novel low-cost and environmentally-friendly synthesis of ... · 19.05.2014 · particles prepared...
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Novel Low-Cost and Environmentally-Friendly Synthesis of
Core-Shell Structured Micro-Particles for Fossil Energy Applications
Howard UniversityJason Matthews, PhD
The Ohio State UniversityCheng Chung
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Project TeamHoward University (MOCVD Particle Growth)PI-Jason Matthews, PhDAbu Kamara (G)Alyssa Buchannan (U)
The Ohio State University (Ionic Diffusion)L.S. Fan, PhDCheng Chung (G)Liang Zeng, PhDZhenchao Sun, PhD
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Background
• Core-shell structure exhibits high surface area and catalytic-like properties
• Conventional coating techniques for core-shell particles require both high capital and operating cost
• Some coating techniques involve toxic solvent. 3
Shell
Core
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Proposed Synthetic Methods
• Metal Organic Chemical Vapor Deposition• Utilize a low cost hot walled reactor as an alternate route
for the preparation of core-shell structures.
• Ionic Diffusion via Redox Cycles • Utilize the movement of atoms during redox, forming a
core-shell like structure• OSU has rich experience with particle development for
chemical looping system• In depth testing of different metal oxides particles under
redox environment
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Potential Significance
• Reduce the cost of synthesis
• Improve the performance of catalytic fossil fuel conversion, chemical looping combustion/gasification and sorbent-based fossil fuel applications
• Environmental friendly since no solvent is required for ionic diffusion
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Chemical Looping
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Statement of Project Objectives• Synthesize stronger and more chemically reactive particles
for use in fossil energy applications
• Synthesize and characterize Fe2O3-shell/Al2O3-core micro-particles prepared via the cyclic ionic diffusion and MOCVD methods.
• Gain control of shell thickness
• Comparison of morphology, mechanical strength, and reactivity of synthesized core-shell structured particles synthesized via vapor deposition and ionic diffusion
• Demonstrate the applicability of proposed method by preparing and test a CaO-core/Fe2O3-shell particle
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MOCVD
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Tunable β‐ketoiminate ligand backbone TGA Analysis of a MOCVD Precursor
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• Films with uniform thickness under mild conditions (<700°C)
• High quality thin films with less impurities
• High growth rate
• Highly crystalline films
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Volatile and thermally stable
Produce uniform and reproducible coatings
Decompose to afford high purity material
No premature decomposition of the
precursor prior to reaching the substrate
MOCVDPrecursor Requirements
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More attractive than their β-diketonateanalogs:
Volatile and thermally stable
Ability to tune the volatility and thermal stability by varying the R groups
β‐KetoiminesR1 R2
O HNR3
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‐Ketoimine Synthesis
R
O O O HNR
1o amine H2O+ +
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H3C
R''' O
R'
CH3R'''
O
R'H3C
R'''
OR' FeR'
R
R''
O
CH3
CH3
CH3
CH3
CH3CH2O
CH3O
CH3
CH3
CH3CH2O
CH3O
CH3CH2O
CH3O
(CH3)2CHN
CH3OCH2CH2CH2N
(CH3)2CHN
CH3CH2CH2N
(CH3)2CHCH2N
CHN
CH3 CH3 O
R' R'' R'''
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30
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1. KOH/EtOH
2. FeCl3/H2O
3H
Synthesis of Fe(III) Complex
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H3C
N O
O
CH3
CH3N
O
OCH3H3C
N
OOH3C Fe
H3C
CH3
H3CCH3H3C
H3C
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0
20
40
60
80
100
120
0 50 100 150 200 250 300 350 400 450 500
Weight %
Temperature (Celsius)
TG Analysis of Complex 31
H3C
O O
CH3
CH3O
O
CH3CH3
O
OH3C Fe
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MOCVD Coating of Particles
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Future Work
• Continued preparation of volatile and thermally stable precursors.
• Growth and characterization of core shell particles via MOCVD.
• Defining the relationship between CVD reaction time and shell thickness.
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Technical Approach: Synthesis
• Ionic Diffusion via Cyclic Redox Cycles
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Technical Approach - OSU
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• Synthesis of ⁄ via cyclic redox reaction– Confirmation from SEM and EDX analysis
• Application of 2-D diffusion model and diffusion mechanism study
• Control of shell thickness and synthesis optimization – Amount of iron loading– Number of cycles required
• Performance characterization for both synthesis method ( ⁄– Reactivity comparison via TGA– Mechanical Strength measurement– Surface Area comparison
• Synthesis of ⁄ particle– Universal application of the redox cycle synthesis method
Completed
In Progress
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Parametric Study• Percent Iron Loading
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Homogeneous 20/80 Fe/Al Particle Homogeneous 40/60 Fe/Al Particle
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Parametric Study• Particle Size
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D = 0.35mm D = 2.00 mm
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Characterization
• 40/60 Fe/Al
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EDAX Analysis
SEM Analysis
Both Fe and Al are detected
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Cyclic Redox via TGA
29Condition: 100 cycles. Reduction under Hydrogen. Oxidation under Air.
Wave-like Reactivity
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Cyclic Redox via TGA
• Wave-like Profile– Increased Reactivity
• Migration of iron atoms toward the surface
– Decrease in Reactivity• Sintering of surface iron oxide
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Characterization• Post Cyclic Redox
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No Alumina is detected on the surface
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Characterization• Post Cyclic Redox
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EDAX Mapping reveal concentrated Alumina under fractured shell
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Summary-OSU
• Successful formation of core-shell particle via cyclic redox
• Homogeneous particles of various parameters have been prepared
• Two competing phenomenon has been proposed. Further investigation is needed
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Future Work-OSU
• The competing phenomena during redox cycles will be examined by varying the number of cycles and end state.
• TGA profile for the larger particle will also be studied.
• Synthesis of varying degree iron loaded core-shell particles will continue in order to study the effect of iron loading.
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Acknowledgements
• DOE‐NETL DOE‐FE0011515• Howard University Graduate School• Ohio State University
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