journal of catalyst & catalysis (vol1, issue1)

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STM JOURNALS

1. A One-Step Selective Oxidation of Benzene to Phenol over CuCr O Spinel Nanoparticles Catalyst 2 4

with Air as Oxidant Shankha Shubhra Acharyya, Shilpi Ghosh, Rajaram Bal 1

2. In Situ Synthesized Cu(OH) -Al O : A Novel and Highly Efficient Nano-Catalyst System for One pot 2 2 3

Synthesis of N-Substituted Triazole at Room Temperature Ravi Kant Shukla, Yogesh Somasundar, Radha Sawana, Babita Baruwati 8

3. Alcohol Oxidation in Ionic Liquids Catalysed by Recyclable Platinum Nanoparticles: A Green ApproachDeb Kumar Mukherjee, Arijit Mondal, Amit Das 15

4. H Production by Methanol Steam Reforming over Copper Impregnated Anodized Aluminum 2

Oxide (AAO)M. Jhansi L. Kishore, Dong Hyun Kim 23

5. Ru(III)-Catalyzed Oxidative Cleavage of Ritodrine Hydrochloride: A Kinetic and Mechanistic StudyPuttaswamy, S. Dakshayani, A. S. Manjunatha 29

6. Synthesis of Zeolite Y-Encapsulated Copper(II) Complexes with Aminobenzonitriles and Carbonitriles by Flexible Ligand MethodPoonam Ghansiala 41

7. Synthesis, Structural Studies and Catalytic activity of Copper(II) Complex Supported by N, N′-bis (2-Hydroxy-3-Methoxybenzaldehyde) 4-Methylbenzene-1, 2-DiamineAlekha Kumar Sutar, Yasobanta Das, Sasmita Pattnaik, Anita Routaray, Nibedita Nath, Prasanta Rath, Tungabidya Maharana 53

ContentsJournal of Catalyst & Catalysis

JoCC (2014) 1-7 © STM Journals 2014. All Rights Reserved Page 1

Journal of Catalyst and Catalysis Volume 1, Issue 1

www.stmjournals.com

A One-Step Selective Oxidation of Benzene to Phenol

over CuCr2O4 Spinel Nanoparticles Catalyst

with Air as Oxidant

Shankha Shubhra Acharyya, Shilpi Ghosh, Rajaram Bal* Catalyst Conversion & Process Division, CSIR-Indian Institute of Petroleum, Dehradun, India

Abstract CuCr2O4 spinel nanoparticles catalyst was prepared by hydrothermal synthesis method in presence of the cationic surfactant, cetyltrimethylammonium bromide and hydrazine.

Detailed characterization of the material was carried out by XRD, BET, ICP-AES, SEM and TEM. XRD revealed the exclusive formation of CuCr2O4 spinel phase and TEM

showed the formation of 30–50 nm particle size. The catalyst was highly active for

selective oxidation of benzene to phenol with air as oxidant. Influence of reaction parameters were investigated in detail. The advantages of the reaction lie behind its

simplicity, low-cost set up and less time consumption.

Keywords: CuCr2O4 spinel, selective hydroxylation, benzene, phenol, air

*Author for Correspondence E-mail: [email protected]

INTRODUCTION The Direct functionalization of C–H bonds has

been developed as a powerful strategy to form

new chemical bonds [1–3]. Among them,

transition-metal-catalyzed hydroxylation of C

has received considerable attention because of

the industrially important alcohol or phenol

products [4–6]. Hydroxylation of benzene is

one of the most important and economically

attractive reactions in industry as phenol is an

important intermediate in the production of

phenolic resins, nylon, polycarbonate resins as

well as used as antioxidants and stabilizers.

Currently, phenol is produced in industry

through the so-called cumene process in which

cumene (i.e., isopropyl benzene) is converted

to phenol via a multi-step peroxidation

reaction. First of all, such reaction requires a

large amount of added reagents such as

aluminum chloride or phosphoric acid and a

radical initiator. In addition to the problem of

disposal of large amounts of waste, this

process also employs the conditions that are

corrosive to the production equipment [7].

Furthermore, because an equimolar acetone is

produced concomitantly as the byproduct, the

cumene route to phenol has lower overall

efficiency than it would be without the

byproduct. The economical efficiency of the

cumene process is strongly dependent on the

market price of acetone. Therefore, many

efforts are in progress for the development of a

new route towards phenol synthesis by a one

step process through the direct oxidation of

benzene. Although there have been several

reports using different oxidizing agents like

N2O [8], H2O2 [9–11], NH3+ O2 [12], air+CO

[13], molecular oxygen [7,14,15] etc. but most

of the cases phenol yield is very low because

phenol is more reactive toward oxidation than

benzene, over oxidation products are usually

formed [16],

and rapid deactivation of the

catalyst by coke deposition during gas phase

reaction [17]. In the light of the green

chemistry, molecular oxygen is regarded as an

ideal oxidant because of its natural,

inexpensive, and environmental friendly

characteristics [18–20]. But activating C–H

bond and thereafter, reaction with molecular

oxygen is not an easy task [15], because C–H

bonds are thermodynamically strong and

kinetically inert [21,22] On the other hand, O2

in the triplet state is kinetically hindered to

undergo formation of highly reactive oxygen

radicals, hydroxyl radicals, hydroperoxides, or

peroxides. Selective oxidations can convert

relatively cheap hydrocarbons into valuable

oxyfunctionalized products as feedstock for

Selective Oxidation of Benzene to Phenol using Air Acharyya et al. __________________________________________________________________________________________


the chemical and pharmaceutical industries.

Therefore, the catalytic aerobic C–H oxidation

is one of the “dream reactions” from both a

laboratory and industrial perspective [15]. The

main challenges of selective functionalization

towards versatile organic building blocks

when employing molecular oxygen are: a)

activation of the C–H bond, b) activation of

the O2 molecule and c) control of selectivity of

the desired product. Although there are several

reports on direct oxidation of benzene to

phenol using molecular O2 as oxidant using

Cu-containing catalysts, yet, self-assembled

architectures (of catalyst) with designed

chemical components and tunable morphology

still remains a challenge in the field of

catalysis.

Copper chromium mixed oxides with a spinel

structure had been recognized as an important

class of bi- metallic oxides that act as a

versatile catalyst [23–25]. Copper chromium

mixed oxides can be prepared by a variety of

synthetic methods, involving the reduction of

Cu-Cr oxide prepared by Adkins’ route [26],

template method [27],

citric acid complex

method [28], sol-gel

method [29] etc. Among

these methods, the sol-gel process using metal

alkoxide shows promising potential for the

synthesis of mixed oxides, owing to its high

purity, good chemical homogeneity and low

calcinations temperature [29].

The major disadvantages of using the metal

alkoxides based sol-gel process are due to its

moisture sensitive nature and the

unavailability of suitable commercial

precursors especially for mixed metal oxides.

The sol-gel synthesis of mixed metal oxides

from alkoxide mixture usually suffers from the

different hydrolysis susceptibilities of the

individual components and the benefits of

improved homogeneity can be lost during the

hydrolysis of the alkoxides, which may

ultimately lead to component segregation and

mixed phases in the final materials. These

preparation methods are not good enough

largely because many of their metal alkoxides

are expensive, and still others are sensitive to

moisture, heat, and light making their use and

long-term storage difficult. In addition, some

metal alkoxide are not commercially available

or are difficult to obtain, thus precluding

detailed studies on the preparation and

application [30].

Here we report the preparation of CuCr2O4

spinel nanoparticles with size 30–50 nm,

promoted by cationic surfactant CTAB and

hydrazine. CuCr2O4 spinels are highly

effective due to the tetragonally distorted

normal structure, where higher higher active

Cu2+

possesses tetrahedral coordination.

Furthermore, spinel (which are considered to

be of single phase) nanoparticles prepared in

our process are devoid of leaching properties,

when they are employed as catalysts. So they

can be used several times, without hindrance

of the stable spinel phase.

The use of oxygen as oxidant is known in

literature and the references are already been

cited. But in maximum cases, the catalyst

cannot be reused due to the deposition of

carbon particles (coke) on the catalyst, or

much higher temperature is being employed to

activate molecular oxygen.

In our case, CuCr2O4 spinel nanoparticles

catalyst is highly effective to activate oxygen

(oxidant) at considerable lower temperature

and can be reused several times without any

significant activity loss. Furthermore, in our

case air is used as oxidant, which is attractive

from both environmental and industrial

viewpoint. So far, there is no report on

benzene oxidation using air (the greenest

oxidant) to date.

Here, we also report a benzene conversion of

38% with a phenol selectivity of 22% over the

so prepared CuCr2O4 spinel nanoparticles

catalyst using air (molecular O2) as oxidant.

To the best of our knowledge, there is no

report for benzene hydroxylation reaction with

air (the greenest oxidant) as oxidant, with

CuCr2O4 spinel nanoparticles catalyst (~35 nm

size).

MATERIALS AND METHODS Materials

Cu(NO3)2.3H2O, Cr(NO3)3.9H2O, cetyltri-

methylammonium bromide and hydrazine

(80% aqueous solution), benzene were bought

from Sigma Aldrich. All chemicals were of

analytical grade and were used without further

purification.

Journal of Catalyst and Catalysis

Volume 1, Issue 1

__________________________________________________________________________________________


Preparation of the Catalyst

The CuCr2O4 spinel nanoparticles were

prepared by modifying our own preparation

method taking nitrate precursors of copper and

chromium [31]. In a typical synthesis, an

aqueous solution of 4.5 g Cu(NO3)2.3H2O was

added with vigorous stirring to 14.4 g

Cr(NO3)3.9H2O (from Sigma Aldrich)

dissolved in 65 g deionized water. By gradual

addition of few drop ammonia solution, the pH

of the solution was made 8. An ethanolic

solution (10%) of 6 g CTAB was added drop

wise to the reaction mixture.

After that few drops of hydrazine hydrate was

added dropwise to it to get a creamy fluffy

solution. The reagents were added maintaining

the molar ratio: Cu: Cr: CTAB: H2O:

hydrazine = 1: 2: 0.9: 200:1. After stirring, the

so obtained solution was hydrothermally

treated at 180°C for 24 h in a Teflon-lined

autoclave vessel under autogenous pressure.

The solid product was collected by means of

centrifugation at 18,000 rpm and dried at

120°C, for 10 h, followed by calcination at

750°C for 6 h in air. For the reusability test,

the catalyst was repeatedly washed with

acetonitrile and acetone and dried overnight at

130°C and used as such, without regeneration.

Characterization Techniques Powder X-ray diffraction patterns were

collected on a Bruker D8 advance X-ray

diffractometer fitted with a Lynx eye high-

speed strip detector and a Cu K radiation

source. Diffraction patterns in the 5–80°

region were recorded at a rate of 0.5 degrees

(2q) per minute. Scanning electron microscopy

(SEM) images were taken on a FEI Quanta

200 F, using tungsten filament doped with

lanthanum hexaboride (LaB6) as an X-ray

source, fitted with an ETD detector with high

vacuum mode using secondary electrons and

an acceleration tension of 10 or 30 kV.

Samples were analyzed by spreading them on

a carbon tape. Energy dispersive X-ray

spectroscopy (EDX) was used in connection

with SEM for the elemental analysis. The

elemental mapping was also collected with the

same spectrophotometer. Transmission

Electron Microscopy images (TEM) were

collected using a JEOL JEM 2100 microscope,

and samples were prepared by mounting an

ethanol-dispersed sample on a lacey carbon

Formvar coated Cu grid. Chemical analyses of

the metallic constituents were carried out by

Inductively Coupled Plasma Atomic Emission

Spectrometer; model: PS 3000 uv, (DRE),

Leeman Labs, Inc, (USA).

Catalytic Evaluation

The vapour phase benzene hydroxylation

reaction was performed in a 100 ml stainless

steel autoclave reactor (batch reactor)

(Autoclave Engineers, a division of snaptite,

INC., USA) with mechanical stirrer and an

electric temperature controller, operated under

pressure (maintained by air) of 30 bar at

350°C and 750 rpm for 6 h. Prior to reaction,

the obtained Cu-Cr oxides were activated by

Ar with a flow rate of 100 cm/min at 300°C

for 2 h in a fluidized bed reactor. 15 ml

benzene, and about 7 wt % catalyst (based on

benzene) were charged into the autoclave

under Air atmosphere. The reactor was sealed

and pressurized to the required air pressure,

and then heated to the desired temperature.

After the reaction, the autoclave was cooled to

ambient temperature, and then brought to

atmospheric pressure. It was then opened to

allow the reaction mass to be discharged and

centrifuged for removal of catalyst. The

products were analyzed with an analysed by

Gas Chromatograph (GC, Agilent 7890)

equipped with flame ionisation detector (FID)

and TCD detector (for the detection of CO2

and CO). An n-butanol solution with a known

amount was used as internal standard for

analysis.

RESULTS AND DISCUSSION Catalyst Characterization

The X-ray diffraction patterns of the Cu-Cr

catalysts presented in Figure 1 showed the

typical diffraction lines of the bulk, single

phased CuCr2O4 spinel exclusively (Figure

1(f)) with the maximum intensity peak at 2θ

value of 35.16° (JCPDS. 05-0657). By using

the Scherrer equation the average crystallite

size (based on 35.16°) was found ~ 28 nm,

which possessed consistency with that

obtained from TEM analysis. Interestingly,

XRD diffractogram (Figure 1 (f)) also predicts

that, the catalyst retains its spinel phase even

after 6 consecutive runs, only negligible

decrement in the intensity was observed,



which was furthermore supported by ICP-AES

analyses. SEM images of the catalyst (Figure

2a, b) showed the formation of almost

homogeneously distributed uniform particles

with size 30–50 nm and devoid of any

agglomeration. From TEM images (Figure

2c,d) revealed that the particles were well

distributed and are seen to be roughly

hexagonal. The lattice fringe with a d-spacing

of 0.30 nm corresponding to [220] plane of

CuCr2O4 spinel [32] with diffraction angle (2θ)

of 29.57° has also been presented (Figure 2d).

20 40 60 80

g

f

e

d

c

b

a

2Theta/ Degree

Inte

nsi

ty(a

mu

)

Fig. 1: XRD Diffractogram of the (a) CuO, (b)

Cu2O, (c) CrO3, (d) Cr2O3, (e) Cu/Cr2O3imp

(imp: impregnation method), (f) CuCr2O4

(prepared catalyst) and (g) CuCr2O4 (spent

catalyst, after consecutive 6 runs).

Fig. 2: SEM (a,b) and TEM Diagram (c,d) of

the CuCr2O4 Spinel Nanoparticles Catalyst.

Catalytic Activity

The results of catalytic hydroxylation of

benzene with air as oxidant have been given in

Table 1. Formation of phenol was detected

using CuCr2O4 spinel nanoparticles (as

confirmed by GC analyses). Apart from

phenol and CO2, a little amount of biphenyl

was detected as side product; additionally, no

product was detected when the reaction was

carried out under a nitrogen atmosphere

(maintaining 30 bar pressure), which

ascertains the fact that, the reaction proceeds

through radical-formation mechanism.

Molecular oxygen (in air) is effectively

activated by Cu2+

(present in CuCr2O4 spinel)

and compels the so generated oxygen species

(probably peroxide) to react with benzene

moiety. 30 bar pressure (air) and 350°C was

proved to be the optimum one.

With the increment of either temperature or

pressure, the selectivity to phenol decreases

owing to the formation of CO2 and over-

oxidation of phenol. Blank experiment was

performed in absence of catalyst maintaining

all the optimum conditions (Entry 15, Table

1), no product was detected in the absence of

catalyst, which indicated its necessity. This

result suggested that a catalytic hydroxylation

of benzene, featuring CuCr2O4 spinel

nanoparticles catalyst and air as oxidant in a

batch reactor.

To further elucidate the role of NPs in this

reaction, we studied the reaction under

identical conditions using different

commercial and conventional catalyst, with

average size ~ 2 µm. The selectivity towards

phenol changed drastically. These

observations substantiated that the success of

the reaction is largely dependent on the NPs

ability to activate oxygen. Maintaining all the

optimum conditions, when the reaction was

allowed to run for hours (Figure 3), it was

noticed that with time, increment in benzene

conversion, with decrement towards the

selectivity of phenol, presumably because of

the formation of CO2 and over-oxidized

products of phenol (quinol/hydroquinone),

including bi-phenyls.


Volume 1, Issue 1

__________________________________________________________________________________________


Table 1: Reaction Conditions of Catalytic Hydroxylation of Benzenea.

Entry Catalyst Temperature (°C) Pressure

(Bar)

CB (%)b SP (%)

c

1 CuOCOM

350 30 5 -

2 Cu2OCOM

350 30 4 -

3 Cr2O3COM

350 30 6 -

4 CuCr2O4COM

350 30 12 0.8

5 CuCr2O4IMP

350 30 10.5 1.0

6 CuCr2O4NP

350 30 38 22

7d CuCr2O4

NP 350 30 30.5 16.5

8 CuCr2O4NP

350 20 14 18

9 CuCr2O4NP

350 40 44 12

10 CuCr2O4NP

200 30 18 8

11 CuCr2O4NP

300 30 32 15

12 CuCr2O4NP

400 30 47 6.5

13e CuCr2O4

NP 350 30 8 55

14f CuCr2O4

NP 350 30 42.5 10.5

15g - 350 30 2 -

aReaction conditions: benzene = 15 ml, CuCr2O4 nanoparticles catalyst= 1.0 g, time = 6 h.

bCB: Conversion of

benzene = [Moles of benzene reacted/initial moles of benzene used] x 100. cSP: Selectivity to phenol=

[phenol]/([phenol] + 1/6[CO2] + 1/6[CO]) x 100. dPrepared CuCr2O4 catalyst after consecutive 6 runs.

eReaction time= 1h.

fReaction time = 12 h.

gNeat reaction. COM: Commercial. IMP: catalyst prepared by

impregnation method.[] is the number of moles produced. The obtained carbon balances were usually more

than 90%.

0 5 10 15 20 25

0

25

50

75

100

Conversion/Selectivity(%)

Time

Fig. 3: Effect of Time on Benzene Hydroxylation Reaction.

[ ■ ] Conversion of Benzene; [●] Selectivity to Phenol; [▲] Selectivity to CO2;

[▼]Selectivity to CO; [♦] Selectivity to other by-products.

Reaction Condition: Benzene =15 ml; Catalyst = 1g; Pressure (air) =30 bar; Temperature = 350°C.



Benzene Hydroxylation Mechanism

The benzene hydroxylation reaction

mechanism can be explained on the basis of

C6H6+•

formation in presence of oxygen and

Cu(II) present in the CuCr2O4 spinel

(Figure 4). 15

Cu(II) in presence of high

temperature produces Cu(II)O2–

species, which

further react with C6H6+•

species to form an

intermediate A, which further generates

phenol moiety over CuCr2O4 spinel surface.

The intermediate A is then converted to the

species Cu(II)O•

species, which enters the

catalytic cycle and takes part in the benzene

hydroxylation reaction. Furthermore,

molecular oxygen is plays the important role

in the generation of C6H6+•

species. At

optimum conditions, when air was substituted

by nitrogen, benzene remained as such in the

reactor; even formation of biphenyl was not

discovered in the medium, emphasizing the

consistency with the suggested mechanistic

path.

H

O O O-O-H +

O O H-O-O-H

H-O-O-H OH

C6H6 O-O-H C6H6

Cu(II)

O O

Cu(II) O2

Cu(II) O O

H

Cu(I) O O

H

+

O-H

OH Cu(II)-O-O-H

C6H6

+

+ + +

Biphenyl2

+

C6H6

Cu(II)-O

+

O-O-H

O2

A B

H H

Fig. 4: Mechanism of Benzene Hydroxylation

Reaction.

CONCLUSION To summarize, we have successfully prepared

CuCr2O4 spinel nanoparticles (with size

~35 nm) in hydrothermal method using

cetyltrimethylammonium bromide as

surfactant. The catalyst is effective enough to

convert benzene to phenol in a single step,

with air as oxidant; it eliminates the use of

precious metal catalyst and of H2 gas. The use

of inexpensive Cu/Cr precursors, simplicity of

the preparation method, use of the cheapest

(and greenest) oxidizing agent air and overall,

recyclability of the catalyst etc. can make this

process valuable both on laboratory scale, but

also on an industrial scale.

ACKNOWLEDGMENTS S.S.A. thanks CSIR and S.G. thanks UGC,

India for the fellowship. The Director, CSIR-

IIP, is acknowledged for his help and

encouragement. The authors thank Analytical

Science Division, Indian Institute of Petroleum

for analytical services.

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17. Panov G. I., Kharitonov A. S., Sobolev

V. I. Appl. Catal. A 1993; 98: 1p.

18. Stahl S. S. Science. 2005; 309: 1824p.


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19. Piera J., Backvall J. E. Angew. Chem.

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JoCC (2014) © STM Journals 2014. All Rights Reserved


Volume 1, Issue 1

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In Situ Synthesized Cu(OH)2-Al2O3: A Novel and Highly

Efficient Nano-Catalyst System for One pot Synthesis of

N-Substituted Triazole at Room Temperature

Ravi Kant Shukla, Yogesh Somasundar, Radha Sawana, Babita Baruwati* Unilever R&D, Whitefield, Bangalore, Karnataka, India

Keywords: Copper hydroxide, Triazole, One pot, Room temperature, Reuse

Abstract One pot room temperature synthesis of N- substituted

Triazoles has been demonstrated using a novel catalyst

system Cu(OH)2-Al2O3. The catalyst has been synthesized by a very simple one step chemical process. The catalyst

is highly efficient and reusable with isolated yield as high as 87% even at the 4

th reuse. The catalyst could also be

used with water as a solvent with a little longer reaction

time.

Graphical Abstract: One pot room temperature

synthesis of N- substituted Triazoles using Cu(OH)2-

Al2O3 novel catalyst system.



Volume 1, Issue 1

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Alcohol Oxidation in Ionic Liquids Catalysed by

Recyclable Platinum Nanoparticles: A Green Approach

Deb Kumar Mukherjee*, Arijit Mondal, Amit Das Ramsaday College, Amta Howrah, West Bengal, India

Abstract The effect of particle size on the catalytic performance of materials in organic reactions is of scientific and industrial importance. In the present case we demonstrate the use of

room temperature ionic liquids as effective agents of dispersion of platinum nanoparticles prepared from potassium tetrachloroplatinate. The platinum nanoparticles

in the range 2.5±0.5 nm are recyclable catalysts for aerobic oxidation of alcohols under

mild conditions. The particles suspended in ionic liquids show no metal agglomeration or

loss of catalytic activity even on prolonged use. The protocol followed supports green

chemistry as uses of hazardous, flammable organic chemicals have been limited.

Keywords: Platinum, nanoparticles, oxidation, agglomeration, ionic liquid

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JoCC (2014)© STM Journals 2014. All Rights Reserved


Volume 1 Issue 1

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H2 Production by Methanol Steam Reforming over

Copper Impregnated Anodized Aluminum Oxide (AAO)

M. Jhansi L. Kishore1*, Dong Hyun Kim

2

1Department of Chemical Engineering and Technology, Birla Institute of technology Mesra, India

2Department of Chemical Engineering, Kyungpook National University, Daegu, South Korea

Abstract Hydrogen production by methanol steam reforming (MSR) is easy and simple as compared to other reforming methods using fossil fuels such as methane steam reforming.

The catalysts for MSR are well developed and available commercially. When constructing

a small or micro reformer, the catalyst often needs to be coated on the wall of the metal substrate. In this case, the bonding between the metal surface and the catalyst layer must

be strong enough to avoid peeling of the layer. Simple catalyst slurry coating on the metal

surface has not been successful due to the inherent weak bonding between the metal and the metal oxide layer. In this study, to develop a robust catalyst layer, we first formed a

strongly bonded porous aluminum oxide layer on an aluminum metal surface and then impregnated it with an active metal, Cu. Copper metal is incorporated into the pores of

alumina by impregnation using different concentrations of copper nitrate solution (Cu-

AAO). The surface morphology of the catalysts has been monitored by FE-SEM at various stages of synthesis and the amount of Cu metal incorporated has been analyzed

by SEM-EDX. This paper discusses the development of Cu-AAO catalyst for methanol

steam reforming.

Keywords: Anodized Aluminum Oxide, Methanol Reforming, H2 Production



Volume 1, Issue 1

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Ru(III)-Catalyzed Oxidative Cleavage of Ritodrine

Hydrochloride: A Kinetic and Mechanistic Study

Puttaswamy*, S. Dakshayani, A. S. Manjunatha Department of Chemistry, Bangalore University, Central College Campus, Bangalore, India

Abstract A systematic kinetic and mechanistic study of the oxidation of ritodrine hydrochloride (RTH) with chloramine-T (CAT) in both HClO4 and NaOH media has been carried out at

303 K. In acid medium, the reaction rate is very sluggish to be measured kinetically. Ruthenium (III) chloride ([Ru(III)]) was found to be an efficient catalyst. The reaction

rate exhibits a first-order dependence on [CAT]0 in both media. It shows a fractional-

order on [RTH]0 in alkaline medium whilst zero-order dependence in presence of HClO4. The order with respect to [NaOH] and [HClO4] is negative-fractional. The order with

respect to [Ru(III)] is fractional. Dielectric effect is negative. Activation parameters have been evaluated. Oxidation products have been identified by LC-MS analysis. Further, it

was found that these oxidation reactions are about five-times faster in alkaline medium in

comparison to acid medium. It was also observed that Ru(III) was an efficient catalyst for

the oxidation of RTH by CAT in acid medium. Nearly a four-fold acceleration in the rate

relative to an uncatalyzed reaction is observed. The observed results have been explained

by plausible mechanisms and the related rate laws.

Keywords: Ritodrine hydrochloride, Chloramine-T, Oxidation-kinetics, Ru(III)

catalysis, Mechanism

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Volume 1 Issue 1

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Synthesis of Zeolite Y-Encapsulated Copper(II)

Complexes with Aminobenzonitriles and Carbonitriles

by Flexible Ligand Method

Poonam Ghansiala*

Department of Chemistry, M K P (PG) College, Dehradun, Uttarakhand, India

Abstract Zeolite Y encapsulated copper(II) sulphate complexes with 2-, 3- and 4- aminobenzonitrile and carbonitrile have been prepared by flexible ligand synthesis method. Complexes are characterized

by magnetic susceptibility, infra-red and electronic spectral techniques. The data clearly suggests

the presence of metal complexes in zeolite matrix.

Keywords: Zeolite Y, Copper(II) complexes, Encapsulation



Volume 1 Issue 1

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Synthesis, Structural Studies and Catalytic activity of

Copper(II) Complex Supported by N, N′-bis (2-Hydroxy-

3-Methoxybenzaldehyde) 4-Methylbenzene-1, 2-Diamine

Alekha Kumar Sutar1*

, Yasobanta Das1, 2

, Sasmita Pattnaik1, Anita Routaray

1,

Nibedita Nath1, Prasanta Rath

2, Tungabidya Maharana

3*

1Catalysis Research Lab, Department of Chemistry, Ravenshaw University, Cuttack, Odisha, India

2School of Applied Sciences (Chemistry), KIIT University, Bhubaneswar, Odisha, India

3 Department of Chemistry, National Institute of Technology, Raipur, India

Abstract A novel robust method for synthesis of 3-MOBdMBn-Cu complex, supported by -

ONNO-tetradentate Schiff-base ligand is presented. This copper complex is prepared

by the reactions of metal solution with one molar equivalent of 3-MOBdMBn (N, N’-bis (2-hydroxy-3-methoxybenzaldehyde) 4-Methylbenzene-1, 2-diamine) Schiff-base ligand

in methanol under nitrogen atmosphere. In contrast to other catalysts, the main advantage of this catalyst system was that the cost of the catalyst was remarkably low

and it can be recycled up to eight times, due to its easily accessible materials and the

simple synthetic route. The higher efficiency of complexation of copper ion on the 3-MOBdMBn Schiff base was another advantage of this catalyst system. The structural

study reveals that copper(II) complex is of square planar geometry. The catalytic

activity of copper complex toward the oxidation of phenol is investigated. Experimental results indicate that the rate of phenol conversion was 6.055 x 10

-6 moledm

-3s

-1 with

turnover number 49.632 g mol-1

Cu hr-1 at 30 min.

Keywords: Schiff base, catalysis, organometallic catalyst, copper, phenol oxidation

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