Electrocatalysis (eBook)

Contents 6
Preface 7
Pt-Based Catalysts for Electrochemical Oxidation of Ethanol 9
Abstract 9
1 Introduction 10
2 In Situ Characterization of New Catalysts for Ethanol Oxidation 12
2.1 In Situ FTIR Experimental Details 12
2.2 In Situ XAS Experimental Details 15
3 In Situ FTIR Study of Ethanol Electrooxidation 18
3.1 In Situ IRRAS Study of Ternary Electrocatalysts for Oxidizing Ethanol to CO2 18
3.1.1 The Role of Rh in the Ternary Pt–Rh–SnO2 Catalyst System 19
3.1.2 Quantitative Optimization of the Pt–Rh Ratio 21
3.1.3 In Situ FTIR as a Quantitative Analysis Method 21
3.2 In Situ ATR-SEIRAS Study of Ethanol Oxidation on a Pt Electrode 24
4 In Situ XAS Study of Ethanol Oxidation 26
4.1 PtRhSnO2 Ternary Catalyst for Ethanol Oxidation 27
4.1.1 EXAFS Fitting of Pt–Rh–SnO2 Nanocatalyst 28
4.2 Optimizing Pt–Rh–SnO2 Nanocatalyst 28
4.3 Ir as an Alternative to Rh 33
5 Platinum Monolayer Electrocatalysts for Ethanol Oxidation 37
6 Conclusions 42
Acknowledgements 42
References 43
Recent Advances in the Electro-Oxidation of Urea for Direct Urea Fuel Cell and Urea Electrolysis 48
Abstract 48
1 Introduction 49
2 Application of Urea Electro-Oxidation 50
2.1 Direct Urea Fuel Cells (DUFCs) 50
2.2 Urea Electrolysis 53
3 Mechanism of Urea Electro-Oxidation 55
3.1 Mechanism in Neutral Cl– Medium 55
3.2 Mechanism in Alkaline OH– Medium 57
4 Development of Anodic Catalysts for Urea Electro-Oxidation 60
4.1 Nickel-Based Metals 61
4.1.1 Single Nickel Metal 61
4.1.2 Nickel-Noble Metal Alloys 62
4.1.3 Nickel-Transition Metal Alloys 62
4.2 Nickel-Based Hydroxide 65
4.2.1 Monovalent Nickel Hydroxide 65
4.2.2 Doped Nickel-Based Hydroxide 66
4.3 Nickel-Based Oxide 68
4.3.1 Monovalent Nickel Oxide 68
4.3.2 Nickel-Based Composite Oxides 70
4.4 Novel Nickel-Based Compounds 71
4.5 Supported Nickel-Based Compounds 75
5 Conclusions 77
Acknowledgements 79
References 79
Determination of Specific Electrocatalytic Sites in the Oxidation of Small Molecules on Crystalline Metal Surfaces 86
Abstract 86
1 Introduction 87
2 The Structure of the Catalytic Substrate 88
3 Determination of Specific Electrocatalytic Sites 90
3.1 Fingerprints of Step and Terrace Sites on Pt Surfaces as Probed by Hydrogen AdsorptionDesorption 90
3.2 Electro-Oxidation of Carbon Monoxide 91
3.3 Pathways of Methanol Electro-Oxidation Toward Carbon Dioxide 96
3.4 Electro-Oxidation of Ammonia 99
3.5 Asymmetric Electrocatalysis of the Glucose Oxidation in Intrinsically Chiral Pt Surfaces 102
4 Concluding Remarks and Prospects 105
Acknowledgements 106
References 106
Bimetallic Electrocatalysts for CO2 Reduction 111
Abstract 111
1 Introduction 112
2 Bimetallic Electrocatalysts for CO2 Reduction 113
2.1 CO Selective Bimetallic Electrocatalysts 113
2.2 Hydrocarbon Selective Bimetallic Electrocatalysts 117
2.3 Oxygenate Selective Bimetallic Electrocatalysts 121
3 Challenges and Opportunities of Bimetallic Electrocatalyts for CO2 Reduction 127
Acknowledgements 127
References 128
Dispersive Single-Atom Metals Anchored on Functionalized Nanocarbons for Electrochemical Reactions 132
Abstract 132
1 Introduction 133
2 Synthesis of Carbon-Based Single-Atom Metal Catalysts 135
2.1 High-Vacuum Deposition 135
2.2 Wet-Chemical Route 136
2.3 High-Temperature Pyrolysis 137
3 Characterization of Carbon-Based Single-Atom Metal Catalysts 138
3.1 Electron Microscopy Techniques 138
3.2 Spectroscopy Techniques 139
4 Applications of Carbon-Based Single-Atom Metal Catalysts in Electrocatalysis 141
4.1 Oxygen Reduction Reaction 141
4.2 Water Splitting 143
4.3 Other Electrochemical Reactions 144
5 Summary and Perspectives 146
Acknowledgements 148
References 148
Electrometabolic Pathways: Recent Developments in Bioelectrocatalytic Cascades 154
Abstract 154
1 Enzyme-Based Catalytic Cascades 154
2 Enzymatic Cascades for Electrometabolic (Oligo)Saccharide Oxidation Pathways 156
3 Hybrid Cascades for Electrometabolic Glycerol Oxidation Pathways 160
4 Applications of Electroenzymatic Cascades 162
5 Emergence of Reductive Electrometabolic Pathways for N2 and CO2 Reduction 163
6 Spatial Orientation and Substrate Channeling 164
7 Conclusion 167
Acknowledgements 167
References 167