to be biocompatible and soluble. In this study, animated carbon nanotubes are bonded to enzymes by means of glutaraldehyde intermediate arm. Change in stability were investigated by examining the activity of obtained enzyme.

In this study, xanthine oxidase enzyme that catalyzes the last two stage of purine degradation are bonded to aminated carbon nanotube by forming imine bond with glutaraldehyde intermediate arm. The activity of obtained xanthine oxidase enzyme which supported carbon nanotubes were examined. Besides activity, an increase in stability has been observed.

References: [1]Godber BL, Doel JJ, Durgan J, Eisenthal R, Harrison R. A newroutetoperoxynitrite: a role

forxanthineoxidoreductase. FEBS Lett. 2000; 475: 93–6.[2]Atieh MA. Effect of Functionalize Carbon Nanotubes with Amine Functional Group on the

Mechanical and Thermal Properties of Styrene Butadiene Rubber. Journal of Thermoplastic Composite Materials, 2011; 24- 613.


THE INVESTIGATION OF DIMETHYGLOXIME LIGAND WHICH CAN BE USED FOR ACCUMULATION OF IRON IN THE BODY ON

GLUTATATHIONE PEROXIDASE ENZYME

Gülüzar Özbolata, Hasan Ulusalb , Yusuf Döğüşa, Abdullah Tulia

a Cukurova University, Faculty of Medicine Department of Biochemistry, 01330 Adana, Turkeyb Gaziantep University, Faculty of Medicine Department of Biochemistry, 27070 Gaziantep, Turkey

Glutathione peroxidase which is one of the most important antioxidant molecules of intracellular medium is one of the most important enzymes which catalyse the reduction of hydrogen peroxide and lipid peroxides. It is accepted that it provides an efficient protection against lipid peroxidation. In this study, it is determined that the degree of complexation of dimethylgloxime ligand which is considered for treatment of excess iron occurs in the body, with the amount of lethal level of iron metal in water and serum. The effect of ligand on activity and stability of glutathione peroxidase enzyme was investigated to research using of ligand as a medicine.

Previously, dimethylgloxime ligand was used in many studies for different purposes in the complexation of metals, but the therapeutic use of dimethylglioxime ligand for iron accumulation in the body and the examination of its effect on enzyme activity are investigated for the first time. In this study, Metal levels are reduced from lethal levels to normal levels. Although promising results oriented using of dimethylglioxime with enzyme studies as medicine are taken, more in vitro and in vivo studies are needed to use dimethylglioxime as a medicine completely.

References: [1] Anderson GJ. Mechanisms of iron loading and toxicity. Am J Hematol. 2007; 82:1128-31[2] Day BJ. Catalase and glutathione peroxidase mimics, Biochem Pharmacol 2009; 77: 285-296.


THE INVESTIGATION OF DIMETHYGLOXIME LIGAND WHICH CAN BE USED FOR ACCUMULATION OF IRON IN THE BODY ON XANTHINE

OXIDASE ENZYME

Gülüzar Özbolata, Hasan Ulusalb , Yusuf Döğüşa, Abdullah Tulia

a Cukurova University, Faculty of Medicine Department of Biochemistry, 01330 Adana, Turkeyb Gaziantep University, Faculty of Medicine Department of Biochemistry, 27070 Gaziantep, Turkey

Xanthine oxidase, has a key role in purine metabolism, is an important enzyme that contains molybdenum. It has many biological functions such as regeneration of NAD, iron absorption and mobilization and reduction of nitrates. In particular, synthesis of uric acid which is final product of purine degradation are catalyzed by means of xanthine oxidase enzyme. This important enzyme was chosen to investigate effect of dimethylgloxime ligand, is thought to be used in the treatment of accumulation of iron in the body, on enzyme activity.

In this study, it is determined that the degree of complexation of dimethylgloxime ligand with iron molecule in serum and in buffer solutions at different pH. The effect of ligand on activity and stability of xanthine oxidase enzyme was investigated to research using of ligand as a medicine. Previously, dimethylgloxime ligand was used in many studies for different purposes in the complexation of metals, but the therapeutic use of dimethylglioxime ligand for iron accumulation in the body and the examination of its effect on enzyme activity are investigated for the first time.

References[1] Lavelli, V., Peri, C. and Rizzola, A. Antioxidant activity of tomato products as studied by model

reactions using Xanthine oxidase, Myeloperoxidase, and copperinduced lipid peroxidation. J. Agric. Food Chem. 2000; 48(5); 1442-1448.

[2] Anderson GJ. Mechanisms of iron loading and toxicity. Am J Hematol. 2007; 82:1128-31


PREPARATION AND APPLICATION OF AlK(SO4)2 .12H2O LOADED CHITOSAN/ POLYVINYLPYRROLIDONE CATALYTIC MEMBRANE

Derya Unlua, Aynur Hacıoglua,Nilufer Durmaz Hilmioglua

aKocaeli University, Chemical Engineering Department, Engineering Faculty, Umuttepe, 41380, Kocaeli

Ethyl acetate is one of the important solvents in the chemical industry. Ethyl acetate has been used in the production of varnishes, plasticizers, synthetic resins and adhesives [1]. Ethyl acetate is produced by esterification of acetic acid with ethanol [2]. These reactions are usually catalyzed by homogeneous catalysts such as sulphuric or p-toluenesulphonic acid. However, homogeneous catalysts have toxic and corrosive properties and it is difficult to separate them from the reaction mixture [3].Therefore, substitution of homogeneous catalyst by heterogeneous catalyst is very important from the point of environment.The use of catalytic membranes as heterogeneous catalysthas gained attention in recent years. In this study, Aluminum potassium sulfate dodecahydrate loaded chitosan/polyvinylpyrrolidone (PVP) catalytic membranes were prepared and used for synthesis of ethyl acetate. AlK(SO

4)

2.12H

2O catalyst was added

to chitosan/PVP blend polymer solution and polymeric membrane solution with catalyst was obtained. The membrane was prepared by solution casting method and ready for usage after drying.Catalytic membranes cut into small pieces and added the reaction mixture as the catalyst. Optimum reaction parameters (catalyst amount, initial molar ratios (acid/alcohol), reaction temperature and reaction time) which were effect the reaction yield were determined. AlK(SO

4)

2.12H

2O loaded chitosan/PVP catalytic

membranes were found as efficient for synthesis of ethyl acetate.

References[1] Otera J., Nishikido J., Esterification Methods, Reactions, and Applications, 2nd ed., Wiley,

Germany, 2010. [2] Xia S., Dong X., Zhu Y., Wei W., Xiangli F., Jin W., Separation and Purification Technology,

2011, 77, 53–59.[3] Hanumant G., Vijay V. B., Journal of Natural Gas Chemistry 19 (2010) 161–164.


PHOSPHOTUNGSTIC ACID LOADED CELLULOSE MEMBRANE PREPARATION FOR CATALYTIC MEMBRANE REACTOR

Filiz Ugur Nigiza, Nilufer Durmaz Hilmioglua

a Kocaeli University, Chemical Engineering Department, 41380, Kocaeli

Beside the process performance and reaction yield, it is also important to produce the end product by using more effective input. Most of chemical reactions are carried out by catalytically and catalyst consuming consists of non-ignorable part of the total operation cost. Therefore, catalyst reuse and recycle become more important. Catalytic membranes offer some advantages over the free catalysts such as easy processability. It can be separated from the reaction media by simple separation techniques. Also it can be used over and over without any activity loss. Either catalytic membrane particles can be used as heterogeneous catalyst in a classical reactor or a catalytic membrane module can be employed inside a reactor. For this purpose, homogeneous, heterogeneous catalyst and lipases are distributed in a polymeric or inorganic matrix. Recently, heteropoly acids (HPAs) loaded mixed matrix membranes have been used owing to unique chemical, electronic properties and inherent catalytic activities [1-3]. In this study, phosphotungstic acid (PWA) filled carboxymethyl cellulose (CMC) catalytic membrane was prepared by solution-casting method. The activity of catalytic membrane was tested by producing ethyl lactate in a three-necked glass reactor. Effect of temperature was investigated as function of lactic acid conversion. In Figure 1, PWA particles were seen on the top surface of CMC matrix.

Figure 1. Surface SEM micrograph of catalytic membrane


References[1] J.Pandey, A.Shukla, PVDF supported silica immobilized phosphotungstic acid membrane for

DMFC application, 262, 811–814.[2] P.S. Rachipudi, A.A. Kittur, S.K. Choudhari, J.G. Varghese, M.Y. Kariduraganavar, Development

of polyelectrolyte complexes of chitosan and phosphotungstic acid as pervaporation membranes for dehydration of isopropanol, 45, 3116–3126.

[3] J. Pandey, F.Q. Mir, A. Shukla, Synthesis of silica immobilized phosphotungstic acid (Si-PWA)-poly(vinyl alcohol) (PVA) composite ion-exchange membrane for direct methanol fuel cell, 39, 9473–9481.


Palladium(II)-Schiff base complex supported on mwcnt for using as catalyst in the Suzuki-Miyaura reaction

Ayşen Berna Tekina, Bilgehan Güzela

aÇukurova University, Science and Literature Faculty Chemistry Department, 01330, Adana

Biaryl compounds play an important role in the biologically active substance and synthesis engineering materials such as molecular wires, nonlinear optical devices and liquid crystals. Suzuki-Miyaura cross coupling reaction is one of the most preferred carbon-carbon bond-forming reaction for synthesis these compounds. Phosphine ligands are generally heterogeneously or homogenously used in this kind of catalysis reactions. The difficulty in synthesis, high cost, toxicity and low air and moisture stability of phosphines are restrict the usability. Recently,metal complexes of various ligand such asN-heterocyclic carbenes, Schiff bases and dendrimers have been used in Suzuki-Miyaura reactions. These complexes have used as heterogeneously catalyst by supporting on various inorganic and organic supports such as mesoporous silica, ionic liquids, carbon nanotubes and polymersas well as homogenously using.

Figure 1.Preparation of MWCNT supported Schiff Base

In this work,palladium complex of Schiff Base-supported on multi walled carbon nanotube (MWCNT)was synthesized and characterized. The catalytic activity and reusability of synthesized complex was investigated heterogeneously in Suzuki-Miyaura cross-coupling reaction was researched.

References: [1]Mozhgan Navidi, Nasrin Rezaei, Barahman Movassagh, J. Organomet. Chem.,743, 2013, 63–69.This study was supported by the Management Unit of Scientific Research Projects of Çukurova

University (BAP project no: FYL-2015-3633 under thesis).


Metal Organic Framework (MIL-101) Stabilized Ruthenium(0) Nanoparticles: Highly Efficient Catalytic Material for the

Selective Hydrogenation of Phenol to Cyclohexanone

Ilknur Efecan Ertas, aMehmet Gulcan, aAhmet Bulut, aMehmet Yurderi,aMehmet Zahmakirana*

a Nanomaterials and Catalysis (NanoMatCat) Research Laboratory, Department of Chemistry, Yüzüncü Yıl University, 65080, Van, Turkey

Ruthenium(0) nanoparticles stabilized by MIL-101 metal-organic framework (Ru/MIL-101) were preparedvia gas phase infiltration of Ru(cod) (cot) (cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene)followed by hydrogenolysis of Ru(cod) (cot)@MIL-101 at 3 bar H

2 and 323 K. The resulting material was characterized by using various analytical

tools including ICP-OES, EA, P-XRD, XPS, DR-UV-VIS, SEM,BFTEM, HRTEM, STEM-EDX,CO-chemisorption and N

2-adsorptione desorption technique, which revealed that

the formation of ruthenium(0) nanoparticles (4.2 ± 1.2 nm) mainly exist on the surface ofMIL-101 by keeping the host framework intact. The application of Ru/MIL-101 in catalysis by consideringtheir activity, selectivity and reusability was demonstrated in the phenol hydrogenation under mild conditions. Ru/MIL-101 acted as active (lower-limit TOF = 29 mol cyclohexanone/mol Ru x h; correctedTOF = 88 mol cyclohexanone/mol Ru x h at ≥ 90% conversion) and selective (≥ 90%) catalyst in the hydrogenation of phenol to cyclohexanone in water at 323 K and 5 bar initial H

2 pressure. More

importantly, the resulting ruthenium(0) nanoparticles in Ru/MIL-101 were found to be highly durablethroughout the catalytic reuse in the phenol hydrogenation (retain ≥ 85% of their inherent activity andselectivity at 5th reuse), which makes Ru/MIL-101 a reusable catalytic material for the liquid phasemediated catalytic transformations.

Figure 1: The network and pore structure of MIL-101metal-organic framework.

The financial support by the Scientific and Technological Research Council of Turkey (TUBITAK, Project No: 113Z307) is gratefully acknowledged.


Trimetallic PdAuNi Alloy Nanoparticles Supported on Amine Functionalized Reduced Graphene Oxide for the Dehydrogenation of Formic Acid Under Mild Conditions

Mehmet Yurderia, Metin Çelebia, Ahmet Buluta, Mehmet Zahmakırana

a Nanomaterials and Catalysis (NanoMatCat.) Research Group, Department of Chemistry, Faculty of Science, Yüzüncü Yıl University, 65080, Van

Herein we report the development of a new highly active, selective and reusable nanocatalyst; trimetallic PdAuNi alloy nanoparticles supported on amine-functionalized reduced graphene oxide for additive-free dehydrogenation of formic acid (HCOOH), which has great potential as a safe and convenient hydrogen carrier for fuel cells, under mild conditions. This new catalytic material was characterized by the combination of multi-pronged analytical techniques including ICP-OES, P-XRD, XPS, DR-UV/vis, BFTEM, HRTEM, STEM-EDX, HAADF-STEM, FTIR and Raman spectroscopy.The sum of their results indicative of the formation of trimetallic PdAuNİ alloy nanoparticles on the surface of reduced graphene oxide at high dispersion.The catalytic performance tests performed for the additive-free dehydrogenation of formic acid showed that our new catalytic material acts as a highly active and selective heterogeneous catalyst for this important catalytic transformation.


Synthesis and insitu catalytic aplication of 7-BER-NHC ligands on Suzuki reaction

Sedat YAŞARªb, Emine Özge KARACAa, Nevin GÜRBÜZa,b,İsmail ÖZDEMİRa,b

ª Inönü University, Catalysis, Research and Application Center,44280, MALATYA, TURKEYb Inönü University, Faculty of Science and Art, Department of Chemistry, 44280, Malatya, TURKEY

Suzuki crosscoupling involves the reaction of an organo Halide with an organoborane, which is an electrophile, to give the coupled product using a palladium catalyst and base [1]. In order to reduce the generation of hazardous substances, variation in the coupling reactions has been developed using green solvents, particularly water [2].Biphasic catalysis is normally based on the conversion of known reactions from a one-phase homogeneous system (solvent phase) to a two-phase homogeneous system (water/solvent/reagents phases). Thecatalyst dissolved in the water phase could be collected by decantation, extraction, or distillation. In such systems the advantages of homogeneous and heterogeneous catalysis can be combined. Changing from volatile organic solvents to water has enormous economic potential, avoids health risks, and eases the separation of products from the catalyst. In these processes the water solubility of the catalyst was increased via ligands with hydrophilic functionalities like-SO

3-, -COO-, -OH, NR

4+.

This study we study here the synthesis and characterization of new ring-expanded NHC ligands. This ligands were tested as catalysts in the Suzuki coupling reactions of arylchlorides in two-phase homogeneous system. These ligands exhibited moderate to high catalytic activities under the given conditions.

References[1] S. Yaşar, S. Çekirdek, İ. Özdemir, Heteroatom Chemistry, 25 ( 2014) 157.[2] N. Gürbüz, E. Ö. Karaca, İ. Özdemir, B. Çetinkaya.,Turk. J. Chem., 39 (2015) 1115.


Improvement of Sulfur Regenaration Ability of NSR Catalysts via Reducible Mixed Oxide Promoters

Z.Aybegum Samast, Emrah Ozensoy

Bilkent University, Chemistry Department, 06800, Ankara, Turkey

A common disadvantage of the NOx Storage Reduction (NSR) catalysts is the

deactivation and loss of NOx trapping ability due to sulfur poisoning [1].CeO

2 promoted

catalysts can be used to enhance the regeneration ability of NSR systems due to their favorable redox properties, high oxygen storage and transport capacity[2,3,4]. In order toenhance thermal stability of ceria based systems; ZrO

2 can be used as an additive.

Zhuet al. reported that incorporation of ZrO2 to Pt/CeO

2 catalysts led to better DeNO

x

catalytic performance [5].A recent study done by Jiang et al.revealed that Pt/Ba/Al

2O

3/Ce

0.6Zr

0.4O

2 has a highNSR performance, strong resistance against SO

2 and good

regeneration ability [6]. In the current work, thermal sulfate/sulfite decomposition (i.e. regeneration) capabilities ofvarious Pt/Ce/Zr/Ba/Al variants were compared via in-situ FTIR and TPD. Pt10-10CeZrAl catalyst revealed complete thermal regeneration surpassing that of a conventional Pt20BaAl commercial benchmark. Improvement of the desulfationability via the addition of Ce/Zr mixed oxides to PtBaAl system can be associated to the reversible redox chemistry of Ce/Zr oxides, enhanced Pt dispersion and formation of novel Pt-O-Ce sites.

Figure 1.SOxdesorption via TPD for(a) Pt20BaOAl,(b)Pt10Ce-10ZrAl, (c) Pt10Ce-10Zr8BaAl, and (d) Pt10Ce-10Zr20BaAl.Catalysts were initially exposed to 2.0 Torr SO

2

+ O2 (g) mixture (SO

2 : O

2 = 1:10) at 673K and subsequently heated to 1100K in vacuum

during the TPD experiments.

References:[1] S. Roy, A. Baiker, Chemical Reviews 109 (2009) 40-54.[2] Z. Say, E.I. Vovk, V.I. Bukhtiyarov, E. Ozensoy, Topics in Catalysis, 56 (2013) 950.[3] Z. Say, E.I. Vovk, V.I. Bukhtiyarov, E. Ozensoy, Applied Catalysis B: Environmental 142, 143, 89

(2013).


[4]Kwak, J.H., Kim, D.H., Szanyi, J. and Peden, C.H.F.: 2008, Excellent sulfur resistance of Pt/BaO/CeO2 lean NOx trap catalysts, Appl. Catal. B, 84, No. 3-4, 545–551.

[5] H. Zhu, J. Kim, S. Ihm, React. Kinet.Catal.Lett 97 (2009) 207.[6] X.Wang, J.Mi, W. Wen, Z. Chen, L. Jiang, R. Wang, Materials Research Bulletin 75 (2016) 41-

46.


Selective CO2 adsorption studies on NaOH impregnated AC Adsorbents

B. M. Eropaka, B. S. Çağlayanb, A. E. Aksoylua

a Boğaziçi University, Department of Chemical Engineering, 34342, Istanbul, Turkeyb Advanced Technologies R&D Center, Boğaziçi University, 34342 Bebek, Istanbul, Turkey

The combustion of fossil fuels is one of the major sources of the greenhouse gases, especially CO

2, which accounts for 40% of total CO

2 emissions. It is crucial to develop

energy efficient CO2 capture (CC) technologies to reduce CO

2 emissions and meet

the global demand of CO2 reduction. Selective CO

2 adsorption has attracted great

interest, since it can be used in both pre-combustion and post-combustion technology applications. In the current study, activated carbon (AC) based adsorbents, which have advantages of large surface area and suitable porosity, were investigated in terms of their CO

2adsorption capacity, especially for CH

4-CO

2 feed mixtures. CO

2 adsorption properties

can be enhanced by structural and chemical modifications applied on AC. Air or HNO3

oxidation procedures followed with NaOH impregnation, were applied. Selective adsorption of CO

2 from CO

2-CH

4 mixtures was studied on AC-based adsorbents with

different parameters, such as temperature, pressure, and adsorbate gas composition.CO

2 adsorption was found to be more favorable on NaOH impregnated AC-based

adsorbents than CH4 adsorption. It was observed that air oxidized AC adsorbents have

higher adsorption capacity than HNO3 oxidized AC adsorbents. NaOH impregnated

ACs were found to be promising adsorbents as they have high adsorption capacity and selectivity towards CO

2 adsorption. Increasing pressure leads a positive effect on

both CO2 and CH

4 adsorption. Langmuir, Freundlich, and Dubinin Radushkevich(D-R)

isotherm models were investigatedon each experiment. ExplainingCO2 adsorption

behavior by Freundlich and D-R models was found to be convenient.


Spectroscopic Investigation of NOx Storage and Reduction Pathways on Pt/K2O/ZrO2/TiO2/Al2O3 as NSR/LNT Catalysts

Merve Tohumeken, Zafer Say, Emrah Ozensoy

Bilkent University, Chemistry Department, 06800, Ankara, Turkey

NOx Storage Reduction (NSR) materials have two major drawbacks namely, sulfur poisoning [1] and thermal aging [2].Matsumoto et al. [3] reported that TiO

2could be

used as a promoter against sulfur poisoning due to its high acidity. However, titania can readily loseits functionality due to thermal deterioration at high temperatures[4]. In order to overcome this issue, ZrO

2can beused together with TiO

2in an attempt

to stabilize the titania component [5]. In this work, we analyzed NSR materials with varying K

2O loadingsin order to fine-tune the NOx storage capacity and NO

xsurface

binding properties.NOxadsorption and desorption characteristics were investigated by means of in-situ FTIR and TPD techniques. Figure 1 shows the in-situ FTIR spectra of Pt functionalized ZrO

2/TiO

2/Al

2O

3(AZT) mixed oxides as a function of K

2O loading in

the presence of NO2(g).NOx exposure on K

2O-based materials yieldsvarious vibrational

features associated with monodentate surface nitrates on K2O and Al

2O

3(1510 and

1306 cm-1) and ionic/bulk like potassium nitrate (1392 and 1369 cm-1). Increase in K2O

loading leads to an increase in the formation of ionic/bulk like potassium nitrate and suppression of surface nitrates. Moreover, the relative NOxstorage/releaseamounts of these materials (obtained via TPD) can be ranked in the following order: Pt/10K/AZT>Pt/5.4K/AZT>Pt/2.7K/AZT>Pt/AZT.

Figure 1. FTIR spectra showing the stepwise NOX adsorption on (a) Pt/AZT, (b) Pt/2.7K/AZT ,


(c) Pt/5.4K/AZT, (d) Pt/10K/AZT at 323 K.Red spectrum in each panel corresponds to the NOX-

saturated surface(5.0 Torr NO2(g) for 10 min at 323K).

References:[1] R. Hummatov, D. Toffoli, O. Gulseren, E. Ozensoy, H. Ustunel, J.Phys.Chem.C 116 (2012)

6191.[2] S.M. Andonova, G.S. Senturk, E. Kayhan, E. Ozensoy, Journal of Physical Chem-istry C 113

(2009) 11014.[3]S. Matsumoto, Y. Ikeda, H. Suzuki, M. Ogai, N. Miyoshi, Applied Catalysis B:Environmental 25

(2000) 115.[4]S.M. Andonova, G.S. Senturk, E. Ozensoy, Journal of Physical Chemistry C 114(2010) 17003.[5] K. Ito, S. Kakino, K. Ikeue, M. Machida, Applied Catalysis B: Environmental 74(2007) 137.


Removing of Synthetic Dyes from Aqueous Solutions By Using Photocatalysis and Adsorption Methods

Ali Karaa, A.Çiğdem Karaerkekb

a Chemistry Department, Uludağ Univ.,16285 Bursa, Turkeyb Chemistry Department, Bursa Technical Univ., 16190, Bursa, Turkey

Synthetic dyes are mostly used in the textile, paper, plastics, leather and cosmetic industry in recent times. Textile wastewater contain a large group of organic dye compounds that causes serious threat to the environment owing to their non-biodegradability, toxicity and potential carcinogenic risk. Several technologies such as adsorption, sedimentation, filtration, photocatalytic degradation, etc. have been investigated and applied for dyes treatment. Among these techniques, photocatalytic degradation of organic pollutants under UV irradiation has received much attention for pollutants removal.Adsorption method is one of the major traditional methods for the removal of synthetic dyes from wastewater. Various inexpensive and efficient adsorbents have been developed for dye adsorption. Recently, also photocatalytic degradation of organic pollutants under UV irradiation has received much attention for pollutants removal.

In this work, we have synthesized a novel specific cross-linkedpolymer by suspension polymerizationand characterized (FT-IR, SEM, H-NMR etc.). After characterization studies, adsorption conditions for dyes are optimized at different parameters such as pH and initial dye concentration. Polymers as adsorbents were applied to the removal of sythetic dyes from aqueous solutions. Adsorption process was clarified by kinetic and thermodynamic approachs.And than photocatalytic degradation of dyes were investigated under photocatalytic conditions inaqueous solutions. Both of adsorption and photocatalytic degradationefficiency were evaluated.

References: [1] A.R. Khataee, M.B. Kasiri, Journal of Molecular Catalysis A: Chemical,Volume 328, Issues 1–2, 3

August (2010), Pages 8–26.[2] Keith K.H.Choy, McKay G, Porter J F, Resources, Conservation and Recycling, 27, 1-2, (1999),

Pages 57-71.[3] Kumar, M.N.V.R., Sridhari T.R., Bhavani K.D., Dutta P.K., Colorage 40, (1998), Pages 25-34.[4] Ali Kara, Emel Demirbel, Nalan Tekin, Bilgen Osman, Necati Beşirli,Journal of Hazardous

Materials, Volume 286, 9 April (2015), Pages 612–623.


ANODIC BEHAVIOR OF CARBON SUPPORTED Ni-Co, Ni AND Co ELECTROCATALYST IN DIRECT BOROHYDRIDE FUEL CELL

Alpay ŞAHİNa, İrfan ARb,a,bGazi University, Faculty of Engineering, Department of Chemical Engineering, Ankara

Scope of this study is to synthesis catalyst for the direct borohydride fuel cell (DBHFC). Synthesized anode catalyst must have the high thermal and mechanical stability, suitable for the oxidation reaction of borohydride at anode and especially it has to ability to prevent the hydrolysis. Direct borohydride fuel cells have received considerable attention over the past decade due to their high power density and open circuit voltage, high number of transferred electron and avoidance of CO poisoning of catalyst. In this study, Ni/C, Co/CandNi–Co/C anode catalysts with remarkably high performance were introduced to use in direct borohydride fuel cell (DBFC) andthey compared with the conventional 10 wt% Pt/C anode catalyst. The structural and morphological properties of the synthesized catalsyts were determined. In order to determine them, Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FT-IR) analyses were performed. After obtaining the structural and morphological properties of the catalysts, thermo gravimetric analysis (TGA) and thermal behavior of them were determined. After the characterization tests, electrochemical tests like cyclic voltammetry (CV), chronopotentiometry (CP), linear scan voltammetry (LSV) and in situ Fourier transform infrared (FTIR) spectroscopy simultaneously with CV were done.The results indicated that the Ni–Co/C, Ni/C and Co/C anode catalysts had higher activity compared to the 10 wt% Pt/C in borohydride oxidation reaction (BOR).

References: [1] Atwani M.H., Norhwood, D.O. 2007. “Evaluation of collidal Ag andA g-alloys as anode

electrocatalysts for direct borohydride fuel cells”, International Journal of Hydrogen Energy, 32, 3116-25.

[2] Duan, D., You, X., Liang, J., Liu, S., Wang, Y. 2015. “Carbon supported Cu-Pd nanoparticles as anode catalyst for direct borohydride-hydrogen peroxide fuel cells”, Electrochimica Acta, 176, 1126-35.

[3] Li, S., Yang, X., Zhu, H., Wei, X., Liu, Y. 2013. “Ultrafine amorphous Co-W-B alloy as the anode catalyst for a direct borohydride fuel cell”, International Journal of Hydrogen Energy, 38, 2884-88.

[4] San, F.G.B., Okur, O., Karadağ, Ç.İ., Isik-Gulsac, I., Okumuş, E. 2014. “Evaluation of operating conditions on DBFC(direct borohyride fuel cell) performance with PtRu anode catalyst by response surface method”, Energy, 71, 160-9.

[5] Yi, Lanhua., Wei, W., Zhao, C., Tian, L., Liui J., Wang, X. 2015. “Enhanced acitivity of Au-Fe/C anodic electrocatalyst for direct borohydride-hydrogen peroxide fuel cell”, Journal of Power Sources, 285, 325-33.


THE POLYANILINE FILMS on ZnNi PLATED COPPER ELECTRODE

Nureddin Colak, A.Tuncay Ozyilmaz, Ibrahim Filazi


In industrial, metallic coatings such as zinc and nickel plating are among those most widely used for protecting oxidizable metals in account of their high corrosion resistance as well as good mechanical properties [1], [2]. The nickel plating and its alloying component application in various industrial sectors including the automotive, electric and electronic industry are insufficient to protect the oxidizable metals. So, polyaniline, polypyrrole, polythiophen and their copolymers have attracted much interest for many investigators [3], [4] and [5].

In this study, ZnNi coatings were successfully deposited on copper (Cu) applying current of 2.5 mA with galvanostatic technique in 45 oC.ZnNi particles had homogenous, smooth with light blue color. Polyaniline film (PANI), was covered with a dark green-brown homopolymer film of strongly adherent homogeneous characteristic, was synthesized with cyclic voltammetry technique from 0.10M aniline containing 0.20 M sodium oxalate solution on zinc–nickel plated copper (Cu/ZnNi) electrode (Fig. 1).

Figure-1: Images of Cu (a), Cu/ZnNi (b) and CS/ZnNi/PANI electrodes, before (c) after (d) 360 h of exposure time in 3.5 % NaCl solution

Corrosion performances of electrodes were evaluated using AC impedance spectroscopy, anodic polarization curves and open circuit potential -time in 3.5 % NaCl solution. The PANI homopolymer film provided an effective barrier property on zinc–nickel coating due to this electrocatalytic behavior and a remarkable anodic protection to substrate for longer exposure time.

References[1] Lodhi, Z.F.S., Tichelaar, F.D., Kwakernaak, C.K., Mol, J.M.C., Terryn, H., de Wit, J.H.W., Sur.

Coat. Tech. 202 (2008) 2755 [2]Bajat, J.B., Maksimovic, M.D., Miskovic-Stankovic, V.B., Zec, S., J. Appl. Electrochem. 31 (2001)

355[3] Tan, C.K., Blackwood, D.J., Corros. Sci. 45 (2003)545 [4] Ozyilmaz, A.T., Akdag, A., Karahan, I. H., Ozyilmaz G., Prog. Org. Coat. 76 (2013) 993.[5] Ozyılmaz, A.T., Kardaş, G., Erbil, M., Yazici, B., Appl. Surf. Sci. 97 (2005) 242


Mn3O4 BASED ELECTROCATALYST SYNTHESIS FOR VANADIUM REDOX FLOW BATTERIES

Büşranur DUMAN, Berker FIÇICILAR

Ondokuz Mayıs University, Department of Chemical Engineering Kurupelit Campus Atakum,55139, Samsun

Electrical energy storageis a critical requirement for renewable energy systems such as solar and wind energy for which energy is produced intermittently. Efficient energy storage systems are needed so as to benefitoptimallyfrom solar and wind energy.In the last two decades,flow batteries have made considerable progress and promising efficiencies of these vanadium redox flow batteries (VRFB) systems made them to be the pioneer in this field.

During the course of operation, two flow able electrolytes are circulated through the anode and cathode side of the battery. Anode and cathode compartments are separated by a proton conducting membrane. Both sides of the membrane are covered with electrodes in which the half redox reactions take place. During the discharge of the battery, anode goes under V+4/V+5 oxidation reactions, while the cathode electrode goes under V+3/V+2 reduction reactions for the reversible VRFB cell. As electrons pass through the external circuit, electricity is produced and protons are transferred from anode to cathode side with the ion exchange membrane[1,2].

In thepresentstudy,major goal is to synthesize a suitable and durable electrocatalyst for optimal operation of vanadium redox flow batteries. Instead of loading Mn

3O

4onto

graphite felt directly, we prefer to prepare electrodes by using hydrothermal method in which solutions of manganese (II) acetate (Mn(CH

3COO)

2·4H

2O) are used as

Mn3O

4source. Consequently, graphite felt is placed within this solution to obtain the

working electrocatalyst. Finally, electrocatalyst loaded electrodes are characterized with the aid of XRD, SEM, N

2 adsorption instruments and the findings related to the electrical

and structural properties of the electrocatalysts will be presented in the conference.

References[1]Rahman F., Skyllas-Kazacos M., Journal of Power Sources, 189 (2009),1212-1219.[2]Kılavuz, K., 2011,Determınatıon Of Electrıcal Characterızatıon And Measurıng Performance Of

The Vanadıum Redox Flow Battery, Master thesis, İstanbul University, Energy Institute, İstanbul.


Synthesis, Characterization and Photocatalytic Performance of Ag\ZnO in the Photodegradation of Methylene Blue under UV

Irradiation

Kadir KARAKAŞa, Metin ÇELEBİa, Mehmet ZAHMAKIRANa


Heterogeneous photocatalysis using novel functional materials could provide efficient and important technologies for treatment of organic wastewater[1].Over the last decade, ZnO with a wide band gap (Eg = 3.37 eV) is one of the most important photocatalysts, which has been widely used in photocatalytic degradation of organic pollutants[2]. Herein we report the preparation, characterization and the photocatalytic use of silver nanoparticles supported on ZnO support material (Ag/ZnO). Ag/ZnO was synthesized by wet-impregnation of PVP stabilized Ag(0) nanoparticles onto ZnO surface followed by removing of surface bound PVP via heat treatment. The resulting material was characterized by using various analytical tools, which showed that formation of well-dispersed Ag(0) nanoparticles on ZnO support material. The photocatalytic performance of Ag/ZnO was tested in the photodegradation of methylene blue under UV irradiation. The results of these experiments have showed that Ag/ZnO acts as highly active and reusable photocatalytic material for the photodegradation of methylene blue.

Figure 1. BFTEM image of silver(0) nanoparticles supported on ZnO support material.

References:[1] A. Akhundi, A. Habibi-Yangjeh, Ternary, Appl. Surf. Sci. 358 (2015) 261–269.[2] M. Sun, T. Li, Z. Zhang, N. Wang, A. Xie, X. Lv, Y. Wang, F. Wu, M. Wang, RSC Adv. 5 (2015)

84406–84409.


SYNTHESIS OF CNT-TiO2-SiO2 NANOCOMPOSITE THIN FILMS: THE EFFECT OF HEAT TREATMENT ON PHOTOCATALYTIC ACTIVITY

Tuğçe Kırbaş, Gürkan KARAKAŞ

Middle East Technical University, Chemical Engineering Department, 06800 Ankara

CNT-TiO2-SiO

2 nanocomposites was synthesized by sol-gel process and the thin

films over glass substrates were fabricated by dip coating method. The effect of CNT addition, heat treatment temperature and atmospheres on the structure and photocatalytic properties was examined. Thin film samples were prepared with and without carbon nanotubes and the heat treatment process was carried out at different temperatures under air and nitrogen atmosphere. Characterization of the samples was performed by thermal analysis, XRD, SEM&EDS, elemental carbon analysis, XPS and UV-Vis spectroscopy. Thermal analysis indicated that the oxidation temperature of carbon nanotubes was reduced by the TiO

2-SiO

2 matrix and the weight loss for

CNT- TiO2-SiO

2 sample heat treated under nitrogen was same with the sample heat

treated under air. XRD studies showed that the presence of CNT and also increasing heat treatment temperature improved the crystallinity. The SEM images revealed that CNTs were successfully incorporated in thin film structure. XPS studies showed that there were oxygen vacancies on the surface which are very effective for photocatalysis. In addition, heat treatment under inert atmosphere caused the reduction of Ti(IV) to Ti(III) on the surface. The photocatalytic activity tests were performed by monitoring the degradation of methylene blue under UV irradiation in the presence of the thin film. The CNT-added samples have higher photocatalytic activity than the TiO

2-SiO

2 sample. And also heat treatment temperature can favor the photocatalytic activity until the sintering whereas the heat treatment atmosphere did not have a significant effect on activity.


Determination of Reaction Kinetics for Electrochemical Oxidation of Tetracycline Antibiotic using Boron-Doped Diamond Anode

Bahadır K. KÖRBAHTİ, Selin ALACA

Mersin University, Faculty of Engineering, Chemical Engineering Department, 33343, Çiftlikköy, Mersin

In this study, electrochemical oxidation of tetracycline antibiotic was investigated using boron-doped diamond (BDD) anode in a batch electrochemical reactor. Reaction conditions were operated at 200-1000 mg/L initial tetracycline concentration, 0-8 g/L supporting electrolyte (NaCl), 4-20 mA/cm2 current density, and 25-45°C reaction temperature at 120 min reaction time. Tetracycline concentrations were determined using Shimadzu Prominence LC-20AD HPLC system, and chemical oxygen demand (COD) analyses were done using Merck Spectroquant COD cell test method.Process optimization was accomplished through response surface methodology in CCD designed experiments using Design-Expert 9.0 software in order to determine the influence of independent factors on tetracycline removal and COD reduction along with the experimental conditions. Optimized conditions under specified constraints were obtained for the highest desirability at 618 mg/L initial tetracycline concentration, 3.6 g/L supporting electrolyte, 13.4 mA/cm2 current density, and 36°C reaction temperature. In a batch electrochemical reactor, the reaction rate of tetracycline degradation was expressed based on tetracycline concentration, and overall electrochemical conversion rate of pollutants was expressed based on COD concentration. Reaction kinetics was determined by the method of initial rates, and specific reaction rate constants (k) were obtained using Arrhenius equation. Under response surface optimized conditions, reaction kinetic parameters for electrochemical oxidation of tetracycline antibiotic using boron-doped diamond anode were evaluated and outlined in Table 1. The activation energy (Ea) depends on the nature of the reaction, and fast reactions generally have small Ea values.

Table 1. Reaction kinetic parameters for electrochemical oxidation of tetracycline antibiotic using boron-doped diamond anode


AcknowledgementThis project was supported by TÜBİTAK (The Scientific and Technological Research Council of

Turkey) with Grant No. 111M341.


THE ELECTROCATALYTIC BEHAVIOR OF COPOLYMER FILMS ON ZnFeCo DEPOSITED CARBON STEEL ELECTRODE

A.Tuncay Ozyilmaza, Gul Ozyilmaza, İ.Hakkı Karahanb,

Mustafa Kemal University, Department of Chemistrya and Physicsb31000, Hatay

In recent years, electrochemically synthesized polymer films have attracted much interest for the improvement of substrate corrosion resistance as new anticorrosion technology [1]. In this study, Zinc-iron-cobalt (ZnFeCo) plating was successfully deposited on carbon steel (CS) applying current of 3 mA with chronopotentiometry technique in acidic solution. The poly(aniline-co-o-anisidine) films were deposited on ZnFeCo plated carbon steel electrode. The synthesis processes of copolymer films were carried out under cyclic voltammetry condition from different monomer concentration (1:9, 5:5, 9:1) containing 0.20 M sodium tartrate solution. SEM images clearly show that ZnFeCo plated carbon electrode was covered with different copolymer film structure of strongly adherent homogeneous characteristic (Figure 1.).

Figure 1. SEM images of CS/ZnFeCo(a), CS/ZnFeCo/1PANI-co-9POA(b), CS/ZnFeCo/5PANI-co-5POA (c) and CS/ZnFeCo/9PANI-co-1POA (d) electrodes.

Corrosion performances of copolymer film coated and uncoated CS/ZnFeCo electrodes were evaluated using AC impedance spectroscopy, anodic polarization curves and corrosion potential-time in 3.5 % NaCl solution.ZnFeCo plating on carbon steel electrode exhibited anodic protective on CS electrode. Changes in resistance of copolymer film coated electrodes were related to strong adsorption of copolymer films on the CS/ZnFeCo surface which led to the formation of a protective oxide layer due to their electrocatalytic behavior.

AcknowledgementThe research project was funded by Technical Research Council of Turkey (TUBITAK), Project No:

TBAG- (110T745)

References[1] A.T. Ozyilmaz, A. Akdag, I. H. Karahan, G. Ozyilmaz, Prog. Org. Coat. 76, (2013) 993.[2]C.K. Tan, D.J. Blackwood, Corros. Sci. 45, (2003) 545.


ELECTROCATALYTIC CONDUCTING POLYMER FILMS ON Zn DEPOSITED CARBON STEEL ELECTRODE

A.Tuncay Ozyilmaza, Gul Ozyilmaza, İ.Hakkı Karahanb,

Mustafa Kemal University, Department of Chemistrya and Physicb, 31000 Hatay

In this study, Zn plating was successfully deposited on carbon steel (CS) applying current of 4 mA with galvanostatic technique in acidic medium. Depending on the method and condition of plating, different results of protection are obtained. In order to suitable passivation of zinc plated carbon steel (CS/Zn), only anodic polarization of Cs/Zn electrode is required to generate a suitable surface prior to the electropolymerization process. Polypyrrole (PPy) and poly(N-methylpyrrole) (PNMP) films were synthesized on CS/Zn in sodium oxalate medium. Homopolymer films were achieved as homogenously and adherently as shown in SEM (Figure 1).

Corrosion performances of homopolymer film coated and uncoated Cu/Zn electrodes were evaluated using AC impedance spectroscopy, anodic polarization curves and open circuit potential -time in 3.5 % NaCl solution (Figure 2). The homopolymer films which had electrocatalytic efficiency provided aneffective barrier property on zinc coating and a remarkable anodic protection to substrate for longer exposure time.

AcknowledgementThe research project was funded by Technical Research Council of Turkey (TUBITAK), Project No:

TBAG- (110T745)

References[1]J.B. Bajat, M.D. Maksimovic, V.B.M.-Stankovic, S.Zec, , J. Appl. Electrochem. 31, (2001), 355.


COBALT-BASED COORDINATION COMPOUNDS FOR ELECTROCATALYTIC WATER OXIDATION

Emine Ülkera,b, Aysun Tekina, Satya Vijaya Kumar Nunea, Ferdi Karadaşa,a Department of Chemistry, Bilkent University, 06800 Ankara, Turkey

b Department of Chemistry, Recep Tayyip Erdogan University, 53100Rize, Turkey

The development of alternative renewable energy sourceshas recently received much attention due to limited suppliesof fossil based fuels and their damage to the environment as a result of carbon emissions.[1].Hydrogen economy, which involves the use of solar energy to split water to hydrogen and oxygen, has the potential to fulfill our demanda clean and renewable energy source [2]. The main bottleneck in Hydrogen Economy is considered to be oxygen evolution half-reaction since this four-electron process requires high overpotentials. Efficient, stable, and cheap catalysts for water oxidation are needed to overcome this problem [3].

It is aimed to useamorphous cobalt-based coordination compounds as water-oxidation catalysts in this study. Synthesis and characterization of amorphous Co-Fe Prussian Blue coordination compounds have beencarried out. Electrochemical and electrocatalytic water oxidation studies have also been performed on samples deposited on FTO electrode.

References[1] A. Singh, L. Spiccia, Coordination Chemistry Reviews, 257 (2013) 2607– 2622. [2] M.L. Wald, Scientific American ed., Guilford, USA, 2007.[3] T. Kuwabara, B. Nishizawa, K. Nakamura, Y. Ikeda, T. Yamaguchi, K. Takahashi, Journal of

ElectroanalyticalChemistry, 740 (2015) 14–20


Determination of optimum Cu-CeO2 ANODE composition for direct methane solid oxide fuel cell

Vedat Sarıboğaa, M.A. Faruk Öksüzömera

aDepartment of Chemical Engineering, Istanbul University, Avcilar/Istanbul, 34320, Turkey

Solid oxide fuel cells (SOFCs) have a great attention in the last decades. Solid oxide fuel cells work at high-temperatures (~800ºC), which provides advantages like using Pt-free electrodes compatible with combined heat and power system and different types of fuels[1,2].

Figure 1.Fracture cross-section SEM images of 30CeO2/70 Cu sample

In this work, the optimum compositions for Cu-CeO2-YSZ anode were introduced

as a solid oxide fuel cell anode structure. Minimum Cu content, suitable infiltration technique and optimum CeO

2 amounts were determined. Continuum percolation

limit of metallic Cu was demonstrated as %30 by mass in YSZ matrix. Simultaneous/ sequential impregnation of Cu and CeO

2 salt solutions were investigated with XRD

and SEM techniques. It was concluded that the phase distribution in YSZ scaffold was more efficient and no chemical interaction between Cu and CeO

2 with co-calcination

process with simultaneous infiltration. The corresponding optimal Cu /CeO2 loading

was investigated with single cell I-V characterization and %35 Cu- %15 CeO2- %50 YSZ

cermet structure has been put forward as an ideal cell composition.

References[1] A.B. Stambouli, E. Traversa, Renewable and Sustainable Energy Reviews, 6 (2002) 433. [2] S. McIntosh, R.J. Gorte, Chemical Reviews, 104 (2004) 4845.


Characterization of PAni-Fe Electrocatalyst Loaded on Multi-walled Carbon Nanotube Support

Göknur Dönmeza, Merve Deniza, Hüseyin Deligöza,aIstanbul University,Faculty of Engineering, Department of Chemical Engineering, 34320, Avcılar,

İstanbul

Fuel cells are devices that convert the chemical energy of a fuel directly into electrical energy in an electrochemical reaction. Fuel cells are popular among the alternative energy sources because of their high efficiency, low working temperature depending on the fuel type, fast response time, low mechanical parts, modularity and fuel diversity. The oxygen reduction reaction is an important electrochemical reaction in the polymer electrolyte membrane fuel cells. Because this reaction is critical for electrochemical energy storage and conversion technologies. However, there is a restrictive parameter for using the PEMFCs. ORR electrode kinetics are very slow at high over-potential. Consequently, an efficient electrocatalyst is needed to accelerate the ORR kinetic. Platinum based catalysts are very useful because of their activity and durability for ORR, also they are very rare and expensive. Therefore, it has to be developed a new catalyst having high activity, durability with cheapness for some technological device like PEMFCs [1]. This research deals with the synthesis of electrocatalyst containing polyaniline. This non-precious catalyst for ORR was synthesized by oxidative polymerization ofaniline on the surface of multi-walled carbon nanotube in an aqueous medium in the presence of iron salt. After polymerization, vacuum dried mixture was heat-treated at different temperaturesunder an inert atmosphere for a known time. Then heat-treated sample was leached with acid and washed with deionized water for removing unstable and inactive species from the catalyst. Finally, the cathode catalyst was heat-treated again [2, 3].

References[1] Gang W., Zhongwei C., and Jiujun Z., Editors: San P. J., Pei K. S., CRC Press, Boca Raton, 2014.[2] Zaiyong M., Hongliang P., Huagen L., Shijun L., Electrochimica Acta, 99 (2013) 30-37.[3] Gang W., Karren L. M.,Christina M. J.,Piotr Z., Science,332 (2011) 443-447.


Benzene Oxidation as an Alternative Method for Assessing Photocatalytic Activity

M.M. Oymaka, T. Tabarib D.Unerb

aHantek,Öveçler Mah. 1328. Cad., Çankaya Ankara, 06460, TurkeybMiddle East Technical University Chemical Engineering Department, Ankara, 06531, Turkey

The standard method of assessing photocatalytic activity of the materials is NO oxidation [1]. However, NOx analyzer is not a widely accessible instrument and as such simpler assessment techniques are needed. In this study, we reportphotocataytic oxidation of benzene as an alternative and complementary method to determine photocatalytic activity. Benzene is chosen as a test material due to the its known stability to catalytic reactions and photolysis reactions, especially at room temperature [2]. A batch reactor system was used to determine benzene photo-oxidation over photocatalytic materials. Baseline studies involved TiO

2from different manufacturers and comparing the activity

with standard NO oxidation tests. The reactor system was described in detail elsewhere [3]. The results revealed that benzene oxidationunder batch conditions can be used as analternative method to determine the photocatalytic activity.

Figure 1.Comparison of NO and Benzene photocatalytic oxidation activity.using grout samples with different TiO

2%.


References[1] ISO 22197-1:2007 e Fine ceramics (advanced ceramics, advanced technical ceramics) e Test

method for air-puri fi cation performance of semiconducting photocatalytic materials e Part 1: Removal of nitric oxide; 2007.

[2]Zuo G-M., Cheng Z-X., Chen H., Li G-W., Miao T., J. Hazard. Mater.B128 (2006) 158.[3]Oymak M.M., Photocatalytic Activity in Nano Sized Titanium Dioxide Structures, PhD Thesis,

Chemical Engineering Department, METU, Ankara (2012).Pd-PEPPSI-Type N-Heterocyclic Carbene Complexes:


Synthesis, Characterization and Catalytic Activityin The Direct Arylation Reactions

Murat Kaloğlua,b, İsmail Özdemira, Henri Doucetc, Christian Bruneauc

ª İnönü University, Catalysis Research and Application Center, 44280, Malatya / TURKEYb İnönü University,Faculty of Science and Arts,Chemistry Department, 44280, Malatya / TURKEY

c Université de Rennes 1, Sciences Chimiques de Rennes, 35042, Rennes / FRANCE

N-Heterocyclic carbenes (NHCs) and their transition metal complexes have attracted increasing attention in recent years, due to their wide applications in catalysis and material sciences [1]. Numerous of NHC containing transition metal complexes were developed until now, including metals such as Co, Pd, Cu and Ni. Among them, complexes composed with NHCs and Pd constituted one of the prominent representatives owing to their robustness against air, moisture and heat, which also exhibited excellent catalytic activities in cross-coupling reactions [2,3].

Over the last twenty years Pd-PEPPSI-Type NHC complexes(PEPPSI= Pyridine-Enhanced Precatalyst Preparation Stabilization and Initiation) have gained real practical importance in numerous catalytic processes, the most prominent application for such ligands being their use in palladium-catalysed cross-coupling reactions.

In this study Pd-PEPPSI-type NHC complexes have been synthesised and have been characterised by an X-Ray diffraction study. The catalytic properties of these palladium complexes were evaluated in the direct arylation reactions of the heteroatom-containing aromatic compound derivatives by using electron-deficient aryl halides as coupling partners.

References:[1] F. Bellina, Recent Developments in Pd-Catalyzed Direct Arylations of Heteroarenes with Aryl

Halides, Springer International Publishing, Switzerland, (2015).[2] F. Zhu, Z. X. Wang, Organic Letters, 17 (2015) 1601-1604.[3] H. Ren, Y. Xu, E. Jeanneau, I. Bonnamour, T. Tu, U. Darbost,Tetrahedron, 70 (2014) 2829-

2837.


SYNTHESIS STUDIES OF THE PROMISING CATALIST; MIL-101

Emine EKİNCİ a

aGazi University, Engineering Faculty, Chemical Engineering Department, 06570,Maltepe- Ankara, Turkey.

MIL-101 is a kind of Metal Organic Frameworks (MOFs), which have attracted much attention in the past decade due to its promising application in chemical industries.MIL-101 also known as “Porous Chromium Terephthalate”wasinitially synthesized by “Material Institut Lavoisier”.It has very high surface area and pore volume. MIL-101 exhibits exceptional stability against moisture and other chemicals and is composed of coordinately unsaturated Cr- sites with high concentration available for catalysis and adsorption [1]. The surface area of MIL-101 can be greater than 4000 m2/g which, however,isvery difficult to obtain due to the impurities coming from the synthesis chemicals. The aim of the presented study is to developasynthesis procedure to obtain MIL-101 crystalline structure with high surface are and pore volume. MIL-101 was synthesized by hydrothermal method andcharacterized by XRD, N

2 adsorption

and desorption analyses (BET surface area, particle size, etc.), andSEM.XRD patterns show the presence ofMIL-101’s crystal structure with high surface area (~2400 m2/g). Adsorption-desorption isotherms indicated atype IV isotherm according to the IUPAC classification of adsorption isotherms typical of mesoporous solids. According to BJH pore size distribution homogeneous pore size distributions both in micro and mesoporous zones were obtained.

Acknowledgements:Financial support from University Research Funds through Gazi University (06/2015-09) is gratefully

acknowledged.

References: [1] Henschel, A.,Gedrich, K., Kraehnert, R., Kaskel, S., Chem. Comm, (2008)4192-4194


Synthesis of Chiral Catalysts and Their Catalytic Activities in ScCO2

Aysen DEMİR*, Burcu DARENDELİ, Bilgehan GÜZEL

Çukurova University, Faculty of Science and Letters, 01330 Adana, TURKEY

Enantiopure chiral complexes play a significant role in performing asymmetric synthesis in homogeneous catalysis reactions. There is a lot of interesting about chiral binaphthyl Schiff base complexes for using asymmetric reactions. [2,3] This type of catalytic reactions showed high yield and selectivity with schiff base derivative metal complexes. It is known that various metal complexes have been used widely in C-C coupling reactions.

In this work,chrial schiff base ligands with perflourinated aldehydes and binaphthyl amines will be synthesized (Figure 1.).Transition metal complexes of this ligand will be prepared as catalysts and their catalytic activities will be performed in scCO

2.

Effect of some parameters such as pressure, temperature and reaction timeon the enantioselectivity of the synthesised catalyst will be investigated.

Figure 1. The structure of chiral binaphthyl Schiff base metal complexes

References:[1]Pozzi G. , Shepperson I., Fluorous chiral ligands for novel catalytic systems, Coordination

Chemistry Reviews,242, 115-124, 2003.[2] Kainz, S., Koch, D., Baumann,W. Ve Leıtner, W., Perfluoroalkyl –Substituted Arylphosphanes as

Ligands for Homogeneous Catalysis in Supercritical Carbon Dioxide. Angew. Chem. Int. Engl., 36 (15) : 1628-1630, 1997

[3] Birdsall D. J.,Hope E. G., Stuart A. M., Chen W.,Hub Y., Xiao J.,Synthesis of fluoroalkyl-derivatised BINAP ligands,Tetrahedron Letters 42, 8551–8553, 2001.


GREEN DEHYDROGENATION OF DIMETHYLAMINE-BORANE CATALYZED BY PVP, Al2O3AND PS-co-MASTABILIZED Ru NPs

BERİVAN BUKAN, Sibel DUMAN

Bingol University, Chemistry Department, 12000, Bingol

There are many methods for hydrogen obtained from dimethylamine-borane (DMAB) used as the solid hydrogen storage materials. Generally, hydrogen is obtained from DMAB activated by suitable catalysts in the solvent medium or thermally at high temperatures[1, 2]. Although good results are also obtained with both approaches, these methods are toxic, time consuming, costly and not atom-economic because in these methods are used solvents that are expensive and pollution created or carried out in unsuitable reaction temperature for practical applications. However, thanks to solvent-free reaction applications (green synthesis) will not need to expensive and environmental pollution created solvents and additional energy and cost for removal of solvents, therefore environmental pollution will be prevented while both energy and solvent savings will be provided[3,4].

Herein, DMAB that has low melting point (~35ºC) was used as reducing agent for synthesis of Polyvinylpyrrolidone (PVP), Aluminum oxide (Al2O3) and Poly(styrene-co-maleic anhydride (PS-co-MA)-stabilized Ru NPs. We report thatthese RuNPs are normally obtained by decomposition of Ru(acac)3 during the solvent-free (green) dehydrogenation of DMAB under inert gas atmosphere at nearly room temperature (35+0.1°C).These Ru NPs were characterized HRTEM-EDX, SEM, XRD, XPS, NMR and UV-Vis spectroscopy. The quantitative heterogeneity of the in situ generated these Ru NPs in the green dehydrogenation of DMAB was identified by 1,10-phenanthroline poisoning experiments. Also, the detailed kinetics in the green dehydrogenation of DMAB was studied by varying catalyst and substrate loadings and temperature. All results were compared with each other investigating by many parameters (ratio of DMAB/catalyst, catalytic activity, temperature, time, %yield, activation energy, reusability, TOF, particle size etc) in the synthesis of active these Ru NPs.

References[] Barın E.Ü., Masjedi M., Özkar S., Materials, 8 (2015) 3155-3167.[2] Duman S., Masjedi M., Özkar S., Journal of Molecular Catalysis A: Chemical, 411 (2016) 9-18.[3] Kalidindi S.B., Sanyal U., Jagirdar B.R.,Inorganic Chemistry,49 (2010) 3965–3967.[4] Demir H., Duman S.,International Journal of Hydrogen Energy, 40 (2015) 10063-10071.


Catalytic applications andsynthesis of Pd-PEPPSI N- Heterocyclic Carbene Complexes

Nazan Kaloğlua, İsmail Özdemirb, Henri Doucetc, Christian Bruneauc

aİnönü University, Pharmacy Faculty, 44280, Malatya / TURKEYbİnönü University, Catalysis Research and Application Center, 44280, Malatya / TURKEY

cUniversité de Rennes 1, Sciences Chimiques de Rennes, 35042, Rennes / FRANCE

Intensive attention has been paid to the properties and application of N-heterocyclic carbene (NHC) complexes of transition metals, and the pioneering work on the coordination chemistry of NHC ligands was independently reported by Wanzlick and Öfele in 1968 and Lappert and co-workers in the early 1970s[1]. The isolation of free NHC and utilization of NHC complexes in catalysis stimulated the search further. Among the NHCs reported, five-membered NHCs derived from imidazol-2-lidenes, imidazolin-2-ylidenes, triazolylidenes, and thiazolylidenes (abbreviated as 5-NHC) have been extensively studied [2].

Ohta and co-workers reported the direct 2- or 5-arylation of furans and thiophenes, with aryl halides, in moderate to good yields by using [Pd(PPh

3)

4] as the catalyst [3].

Since then, the palladium-catalyzed direct arylation of heteroaryl derivatives with aryl halides has proved to be a powerful method for the synthesis of a wide variety of arylated heterocycles. Only a few examples of (NHC)Pd-catalyzed direct arylations of heteroaromatics have been reported to date[4].

In this study Pd-PEPPSI type NHC complexes have been synthesised. The catalytic properties of these palladium complexes were evaluated the direct Arylation of Furan, Thiophene and Thiazole Derivatives.

References:[1] (a) Cardin, D. J.; Çetinkaya, B.; Lappert, M. F.; Manojlov, L.; Muir, K. W. J. Chem. Soc., Chem.

Commun. (1971) 400−401. (b) Cardin, D. J.; Çetinkaya, B.; Lappert, M. F. Chem. Rev. 72(1972)545−574.

[2] Herrmann, W. A. Angew. Chem., Int. Ed. 41(2002)1290−1309.[3] Alberico, D.; Scott, M. E.; Lautens, M. Chem. Rev. 107(2007)174−238. [4] Özdemir, İ .; Gö k, Y.; Ö zeroğlu, Ö.; Kaloğlu, M.; Doucet, H.; Bruneau, C. Eur. J. Inorg. Chem.

12(2010) 1798−1805.


Synthesis of poly(cyclooctene) derivatives bearing imidazole end group by ROMP Reactions

Gülşah ÇALIŞGAN, Bengi Özgün ÖZTÜRKa, Solmaz KARABULUT ŞEHİTOĞLUa

aHacettepe University, Chemistry Department, 06800, Beytepe-ANKARA

Ring opening metathesis polymerization is an efficient method, used in the polymerization of strained cyclic olefins bearing functional groups [1]. One of the disadvantages of these reactions that are catalyzed Ru, Mo and W based transition metal catalysts, is the poisoning of the catalyst in the presence of imidazole and pyridine functional groups. Up to date, various methods were developed for the to end functionalize the ROMP polymers [2]. Although several ROMP polymers with various functional groups were developed with these methods, there are no imidazole end functionalized ROMP polymers were reported in literature up to date.

In this study, cyclooctene monomer were polymerized using Grubbs first generation catalyst and methyloleate as chain transfer agent, and one end ester capped polymers were obtained in high yields (Scheme 1). With the modification of ester end groups with imidazole substituted primary amines in the presence of Ti(O-i-Pr)

4 and Sn(Oct)

2,

imidazole end-capped novel poly(cyclooctene) derivatives were observed. Temperature, catalyst type and amount, ester/amine mol ratio and such parameters were evaluated to determine the optimum reaction conditions.

Scheme 1.Synthesis of imidazole end functionalized ROMP polymers

References

[1] S. T. Nguyen, L. K. Johnson, R. H. Grubbs, J. Am. Chem. Soc., 114 (1992), 3974–5.[2] A. E. Madkour, A. H. R. Koch, K. Lienkamp, G. N. Tew, Macromolecules, 43 (2010), 4557-61


Direct Arylation with Palladium-NHC Complexes

Emine Özge KARACA,a,bNevin GÜRBÜZ,a,bSedat YAŞAR,a,bİsmail ÖZDEMİRa,b

aİnönü University, Catalysis Research and Application Center,44280, MALATYAbİnönü University, Faculty of Science and Arts, Department of Chemistry, 44280, MALATYA

In recent years, the transition-metal-catalyzed socalled direct arylation has undergone rapid development, and itrepresents a viable alternative to traditional cross-couplingreactions with organometallic reagents [1]. Direct arylationreactions through cleavage of C−H bonds is considered as anenvironmentally and economically more attractive strategy [2].Consequently, the procedure provides a valuable andstraightforward technique for the synthesis of biaryls. Ohta and co-workers reported the direct 2- or 5-arylation offurans and thiophenes, with aryl halides, in moderate to goodyields by using [Pd(PPh

3)

4] as the catalyst. Since then, thepalladium-

catalyzed direct arylation of heteroaryl derivativeswith aryl halides has proved to be a powerful method for the synthesis of a wide variety of arylated heterocycles. Only a few examples of (NHC)Pd-catalyzed direct arylations ofheteroaromatics have been reported to date [3].

The synthesis and characterization N-heterocycliccarbene palladium(II) complexes synthesized and characterized. Pd(II) complexes were tested as catalysts in the direct arylation of furans, thiophenes, and thiazoles, with various aryl bromides. These complexes exhibited moderate to high catalyticactivities under the given conditions.

References[1] M. He, J. F. Soule, H. Doucet, Chem. Cat. Chem., 6(2014), 1824.[2] M. Miura, T. Satoh, In Modern Arylation Methods; Ackermann, L., Ed.; Wiley-VCH: Weinheim,

2009; pp 335.[3]E. Ö. Karaca, N. Gürbüz, İ. Özdemir, H. Doucet, O. Şahin, O. Büyükgüngür, B. Çetinkaya.

Organometallics 34(2015), 2487.


Magnetic Nanoparticle Supported Latent Ruthenium Metathesis Catalysts for Olefin Metathesis Reactions

Bengi Özgün ÖZTÜRKa, Solmaz KARABULUT ŞEHİTOĞLUa,aHacettepe University, Chemistry Department, 06800, Beytepe-ANKARA

In recent years, reusable catalysts are become one of the most popular topics in catalytic chemistry. In this content magnetic nanoparticles were used as novel support materials in the development of novel and environmental friendly catalytic procedures. Ruthenium based olefin metathesis catalysts were supported on surface modified or coated nano Fe

2O

3 and Fe

3O

4 materials. With this method, reusable and magnetically

separable novel and efficient ruthenium catalysts were developed.

Scheme 1. Magnetic nanoparticle supported Grubbs first and second generation catalysts

In this study, -Fe2O

3 core with an average particle sizes of 20-40 nm were coated with

poly(N-vinylimidazole) [PVI]. Grubbs first and second generation catalysts were supported on PVI coated magnetic nanoparticles (Scheme 1). The obtained ruthenium complexes were characterized by TEM, XPS, FT-IR and ICP-MS methods. These catalysts were activated by acid addition or sonification and ring opening metathesis polymerization (ROMP) and ring closing metathesis (RCM) reactions were carried out in a controlled manner. While polymers with molecular weights (M

n) between 100-

450 kDa were obtained in ROMP reactions, sterically hindered RCM products were synthesized in high yields.

References[1] C. Che, W. Li, S. Lin, J. Chen, J. Zheng, J. Wu, Q. Zheng, G. Zhang, Z. Yang, B. Jiang.Chem.

Commun., 2009, 5990–5992[2] D. Wang, D. Astruc, Molecules, 19, 2014, 4635-4653


Modification of Functional Polyesters by Metathesis Reactions in the Presence of Hoveyda-Grubbs Type Catalysts

Didem OKUR, Bengi Özgün ÖZTÜRKa, Solmaz KARABULUT ŞEHİTOĞLUa,aHacettepe University, Chemistry Department, 06800, Beytepe-ANKARA

Polyesters are one of the most important polymeric materials that are frequently used in daily life, industrial and high-tech applications [1]. With the variation of monomers (diols, diamines, polyamines, etc.) a wide range of polyesters with different physical and chemical properties can be synthesized. One strategy to modify polyesters bearing unsaturated cyclic groups is to use olefin metathesis reactions [2].Olefin metathesis is an efficient method that is used organic and polymer chemistry. Among these reactions, strained cyclic olefins can be modified by using ring opening/cross-metathesis (ROM/CM). With the adaptation of these reactions into the polymer chemistry, various functional polymers can be efficiently synthesized.

Scheme 1.Sn(Oct)2 catalyzed polyesterification reactions and modification procedures

In this study, 5-norbornene-2-carboxylate and 1,6-hexanediol were polymerized in the presence of Sn(Oct)

2 and polyesters with molecular weights (M

n) varying between 2-10

kDa were obtained. These polymers were modified by ring opening-cross metathesis reactions in the presence of methyl acrylate and various olefin derivatvies and Hoveyda-Grubbs second generation catalysts (Scheme 1). Obtained polymeric structures were characterized by GPC, 1H, 13C NMR and DSC-TGA analysis.

References[1] S. T. Nguyen, L. K. Johnson, R. H. Grubbs, J. Am. Chem. Soc., 114 (1992), 3974–5.[2] N. Kolb, M. A. R. Meier, Eur. Polym. J., 49 (2013), 843-852


Synthesis of Fe3O4@SiO2@RN(CH2PPh2)2PdCl2 Type Nanocomposite Catalystsfor Vitamin K3 Synthesis

Serhan Uruş

Chemistry Department, Faculty of Science and Letters, Kahramanmaraş Sütçü İmam University, 46100, Kahramanmaraş¸ Turkey.

Research and Development Centre for University-Industry-Public Relations, Kahramanmaraş Sütçü İmam University, 46100, Kahramanmaraş Turkey.

The synthesis of aminomethylphosphine-metal complexes have opened a new door to the catalytic applications of organic compounds[1,2]. Magnetic Fe

3O

4nano-core was

synthesized using microwave power in 1h. Novel nano-composite supported;Fe3O

4@

SiO2@RN(CH

2PPh

2)

2PdCl

2bis(diphenylphosphinomethyl)amino ligands and their

Pd(II) complexes have been synthesized and characterized with FT-IR, SEM, EDX, TEM, UV-Visible, XRD and TG/DTA techniques. All the complexes were used as heterogeneous catalysts in the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1, 4-naphthoquinone (Vitamin K

3, menadione, 2MNQ) in the presence of hydrogen

peroxide. Selectivity reached about 55-60 % with a conversion of 90-96 % using the nano-magnetite supported aminomethylphosphine-Pd(II) complexes. The complexes were very active in three times in the catalytic recycling experiments in five catalytic cycles.

Figure 1. Fe3O

4@SiO

2@RN(CH

2PPh

2)

2PdCl

2 TypeAminomethylphosphine Complex and Its EDX

Spectrum.

*This study has been supported by Kahramanmaraş Sütçü İmam University (Project No: 2013/6-33 M and 2015/2-13 YLS).

References:[1] B. P., Esposito, , R. Najjar, Coord Chem Rev. 232 (2002) 137.[2] S. Uruş, M. Keleş, O. Serindağ, J. Inorg. Organomet. Polym., 20 (2010) 152-160.


Modification of Poly(norbornenediester) Derivatives with Primary and Secondary Amine Groups

Elif Ak, Elif Yakut, Bengi Özgün ÖZTÜRK, Solmaz KARABULUT ŞEHİTOĞLUa,aHacettepe University, Chemistry Department, 06800, Beytepe-ANKARA

Ring opening metathesis polymerization (ROMP) is an efficient polymerization method to produce polymeric materials with advanced structures [1]. With the invention of ruthenium based Grubbs type catalysts that are tolerant to air and moisture, there have been a tremendous increase in ROMP related applications [2]. Although a huge progress was achieved in ROMP reactions, ruthenium based metathesis catalysts are still not tolerant to some coordinating functional groups such as imidazoles. In order to overcome these obstacles, we developed a novel method to obtain imidazole substituted poly(norbornene) which cannot be synthesized directly by conventional ROMP reactions.

Scheme 1. ROMP polymers bearing functional groups

In this study, 5-norbornene-2,3-dicarboxylate derivatives were polymerized via ROMP in the presence of Grubbs third generation catalysts. These polymers were then modified by different amine groups such as 1-(3-aminopropyl)imidazole, octyl amine and diallylamines in the presence of Ti(O-i-Pr)

4, Sn(Oct)

2 and 1,5,7-triazabicyclo[4.4.0]

decene (Scheme 1). All polymers were characterized by means of GPC, FT-IR, 1H and 13C NMR analysis.

References[1]T.M. Trnka, R.H. Grubbs, AccChem Res, 34 (1) (2001), 18–29[2] P. Schwab, R.H. Grubbs, J.W. Ziller, J Am Chem Soc, 118 (1) (1996), 100–110


Reusability of nano-12-tungstophosporic acid cesium salt in alkylation of benzene with dec-1-ene reaction

Elif AKBAYa, Gülberk DEMİRa Anadolu University, Dept. of Chemical Engineering, Eskişehir, 26470, Turkey

Alkylation of aromatic hydrocarbons with olefins is an important industrial process for the production of linear alkyl benzenes (LABs) which are the primary raw material of LAB sulfonates, a surfactant detergent intermediate[1-4].In this study, Reusability of nano 12-tungstophosphoric acid cesium salt in benzene alkylation with 1-decene in liquid phase was studied.

Reusability of catalyst was investigated at 343 K 7.4/1 for 3 hr, in the presence of 0.9g cat./10 ml dec-1-ene nano Cs-TPA catalyst for five cycles.. In the presence of used catalyst after five cycles, conversion of dec-1-ene and selectivity of products decrease only about 4 and 6.5 % respectively while selectivity of isomer increase about 35 % compared with fresh catalyst. This attributes that nano Cs-TPA activity still proceed in isomerization step while decrease in alkylation step depending on shrinking pore.

After five reused cycles, the used catalyst was also characterized by XRF, XRD, N2adsorption/desorption isotherms, average pore diameter, pore volume and BET surface area. Characterization results demonstrates that mesopore structure of nano Cs-TPA is roughly retained after the reactions, although the decreasing in the surface area and pore volume and pore diameter suggest that some organics stuffed the pores were not to be insufficiently removed in regeneration step.

References: [1] Y. Liu, L. Xu, B. Xu, Z.Li, L. Jia, W. Guo, J. Mol. Catal. A: Chem. 297 (2009) 86–92[2] J.L. Berna, L. Cavalli, C. Renta, TensideSurfact Det. 32 (1995) 122.[3] C. Perego. P. Ingallina. Catal. Today 73 (2002) 3-22.[4] Z. Da. P. Magnoux. M. Guisnet, Catal. Lett. 61 (1999) 203-206.


Alumina Supported Mn-Ce Sorbents for High Temperature Desulfurization of Hydrogen Rich Gas Mixtures

Melike Kucukera, Sena Yasyerlia, A. Derya Deniz Kaynarb

aGazi University,Chemical Engineering Dept., 06530, AnkarabVestelDefence Industry, 06830, Ankara

Hydrogen-rich gas mixtures derived from fossil fuel processes such as auto thermal reforming (ATR), integrated gasification combined cycle (IGCC) system, contains hydrogen sulfide. H

2S should be safely removed from these gases at high temperatures

due to its corrosive and toxic nature. It also causes poisoning of thecatalysts in units such as solid oxide fuel cells (SOFC). High temperature desulfurization is based on the reaction between solid metal oxide sorbent and H

2S gas. In this study, γ-Al

2O

3 pellet supported

Mn-Ce oxide sorbents containing 20 wt% metalwere prepared by wet (3Mn1Ce@Al

2O

3-w; Mn/Ce:3/1) and dry (3Mn1Ce@Al

2O

3-d; Mn/Ce:3/1) impregnation methods.

BET surface areas of γ-Al2O

3, 3Mn1Ce@Al

2O

3-w and 3Mn1Ce@Al

2O

3-d were found as

173, 139 ve 135 m2/g, respectively. In the XRD patterns of all alumina supported Mn-Ce sorbents, the characteristic peaks of γ-Al

2O

3 and CeO

2 were detected while there was no

peak corresponding to Mn or Mn oxides. In order to determine the distribution of Mn and Ce in the synthesized sorbent, EDS analysis were performed at different locations of the pellets.The values of Mn+Ce amount in the sorbents were changed in the range of 15-26 wt% for 3Mn1Ce@Al

2O

3-w and in the range of 18-31 wt% for 3Mn1Ce@Al

2O

3-d.

Desulfurization tests were carried out in fixed bed reactor system at 800oC using 1% H

2S in He. After desulfurization tests,the EDS analysis gavesulfur retention capacities

as 0.032 g S/ g sorbent ve 0.029 g S/g sorbent for 3Mn1Ce@Al2O

3-wand 3Mn1Ce@

Al2O

3-d, respectively. Sorbent utilization values based on MnS formation which is the

theoretical sulfur retention capacities, were determined as 40% for 3Mn1Ce@Al2O

3-w

and 38% for 3Mn1Ce@Al2O

3-d.

AcknowledgementTUBITAK (Grant No:213M027) is gratefully acknowledged.

References[1] P. R. Westmoreland and D. P. Harrison, Environ. Sci. Technol., 10(1976), 659–661.[2] S. Yasyerli, Chem. Eng. Process. Process Intensif., 47(2008), 577–584.[3] L. Espinosa-Alonso, K. P. De Jong, and B. M. Weckhuysen, J. Phys. Chem. C, 112(2008),

7201–7209.


Catalytic Wet Peroxide Oxidation of Bisphenol A in Water

Fatma TOMUL

Mehmet Akif Ersoy University, Faculty of Arts and Sciences, Department of Chemistry, İstiklal Campüs, 15100, Burdur,

Bisphenol A (BFA), an endocrine disrupting compound (EDC), is considered to be one of the most important pollutants due to its adverse effects even at low concentrations [1].BPA is only partially removed by the conventional treatment methods employed in wastewater treatment systems, it has recently been detected in natural water bodies, in potable water resources, and in wastewater treatment plant effluents[2-3]. It is therefore important that organic pollutants that bear a potential risk to human health and the environment are removed during water supply and/or wastewater treatment. In this respect, the complete removal of BPA from aqueous solutions is of significance. Notably, satisfactory results are obtained in the removal of organic pollutants by advanced oxidation methods (AOPs) because hydroxyl radicals are not selective and have high oxidation capacity[4].

In this study, the removal of BPA by the catalytic wet peroxide oxidation method (CWPO), which is an economical and environmentally friendly AOP, is investigated. The oxidation studies were carried out using Cu-Ti-pillared bentonite, Ag-Ti-pillared bentonite and Fe-Ti-pillared bentonitesamples as catalysts at the conditions of 20 ppm BPA, H2

O2/BPA=68, 25ºC, pH 4 and 5 g/L m

cat for a reaction time of 60 minutes. By 30

minutes, values close to complete conversion were observed in two samples except Ag-Ti-pillared bentonite. For the Ag-Ti-pillared bentonite, a BPA conversion rate of 87% was achieved at the end of 60 minutes. Although values close to complete conversion were achieved for BPA within short oxidation times, the conversion rates attained for total organic carbon were rather low even after 240 minutes. However, CWPO results showed that increasement of pH causes a increase the time of oxidation. On the other hand, by the time catalyst and BPA concentration is increased, the time of oxidation is decreased as well [5]

AcknowledgementsThis work was supported by the Scientific Research Project Department of Mehmet Akif Ersoy

University (Project No: 0198-NAP-13).

References[1]Y.-H. Kim, B. Lee, K.-H. Choo, S.-J. Choi, Microporous Mesoporous Materials, 138 (2011) 184-

190. [2]D.P. Subagio, M. Srinivasan, M. Lim, T.-T. Lim, Applied Catalysis B: Environmental, 95 (2010)

414-422.[3] C. Li, Z. Wang, Y.J. Yang, J. Liu, X. Mao, Y. Zhang, Chemosphere 125 (2015) 86–93.[4]A. Cihanoglu, G. Gündüz, M. Dükkancı, Applied Catalysis B: Environmental, 165 (2015) 687-

699.[5]F. Tomul, F.T. Başoğlu, H. Canbay, Applied Surface Science, 360 (2016) 579-593.


Graphene Supported Aminomethylphosphine-Pd(II) and Pt(II) Complexes: Highly Efficient Catalysts on Vitamin K3 Synthesis

Serhan Uruş1,2*, Mahmut Çaylar2, İbrahim Karteri3

1Chemistry Department, Faculty of Science and Letters, Kahramanmaraş Sütçü İmam University, 46100, Kahramanmaraş¸ Turkey

2Research and Development Centre for University-Industry-Public Relations, Kahramanmaraş Sütçü İmam University, 46100, Kahramanmaraş Turkey

3Materials Science and Engineering Department, Graduate School of Natural and Applied Sciences¸ Sütçü İmam University, 46100, Kahramanmaraş¸ Turkey.

Novel graphene oxide (GO) supported bis(diphenylphosphinomethyl)amino [GO@CHO-NHArN(CH

2PPh

2)

2] type ligands and their Pd(II) and Pt(II) complexes have been

synthesized and characterized with FT-MIR/FAR, SEM, EDX, TEM, XRD, TGA and UV-Visible techniques. Additionally, GO@CHO-NHArN(CH

2PPh

2)

2MX

2 (M: Pd(II) and

Pt(II)) type eight complexes were used as heterogeneous nano-catalysts in vitamin K3

(2-methyl-1,4-naphthoquinone) synthesis. Especially, graphene oxide-supported Pd(II) complexes showed the best catalytic activities with high selectivities[1,2]. Conversions and selectivities were about 95-99 % and 60-65 % respectively for GO supported-Pd(II) complexes. It is obtained that the area ratio of the D and G peaks as GO sheets is ID/IG = 1.19. The average grain size of the GO and GO-Pd(II) are determined as 18.02 nm and 46.06 nm from Scherrer’s equation, respectively. The band gap (Eg) values of the GO based structures are analyzed and enhanced from 3.31 eV to 4.21 eV.

Figure 1. Fe3O

4@SiO

2@RN(CH

2PPh

2)

2PdCl

2 TypeAminomethylphosphine Complex

and Its EDX Spectrum.

*This study has been supported by Kahramanmaraş Sütçü İmam University (Project No: 2013/6-33 M and 2015/2-13 YLS).


References:[1] E. Shimanskaya, V. Doluda, M. Sulman, V. Matveeva, E. Sulman, Chem. Eng. J. 238 (2014) 206.[2] S. Uruş, M. Keleş, O. Serindağ, J. Inorg. Organomet. Polym. 20 (2010) 152.


N-Alkylation Reaction with Functionalized Ionic Liquids

Nevin GÜRBÜZ,a,bEmine Özge KARACA,a,bSedat YAŞAR,a,b İsmail ÖZDEMİRa,b


The chemistry of imidazolium derivatives has a wide variety of applications: with many anions their salts form ionic liquids (ILs) which are regarded as promising solvents for different applications, due to their low volatility, non-flammability and good thermal stability. From 1,3-dialkylimidazolium cations N-heterocyclic carbenes (NHCs) can be derived by a single deprotonation [1]. These compounds are of high interest as organocatalysts;4 furthermore NHCs as ligands in transition metal complexes were shown to have excellent catalytic [2] and also medical [3] effects. Ionic liquids (ILs) are a class of organic salts that are liquid at or near room temperature. They are generally composed of a large asymmetric organic cation and either an organic or inorganic anion. The application of ILs is also growing very rapidly in chemical reaction and catalysis [4].

In this study novel functionalized ionic liquids based on pyrimidinium cation are synthesized and characterized by studying its 1H, 13Cand elemental analysis. These ionic liquids have been reported as a highly efficient catalyst for N-alkylation reaction of aniline with alkyl chloride. Pyrimidinium cation employed as solvent for N-alkylation reaction of aniline and butyl chloride to form secondary amine without using transition metal additives and co-solvent.

References[1] H. Oldamur, G. Dirk, M. Klemens, S. Laszlo´, N. Balazs, V. Tamas, N. Laszlo´; New J. Chem.,

34(2010), 3004.[2] R. H. Crabtree, Coord. Chem. Rev., 251(2007), 595.[3] K. M. Hindi, M. J. Panzner, C. A. Tessier, A. L. Cannon, W. J. Youngs, Chem. Rev., 109(2009),

3859.[4] S. Demir, Y. Damarhan, İ. Özdemir, J. Molecular Liquids 204 (2015) 210.


The Coupling Reaction With Aryl Grignard Reagents in the Presence of Iron/NHC Catalyst

İsmail Özdemir,a,bSerpil Demir Düşünceli,a,b Nevin Gürbüza,b


Transition-metal-catalyzed cross-coupling is one of the mostpowerful tools in organic synthesis [1]. After dormancy fordecades, iron has attracted renewed attention as a practicalcoupling catalyst due to its economic and ecological advantagesover the other rare metal catalysts [2,3].

Biaryls are important structural units for a wide range offunctional molecules, such as chiral ligands and catalysts,drug intermediates, liquid crystals, physiologically activenatural products, organic electronic materials, and functionalpolymers. Therefore we report a simpleand highly selective biaryl synthesis based on iron catalyzedcross-coupling of aryl chlorides with aryl Grignardreagents. The reactions are easilycarried out with catalytic amounts of iron salt and N-heterocycliccarbene (NHC) ligands(Figure1).

Figure 1. Iron/NHC Catalyzed Biaryl Coupling Reaction

This work was financially supported by the Technological and Scientific Research Council of Turkey TUBİTAK-BOSPHORUS (France) [113Z605].

References[1] N. Miyaura, Cross-Coupling Reactions: A Practical Guide in Topics in Current Chemistry, ed. by

N. Miyaura, Springer, Berlin, 2002, Vol. 219, pp. 1159[2] E. Nakamura, N. Yoshikai, J. Org. Chem. 75 (2010) 6061-6067[3] A. Fürstner, R. Martin, H. Krause, G. Seidel, R. Goddard, C. W. Lehmann, J. Am. Chem. Soc.

130 (2008) 8773-8787.


Palladium-NHC Complex Catalyzed Cross Coupling Reactions

Serpil Demir Düşüncelia, Rukiye Zengin Yamana,İsmail Özdemira

aInönü University, Catalysis Research and Application Centre, 44280 Malatya, Turkey

Palladium catalyzed carbon-carbon cross-coupling reactions exemplify one of the important processes in organic chemistry [1]. The Heck [2] and Suzuki [3] reactions are among the most widely used reactions for the formation of carbon-carbon bonds. These reactions are generally catalyzed by Pd complexes with various ligands [4,5].

Therefore, we report here the synthesis and characterization of palladium complex bearing N-heterocyclic carbene (NHC) ligand. We investigated the catalytic activity of new Pd-NHC complexes for Mizoroki-Heck and Suzuki-Miyaura C-C coupling reactions (Figure1).

Figure 1.Palladium-NHC Catalyzed Cross Coupling Reactions

References[1] Yin, L.; Liebsher, J. Chem. Rev. 107 (2007) 133-173[2] Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 100 (2000) 3009-3066[3] Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 36 (1979) 3437-3440[4] Kotha, S.; Lahiri, K.; Kashinath, D. Tetrahedron 58 (2002) 9633- 9695[5] Herrmann, W. A.; Cornils, B. Angew. Chem., Int. Ed. 36 (1997) 1048-1067


PHOTOCATALYTIC WATER SPLITTING OVER Au/SrTiO3CATALYST

Ramazan Yıldırıma, Dilara Saadetnejadb

aBoğaziçi University,Bebek, 34342, İstanbulbBoğaziçi University,Bebek, 34342, İstanbul

In this study, it’s aimed to produce hydrogen via photocatalytic water-splitting under UV and visible light. Photocatalytic water splitting offers many potential advantages over other solar hydrogen production methods such as reasonable efficiency, lower cost, small volume reactors [1]. Photocatalytic water splitting occurs on the surface of photocatalyst which is at the heart of photocatalytic water splitting technology; therefore new materials have been tried to be improved. Among them, several oxide photocatalysts have been widely studied and most of the active materials are found to be perovskite types [2]. By doping perovskites with plasmonic metals such as Au, Ag and Cu, which are excellent cocatalysts that can promote visible light absorption, high photocatalytic efficiency can be obtained. Recent studies show that plasmonic metals on semiconductor such as TiO

2, Bi

2WO

6 and La

2Ti

2O

7 etc. enable to prevent charge

recombination and make light absorption higher [3].

In this work, semiconductor-based photocatalytic water splitting was done with Au doped SrTiO

3(perovskite) photocatalyst; Au dopping wereperformed using

homogenous deposition-precipitation method. A batch reactor was designed with a homogeneous and efficient light-irradation quartz window. Both UV and visible ligh sources were utilized. The results were analyzed using Gas chromatography.

References[1] Liao C., Huang C., Wu J., Hydrogen Production from Semiconductor-based Photocatalysis via

Water Splitting, Catalysts, 2 (2012) 490-516.[2] Ikada S., Fubuki M., Takahara Y., Matsumura M., Photocatalytic of hydrothermally synthesized

tantalate pyrochlores for overall water splitting , Applied Catalysis A General : 300 (2006), 186-190.

[3] Bi J., Fang W., Li L., Li X., Liu M., Liang S., Zhang Z., He Y., Lin H., Wu L., Liu S., Wong P., Ternary reduced-graphene-oxide/Bi2MoO6/Au nanocomposites with enhanced photocatalytic activity under visible light, Journal of Alloys and Compounds 649 (2015), 28-34.


IN SITU GENERATION COPPER(0) NPs AND CONCOMITANT GREEN DEHYDROGENATION OF DIMETHYLAMINE-BORANE

Sibel DUMAN

Bingol University,Chemistry Department, 12000, Bingol

Use of catalysts that located in the 12 principles of Green Chemistry is an important area of research. Application and investigation of catalysts how are non-perishable after use, non-toxic, easily separated and reusable after reaction can be considered one of the vital areas for the chemical industry [1]. Because of the relatively high use of oil derivatives many chemical industry attempts to produce solvents with high E-factor [2,3]. In addition to supercritical fluids, ionic liquids and fluorinated solvents produced and used for this purpose, “The best solvent is no solvent” approach has been the focus of our attention in this project [4,5].

In this study, dimethylamine-borane (DMAB) which has low melting point (35°C) was used as both stabilizing and reducing agent while copper(0) nanoparticles (NPs) were used as the active catalyst in the solvent-free (green) dehydrogenation of DMAB. Catalytic activity of in situ generated copper(0) nanoparticles by stabilizing cyclic bis(dimethylamino) borane, (Me2N)2BH, obtained as a result of interaction of Cu(acac)2 and melted DMAB at nearly room temperature(30°C) in solvent-free medium was examined and activation energy, Ea, was determined as 18 + 2 kjmol-1. Average particle size of reusable, relatively inexpensive, active and stable copper(0) nanoparticles was calculated from TEM images as 2,9 + 0,2 nm. It was clearly observed that the resulting copper(0) nanoparticles were provided 200 total turnovers over 50 h with an initial turnover frequency (TOF) value of 19 h−1 at nearly room temperature with the generation of 1,0 equiv H2 at the almost complete conversion of dimethylamine borane to cylic dimethylamino borane, [Me2NBH2]n units. These nanoparticles obtained under solvent-free medium were charactarized by TEM, EDX, HRTEM, P-XRD, 11B{1 H}-NMR, ATR-IR and UV-Vistechniques.

References[]Paluri S.L.A., Edwards M.L., Lam, N.H., Williams, E.M., Meyerhoefer A., Sizemore, I.E.P. Journal

of Chemical Education, 92 (2015) 350-354..[2] Quinones L., Grazul J., Martinez-Inesta M.M.,Materials Letters, 63 (2009) 2684-2686.[3] Dahl J.A., Maddux B.L.S., Hutchison J.E.,Chemical Reviews,, 107 (2007) 2228-2269.[4] Kalidindi S.B., Sanyal U., Jagirdar B.R.,Inorganic Chemistry,49 (2010) 3965–3967.[5] Demir H., Duman S.,International Journal of Hydrogen Energy, 40 (2015) 10063-10071.


Synthesis of Palladium(II) Schiff Base Complex And it’s Catalytic Activities C-C Coupling Reactions

Sinan SEVEN, Figen KOÇAK, Bilgehan GÜZEL

Çukurova University, Faculty of Science and Letters, 01330 Adana, TURKEY

The ligand assisted palladium (Pd)-catalyzed Suzuki–Miyaura cross-coupling reaction is one of the most attractive methods in organic chemistry and phosphines have been established as the best ligand system for this transformation. However, these phosphines have significant limitations, such as;high toxicity and sensitivity to air. Recently, Schiff bases have been recognized as excellent alternatives to phosphines in Suzuki–Miyaura reactions [1,2].

This work has been included; the synthesis of Schiff base ligand by condensation of 4-fluoromethyl aniline with 2-hydroxy- 5-methyl benzaldehyde and its palladium complex. All of the synthesized molecules were characterized by elemental analysis, FT-IR, 1H NMR, 13C NMR. This palladium complex was used as catalyst for suzuki-miyaura cross-coupling reaction over phenyl boronic acid and bromobenzene (Figure 1.)

Figure 1. The mechanism of Suzuki-Miyaura

References:[1] P. Das, W. Linert, “Schiffbase-derivedhomogeneousandheterogeneouspalladiumcatalystsforthe

Suzuki–Miyaurareaction” CoordinationChemistryReviews, 311, (2016), 1-23[2] Knozinger. H. “Heterogeneous Catalysis and Solid Catalysts” Ulmann’s Encyclopedia Of

Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA. (2003)


HYDROBENZOIN TYPE LIGANDS FOR ASYMMETRIC CATALYSIS

Seda KILIÇARSLAN, Halil Zeki GÖK, İlker Ümit KARAYİĞİT,Yaşar GÖK*

Department of Chemistry, Faculty of Arts and Sciences, OsmaniyeKorkut Ata University,80000 Osmaniye, Turkey.

Asymmetric catalysis has become a growing field of study as the demand for more enantiomerically pure compounds arises. Asymmetric catalysis requires that a chiral catalyst be used in order to transfer its chirality to the substrate. An effective asymmetric catalyst will quickly produce a chiral product in good yield with high enantiomeric purity of the desired enantiomer[1].The discovery of new chiral auxiliaries or ligands for catalysis continues to broaden the scope of many asymmetric processes.In this study, chiral ligands, derived from C2-symmetric (R, R)-hidrobenzoin skeleton were synthesized and applied as catalysts in different enantioselective reactions[2].

References: [1] Ghent, B. L., Martinak, S. L., Sites, L. A., Golen, J. A., Rheingold, A. L., Nataro, C. J.

Organomet. Chem., 692 (2007), 2365-2374.[2](a) Gök, Y., Kekeç, L. Tetrahedron Lett.55(2014),2727-2729.(b) Gök, Y., Küloğlu, S., Gök, H.Z.,

Kekeç, L. Applied Organometallic Chem.28 (2014) 835-838. (c) Gök, Y., Gök, H. Z. Helv. Chim. Acta 98(2015) 490-495.


THE SYNTHESIS OF MAGNETIC NANOPARTICLES SUPPORTED AZOMETHINE-OXIME-PD COMPLEX AND ITS CATALYTIC ACTIVITY

Eylül Büşra Hereytania, Fatma Ulusala, Bilgehan Güzela

a Çukurova University, Science and Literature Faculty Chemistry Department, 01330, Adana

Metal nanoparticles are used extensively as catalysts for a wide variety of reactions. Among these catalysts, supported Pd catalysts are commonly used for hydrogenation, oxidation, Heck and Suzuki-Miyaura cross-coupling reactions. Various materials such as alumina, silica gel, magnetic nanoparticles, activated carbon, carbon nanotube, polymers are used as support materials for these catalyst. Magnetic nanoparticlesare prefered due to easy separable after using by magnet from reaction medium and forming the desired functional groups of the ligands.

Figure 1.Preparation of catalyst

In this work, bifunctional Schiff Base-vic-dioxime ligand was synthesized and bonded via oxime group to magnetic nanoparticles (Figure 1.). Pd complex of this MNP supported ligand was synthesized and characterized by XRD, SEM, FT-IR, elemental analysis. Synthesized magnetic complex was used in transfer hydrogenation reaction of styrene. We present the first synthesized of magnetic nanoparticles supported bifunctional Schiff Base-vic-dioxime ligand and Pd complex.

References:[1] A. Kakanejadifard, Farnia, S. Morteza and Najafi, Golamreza Iran. J. Chem. & Chem. Eng., 23

(2004) 117-118.[2] W.Ungnadel, Narath, And D. Barham, The Journal Of Organic Chemistry 28 (1962) 134-136.


N-Substitutedbenzimidazole-Ruthenium(II) Complexes and Their Catalytic Activity

Kenan Buldurun,a Nevin Gürbüz,b,c İsmail Özdemirb,c

a Muş Alparslan University, Faculty of Science and Arts, Departmant of Chemistry, 49250-MUŞaİnönü University, Catalysis Research and Application Center,44280, MALATYA

bİnönü University, Faculty of Science and Arts, Department of Chemistry, 44280, MALATYA

The chemistry of azo-ligands have attracted considerable of attention because of the interesting physical, chemical, photophysical and photochemical, catalytic properties particulary in the low valent transition metal coordination and organometallic compounds [1]. The Ru(II) complexes with ligands bearing N-donor atoms are attracting interest of researchers due to their potential to promote the catalytic reaction of organic compounds. For several reasons, nitrogen-containing ligands have been found to be among the most convenient and attractive ligands for ruthenium complexes [2,3]. A large number of ruthenium complexes with arene ligands have been employed in different catalytic reactions including allylic alkylation, amination, cyclization, cycloisomerization of dienes and hydroformylation and transfer hydrogenation [4,5].

In this study, N-coordinated 5-nitrobenzimidazole ruthenium(II)complexes were synthesized by the reaction of [RuCl

2(p-cymene)]

2 with N-substituted

5-nitrobenzimidazole. These complexes that prepared and characterized has used as catalyst in hydrogen transfer reaction.

Reference[1]. M.S. Jana, A. K. Pramanik, S. Kundu, D. Sarkar, S. Jana, T. K. Monda, InorgChimActa, 394

(2013) 583–590.[2]. D. Mercan, S. Dayan, N. Kayacı, N.O. Kalaycioglu, O. Dayan, E.Ç. Öztürk, InorgChimActa,

400 (2013) 74–81.[3]. L. Gök, H. Türkmen, Tetrahedron 69 (2013) 10669-10674.[4]. B. Çetinkaya, İ. Özdemir, C. Bruneau, P.H. Dixneuf, Eur. J. Inorg. Chem, (2000) 29-32.[5]. D. Pandiarajan, R. Ramesh, J Org Chem, 723 (2013) 26-35.


Determination of Radiation Absorption Properties of Gamma Irradiated Polyoxovanadate Based Catalysts

A.Çiğdem Karaerkeka, Faruk Demirb, Ali Karac

aChemistry Department, Bursa Technical Univ., 16190, Bursa, TurkeybMetall. and Materials Engineering Department, Bursa Technical Univ.,16190, Bursa, Turkey

cChemistry Department, Uludağ Univ.,16285 Bursa, Turkey

Determination of the mass attenuation coefficient μ/ρ, and the effective electron number Neff, the effective atomic number Zeff, is very important in the fields of, radiation protection, nuclear diagnostics, radiation dosimetry, nuclear medicine. μ/ρ, Neff and Zeff, represent radiation interaction with materials. Zeff is one of the most convenient parameter and represents characteristics of a multi element material especially in the radiation field depending on atomic numbers of the constituent elements and incident radiation energy. Recently, researchers have made extensive effective atomic numbers studies on a variety of materials such as dosimetric materials, alloys, semiconductors, building materials, glasses, soils, amino acids, minerals, and biological samples and polymers. γ-ray irradiation changes the concentration of catalytically active sites and alters the reducibility of the catalysts. Effect of such irradiations on the catalytic properties of several compounds has recently been described for the different reactions. In the literature it is described that the effect of varying doses of gamma ray irradiation of novel polyoxovanadate based material on its catalytic performance for the oxidative dehydrogenation of propane has been studied. In this work, we have computed theoretical values of µ/ρ, Zeff and Neff of the polyoxovanadate compounds by using the Direct- Zeff software program in different energy regions.

References: [1] Adem Ün, Tanfer Caner, Annals of Nuclear Energy, Volume 65, March (2014), Pages 158–165[2] Adem Ün, Faruk Demir, Applied Radiation and Isotopes,Volume 80, October (2013), Pages

73–77[3] Hine, Phys. Rev., 85, (1952), pp. 725–737.[4] M.Ishaque Khan, Kadir Aydemir, M.Rafiq H.Siddiqui, Abdulrahman A. Alwarthan, James A.

Kaduk, Christopher L.Marshall, Radiation Physics and Chemistry 88 (2013) 56–59.[5] N. G. Kostova*, A. A. Spojakina,Journal of Optoelectronics and Advanced Materials, Vol. 7, No.

3, June (2005), p. 1347 – 1352.


EFFECTS OF THE PREPARATION METHOD AND CALCINATION TEMPERATURE ON THE CHARACTERISTIC PROPERTIES OF NiO-

Fe2O3-SiO2 CATALYSTS

Filiz BALIKÇI DEREKAYAa

a Gazi University, Graduate School of Natural And Applied Sciences, Advanced Technologies Department, 06500, Teknikokullar, Ankara, TURKEY

In this study the NiO-Fe2O

3-SiO

2 catalysts were prepared by using two different methods

which are co-precipitation and surfactant assisted co-precipitation method. All prepared catalysts were calcined at two different temperatures which are 500oCand 700oC. Catalysts were characterized by using different techniques which are N

2physisorption,

x-ray diffraction and scanning electron microscopy (SEM-EDX). Multipoint BET surface area results indicate that surface areas of the catalysts decreased by increasingthe calcination temperature as a result of increase in average pore diameter which might be due to the pore degradation to form big pores. Using of surfactant at preparation has not good effect on the surface areas of the catalysts since catalysts prepared by the co-precipitation method have higher surface area values. The Fe

2O

3 has positive effect

on the surface area of the catalysts that prepared by the co-precipitation method and calcined at 500oC. Results indicate that 700oC calcination temperature is not convenient in comparison with the 500oC. According to the x-ray diffraction studies the crystal phases obtained from the catalysts calcined at 500oC are NiO, Fe

2O

3 and SiO

2. The NiO

peaks observed at 2q=37°, 43°, 63° and 75°; the Fe2O

3 peaks observed at 2q= 35° and

SiO2 peaks observed at 43° and 36.5° [1]. The broader peak of SiO

2 which is at 2q=23°

was not observed. Wang Y. et.al. [2] and Wang W. et.al. [3] did not see this peak at their studies over the Ni/SiO

2 and Ni-Fe-SiO

2 catalysts, respectively.

References: [1] Dopminguez I., Barrio I., Catalysis Today, 133-135 (2008) 467-474.[2] Wang Y., Li F., Cheng H., Fan L., 41 (8) (2013) 972-977.[3] Wang W., Wang H., Yang Y., Jiang S., International Journal of Hyrogen Energy, 37 (11)(2012)

9058-9066.


Modular Ligands Allowing Tunable Steric and Electronic Effects for Transition Metal Catalysis

Yaşar GÖK, Seda KILIÇARSLAN, Halil Zeki GÖK, İlker Ümit KARAYİĞİT

Department of Chemistry, Faculty of Arts and Sciences, OsmaniyeKorkut Ata University, 80000 Osmaniye, Turkey.

Nowadays, the syntheses of enantiomerically pure compounds are of primary importance due to containing stereogenic centers in a large amount of the pharmaceuticals and agrochemicals. Catalytic enantioselective reactions are the most widespread way because of obtaining a large amount of chiral target product with a small amount of catalyst. Among the enantioselective catalysts, the use of transition metal complexes containing chiral organic ligands is the most faced one [1].

Herein, we report the synthesis of optically pure ligands in a straightforward manner with high yields and enantioselectivites (Figure 1). As part of our research on enantioselective catalysis we decided to evaluate these chiral ligands in different enantioselective reactions [2].


References: [1] Jacobsen, E. N., Pfaltz, A., Yamamoto, H.,Springer, Berlin,1-3, 1999.[2] (a) Gök, Y., Kekeç, L. Tetrahedron Lett. 55 (2014), 2727-2729. (b) Gök, Y., Küloğlu, S., Gök,

H. Z., Kekeç, L. Appl. Organometal. Chem. 28 (2014) 835-838.(c) Gök, Y., Gök, H. Z. Helv. Chim. Acta98 (2015) 490-495.


Synthesis of Tungstophosphoric Acid Incorporated Mesoporous Alumina Catalysts for Methanol Dehydration in DME Synthesis

M. İlker Şenera, Naime Aslı Sezgia,Timur Doğua, Gülşen Doğub, Nuray Oktarb

aChemical Engineering Department, Middle East Technical University, Ankara, 06800bChemical Engineering Department, Gazi University, Ankara, 06570

Dimethyl ether (DME) is considered as a highly promising environmentally clean diesel fuel alternate, which can be produced from synthesis gas. It has high cetane number (55-60) and clean burning properties [1]. Possibility of using CO

2 as the carbon source

in DME production makes this process even more attractive as a carbon neutral technology. Production of DME from synthesis gas requires a bifunctional catalyst combination, for methanol synthesis and dehydration functions. As for the methanol synthesis function, commercial Cu-ZnO based catalysts are available. Heteropolyacids with very high Bronsted acidity are considered as highly promising catalytic materials for dehydration of methanol to DME [2, 3]. However, they have very low surface area [3]. In the present study, tungstophosphoric acid incorporated mesoporous alumina catalysts with high surface area and ordered pore structures were synthesized, to be used as the methanol dehydration catalysts in DME synthesis. Mesoporous alumina (MA) was synthesized by an evaporation-induced self-assembly (EISA) method [4], using Pluronic-123 as the surfactant. In order to improve dehydration activity of this material 5% TPA was impregnated on this material (MA), as well as on commercial γ-alumina (Toyo). Nitrogen physisorption results exhibit Type IV isotherms for both MA (209.7m2/g) and commercial Toyo (147.7m2/g).Results revealed that impregnation of TPA did not cause significant change of the structure of commercial γ-alumina and the synthesized materials had high acidity, which is required for methanol dehydration in DME synthesis.

AcknowledgementFinancial support of TUBITAK through Project No. 115M377 is gratefully acknowledged.

References[1] A. Ciftci, N. A. Sezgi, T. Dogu, Ind. Eng. Chem. Res. 49 (2010) 6753–6762.[2] A. Thomas, C. Dablemont, J.M. Basset, F. Lafebre, C.R. Chimie 8 (2005) 1969–1974.[3] D. Varisli, K. C. Tokay, A. Ciftci, T. Dogu, G. Dogu, Turk J Chem 33 (2009) 355– 366.[4] A. Bayat, MSc Thesis, Middle East Technical University, Ankara, 2013.


Production of 2,6-Dimethylnaphthalene with Methylation of Naphthalene over Au/Mordenite Zeolite Catalysts

Eda Karayılan1, Aysun Özen1, Fatih Güleç1, Ali Karaduman1

¹Ankara University Faculty of Engineering, Dept. of Chemical Eng. 06100 Ankara, TÜRKİYE

Methylation of Naphthalene is crucial reaction to obtain 2-Methylnaphtalene (2-MN) and 2,6Dimethylnaphtalene (2,6-DMN). 2-MN is significant raw material for the synthesis of vitamin K and 2,6-DMN [1,2]. 2,6 DMN is also one of the most important Dimethylnaphtalene isomers in terms of used in precious polymers such as Polyethylene naphthalate (PEN). PEN is valuable and expensive polymer which has better features compare to Polyethylene terephthalate (PET) [2,3]. In this study, the effect of metal doping and calcination temperature on the performance of Mordenite zeolite catalysts were investigated for methylation of Naphthalene with methanol in order to enhance 2,6-Dimethynaphthalene (2,6-DMN) selectively. For catalyst preparation, 0.1 wt% Au was doped on Mordenite catalysts using wet impregnation method and the catalystswere calcined at two different temperatures (550°C and 750°C).The methylation experiments were carried out in a fixed bed reactor at atmospheric pressure. The reactor was operated at450°C, weight hourly space velocity (WHSV) was 2h-1, volume of catalystswas 2cm3(approximately 1g) and flow rate of inert carrier gas (N

2) was selected10 ml/min.

Naphthalene, m-Xylene and Methanol mixture was prepared as a feedstock with mass ratio of 1:3:5, respectively.The products were analyzed using a GC-MS which has 60 meter DB-1 capillary column. Conversion of Naphthalene, selectivity of 2-MN, 2,6-DMN, DMNs, ratio of 2-MN/1-MN and 2,6-DMN/2,7-DMN were determined.

Acknowledgement

We are thankful and greatfully appreciate Ankara University Scientific Research Projects (AÜ-BAP) for the support of this work. (Project No: 15B0443009)

References[1] Park, J., Wang, J., Lee, C.W., Park, S., Bul.Korean Chem. Soc., 23, (2002),1011-1013.[2] Zhao,L., Guo,X., Liu,M., Wang,X., Song, C., Chinese Journal of Chemical Engineering 18 ,(2010),

742-749.[3] Niftaliyeva, A., Güleç,F., Şimşek,E,H., Güllü,M., Karaduman,A., Anadolu University Journal of

Science and Technology,16, (2015),167-178.


CHARACTERIZATION OF Ni/ZrTiO4CATALYSTFOR THE PARTIAL OXIDATION of METHANE

Burcu Aygüna, Hasan Özdemira, M.A. Faruk Öksüzömera, Serkan Naci Koça

aDepartment of Chemical Engineering, Istanbul University, Avcilar/Istanbul, 34320, Turkey

Processes such as coal gasification, dry reforming, steam reforming and partial oxidation of hydrocarbons, are well known to be used for syngas production.Catalytic partial oxidation of methane/natural gas (POM)into syngas has recently become a process of the utmost interest due to its availability and low cost. The most active catalysts of POM are based on Ni, Pt, Ru and Rh supported on irreducible metal oxides like Al

2O

3,

SiO2, ZrO

2 etc. High catalytic performance and low price of Ni compared to noble metals is an advantage, however Ni-based catalysts are prone to rapid deactivation due to formation and sintering of active sites. Therefore, researches are concentrated on the solvation of these problems.

The effect of the support on sintering and carbon deposition was investigated much and pure supports, such as ceria and zirconia, have been shown to be especially efficient for decreasing coke deposition by carbon gasification due to their oxygen storage capacity [1]. TiO

2 was also beneficial to decrease carbon deposition but deactivation

was prominent due to the formation of NiTiO3 [2].This formation could be prevented

maybe with the interaction of different metal oxides like ZrO2 to form ZrTiO

4 structure.

In this work, ZrTiO4

support will be synthesized by using the sol-gel method and characterized for POM which is not available in literature. For this purpose, 10(wt%) Ni will beloaded onto ZrTiO

4 and characterized by using BET, XRD and SEM analysis.The

reactions will be actualized with Microreactor-GC system, and it will be compared with 10(wt%) Ni/ZrO

2 and Ni/TiO

2 catalysis.

References [1]W-S. Dong, K-W. Jun, H-S. Roh, Z-W. Liu, S-E. Park, Catalysis Letters, 78 (2002) 215-222.[2] T. Wu, Q. Yan, H. Wan, Journal of Molecular Catalysis A: Chemical, 226 (2005) 41-48.


Characterization and Catalytic Performance of MnxOy-Na2WO4/SiO2 for the Oxidative Coupling of Methane

Mahmut Yildiza,b*,Reinhard Schomaeckera

aDepartment of Chemistry, Berlin Institute of Technology,10623 Berlin, GermanybDepartment of Chemistry, Gebze Technical University, 41400 Kocaeli, Turkey

Natural gas is still an underutilized resource for the production of valuable chemicals and liquid fuels. On-site conversion of methane, the main constituent, to more useful and value added chemicals (e.g. ethylene, methanol) could be of great importance for using it more effectively in industry [1]. The oxidative coupling of methane (OCM) to ethane and ethylene is one of the most important direct ways for methane utilization. However, up to date, this reaction has not reached the stage of commercial application, even though a large number of catalystshave been tested [2].Among the known OCM catalysts, Mn

xO

y-Na

2WO

4/SiO

2 is a promising one in the literature for the

commercialization of an industrial process [3, 4].Despite the large number of studies on this catalyst, structural characterizations are very difficult due to its complex supported trimetallic and multiphase nature.

In the present study, the MnxO

y-Na

2WO

4/SiO

2 was characterized via ex-situ X-ray

diffraction, BET surface area, XPS surface composition, ICP chemical composition analyses and TEM-SEM imaging techniques. Besides that in-situ X-ray diffraction method was applied to detect which phases are present under reaction conditions and during calcination process. Furthermore influences of reaction temperature, reactant flow rate, catalyst bed dilution and calcination temperature of the catalyst on catalytic performance were investigated. Moreover long-term catalytic activity experiments (approx. 16 h) were performed in a packed-bed reactor made of quartz glass in order to evaluate the stability of the catalyst.

References[1] R. Horn, R. Schlögl, Catal.Lett. 145 (2015) 23-39.[2] U. Zavyalova, M. Holena, R. Schlögl, M. Baerns, ChemCatChem 3 (2011) 1935-1947.[3] X. Fang, S. Li, J. Lin, Y. Chu, J. Mol. Catal. (China) 6 (1992) 427-433.[4] S. Arndt, T. Otremba, U. Simon, M. Yildiz, H. Schubert, R. Schomäcker, Appl. Catal. A-Gen.

425-426 (2012) 53-61.


The Effect of Metal Adding Sequence and Synthesis Media on the Properties of SnSBA-15 Catalysts at Low Metal Ratio

Filiz AKTI a, Suna BALCI b, Timur DOĞU c

aHitit University, Chemical Engineering Department, 19030, ÇorumbGazi University, Chemical Engineering Department, 06570, Ankara

cMiddle East TechnicalUniversity, Chemical Engineering Department, 06531, Ankara

In this study, the effects of tinadding sequences to the synthesis solution and synthesis media on the structural and chemical properties of tin loading SBA-15 catalysts were investigated. The tin SBA-15 catalysts were obtained by using the tin metal source as tin chloride and keeping the Sn/Si mole ratio as 0.03 in all synthesis. The tin source was dissolved in the ethylalcoholor isopropyl alcohol and in the presence of aluminumsulphate(Al/Si mole ratio: 0.001) and then added to the synthesis solution before and after silica source (TEOS) addition. The synthesized catalysts were characterized with nitrogen adsorption/desorption isotherms, XRD and FTIR techniques. The BET surface area, total pore volumeand pore diameter valuesof SBA-15 were increasedfrom 800 m2/g, 1.14 cm3/g and 6.73 nm to1027 m2/g, 1.49 cm3/g and 6.87 nmby metal loading,respectively. The surface area and total pore volume values of catalysts prepared by dissolving the tin sourcein the isopropyl alcohol were higher than that of the ethyl alcohol.While the tin addition after the TEOS caused decreases in the surface area and total pore volume values, it wasn’t affectedthe pore diameter values. The XRD results showed that thebasal spacing(d

100), lattice parameter (a) and

pore wall thickness (δ) values of the SBA-15 were increased with the tin loading. The tin adding sequence wasn’t caused much influence on these properties. The XRD patterns showed thetinwas incorporated to the SBA-15 structure in the tin oxide form in all catalysts. The FTIR analyses were performed after pyridine adsorption and it showed that increase the peak intensitiesof acid sites and silanol groups in the structure with metal loading. These peakintensities in the catalysts synthesizedby dissolving the tin sourcein the isopropyl alcoholwere increased much more than the other catalysts.


Effect of Ti-Ce Contenton the Catalytic Activity of Alumina Supported Catalysts in Selective Oxidation of H2S

H.Mehmet Tasdemirª, Yavuz Yagizatliª, Sena Yasyerliª, Nail Yasyerliª, Gulsen Doguª

ª Department of Chemical Engineering, Gazi University, 06570, Ankara

H2S is an important air pollutant and usually converted to elemental sulfur by using well-

known Claus process. The development of active catalyst is a necessity for the success of Claus process. Iron, titanium and vanadium based catalysts showed high potential for selective oxidation of H

2S to elemental sulphur (H

2S+1/2O

2®S+H

2O; 200°C≤T≤350°C)

[1–3]. In this study, alumina was synthesized by classical sol-gel method [4]. Alumina (SG-Al

2O

3) supported Ti-Ce catalysts (Ti/Ce molar ratio of 4/1) with different weight

percentages (5%, 10% and 20%)were prepared by wet impregnation method. The synthesized catalysts showed mesoporous structure. XRD patterns of sol-gel alumina supported Ti-Ce catalysts showed the formation of maincharacteristic peaks of γ-Al

2O

3

and amorphous structure. There was no peak corresponding to Ti and/or Ce in the XRD pattern of the catalysts.Catalytic activities were tested in a fixed-bed flow reactor using a feed stream containing stoichiometric ratio of H

2S-O

2 in He at 250°C. H

2S conversions

and sulphur selectivities are given in Figure 1. Complete conversion of H2S was achieved

over Ti80Ce20@SG-Al2O

3-10w and high sulphur selectivities (≥% 99) were obtained for

all catalysts. The EDS analysis of the used catalysts showed small amount of sulphur deposition on the catalysts after reaction.

Figure1. H2S conversions and sulphur selectivities ( T=250°C, O

2/H

2S=0.5, Total flow rate= 100 mL/

min)


AcknowledgementsTUBITAK (114M185) is gratefully acknowledged.

References: [1] D.D. Eslek Koyuncu, S. Yasyerli, Ind. Eng.Chem. Res., 48 (2009), 5223-5229.[2] H.M.Tasdemir, S.Yasyerli, N. Yasyerli, Int. J. of Hydrogen Energy, 40 (2015), 9989-10001.[3] V. Palma, D. Barba, Int. J. of Hydrogen Energy, 39 (2014), 21524-21530.[4] E. Seker, N. Yasyerli, E. Gulari, C. Lambert, R.H. Hammerle, 208 (2002), J. of Catalysis,15–20.


INVESTIGATION and CHARACTERIZATION of Ni/MgO CATALYST PREPARED BY ELECTROSPINNIG TECHNIQUE for the PARTIAL

OXIDATION and DRY REFORMING of METHANE

Burcu Aygüna, Hasan Özdemira, M.A. Faruk Öksüzömera, M. Ali Gürkaynaka

a Department of Chemical Engineering, Istanbul University, Avcilar/Istanbul, 34320, Turkey

Methane, which is the main component of natural gas is generally used for residential or industrial heating and generation of electrical power. Efficient use of natural gas have raised interest in synthesis gas (CO+H

2) production, which is necessary for methanol,

fuel and higher hydrocarbon synthesis. There are three well known methods for the production of synthesis gas in literature and these methods are steam methane reforming (SMR), carbon dioxide reforming of methane (CDR) and partial oxidation of methane (POM). Researches about POM and CDR are still ongoing in the literature.

Figure 1: SEM photograph of 20(wt%)Ni/MgO catalyst prepared via electrospinning technique, before (left side) and after calcination at 800°C for 5 h (right side)

Noble metals are relatively stable and active for the POM reaction but their high cost and low availability limited their use in the reaction. Thus, nickel based catalysts are considered to be good alternatives due to their high activity and selectivity. However, carbon deposition and sintering are the main problems of these catalysts. Ruckenstein et al. [1-2], was determined that the NiO/MgO catalyst had high activity and stability due to formation of solid solution which limits the sintering and carbon deposition to certain extent for POM and CDR reaction. Considering this fact, 20(wt%)Ni/MgO catalyst (Figure 1) was prepared by a simple electrospinning technique and will be tested for the POM and CDR reaction for the first time in literature. For the comparison, the same catalyst will be synthesized with the wet impregnation method. The catalysts will be characterized with BET, XRD and SEM analysis and the reactions will be actualized with Microreactor-GC system.


References[1]E. Ruckenstein, Y.H. Hu, Industrial & Engineering Chemistry Research, 37 (1998) 1744.[2] H.Y. Wang, E. Ruckenstein, Appl. Catal.,204 (2000) 143–152.


THE CATALYTICACTIVITY OF AZO CONTAINING SCHIFF BASE COMPLEXES

Mesut İKİZa, Esin İSPİRa

aDepartment of Chemistry, Faculty of Science and Arts, Kahramanmaraş Sutçu Imam University, Kahramanmaraş 46050-9, Turkey

Azo compounds with two phenyl rings separated by an azo (-N=N-) group, are versatile molecules and have received much attention in research both fundamental and application [1].A wide variety of cobalt(II) complexes are known to bind dioxygen more or less reversibly and are therefore frequently studied as model compounds for natural oxygen carriers and for their use in O

2 storage, as well as in organic synthesis due

to their catalytic properties under mild conditions.

In the first systematic study on the catalytic activity of model copper complexes towards the oxidation of 3,5-di-tert-butylcatechol (DTBC) which contemplated both mononuclear complexes and dinuclear complexes, Nishida et al. [2] found that in some cases mononuclear complexes could be better catalysts that dinuclear ones.

Figure 1.

In continuance of the interest in syntheses of azo-based compounds, herein syntheses and characterization of a series of azo-linked salicylidenic Schiff bases their metal complexes, are reported. Also the oxidative C–C coupling properties of the CoII and CuII complexes have been investigated on the sterically hindered 2,6-di-tert-butylphenol (DTBP).

References: [1].Nejati K, Rezvani Z, Massoumi B. Dyes Pigm., (2007);75:653.[2]. L’Argentiere PC, Cagnola EA, Quitoga ME, Liprandi DA. Appl. Catal., A, (2002);226:253.


TRANSITION METAL COMPLEXES OF NOVEL CHROMONE SCHIFF BASES: SYNTHESIS, CHARACTERIZATION AND CATECHOLASE-

LIKE ACTIVITY

Cahit Demetgüla, Neslihan Beyazıta

a Mustafa Kemal University, Faculty of Arts and Sciences, Department of Chemistry 31040Hatay

Catecholase enzymes, usually observed in plant tissues and in some insects and crustaceans to catalyze the oxidation of catechols to the corresponding o-quinones are type-3 copper active site proteins[1]. Consequently, the search for model complexes capable of mimicking the function of catechol oxidases is primarily involved with copper(II) complexes and complexes of other transition ions, particularly iron [2, 3]. In this context, Fe(II) and Cu(II) Schiff-base complexes are interesting compounds because of their capability to bind dioxygen reversibly and their catalytic activity in oxidation reactions [4].

In this study, two new Schiff bases and their Cu(II) and Fe(II) complexes were synthesized by condensation of two diamine compounds with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one and by using appropriate metal salts, respectively (Figure 1). The prepared compounds were characterized by elementel analysis, FT-IR, and NMR. In order to determine the kinetics parameters of catechol oxidase-like activity of Schiff base metal complexes, the oxidation of the catechol derivative (3,5-DTBC) was measured at 25°C by monitoring the increase of the absorption band at 390-400nm of the product catequinone (3,5-DTBQ) derivative.

3,5-DTBQ 3,5-DTBC

O

O

O

O

N N

O

O

O

O

[ML]

H3C

M

M= Cu(II) ve Fe(II)

00,5

11,5

2

300 400 500Absorbance

Wavelength (nm)

Figure 1.Schiff base metal complex

AcknowledgmentsThis study has been supported by The Scientific and Technological Research Council of Turkey

(TÜBİTAK) through project no: 113Z604


References [1] Panda, M.K.; Shaikin, M.M.; Butcher, R.J.; Gosh, P., Inorganica Chimca Acta 2011, 372(1),

145-151.[2] Sarkar, S.; Sim, A.; Kim, S.; Lee, H., Journal of Molecular Catalysis A: Chemical 215, 410, 149-

159.[3] Mal, S.K.; Mitra, M.; Biswas, B.; Kaur, G.; Bag, P.P. Reddy, C.M.; Choudhury, A.; Aliaga-Alcalde,

N.; Ghosh, R., Inorganica Chimica Acta 2015, 425, 61-66. [4] Bnowmik, P.; Das, L.K.; Chattopadhyay, S.; Ghosh, A., InorganicaChimicaActa 2015, 430, 24-

29.


Hydrothermal Synthesis and Characterization of Heterogeneous Catalysts for the Oxidation of the Thymol To Thymoquinone

Burak AY, Emel YILDIZ

Çukurova University, Department of Chemistry, Arts and Science Faculty, 01330, Adana

Some reactions of considerable commercial importance are: epoxidation of limonene to limonene oxide; and oxidation of carvacrol or thymol to thymoquinone, a compound with antitumor and hepatoprotective effects. In this vein, thymol can be oxidized to thymoquinone (Fig. 1), which has a commercial value considerably higher than that of the precursor. Since the natural sources of thymoquinone are limited to certain plants such as Nigella sativa, Callitrisarticulate, there is a growing interest in its production from other sources. It is well established that the chemical transformation of abundant and cheap natural products can make available other more valuable products [1].Thymol can be oxidized to thymoquinone only using metal catalysts. Hydrothermal synthesis is an efficient method for the preparationof heterogeneous catalysts because of advantages over other methods. [2]. In this study, we report the hydrothermal synthesis and crystalstructure of Cu(II) and Ni(II) catalysts containing pyridinedicarboxylic acid ligands. These catalysts were characterized by elemental analysis, FT-IR, TGA, ICP and single crystal X-ray diffraction techniques. The metal catalysts act asefficient heterogeneous catalysts and showed 100% selectivity on the oxidation of thymol to thymoquinone.

Figure 1. Oxidation of thymol to thymoquinone using heterogeneous catalyst.

AcknowledgementsThis work was financially supported by Çukurova University Research Fund (Project No: FBA-2016-

5543).

References[1] B. Ay, E. Yildiz, S. Jones, J. Zubieta, Inorg. Chim. Acta, 387 (2012) 15-19.[2] J. Maa, X. Huang, R. Wei, L. Zhou, W. Liu, Inorg. Chim. Acta, 362 (2009) 3440.


SUITABLE CATALYST OBTAINING FOR ALKANE OXIDATION AND ALKENE EPOXIDATION REACTIONS


Chemistry Department, K.Maraş Sütcü Imam University, 46100, K.Maraş, Turkey

Finding the ideal catalyst [1] is one of the most intriguing challenges in chemistry today. Interestingly, most often the strategy of empirical trial and error is applied still. This trial-and-error-process can be accelerated e.g. with combinatorial or high-throughput approaches or syntheses of multiple ligand derivatives. Additionally, one can study the basic principles underlying catalysis, or improve the analytical tools. In this study, we obtained the sterically hindered solid state polymer Schiff base ligands from the reaction of the N- salicylidene (2,6-di-tert-butyl-4-imino)phenol with Merrifield resin in the ethanol solution. The polymer anchored ligands were characterized by the FTIR, SEM, TGA and DTA methods. Some transition metal complexes of the polymer supported ligands were synthesized. The metal detection in the complexes was done by ICP method. The oxidation and epoxidation properties of the metal complexes were very high. SEM images of the Mn(II) complexes were given in Figure 1.

Figure 1. SEM images of the Mn(II) complexes.

References[1] J.A. Gladysz, Pure Appl. Chem. 73 (2001) 1319


POLYMER SOLID SUPPORT CATALYSTS FOR ALKANE OXIDATION

Mehmet TÜMER, Muhammet KÖSE,Ferhan TÜMER


The oxidation of the organic compounds is one of the most important cycle reactions in industrial chemistry. The immobilization of the homogeneous catalysts onto the solid supports supplies potential for enlarging the utilities of the heterogeneous catalysts to the homogeneous systems. In addition inorganic supports [1], the polymeric supports have attained care because they are inert, nontoxic, nonvolatile, insoluble, and often recyclable.In this study, we prepared three polymer-anchored Schiff base ligands and their Cu(II), Co(II) and Ni(II) transition metal complexes (Figure 1). We did alkane oxidation reactions of the metal complexes and used the cyclohexane and cyclooctane as the substrate and they show the low activity. The metal complexes have not any selectivity in the oxidation reactions. The polymer anchored Schiff base ligands and their metal complexes have high thermal stability at higher temperatures.

Figure 1. PS-L2-M(II) for cyclohexane oxidation.

References[1] B. K. Das, J. H. Clark, Chem. Commun., (2000) 605-606.


CATALYST DESIGN FOR ALKENE EPOXIDATION

Mehmet TÜMER, Muhammet KÖSE,Ferhan TÜMER


Transition metal complexes on polymer support have indicated various uses in organic synthesis [1], curing agent for epoxy resin, as catalyst, as ion exchangeretc. This technique of immobilization on an inert support have ground much care due to their simple separation from the reaction mixture arrives to operational flexibility, selectivity, efficiency, stability and ease of handling and economy in various industrial processes.In this study, the Schiff base ligands were synthesized from the reaction of the diamines 1,4-diamino butane, 1,4-diaminobenzene and trans-1,4-diaminocyclohexane with 1,4-dihydroxy benzaldehyde in the ethanol solution. The imines prepared in this way are formed in nearly quantitative yields and are of high purity.All compoundsare very stable at room temperature in the solid state.In this study, we prepared three polymer-anchored Schiff base ligands and their Cu(II), Co(II) and Ni(II) transition metal complexes. Scanning electron micrographwas also recorded to investigate the surface of the polymer-anchoring Schiff bases and their transition metal complexes. SEM images of the free PS, PS-L3-Co, PS-L3-Ni and PS-L3-Cu complexes are shown in Figure 1.

Figure 1. SEM images of the Cu(II) and Ni(II) complexes.

References[1] M. Roice, K. S. Kumar, V. N. R. Pillai, Tetrahedron, 56 (2000) 3725-3734.


New Ferrocene Based Schiff Bases Metal Complexes: Synthesis and Investigation of Catalytic Activities

Gökhan CEYHANa

aResearch and Development Centre for University-Industry-Public Relations, Kahramanmaraş Sütçü İmam University, 46100, Kahramanmaraş Turkey

Technological and economic innovations often induce changes in the chemical raw material used to produce goods organic chemicals [1].These reasons caused olefins to replace acetylene in many commercial processes different decades ago. Alkanes, however, are the least expensive and most abundant hydrocarbon resource and thus represent an important potential feedstock for the chemical industry [2]. Unfortunately, very few selective methods are available for converting alkanes into more significant products [3]. Furthermore, several desirable reactions utilizing alkanes are not thermodynamically favorable at reasonable temperatures. New Ferrocene based Schiff base metal complexes are used as a catalyst to initiate the radical oxidation of cyclohexane using molecular oxygen from the air at 150 °C and 30 bar pressure. On completion of the reaction, only 28% of CyH is converted to oxidized products and with selectivity towards Cy=O and Cy-OH. In this paper were cyclo alkane oxidation with new Ferrocene based Schiff base metal complexes investigated under microwave irradiation. The Ru(III) and Pd(II) complexes showed good catalytic activity in the oxidation of cyclohexane to desired oxidized products.

Figure 1. Catalytic oxidation of cyclohexane under microwave irradiation


References: [1] G. Ceyhan, M. Köse, V. McKee, S. Uruş, A.l Gölcü, M. Tümer, Spectrochimica Acta Part A:

Molecular and Biomolecular Spectroscopy, 382-398, (2012), 95.[2] B. Retcher, J.S. Costa, J. Tang, R. Hage, P. Gamez, J. Reedijk, J. Mol. Catal. A:Chem. 286 (2008)

1–5.[3] S. Tanase, J. Reedijk, R. Hage, G. Rothenberg, Top. Catal. 53 (2010) 1039–1044.


Oxidation of alkanes with hydrogen peroxide catalyzed by ferrocene

Gökhan CEYHANa

a Research and Development Centre for University-Industry-Public Relations, Kahramanmaraş Sütçü İmam University, 46100, Kahramanmaraş Turkey

Transition metal complexes, specially, iron derivatives, often play roles of good catalysts in the oxidation of saturated and aromatic hydrocarbons with peroxides, especially with green oxidants such as hydrogen peroxide [1,2]. In contrast, organometallic compounds, particularly iron complexes, have so far been rarely used as catalysts in oxidation processes [3].Ferrocene based Schiff base metal complexes are used as a catalyst to initiate the radical oxidation of cyclohexane andcyclooctane using molecular oxygen from the air at 185 °C and 60 bar pressure.In this paper were cyclo alkane oxidation with Ferrocene based Schiff base metal complexes investigated under microwave irradiation. The Cu(II), Co(II), Ni(II), Pd(II) and Ru(III) complexes showed catalytic activity in the oxidation of cyclohexane and cyclooctane to desired oxidized products.

Figure 1. Catalytic oxidation of cyclohexane under microwave irradiation

References: [1] I. Gryca, B. Machura, J.G. Malecki, L.S. Shul’pina, A.J.L. Pombeiro, G.B. Shul’pin,Dalton Trans.

43 (2014) 5759-5776.[2] M. Canta, D. Font, L. Gomez, X. Ribas, M. Costas, Adv. Synth. Catal. 356 (2014) 818-830.[3]G.B. Shul’pin, in: A.J.L. Pombeiro (Ed.), Advances in Organometallic Chemistry and Catalysis,

Wiley, 2014, pp. 1-13.


Transition Metal Complexes of Ligand in a Liquid Crystal Properties: Investigation of the Catalytic Activity

Gökhan Ceyhana*, Savaş Purtaşb

a Research and Development Centre for University-Industry-Public Relations, K.Maraş Sütçü İmam University, 46100, Kahramanmaraş Turkey

b K.Maraş Sutcu Imam University, Faculty of Science and Letters, Department of Chemistry, 46100, K.Maraş.

The environmentally harmful oxidants are used in the endustrial oxidation processes and there has been intensive investigation into developing oxidation processes which utilize environmentally friendly oxidants such as molecular oxygen and hydrogen peroxide [1]. However, suitable catalyst systems are required in order for these oxidants to be implemented effectively on an industrial scale. In recent years there has been an increase interest in transition metal complexes based on porphyrins, phthalocyanines and Schiff bases [2]. The metal complexes of the polymer supported Schiff base ligands are preferred in the heterogeneous catalytic systems. Inorganic and organic polymers are used as a polymer support [3]. These are polymeric materials such as the chloromethylated polystyrene(PS)-di(vinyl)benzene(DVB) [PS-DVB] resin, silanol, poly(dichlorophosphazenes), zeolite, PVC. In this paper, we obtained a complex as a single crystal and characterized by analytical and spectroscopic methods. Thermal properties of the complexes were investigated by TGA and DSC methods. The electrochemical properties of the complexes were studied in different solvents and at various scan rates. The photoluminescence properties of the complexes in different solvents and at different pH values have been investigated. Cyclo alkane oxidation with Cu(II) complexes investigated under microwave irradiation.

Figure 1.The structure of the novel copper complexes.

References: [1] C.J. Pereira, Chem. Eng. Sci. 54 (1999) 1959.[2] M.T. Hassenein, S.S. Gerges, M.A. Abdo, S.H. El-Khalafy, J. Porphyr. Phthalocyan. 9 (2005)

621.[3] D.C. Sherrington, Pure Appl. Chem. 60 (1988) 401.


Novel Gallic Esters: Its Synthesis, Structural Characterization, Photoluminescence, Electrochemical Properties And Alkene

Epoxidation

Gökhan Ceyhana*, Savaş Purtaşb

a Research and Development Centre for University-Industry-Public Relations, K.Maraş Sütçü İmam University, 46100, Kahramanmaraş Turkey

b K.Maraş Sutcu Imam University, Faculty of Science and Letters, Department of Chemistry, 46100, K.Maraş.

Epoxides are important classes of chemicals used extensively for the preparation of a variety of fine or special chemicals such as natural products, drugs, polymer materials [1]. Epoxides are highly useful intermediates for the production of a variety of important commercial products and therefore their synthesis is a subject of substantial academic and industrial interest [2]. Epoxides are well known as one of the most valuable building blocks that can be used as intermediates and precursors for chemical production. The oxidation of alkenes with aqueous hydrogen peroxide (H

2O

2) is very attractive from

the viewpoint of industrial production and synthetic organic chemistry, since aqueous H

2O

2 is cheap, environmentally clean and easy to handle, and [3]. In this paper, we

obtained a novel gallic esters as a single crystal and characterized by analytical and spectroscopic methods. Thermal properties of the gallic esters were investigated by TGA, DTA and DSC methods. The electrochemical properties of the gallic ester were studied in different solvents and at various scan rates. The luminescence properties of the gallic esters in different solvents and at different pH values have been investigated. Cyclo alkene epoxidation with gallic esters investigated under microwave irradiation.

Figure 1. Cyclohexane oxidation reaction.

References: [1] YuLin Hu, J Iran Chem Soc (2015), 12, 2179–2184[2] P. Farràs, Green Chem., (2016), 18, 255[3] Weizheng Fan, Applıed Catalysıs A-General, (2015), 506, 173-179


Catalytic activity of Schiff Base Mn(III)/Co(III) complexes on bleach catalyst

Büşra GENÇOĞLUa, Pınar Şena, Salih Zeki Yıldıza

a Sakarya University, Faculty of Arts and Sciences, Department of Chemistry, 54187, SAKARYA, TURKEY

The detergents of the next century will be routinely required to contain bleaching agents that are not only more active than those currently available but also environmentally safe and cost-effective. Hydrogen peroxide, are used as traditional bleaching agent [1]. However, it loses activity as the washing temperature decreases. In order to solved this problem, bleach activator systems such as N,N,N’,N’-tetraacetylethylenediamine (TAED) and nonanoyloxybenzene sulfonate (NOBS) have been developed and applied in many laundry detergent [2]. Bleach activators are also effective at lower temperature (at 40oC and above) due to having more oxidizing power than bare hydrogen peroxide [3].But still lower temperatures are desirable. It is generally recognized that manganese and iron complexes are less environmentally damaging reagents than other transition-metal compounds, and such complexes have received considerable attention as bleaching catalysts[4].

In this study we described new catalyst for oxygen-based bleaching as Schiff base Mn(III)/Co(III) complexes. We evaluated the performance of the catalyst in bleaching activity presence of hydrophilic and hydrophobic type of natural characteristic dyes.

References: [1] R.G. Konsler, J. Karl, E.N. Jacobsen, J. Am. Chem. Soc. 120(1998) 10780[2] G. Reinhardt, M.Loeffler, Tenside Surfact. Deterg. 1997, 34, 404.[3] C. Xu, D. Hinks, A. El-Shafei, P. Hauser, M. Li, M. Ankeny, K. Lee, Journal of Fiber

Bioengineering&Informatics2011, 4, 209.[4]M. Bösing , Bernt Krebs, B. Nestler, M. Seebach , G. Reinhardt, M. Wohlers, U. Dingerdissen,

Applied Catalysis A: General1999, 184, 273.


Catalytic Oxidation of Nitrogen Containing Compounds for Nitrogen Determination

Alper SEVİNÇ1,2*, Gürkan KARAKAŞ1, İ. Bülent ATAMER2

1 Middle East Technical University , Chemical Engineering Department, Dumlupinar Blv., 06800 Ankara, Turkey

2 Research and Development Department, Terralab A.Ş., Dumlupinar Blv., 06800 Ankara, Turkey

High temperature catalytic oxidation of nitrogen containing compounds has great importance for the analysis of environmental and industrial samples. The complete oxidation of nitrogen in different functional groups, ammonia and nitrates to NO and NO

2 is a crucial step for the determination of nitrogen in samples[1,2]. In this study, the

catalytic activities of four different catalyst samples, CuO/ Al2O

3, CuO-CeO

2 / Al

2O

3

and Pt/ Al2O

3, Fe

2O

3/ Al

2O

3 for total oxidation of nitrogen containing compounds

were analyzed. The catalyst samples were prepared to obtain a loading of 10% Cu, 3%Cu-7%Ce, 1% Pt, %5 Fe over the Al

2O

3 as a suppport by impregnation method.

Characterization of the catalyst samples was performed by X-ray powder diffraction (XRD) and BET. EDTA, urea, ammonium nitrate, ammonium sulfate, pyridine, glutamic acid were selected as model components representing various nitrogen functional groups. The experiments were performed in a quartz tubular reactor in two zone furnace and the sample first oxidized at 700-850 oC under air flow of 500 ml/min and the waste gases treated in second zone at 700oC over catalyst bed. The catalytic activities of the samples were investigated by mass spectrometry by analyzing combustion products. According to experiments results, Fe

2O

3/ Al

2O

3 and Pt/ Al

2O

3 catalysts showed good

catalytic activity for all nitrogen containing model compounds ;however, CuO/ Al2O

3,

CuO-CeO2 / Al

2O

3 were found to be poorcatalytst for the oxidation of nitrogen of

pyridine and ammonium nitrate.

References: [1]: Merriam, J., Mcdowell, W., & Currie, W. (n.d.). A High-Temperature Catalytic Oxidation

Technique for Determining Total Dissolved Nitrogen. Soil Science Society of America Journal, 1050-1050.

[2]: Chen, C., Xu, Z., Keay, P., & Zhang, S. (n.d.). Total soluble nitrogen in forest soils as determined by persulfate oxidation and by high temperature catalytic oxidation. Australian Journal of Soil Research, 515-515.


Catalytic Properties of ONO Type Salicylaldimine Copper(II) Complexes

Gökhan Ceyhana,b, Münire Sarıgüla, Muhammet Kösea, and Mukerrem Kurtoglua

a Department of Chemistry, Kahramanmaraş Sutcu Imam University, 46100, Kahramanmaraş Turkey

b Research and Development Centre for University-Industry-Public Relations, Kahramanmaraş Sütçü İmam University, 46100, Kahramanmaraş Turkey

Azo compounds are versatile molecules that find widespread applications as dyes and pigments in textile industry. They also have advanced applications in organic synthesis and high technology areas such as laser, liquid crystalline displays and ink-jet printers [1].Three azo-Schiff base copper(II) complexes were used as a catalyst to initiate the radical oxidation of cyclohexane using molecular oxygen from the air at 180 °C and 45 bar pressure.. In this paper were cyclo alkane oxidation with azo-Schiff base copper(II) complexes investigated under microwave irradiation. Catalytic activities of the copper complexes were investigated at different conditions and the results were compared with the literature data. These complexes were found to be active in the catalytic oxidation of some hydrocarbons, such as cyclohexane and cyclooctane.

Figure: The proposed structure of the new Cu(II) complexes used as catalysts.

References [1] M.Sarigul, P. Deveci , M. Kose, U. Arslan, H. Türk Dagi, M. Kurtoglu. J. Mol. Struct. 1096

(2015) 64–73


Copper Complexes with Bidentate NO Ligands as Novel Catalysts for the Homogeneous Partial Oxidation of Alkanes

Gökhan Ceyhana,b, Sevgi Kahramana, Muhammet Kösea, and Mukerrem Kurtoglua

a Department of Chemistry, Kahramanmaraş Sutcu Imam University, 46100, Kahramanmaraş Turkey

b Research and Development Centre for University-Industry-Public Relations, Kahramanmaras Sütçü İmam University, 46100, Kahramanmaraş Turkey

Azo-azomethines are known to be interesting because of theexistence of both hard nitrogen and/or oxygen donor atoms inthe backbones of these compounds, some of which have interestingphysical and chemical properties [1].The transition metalcomplexes have been widely used as a powerful tool in catalytic reactions which has an active role in developingchemical science and technology by the design new types of funtional ligands and useful new synthetic methods.Selective oxidation of hydrocarbons is an important phenomena in view of the economical and ecological use of naturalraw materials. However, catalytic oxidation of unactivated hydrocarbons remains as a challengingtopic due to the high activation energy of the C-H bond. In this work, two new azo-azomethine ligands, which were synthesised previously in our group [2], based copper complexes were synthesised and used as catalysts in the oxidation process of cyclohexaneand cyclooctane under microwave irradiation.

Figure: The proposed structure of the new Cu(II) complexes.

References [1] H. Khanmohammadi, M. Erfantalab, A. Bayat, A. Babaei, M. Sohrabi, Spectrochim. Acta A 97

(2012) 876.[2] S. Eskikanbur, K. Sayin, M. Kose, H. Zengin, V. McKee, M. Kurtoglu. J. Mol. Struct. 1094

(2015) 183–194


The comparison of catalytic activity of non-ionic and ionic Mn(III)/Co(II) Phthalocyanine complexes on bleach systems

Pınar ŞENª, Salih Zeki YILDIZªa Sakarya University, Faculty of Arts and Sciences, Department of Chemistry, 54187, SAKARYA,

TURKEY

Oxidation reactions are of great importance in the chemical industry. Hydrogen peroxide and molecular oxygen are used as potent oxidant frequently [1]. But, their activity is kinetically low under many experimental conditions. In further studies such as design and development transition metal complexes have attracted great attention due to catalyze substrate oxidation effectively by hydrogen peroxide or molecular oxygen [2]. In addition to using in organic synthesis, hydrogen peroxide based on bleach catalyst play a major role for the pulp and paper production, waste water treatment and laundry for industrial or domestic applications [3].

So far, several novel coordination compounds of salen, saltren, terpyridine-type ligands and triazole derivatives,possessing significant potential in activating hydrogen peroxide, have been synthesized and tested in bleach process[4]. Several transition metal complexes were reported for the mentioned compounds. Specifically, manganese and iron complexes are preferred as promising bleach catalyst due to environmental compatibility and toxicological point of view[5].

In this study we described new catalysts for oxygen-based bleaching as Mn(III) and Co(II) phthalocyanine compounds. We evaluated the catalytic performances of the prepared catalysts in bleaching process presence of hydrophilic and hydrophobic type of natural characteristic dyes and H

2O

2.

References: [1] G. Parshall, S.Ittel, Homogeneous Catalysis1994, Wiley[2] J.C. Terrence Acc. Chem. Res. 27 (1994) 279-285[3] J.I. Kroschwitz, M. Howe-Grant Kirk-Othmer, Encyclopedia of Chemical Technology, 4rd ed.

Wiley: New York, 1991[4] T. Wieprecht, J. Xia, U. Heinz, J. Dannacher, G. Schlingloff, Journal of Molecular Catalysis A:

Chemical, 203 (2003) 113–128.[5] M. BoÈsinga , B. Krebsa, B. Nestlerb, M. Seebachb , G. Reinhardtb , M. Wohlersc , U.

Dingerdissenc Applied Catalysis A: General, 184 (1994) 273-278.


THE CATALYTIC ACTIVITY OF NOVEL, AZO-CONTAINING SCHIFF BASES AND THEIR METAL COMPLEXES

Ayşe İNANa, Mesut İKİZa, Esin İSPİRa

a Department of Chemistry, Faculty of Science and Arts, Kahramanmaraş Sutçu Imam University, Kahramanmaraş, 46050-9, Turkey

Among the various ligand systems, Schiff base analogues have attracted great interest in recent years. Azo group show donor properties and play an important role in coordination chemistry [1]. A wide variety of cobalt(II) complexes are known to bind dioxygen more or less reversibly and are therefore frequently studied as model compounds for natural oxygen carriers and for their use in O

2 storage, as well as in

organic synthesis due to their catalytic properties under mild conditions. [2].

Because of the importance of azo-containing Schiff base compounds and in continuance of the interest in syntheses of azo-based compounds, herein syntheses and characterization of a series of azo-linked salicylidenic Schiff bases and their CoII and CuII complexes were reported and their structures were confirmed elemental analysis, IR and UV-visible spectral data.

Figure 1.

The analytical data shows that the metal to ligand ratio in the mononuclear Schiff Base complexes is 1:2. Also the oxidative C–C coupling properties of the CoII and CuII complexes have been investigated on the sterically hindered 2,6-di-tert-butylphenol (DTBP).

References: [1]. Z. Shaghaghi, Spectrochim Acta A, 131 (2014) 67-71.[2]. Tümer M, Ekinci D, Tümer F, Bulut A, Spectrochim. Acta, Part A, (2007); 67:916.


Investigation of Oxidation Reaction Pathways of Oxygenates on Au(111) Single CrystalDepending on the Behaviour of Oxygen

Mustafa Karatoka, Evgeny Vovkb,Asad A. Shaha, Emrah Ozensoya,*

a Bilkent University, Chemistry Department, 06800, Ankara, Turkeyb Boreskov Institute of Catalysis,830090, Novosibirsk, Russian Federation

Recently, it has been demonstrated that gold is very active and selective in various partial oxidation (PO) processes and oxidative coupling (OC) reactions [1,2]. However, the behaviour of oxygen species on Au(111) is still under debate [3]. In the current work, we investigated the behavior of adsorbed atomic oxygen layers on the Au(111) model catalyst surface and their reaction with probe molecules, such as CO and methanol.In addition, oxidation reaction of acetaldehyde was investigated under the most active conditions on the Au(111) surface; formation of PO and OC reaction products were demonstrated. Atomic oxygen was created on Au(111) and noticed that it’s reactivity towards CO changes depending on the temperature of the catalyst.TPD desorption profiles of adsorbed oxygen on Au(111) at different temperatures before and after CO exposure are shown in Figures 1 a and b. Figure 1c shows O1s XP spectra demonstrating the presence of three different oxygen species as a function of surface oxygen coverage. The most active surface corresponded to a low-coverage of oxygen exposed to the surface at 140 K temperature. Under these conditions, oxidation of acetaldehyde yields acetic acid and methyl acetate as a PO and OC products; respectively (Figure 1d).

Figure 1. TPD patterns of O/Au(111) prepared at (a) 460K, (b) 140K; (c) O1s XP spectrum of oxygen-covered Au(111); (d) TPRS patterns of acetaldehyde oxidation reaction on O/ Au(111)under the most reactive conditions.

References[1] B. Xu, R.J. Madix, C.M. Friend, Acc. Chem. Res., 47 (2014) 761-772.[2] X. Liu, L. He, Y. Liu, Y. Cao, Acc. Chem. Res. 47 (2014) 793-804.[3] J. Gong, C.B. Mullins, Acc. Chem. Res., 42 (2009) 1063-1073.


Effective Catalysts Derived from Carbazole for Alkene oxidation

Selma Bal

Kahramanmaras Sutcu Imam University, Faculty of Sciences and Literature, Department of Chemistry, 46100, Kahramanmaras, Turkey.

Among alkene epoxidation reactions, styrene and cyclohexene oxidation reactions captured quite high attention due to their versatile usage as strating materials in many synthetic organic reactions. Schiff base ligands and their metal complexes have been exensively used in many oxidation reactions of different organic compounds as catalysts[1,2]. With this work, Carbazole derived two novel ligands and their Cobalt (II), Manganese (II) and Nickel (II) coordination compounds have been synthesized and characterized through various spectroscopic techniques (Figure 1). Synthesized compounds have been examined for their catalytic activities in the oxidation reactions of styrene and cyclohexene.

Figure 1. Synthesized coordination compounds from Carbazole

References[1] Maiti M, Sadhukhan D, Thakurta S, Zangrando E, Pilet G, Signorella S, Bellú S, Mitra S, B

Chem Soc Jpn, 87 (2014):724-732.[2] Mavrogiorgoua A, Papastergioua M, Deligiannakis Y, Louloudi M, J Mol Catal A-Chem

393(2014):8-17.


Schiff base transition metal complexes with ceftazidime: Synthesis and Investigation of Alkane Oxidation

Ozge Erena, Harun Muslub, Gökhan Ceyhanc, Mehmet Tumera and Aysegul Golcua*

aDepartment of Chemistry, Faculty of Science and Letters, Kahramanmaras Sutcu Imam University, 46100, Kahramanmaras, Turkey.

bAfsin Vocational High School, Kahramanmaras Sutcu Imam University, 46100, Kahramanmaras, Turkey.

cK.Maraş Sutcu Imam University, ÜSKİM, 46100, K.Maraş

Ceftazidime (INN) is a third-generation cephalosporin antibiotic. Cephalosporins are the second major group of h-lactam antibiotics, they are classified into four generations. The biological activity of these antibiotics is the h-lactam ring [1]. The possible interaction that may occur between metal ions and these antibiotics is of importance as this may affect the drug absorption through the human membrane. Cyclohexane (Cy-H) oxidation into cyclohexanol (Cy-OH) and cyclohexanone (Cy=O) has a importance in industry. Over a billion tones of Cy=O and Cy-OH are produced each year and are generally used for the synthesis of Nylon-6 and Nylon-6,6 [2]. Schiff base transition metal complexes with ceftazidime are used as a catalyst to initiate the radical oxidation of cyclohexane using molecular oxygen from the air at 160 °C and 15 bar pressure. On completion of the reaction, only 19% of CyH is converted to oxidized products and with selectivity towards Cy=O and Cy-OH. Tanase has synthesized polydentate pyridine based ligand and its iron complexes [3]. These complexes were active in the catalytic oxidation of some hydrocarbons, such as cyclohexane and cyclooctane[3]. In this paper werecyclo alkane oxidation with Schiff base transition metal complexes with ceftazidime investigated under microwave irradiation. The Ru(II),Fe(III) and Ni(II) complexes investigate catalytic activity in the oxidation of cyclohexane to desired oxidized products.

References : [1] Williams DR (1971) The metals of life. Van Nostrand Reinhold, London[2] B. Retcher, J.S. Costa, J. Tang, R. Hage, P. Gamez, J. Reedijk, J. Mol. Catal. A:Chem. 286 (2008)

1–5.[3] S. Tanase, J. Reedijk, R. Hage, G. Rothenberg, Top. Catal. 53 (2010) 1039–1044.


Drug metal complexes: Synthesis and Investigation of Alkane Oxidation

Ozge Erena, Derya Kılıcaslanb , Gökhan Ceyhanc, Mehmet Tumera and Aysegul Golcua*

aDepartment of Chemistry, Faculty of Science and Letters, Kahramanmaras Sutcu Imam University, 46100, Kahramanmaras, Turkey.

bAfsin Vocational High School, Kahramanmaras Sutcu Imam University, 46100, Kahramanmaras, Turkey.

cK.Maraş Sutcu Imam University, ÜSKİM, 46100, K.Maraş

Cefotaxime (INN) is a third-generation cephalosporin antibiotic. Cephalosporins are the second major group of -lactam class of antibodies with broad spectrum of antimicrobial properties. Their antibacterial and pharmacokinetic properties have wide therapeutic use.[1]The cefotaxime drug was used for complexs formation reaction with Cd(II), Pd(II), Ru(II) and Zn(II) metal salts have been synthesized. Then, these complexes have been characterized by spectroscopic and analytical techniques. Thermal behavior of the complexes were also investigated. The electrochemical property of complexes have been investigated by cyclic voltammetry (CV).In this paper werecyclo alkane oxidation with Drug transition metal complexes with cefotaxime investigated under microwave irradiation. The Cd(II), Pd(II), Ru(II) and Zn(II) complexes investigate catalytic activity in the oxidation of cyclohexane to desired oxidized products.

References: [1] Williams DR (1971) The metals of life. Van Nostrand Reinhold, London


Synthesis and Characterization of MCM-41 Supported Ni Catalysts for Acetic Acid Steam Reforming

N. Çakıryılmaz1, H. Arbağ1, N. Oktar1, G. Doğu1, T. Doğu2

1GaziUniversity, Department of Chemical Engineering, 06570 Ankara, Turkey;2Middle East Technical University, Department of Chemical Engineering, Ankara, Turkey.

Developments in fuel cell technology opened new horizons for the production of hydrogen, which is considered as a promising clean energy carrier. Production of hydrogen from non-fossil renewable resources has been considered to have significant environmental and economical advantages. Hydrogen can be produced by steam reforming of acetic acid, which isobtained as the by-product of biomass pyrolysis. Recent research in this area is focused on the development of active and stable catalysts, to increase hydrogen yield and decrease coke and CH

4 formation [1-3]. In this study, nickel

incorporated mesoporous MCM-41 catalysts withhigh surface area were synthesized for the reforming reaction of acetic acid. The catalysts were reduced at 750oCprior to the activity tests. Catalysts were characterized by XRD, N

2 adsorption-desorption,

DRIFTS and SEM techniques. N2 Adsorption-Desorption isotherms of pure and nickel

incorporated MCM-41 catalysts were consistentwith Type IV isotherms and surface area of bare MCM-41 was found as 1213m2/g. XRD analysis of thesematerials showed characteristic peaks corresponding to MCM-41 and metallic Ni. Activity test of Ni impregnated material (10 %wt) (10Ni@MCM-41), which was performed at 750oC(with a feed stream containing AceticAcid/H

2O/Ar =1/2.5/2) gave highly promising results

to achieve high hydrogen yields.Results indicated high and stable activity in steam reforming of acetic acid with an acetic acid conversion of 100%. Coke formation was not also high over the spent catalysts.


Reference[1] Basagiannis A. C.,Verykios X.E., ‘Catalyticsteamreforming of aceticacidforhydrogenproduction’,

International Journal of HydrogenEnergy, 32(2007), 3343–3355.[2] Iwasa, N.,Yamane, T., Takei, M., Ozaki, J., Arai, M., “Hydrogenproductionbysteamreforming

of aceticacid: Comparison of conventionalsupported metal catalystsand metal-incorporatedmesoporoussmectite-likecatalysts”, International Journal of HydrogenEnergy, 35 (2010), 110-117

[3]Pant, K.K.,Mohanty, P., Agarwal, S., Dalai, A.K., “Steamreforming of aceticacidforhydrogenproductionoverbifunctionalNi-Cocatalysts”, CatalysisToday, 207 (2013), 36-43.


COMPARISON OF FRESH FCC CATALYSTS, E-CAT SAMPLES and FCC ADDITIVES FOR COMPREHENSION OF THE PROCESS

Deniz Onay Atmacaa, Melek Bardakcı Türkmena, Burcu Yüzüaka, Ayşegül Bayata, Ersen Ertaşa

aTurkish Petroleum Refineries Co., R&D Department, Körfez, Kocaeli, 41790

Catalytic cracking processes are used for producing lighter products such as LPG, gasoline, naphtha, kerosene and diesel fuels from the crude oil. Aerated catalyst flows like a liquid in fluid catalytic cracking (FCC) process for the production of gasoline from high boiling point fractions [1]. Circulating catalyst samples, named as e-cat, are taken from FCC unit. Analysis of e-cat samples reveals valuable information related with the on-going performance conditions of the process. Additives are introduced into the FCC units for both performance improvement of the unit and environmental aspects in terms of reduction of emissions such as SOx, NOx and CO.Particle size distribution (PSD), surface area, sodium and rare earth content in weight % are several important characterization properties of the fresh FCC catalysts. PSD indicates the fluidization properties of the catalyst and surface area is highly related with the activity of the catalyst. Since deactivation of the zeolite is observed due to the presence of sodium, sodium content should also be monitored. Catalytic activity and hydrothermal stability of the catalyst is attained by the rare earth content [2]. In addition to the comparison between different type of FCC catalysts and additives; fresh FCC catalysts, e-cat samples and e-cat samples after introduction of an additive areinvestigated in terms of XRD, XRF, BET, PSD and TGA analysis to understand the difference of the phases throughout the process of the FCC unit.

References[1] David S.J. Jones, Peter R. Pujado, Handbook of Petroleum Processing, Springer, 2006[1 ]Reza Sadeghbeigi, Fluid Catalytic Cracking Handbook, Gulf Professional Publishing, 2nd

Edition, 2000


Hydrogen Adsorption on M2+-LTL Zeolite Clusters (M = Be, Mg and Ca) : A Density Functional Theory Study

Mehmet Ferdi FELLAHa

a Bursa Technical University, Chemical Engineering Department, Bursa, TURKEY

Since the fossil hydrocarbon resources have been becoming limited, the concept of using hydrogen as a future energy vector has been important for the last three decades. Large scale and safe hydrogen storage should be developed [1]. There are several hydrogen storage methods such as pressurized, cryogenically cooled, vessels containing an adequate adsorbing material. Among adsorbents for hydrogen adsorption, active carbon, zeolites, and several metal alloys are most significant candidates [2]. The aim of this study is to investigate the activity of [M]2+ sites in LTL (Linde Type L) zeolite (where M = Be, Mg and Ca) for the hydrogen adsorption. All calculations in this study were based on Density Functional Theory (DFT) [3] as implemented in the Gaussian 09 software [4]. The hydrogen adsorption capacities of M2+-LTL clusters have been analyzed by using B3LYPmethod [5,6] with 6-31G(d,p) basis set. Since DFT calculations on cluster or periodic zeolite models generally predict very similar reactivity trends [7]. The 24T LTL cluster was used. Two Al atoms were placed in T8 cycle of the framework. The 24T LTL cluster was modeled as [Si

22Al

2O

64H

32]2-. [M]2+ sites where M = Be, Mg and

Ca have been used to obtain a neutral cluster. Metal atoms are only located on oxygen atoms of the T8 structure. The dangling bonds of the terminal silicon atoms were terminated with H atoms. All atoms of the cluster (except terminating H atoms) and the adsorbing molecules were kept relaxed. The optimized geometries for the clusters were obtained with neutral charge and singlet spin multiplicity. In order to determine the hydrogen adsorption energy on metal exchanged LTL clusters, H

2 molecule was

adsorbed on metal site of LTL clusters by Equilibrium Geometry (EG) calculations. H2

adsorption energy values were computed as -3.1, -28.8 and -11.8 kJ/mol for Be-, Mg- and Ca-LTL clusters.

(This work has been supported by Research Fund of the Bursa Technical University. Project Number: 2015-01-005)

References[1] A.A. Strub, G. Imarisio, Hydrogen as an Energy Vector, D. Reidel, Dordrecht, (1980)[2] http://www1.eere.energy.gov/hydrogenandfuelcells/storage [3] W. Kohn, L. Sham, J. Phys. Rev. 140 (1965) A1133-A1138.[4] M. J. Frisch et al. Gaussian 09; Gaussian, Inc.: Wallingford, CT, (2009).[5] A. D. Becke, Phys. Rev. B 38 (1988) 3098-3100.[6] C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 37 (1988) 785-789.[7] M. F. Fellah, J. Phys. Chem. C 115 (2011) 1940-1951.


Investigation of Surface Acidity of Metal/Bimetal Modified Zeolite Catalysts using Pyridine Probe Molecule by FT-IR

Hülya MADENCİOĞLU and Ali KARADUMAN

Ankara University Faculty of Engineering, Dept. of Chemical Engineering 06100 Tandoğan, Ankara - TURKEY

Nowadays using of synthetic zeolites increases due to their properties as high surface area, large pore sizes, high adsorption capacities and replaceable active sites. Otherwise, zeolites contain aluminum, silicium and oxygen in the three-dimensional structure of different properties can be prepared by making changes such as dealumination[1].

Catalytic activities of zeolites are associated with acid sites where in surfaces directly. Therefore, in the zeolite for use as catalyst, acidity is significant[2]. In literature researches, there are two types as Lewis and Bronsted acidity[3]. In the characterization process of the acid sites, a wide number of techniques are used, such as: titration, temperature programmed desorption and the adsorption of basic probe molecules. In the present work, pyridine as a probe molecule was added over the catalyst and the location and amount of pyridine which connected to acid sites is determinated by FT-IR[4].

In this paper, modified zeolites were prepared with MCM-41, Y, Beta and ZSM-5 zeolites with metal (Cu, Ni, Co, La, Zr, Pd, Rb) and bimetal(Cu-Zr, Ni-Co) by impregnation method. Metal/ bimetal modified zeolites were mixed at a certain rate with KBr and FT-IR spectra was taken. When pyridine was used, Bronsted acidity of characteristic peaks was around 1540- 1640 cm-1 and Lewis acidity of characteristic peaks was around 1450- 1620 cm-1. Obtained results was evaluated with these information. There was no significant difference observed between pure and metal/ bimetal modified MCM-41, Y, Beta and ZSM-5 zeolite catalyst. According to acidity tests, the highest Lewis acidity peak is observed with pure MCM-41. MCM-41 and Y zeolite catalyst impregnated with metal were observed to reduce peak intensities. There was found different result from others for Beta zeolites catalyst, acid peaks was reached highest value in Ni-Co/ Beta catalyst. In ZSM-5 zeolite catalysts, characteristic peaks was increased with pyridine which was added the structure.

References:[1] Sadowska, K., Gora-Marek, K., Datka, J., Vibrational Spectroscopy 63 (2012) 418- 425.[2] Jin, F., Li, Y., Catalysis Today 145 (2009) 101-107.[3] Silva, M., Silva, F., Claudio, A., Tellez, S., SpectrochimicaActa Part A 58 (2002) 3159- 3166.[4] Meloni,D., Laforge, S., Martin, D., Guisnet, M., Rombi, E., Solinas, V., Applied Catalyst A:

General 215 (2001) 55-66.


Synthesis and Characterization of CMK-3 and Activated Carbon Based Catalysts

Gülce ÇAKMANa , Nahide NARİNa, Feza GEYİKÇİa

aOndokuzMayis University, Faculty of Engineering, Department of Chemical Engineering, 55139, Samsun

Carbons can be used in many areas. One of such areas is H2/O

2 PEM fuel cells in which

they can be used as a catalyst support. The carbon based catalysts can be used anode and cathode reactions in H

2/O

2 PEM fuel cells. Because ofoxygen reduction reaction

isslow, the catalysts will be used at cathode side to accelerate.The purpose of this study is to improve the catalyst properties in which used in our previous study [1]. Some of important properties of carbonare having high BET surface area, pore dispersion, pore. In this study, CMK-3 and activated carbon will be produced. CMK-3 carbon synthesis route is first started by silica (SBA-15) production. For this purpose, SBA-15 will be synthesized and will be used as template for carbon production. The second catalyst support will be produced from biomass via pyrolysis. Since biomass is cheap and eco-friendly, it was preferred.Rapid and simple synthesis route of biomass based activated carbon is widely use for various catalytic applications.

After carbon productions, metal or bimetallic (such as Ni, Pd, Pt, etc.) will be covered to carbons by using microwave method for different power. The effect of power is investigated for metal distribution on carbon surface. Structural characterizations of the carbon support and catalyst will be analyzedby using SEM, N

2 adsorption, XRD and

TGA analysis. Synthesis and characterization results of these materials will be presented.

References[1] Fıçıcılar, B., Çakman, G., Narin, N., Geyikçi, F., 2015, CMK-3 carbon based

electrocatalysts for use in regenerative fuel cells, Porous and Powder Materials Symposium and Exibition, İzmir, Türkiye, 15-18 Eylül.


IMPACT OF HYDROCRACKING CATALYST CHARACTERISTICS ON THE PERFORMANCE OF HYDROCRACKING UNIT

Melek Bardakcı Türkmena, Burcu Yüzüaka, Ayşegül Bayata, Deniz Onay Atmacaa, Ersen Ertaşa

aTurkish Petroleum Refineries Co., R&D Department, Körfez, Kocaeli, 41790

Hydrocracking is a refining technology which is used for the conversion of a variety of feedstocks to a range of products by adding hydrogen, removing impurities in the presence of catalyst. Hydrocracking feeds, with higher molecular weights and lower hydrogen/carbon ratios can range from heavy vacuum gas oils and coker gas oils to atmospheric oils where products, having a lower molecular weight with higher hydrogen content and a lower yield of coke, usually range from heavy diesel to light naphtha [1, 2]. Catalysts for heavy oil hydrocracking require optimum catalyst characteristics to process heavy molecules that presents in VGO type feedstock in order to obtain high middle distillate yield and conversion. This study covers the investigation of the impact of hydrocracking catalysts characteristics on the performance of commercial hydrocracking unit. Five different unit performance data have been gathered which belong to four different catalyst systems. Unit performance data include operation parameters, middle distillate selectivity, conversion, feed properties and diesel features. The catalysts were characterized by number of techniques and measurements, such as BET surface area, pore volume, pore size, XRD, XRF, TPD acidity and TGA thermal stability. It has been found that the catalyst system withhigh porosity,strong acidic function and low silica/alumina ratio delivers outstanding feed conversion and middle distillate selectivity performance.

References(1)Speight J. G. and Özüm B., Petroleum Refining Process, Marcel Dekker Inc., 2002, pp. 485-499 (2)David, S.J. Jones and Peter R. Pujado, Handbook of Petroleum Processing, Springer, 2006, pp

287-300, 308-306


AMMONIA DECOMPOSITION REACTION OVER ZEOLITE Y SUPPORTED IRON CATALYSTS: EFFECT OF DEALUMINATION

Yeliz DURAK-ÇETİNa,c, Şerife SARIOĞLANb, Alper SARIOĞLANa,Hasancan OKUTANc

aTÜBİTAK Marmara Araştırma Merkezi, Enerji Enstitüsü, P.K.21, 41470 Gebze, KocaelibTÜBİTAK Marmara Araştırma Merkezi, Kimyasal Teknoloji Enstitüsü, P.K.21, 41470 Gebze,

KocaelicKimya Metalurji Fakültesi, Kimya Mühendisliği Bölümü, İstanbul Teknik Üniversitesi, 34469

Maslak, Istanbul

Gasification, is a thermochemical conversion technology applied for the production of synthetic fuels and chemicals from coal and biomass. A syngas containing H

2 and CO is

released as a result of gasification reaction. Synthetic fuels and chemicals are produced from syngas through the Fischer-Tropsch (F-T) method. Nitrogenous (NH

3, HCN) and

sulfurous (H2S, COS) pollutants are formed in ppm level depending upon the content of

the gasified solid fuel and lead to the poisoning of the F-T catalysts. Therefore, it is a must to reduce the levels of these pollutants below 1 ppmv in syngas [1]. NH

3 concentrations

can be reached up to 4000 ppmv in syngas as a function of the nitrogen content of the solid fuel [2]. NH

3 removal can be achieved via three different ways, namely scrubbing,

selective oxidation and catalytic decomposition [3]. NH3 decomposition reaction is a

most promising way of NH3 abatement since it gives the H

2 generation opportunity. In

this study, zeolite supported catalysts has been prepared to have an iron (Fe) content of 10% via wet impregnation method, characterized and tested. HY zeolites with two different SiO

2 to Al

2O

3 ratios of 5.2 and 80 and dealuminated forms of HY (5.2) zeolite at

two different hydrothermal dealumination temperature (350°C and 750°C) were used. Catalytic experiments were carried out with H

2-N

2 gas mixtures containing 800 ppm

NH3 at 700°C and 800°C. Catalyst samples before and after the tests were characterized

with the methods such as temperature programmed reduction (TPR), SEM, N2 isotherm

and XRD. It was shown that there is a certain relationship between aluminum content of the zeolite and their activity. The possible formation of iron aluminate like clusters at the reaction temperature was evaluated as one of the reason for the observed poor activity. It was believed that the aluminum content of the zeolite was determinative in the size and dispersion of active iron clusters.

References[1] Jin Hu, Fei Yu, Yongwu Lu, Catalysts (2012) 303-326[2]J. Zeisler, M. Kleinhappl, H. Hofbauer, http://bioenergy2020.eu/app/webroot/files/file/Download/ICPS10_paper_Zeisler_final.pdf[3] Yeliz Durak-Çetin, Alper Sarıoğlan, Şerife Sarıoğlan, Hasancan Okutan, Reac. Kinet. Mech. Cat.,

(2016)


Palladium (II) Schiff Base Complexes: Precursor for the Deposition onto the mesoporous SBA-15 in scCO2 Media

Asım Eğitmena, Bilgehan Güzela

a Çukurova University, Faculty of Science and Letters, Chemistry Department, 01330 Adana, TURKEY

Deposition of metals ( Pd,Cu, Ni, Rh, etc. ) on different solid support materials is very important due to the numerous applications of its composite materials. For catalytic applications, palladium is the most studied metal due to its versatility. Supported Pd catalysts are used in reduction and oxidation reactions, hydrogenation, hydrocracking, carbonylation and other carbon–carbon coupling reactions [1-2].

In this study, Schiff base ligands were synthesized condensation of 2-fluoro-5-trifluoromethyl aniline with 2-hydroxy- 4-methyl benzaldehyde and 2-hydroxy- 5-methyl benzaldehyde. The synthesized schiff bases and their palladium complexes characterized by elemental analyses, FT-IR, 1H NMR and 13C NMR. In FT-IR spectrum of ligands specific peaks observed at O-H 3300-3400 C-H(Ar) 3005-3060, C=N 1640-1680, C-F 1190-1240. Disappearances of O-H peaks at FT-IR spectrum of Pd complexes were showed the formation of metal complexes and azomethine group shifted to the lower wavenumbers, 1590-1602 cm-1 in all the complexes suggesting the coordination of the azomethine nitrogen to the metal centers. This is further substantiated by the presence of a new band around 450cm-1. The synthesized Palladium complexes were used as precursor for scCO

2 deposition method and characterized by XRD, TEM, SEM and XPS.

The resulting Pd nanoparticles were used as catalyst for Suzuki coupling reaction over phenyl boronic acid and bromobenzene.

Acknowledges We would like to thank TUBITAK for financial support (214Z097).

References: [1] P. Ncube, T. Hlabathe, R. Meijboom, “Palladium Nanoparticles Supported on Mesoporous Silica

as Efficient and Recyclable Heterogenous Nanocatalysts for the Suzuki C–C Coupling Reaction”, J. Clust Sci 26 (2015) 1873–1888.

[2] C. Erkey, “Prepation of metallic supported nanoparticles and films using supercritical fluid deposition”, J. of Supercritical Fluids, 47 (2009) 517–522.


Synthesis and Characterization of SBA15 Mesoporous Materials Functionalized with Boron Metal

Taner Tuncera, Gizem Akbıyıka, Tuğba Candaşb,Alime Çıtaka

a Eskişehir Osmangazi University, Department of Chemical Engineering, 26480, Eskişehir.b Bilecik Seyh Edebali University, Chemical and Process Engineering Department, Bilecik.

In a typical synthesis of B-SBA-15 samples which is easily recyclable catalysts has received increasing attention. Usage of mesoporous materials having adjustable pore size distribution with a high surface area as catalysts in various reactions is quite common. As known, the supporting with various metals and chemicals of catalysts affects the surface activity of the catalyst, thus the yield of the reaction changes. Mesoporous silica materials (SBAn) due to the large BET surface areas have the better adsorption properties and provide surface properties, such as acidity and alkalinity can be able to functionalize with organic groups. Functionalization with metals of mesoporous materials is a method which is frequently encountered in the literature. Metal loaded catalysts are used in almost all areas of industry. According to the other mesoporous materials, SBA15 stands out in terms of larger pore sizes, hydrothermal stability and having a thicker wall structure. SBA15 which is commonly used in industrial separation, adsorption, catalysis, sensor, the reactions of solution and gas and in many areas is to be mainly produced by combining certain proportions of polymer (P123) and silica (TEOS)[1]. In the literature review, it was found that mesoporous materials supported boron (B) affect the surface properties. However, boron-loaded SBA15 is less frequently examined in studies and this also shows that research should be continued over this subject. In addition to this, considering boron reserves of our country, the synthesis of the catalyst material which is the main subject of study has been diversified.

In this study, mesoporous SBA-15 materials (B-SBA-15) were synthesized with B content (Si/B molar ratio 10) by direct hdyrothermal procedure and characterized using BET, SEM, FT-IR and XRD analysis. According to data obtained from analysis results, all of the samples have characteristic structure of SBA15.

References: [1] R. V. Grieken,J.M., Escola,J., Moreno,R., Rodríguez,Chemical Engineering Journal, 155 (2009)

442–450.


Determination of ΔH°, ΔS° and ΔG° valuesof B-SBA15 MesoporousMaterials Using InverseGasCromatographyTechnique

Sercan Koça, Tuğçe Günera,AlimeÇıtaka

a Eskişehir Osmangazi University, Department of Chemical Engineering, 26480, Eskişehir.

According to the other mesoporous materialsSBA-15 stands out in terms of larger pore sizes, hydrothermal stability and having a thicker wall structure. Recently, for the production of certain chemicals harm less to the environment, which is easily recyclable catalysts has receive dincreasingattention. Usage of mesoporous material shaving adjustable pore size distribution with a high surface area as catalysts in various reactions is quite common. SBA-15 which is commonly used in industrial separation, adsorption, catalysis, sensor, the reactions of solution and gas and in many areas is to be mainly produced by combining certain proportions of polymer (P123) and silica (TEOS). Metal loaded catalysts are used in almost all areas of industry. In the literature review, it is found that mesoporous materials supported boron (B) affect the surface properties.

In this study, B-SBA 15 (nSi / nB = 10) synthesized by hydrothermal synthesis method was used.The inverse gas chromatography (IGC) technique was used in order to determine the adsorption thermodynamic parameters of the sample.B-SBA-15 sample was used as filler for the column of the gas chromatography device and was determined adsorption thermodynamic parameters of unknown properties of B-SBA-15 sample using probe gas molecules with known properties. According to data obtained from experimental results, ΔH°, ΔS° and ΔG° values were calculated for all used as a filler B-SBA-15 sample.

References:[1] Aktaş Ö., Development Of SBA-15 And MCF Supported Catalysts For Selective Oxidation

Reaction Of Propane To Propylene, M.Sc. Thesis, Institute Of Science And Technology,Gazi University, Ankara, 2008.


Single Step Synthesis of HPA loaded Al-PILCs

Suna BALCIa, M.Candan KARAEYVAZa, Gulce ACILa, Funda TURGUT BASOGLUa

a Gazi University,Engineering Faculty, Maltepe, 06570,ANKARA.

Clay minerals althoughtheir high acidic properties, have restrictions on applications as catalysts and catalyst support because of small pore size and lack of hydrothermal stability. Pillaring is one of the effective method used in order to eliminate these restrictions. By the incorporating of bulky pillars into the clay layers, micro-meso porous pillared intercalated clay (PILC) with functional surface groups can be obtained.Al Keggin structure has been used commonly as apillaring agent due toits known chemistry, thermal stability and acidic properties [1]. Heteropoly acids (HPA) posses high acidic and redox properties, but they show negative effects such as low surface area and high solubility in polar mediaon their catalytic applications and these disadvantages can be eliminated by loading HPAs on porous support [2].

Synthesis of HPA/Al-PILC structure was achieved withthe advantage of similar Keggin geometry of both Al Keggin cationand HPAanion, using Texas montmorillonite (STx-1) as host clay. This work which was the first one in the literature was planned by considering the structural improvements which might be caused by the synergy between cation and anion.Synthesis of Al-PILC was achieved by using AlCl

3 salt, keeping base/metal

(OH/Al) and Al/gram clay ratiosat2.4 and 3.0, respectively. Single step syntheses of HPA/Al-PILCs were performed by using silicatungstic acid with W/Al ratios of 0.25/1 and 1/1 followed by subsequent calcination at 300 °C. XRD results showed that, pillaring by aluminum resulted in increase in basal spacing value of clay from 1.54nm to 1.89nm with no crystal deformation. In the presence of HPA, higher basal spacing values were obtainedcompared to Al-PILC.Nitrogen adsortion isotherms of all PILCs reflected Type IV isotherm of the IUPAC classification. BET surface area value of Al-PILC was mesured as 245 m2/g and small decrease in this value occurred at low HPA loading. Increase of acid loading quantity caused around 40 % decrease in BET surface area.

References[1] Adams J. M., McCabe R. W., “Handbook of Clay Science”, Developments in Clay Science, 1,

541-581.[2] Corma A., “Solid Acid Catalysts”, Current Opinion in Solid State & Mater. Sci., 2, 63-75.


Zeolite Catalysis for Bio-oil Upgrading via Esterification

Ayşenur YEŞİLYURTª, Ayşe Gül TÜREª, H. Levent HOŞGÜNª

ªBursa Technical University,Department of Chemical Engineering, 16190, Bursa.

There is a need for alternative fuel sources due to a decrease in oil reserves. One promising method is conversion of biomass into bio-oil [1]. The chemical composition of bio-oil obtained from pyrolysis consists of different compounds such as alcohols, organic acids, ethers, esters, aldehydes, ketones, phenols, etc. It is necessary to upgrade the bio-oil because of the problems caused by these chemicals. [2] There are numerous methods for obtained upgrading bio-oil. Among these methods, esterification reaction with zeolite catalysis is widely used [3-4].

In this study, sulphuric acid modified clinoptilolite and sepiolite samples are used as catalyst and esterification reaction of acetic acid with ethyl alcohol is selected as model reaction for bio-oil upgrading. Clinoptilolite samples taken from Gördes, Manisa-TURKEY and sepiolite samples taken from Eskisehir-TURKEY. Both zeolites calcined at 200 °C and 850 °C. Then, all zeolite samples are modified with sulphuric acid. Esterification reaction of acetic acid with ethyl alcohol was carried out under 65°C temperature, 500 rpm stirring speed and 1:1 molar ratio of reactants conditions. All zeolites samples were characterized by N

2 adsorption/desorption and XRD.

The results showed that esterification reaction efficiency of sulphuric acid modified clinoptilolite and sepiolite higher than unmodified clinoptilolite and sepiolite. On the other hand, calcination also increased the conversion of acetic acid. The highest conversion of acetic acid was obtained with 200 °C calcined sulphuric acid modified sepiolite as 42.2%.

References: [1] P.M. Mortensen, J.-D. Grunwaldt, P.A. Jensen, K.G. Knudsen, A.D. Jensen, A review of catalytic

upgrading of bio-oil to engine fuels, Applied Catalysis A: General, 407, 1–2, 2011, 1–19.[2] H.B. Goyal, Diptendu Seal, R.C. Saxena, Bio-fuels from thermochemical conversion of renewable

resources: A review, Renewable and Sustainable Energy Reviews, 12, 2, 2008, 504–517.[3] Liu, Y., Li, Z., Leahy, J. J., Kwapinski, W., Catalytically Upgrading Bio-oil via Esterification,

Energy Fuels, 2015, 29 (6), 3691–3698.[4] Ciddor, L., Bennett, J. A., Hunns, J. A., Wilson, K., Lee, A. F., Catalytic upgrading of bio-oils by

esterification, Journal of Chemical Technology and Biotechnology, 90, 5, 780–795, 2015

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