Catalysts for alcohol-fuelled direct oxidation fuel cells

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.

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 Metals	p. 1
1.1 Introduction	p. 1
1.2 Thermodynamics and Kinetics of Alcohol Oxidation Reactions	p. 2
1.2.1 Thermodynamic Data	p. 2
1.2.2 Kinetics Problems	p. 6
1.3 Preparation and Physicochemical Characterization of Platinum-Based Nanocatalysts	p. 7
1.3.1 Synthesis by Chemical Methods	p. 8
1.3.2 Synthesis by Electrochemical Deposition	p. 10
1.3.3 Synthesis by Plasma-Enhanced PVD	p. 11
1.3.4 Physicochemical Characterizations	p. 11
1.4 Experimental Methods for the Elucidation of Reaction Mechanisms	p. 12
1.4.1 Cyclic Voltammetry and CO Stripping	p. 12
1.4.2 Infrared Reflectance Spectroscopy	p. 12
1.4.3 Differential Electrochemical Mass Spectrometry	p. 14
1.4.4 Chromatographic Techniques	p. 14
1.5 Main Parameters of the Electrode Material Controlling the Electro-reactivity of Alcohols	p. 15
1.5.1 Chemical Nature of the Electrode Material	p. 15
1.5.2 Effect of Crystallographic Structure	p. 15
1.5.3 Modification of the Electrode Properties by Metal Adatoms	p. 17
1.5.4 Binary and Multimetallic Electrodes	p. 17
1.5.5 Effect of the Particle Size and Carbon Support	p. 18
1.5.6 Platinum-Based Nanoparticles and Nanocrystals	p. 19
1.6 Survey of the Results on the Electro-oxidation of Several Alcohols	p. 20
1.6.1 The Electro-oxidation of Methanol	p. 21
1.6.2 The Electro-oxidation of Ethanol	p. 31
1.6.3 The Electro-oxidation of Polyols	p. 48
1.7 Summary	p. 64
References	p. 65
Chapter 2 Nanoalloy Electrocatalysts for Alcohol Oxidation Reactions	p. 71
2.1 Introduction	p. 71
2.2 Preparation of Nanoalloy Catalysts	p. 75
2.3 Electrocatalytic Activity of Bimetallic Catalysts	p. 77
2.3.1 AuPt Alloy and Core-Shell Nanoparticle Catalysts	p. 77
2.3.2 PdCo Alloy Nanoparticle Catalysts	p. 82
2.4 Phase and Surface Properties of Bimetallic Nanoparticle Catalysts	p. 83
2.4.1 Bimetallic Phase Properties	p. 83
2.4.2 Bimetallic Surface Properties	p. 88
2.5 Summary	p. 91
Acknowledgements	p. 91
References	p. 91
Chapter 3 Theoretical Studies of Formic Acid Oxidation	p. 97
3.1 Introduction	p. 97
3.2 Methods	p. 100
3.3 Results and Discussion	p. 101
3.3.1 Gas-Phase Reaction	p. 101
3.3.2 Influence of Water Solvation	p. 105
3.3.3 Eley-Rideal Mechanisms	p. 108
3.3.4 Kinetics Analysis	p. 112
3.3.5 Role of Co-adsorbed CO and OH	p. 114
3.4 Summary	p. 125
Acknowledgements	p. 125
References	p. 126
Chapter 4 Gold Leaf Based Electrocatalysts	p. 129
4.1 Introduction	p. 129
4.2 Nanoporous Gold Leaf	p. 131
4.2.1 History and Formation Mechanism of NPG	p. 131
4.2.2 Structural Properties of NPG Leaf	p. 133
4.2.3 Electrocatalysis of NPG Leaf	p. 135
4.3 Platinum-Plated Nanoporous Gold Leaf	p. 137
4.3.1 Plating Methods	p. 138
4.3.2 Structure and Stability of Pt-NPG Leaf	p. 141
4.3.3 Electrocatalysis of Pt-NPG Leaf	p. 144
4.3.4 Fuel Cell Performance of Pt-NPG Leaf	p. 147
4.4 NPG-Based Electrocatalysts for Formic Acid Oxidation	p. 150
4.5 Summary	p. 154
Acknowledgements	p. 155
References	p. 155
Chapter 5 Nanocatalysts for Direct Borohydride Oxidation in Alkaline Media	p. 158
5.1 Introduction	p. 158
5.2 Thermodynamics and Mechanism of Sodium Borohydride Oxidation	p. 160
5.3 Experimental Details	p. 167
5.3.1 Materials	p. 167
5.3.2 Synthesis of Catalysts by the "Water-in-Oil" Microembulsion Method	p. 169
5.3.3 Electrochemical Measurements	p. 170
5.3.4 TEM, XRD and XPS Characterization Methods	p. 170
5.4 Characterization of the Nanocatalysts	p. 171
5.5 Evaluation of the Catalytic Activity and Selectivity towards Sodium Borohydride Electro-oxidation	p. 177
5.5.1 Electrochemical Methods	p. 177
5.5.2 Evaluation of the BOR on Monometallic Nanocatalysts	p. 181
5.5.3 Evaluation of the BOR on Pd-Based Bimetallic Catalysts	p. 188
5.5.4 Evaluation of the BOR on Pt-Based Multimetallic Catalysts	p. 196
5.6 Summary	p. 199
Acknowledgements	p. 201
References	p. 201
Chapter 6 Bioelectrocatalysis in Direct Alcohol Fuel Cells	p. 206
6.1 Introduction	p. 206
6.1.1 Opportunities for Enzymes at the Anode of Fuel Cells	p. 208
6.1.2 Opportunities for Enzymes at the Cathode of Fuel Cells	p. 211
6.1.3 Limitations in Assembling Energy Devices with Enzymes	p. 211
6.2 Strategies for Wiring Enzyme Electrocatalysts to Electrodes	p. 212
6.2.1 Cofactor Supply to NAD(P) + -Dependent Dehydrogenases	p. 213
6.2.2 Redox Hydrogels	p. 214
6.2.3 Tethers or Conductive Linkers	p. 214
6.2.4 Direct Electron Transfer	p. 216
6.2.5 Wiring Whole Cells for Microbial Fuel Cells: Mediated and Direct Electron Transfer	p. 218
6.3 Examples of Enzyme Electrocatalysis	p. 218
6.3.1 Methanol and Ethanol	p. 219
6.3.2 Sugars and Carbohydrates	p. 220
6.3.3 Glycerol	p. 222
6.4 Microbial Fuel Cells	p. 222
6.5 Summary	p. 223
Acknowledgements	p. 223
References	p. 223
Chapter 7 Challenges and Perspectives of Nanocatalysts in Alcohol-Fuelled Direct Oxidation Fuel Cells	p. 227
7.1 Challenges with Current Direct Oxidation Fuel Cell Catalysts	p. 227
7.1.1 CO Poisoning	p. 228
7.1.2 Oxygen Reduction Catalysts	p. 230
7.1.3 Carbon Corrosion	p. 230
7.1.4 Platinum Dissolution and Growth	p. 232
7.1.5 Ruthenium Dissolution	p. 233
7.2 Approaches to Catalysts Performance Enhancement	p. 233
7.2.1 Development of Composite Catalysts with Noble Metals	p. 233
7.2.2 Novel Carbon Materials as Catalysts and Substrates	p. 240
7.2.3 Non-carbon-Based Catalyst Substrates	p. 242
7.3 Summary	p. 244
References	p. 244
Subject Index	p. 250

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