Cover image for Catalysts for alcohol-fuelled direct oxidation fuel cells
Catalysts for alcohol-fuelled direct oxidation fuel cells
RSC energy and environment series ; 6
Publication Information:
Cambridge : RSC Publishing, ©2012
Physical Description:
254 p. : ill. ; 24 cm.


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Call Number
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30000010321831 TK2931 C38 2012 Open Access Book Book

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Energy and environment issues are of paramount importance to achieve the sustainable development of our society. Alcohol-fuelled direct oxidation fuel cells (DOFCs), as a clean and highly-efficient energy harvesting engine, have attracted intensive research activity over recent decades. Electrocatalysts are the material at the very heart of the cell that determines the performance of DOFCs. The rapid advances in electrocatalysts, particularly nano-sized ones, have left current information only available in scattered journals. To be truly useful to both present and future researchers, a new book is needed to present an insightful review of the reaction nature of this research and to systematically summarize recent advances in nanocatalysts, and convey a more global perspective. Catalysts for Alcohol-fuelled Direct Oxidation Fuel Cells will present a state-of-the-art review on recent advances in nanocatalysts and electrocatalysis in DOFCs, including both proton and hydroxide ion exchange membrane fuel cells. The main topics covered include a molecular-level understanding of electrocatalysis, the design principles of electrocatalysts, recent advances in nanocatalysts and future perspectives for DOFCs. The book presents a cutting-edge collection on nanocatalysts for alcohol-fuelled direct oxidation fuel cells and brings together the most authoritative researchers in the field from both industry and academia, filling the gap between both sides. Finally, the book will provide an insightful review on electrocatalysis at the molecular- level, which will be useful for postgraduate students and junior researchers in this field. It will be an essential resource for postgraduates, researchers and policy-makers globally in academia, industry, and government institutions.

Author Notes

As a full professor of Mechanical Engineering and director of the Center for Sustainable Energy Technology at The Hong Kong University of Science and Technology (HKUST), Tim S. Zhao has been working on fuel cells for more than a decade. Zhen-Xiang Liang is full professor at the School of Chemistry and Chemical Engineering, South China University of Technlogy, Guangzhou, China. He has been working on direct alcohol fuel cells for almost a decade and has a proven track record in electrochemistry, particularly in the area of electrocatalyst developments.

Table of Contents

Claude Lamy and Christophe CoutanceauJun Yin and Bridgid Wanjala and Bin Fang and Jin Luo and Rameshowri Loukrakpam and Lefu Yang and Shiyao Shan and Ming Nie and Chuan-Jian ZhongWang Gao and Timo JacobRongyue Wang and Yi DingChristophe Coutanceau and Stève Baranton and Mário SimõesgH. A. Reeve and K. A. VincentE. H. Yu and X. Wang and X. T. Liu and L. Li
Chapter 1 Electrocatalysis of Alcohol Oxidation Reactions at Platinum Group Metalsp. 1
1.1 Introductionp. 1
1.2 Thermodynamics and Kinetics of Alcohol Oxidation Reactionsp. 2
1.2.1 Thermodynamic Datap. 2
1.2.2 Kinetics Problemsp. 6
1.3 Preparation and Physicochemical Characterization of Platinum-Based Nanocatalystsp. 7
1.3.1 Synthesis by Chemical Methodsp. 8
1.3.2 Synthesis by Electrochemical Depositionp. 10
1.3.3 Synthesis by Plasma-Enhanced PVDp. 11
1.3.4 Physicochemical Characterizationsp. 11
1.4 Experimental Methods for the Elucidation of Reaction Mechanismsp. 12
1.4.1 Cyclic Voltammetry and CO Strippingp. 12
1.4.2 Infrared Reflectance Spectroscopyp. 12
1.4.3 Differential Electrochemical Mass Spectrometryp. 14
1.4.4 Chromatographic Techniquesp. 14
1.5 Main Parameters of the Electrode Material Controlling the Electro-reactivity of Alcoholsp. 15
1.5.1 Chemical Nature of the Electrode Materialp. 15
1.5.2 Effect of Crystallographic Structurep. 15
1.5.3 Modification of the Electrode Properties by Metal Adatomsp. 17
1.5.4 Binary and Multimetallic Electrodesp. 17
1.5.5 Effect of the Particle Size and Carbon Supportp. 18
1.5.6 Platinum-Based Nanoparticles and Nanocrystalsp. 19
1.6 Survey of the Results on the Electro-oxidation of Several Alcoholsp. 20
1.6.1 The Electro-oxidation of Methanolp. 21
1.6.2 The Electro-oxidation of Ethanolp. 31
1.6.3 The Electro-oxidation of Polyolsp. 48
1.7 Summaryp. 64
Referencesp. 65
Chapter 2 Nanoalloy Electrocatalysts for Alcohol Oxidation Reactionsp. 71
2.1 Introductionp. 71
2.2 Preparation of Nanoalloy Catalystsp. 75
2.3 Electrocatalytic Activity of Bimetallic Catalystsp. 77
2.3.1 AuPt Alloy and Core-Shell Nanoparticle Catalystsp. 77
2.3.2 PdCo Alloy Nanoparticle Catalystsp. 82
2.4 Phase and Surface Properties of Bimetallic Nanoparticle Catalystsp. 83
2.4.1 Bimetallic Phase Propertiesp. 83
2.4.2 Bimetallic Surface Propertiesp. 88
2.5 Summaryp. 91
Acknowledgementsp. 91
Referencesp. 91
Chapter 3 Theoretical Studies of Formic Acid Oxidationp. 97
3.1 Introductionp. 97
3.2 Methodsp. 100
3.3 Results and Discussionp. 101
3.3.1 Gas-Phase Reactionp. 101
3.3.2 Influence of Water Solvationp. 105
3.3.3 Eley-Rideal Mechanismsp. 108
3.3.4 Kinetics Analysisp. 112
3.3.5 Role of Co-adsorbed CO and OHp. 114
3.4 Summaryp. 125
Acknowledgementsp. 125
Referencesp. 126
Chapter 4 Gold Leaf Based Electrocatalystsp. 129
4.1 Introductionp. 129
4.2 Nanoporous Gold Leafp. 131
4.2.1 History and Formation Mechanism of NPGp. 131
4.2.2 Structural Properties of NPG Leafp. 133
4.2.3 Electrocatalysis of NPG Leafp. 135
4.3 Platinum-Plated Nanoporous Gold Leafp. 137
4.3.1 Plating Methodsp. 138
4.3.2 Structure and Stability of Pt-NPG Leafp. 141
4.3.3 Electrocatalysis of Pt-NPG Leafp. 144
4.3.4 Fuel Cell Performance of Pt-NPG Leafp. 147
4.4 NPG-Based Electrocatalysts for Formic Acid Oxidationp. 150
4.5 Summaryp. 154
Acknowledgementsp. 155
Referencesp. 155
Chapter 5 Nanocatalysts for Direct Borohydride Oxidation in Alkaline Mediap. 158
5.1 Introductionp. 158
5.2 Thermodynamics and Mechanism of Sodium Borohydride Oxidationp. 160
5.3 Experimental Detailsp. 167
5.3.1 Materialsp. 167
5.3.2 Synthesis of Catalysts by the "Water-in-Oil" Microembulsion Methodp. 169
5.3.3 Electrochemical Measurementsp. 170
5.3.4 TEM, XRD and XPS Characterization Methodsp. 170
5.4 Characterization of the Nanocatalystsp. 171
5.5 Evaluation of the Catalytic Activity and Selectivity towards Sodium Borohydride Electro-oxidationp. 177
5.5.1 Electrochemical Methodsp. 177
5.5.2 Evaluation of the BOR on Monometallic Nanocatalystsp. 181
5.5.3 Evaluation of the BOR on Pd-Based Bimetallic Catalystsp. 188
5.5.4 Evaluation of the BOR on Pt-Based Multimetallic Catalystsp. 196
5.6 Summaryp. 199
Acknowledgementsp. 201
Referencesp. 201
Chapter 6 Bioelectrocatalysis in Direct Alcohol Fuel Cellsp. 206
6.1 Introductionp. 206
6.1.1 Opportunities for Enzymes at the Anode of Fuel Cellsp. 208
6.1.2 Opportunities for Enzymes at the Cathode of Fuel Cellsp. 211
6.1.3 Limitations in Assembling Energy Devices with Enzymesp. 211
6.2 Strategies for Wiring Enzyme Electrocatalysts to Electrodesp. 212
6.2.1 Cofactor Supply to NAD(P) + -Dependent Dehydrogenasesp. 213
6.2.2 Redox Hydrogelsp. 214
6.2.3 Tethers or Conductive Linkersp. 214
6.2.4 Direct Electron Transferp. 216
6.2.5 Wiring Whole Cells for Microbial Fuel Cells: Mediated and Direct Electron Transferp. 218
6.3 Examples of Enzyme Electrocatalysisp. 218
6.3.1 Methanol and Ethanolp. 219
6.3.2 Sugars and Carbohydratesp. 220
6.3.3 Glycerolp. 222
6.4 Microbial Fuel Cellsp. 222
6.5 Summaryp. 223
Acknowledgementsp. 223
Referencesp. 223
Chapter 7 Challenges and Perspectives of Nanocatalysts in Alcohol-Fuelled Direct Oxidation Fuel Cellsp. 227
7.1 Challenges with Current Direct Oxidation Fuel Cell Catalystsp. 227
7.1.1 CO Poisoningp. 228
7.1.2 Oxygen Reduction Catalystsp. 230
7.1.3 Carbon Corrosionp. 230
7.1.4 Platinum Dissolution and Growthp. 232
7.1.5 Ruthenium Dissolutionp. 233
7.2 Approaches to Catalysts Performance Enhancementp. 233
7.2.1 Development of Composite Catalysts with Noble Metalsp. 233
7.2.2 Novel Carbon Materials as Catalysts and Substratesp. 240
7.2.3 Non-carbon-Based Catalyst Substratesp. 242
7.3 Summaryp. 244
Referencesp. 244
Subject Indexp. 250