Preface xiii
1 Measurement Systems and Parameters for CO 2 Photo/Electro-Conversion 1
li li, Zhenwei Zhao, Xinyi Wang, and Zhicheng Zhang
1.1 Introduction 1
1.2 The Measurement Systems for CO 2 Photo/Electro-Conversion 1
1.2.1 The Measurement Systems of Photocatalytic CO 2 Reduction 1
1.2.1.1 CO 2 Reduction System Under Liquid-Phase Reaction System 2
1.2.1.2 CO 2 Reduction System in Gas-Phase Reaction System 2
1.2.1.3 Detection of CO 2 Reduction Products 3
1.2.2 The Measurement Systems of Electrocatalytic CO 2 Reduction 3
1.2.2.1 Electrocatalytic CO 2 Reduction Reaction Test in H-Cell 3
1.2.2.2 Electrocatalytic CO 2 Reduction Reaction Test in Flow Cell 5
1.2.2.3 Electrocatalytic CO 2 Reduction Reaction Test in MEA 5
1.2.3 The Measurement Systems of Photo-Electro-Catalytic CO 2 Reduction 6
1.2.3.1 Basic Device for Photocatalytic CO 2 Reduction Experiment 6
1.2.3.2 Other Devices for Photocatalytic CO 2 Reduction 7
1.2.3.3 Detection of CO 2 Reduction Reaction Products 7
1.3 The Parameters for CO 2 Photo-Conversion 7
1.3.1 The Parameters of Photocatalytic CO 2 Reduction 7
1.3.1.1 Evaluation Parameters of Photocatalytic CO 2 Reduction Activity 8
1.3.1.2 Evaluation Parameters of Photocatalytic CO 2 Reduction Selectivity 10
1.3.1.3 Evaluation Parameters of Photocatalytic CO 2 Reduction Stability 10
1.3.2 The Parameters of Electrocatalytic CO 2 Reduction 10
1.3.3 The Parameters of Photo-Electro-Catalytic CO 2 Reduction 12
1.3.3.1 Overpotential 12
1.3.3.2 Total Photocurrent Density (j ph) and Partial Photocurrent Density (j A) 12
1.3.3.3 Faraday Efficiency (FE) 13
1.3.3.4 Solar Energy Conversion Efficiency 13
1.3.3.5 Apparent Quantum Yield (AQY) 13
1.3.3.6 Electrochemical Active Area (ECSA) 14
1.3.3.7 Electrochemical Impedance (EIS) 14
1.3.3.8 Tafel Slope (Tafel) 14
1.3.3.9 Photocatalytic Stability 14
References 15
2 CO 2 Photo/Electro-Conversion Mechanism 17
Yalin Guo, Shenghong Zhong, and Jianfeng Huang
2.1 Introduction 17
2.2 CO 2 Photo-Conversion Mechanism 18
2.3 CO 2 Electro-Conversion Mechanism 25
2.3.1 Thermodynamics of CO 2 Reduction 25
2.3.2 Pathways of Electrochemical CO 2 Reduction 26
2.3.2.1 Electrochemical CO 2 Reduction to CO 27
2.3.2.2 Electrochemical CO 2 Reduction to Formate 28
2.3.2.3 Electrochemical CO 2 Reduction to Products Beyond CO 29
2.4 Summary and Perspectives 32
References 32
3 Cu-Based Metal Materials for Electrocatalytic CO 2 Reduction 37
Junjun Li, Yongxia Shi, Man Hou, and Zhicheng Zhang
3.1 Introduction 37
3.2 Cu-Based Metal Materials for Electrocatalytic CO 2 Reduction 39
3.2.1 Cu Materials for Electrocatalytic CO 2 Reduction 39
3.2.2 Cu-Based Bimetal Materials for Electrocatalytic CO 2 Reduction 40
3.2.2.1 Cu–Au 40
3.2.2.2 Cu–Ag 42
3.2.2.3 Cu–Pd 43
3.2.2.4 Cu–Sn 44
3.2.2.5 Cu–Bi 46
3.2.2.6 Cu–In 46
3.2.2.7 Cu–Al 49
3.2.2.8 Cu–Zn 49
3.2.3 Cu-Based Trimetallic Materials for Electrocatalytic CO 2 Reduction 50
3.3 Conclusion and Outlook 50
Acknowledgment 53
References 53
4 Cu-Free Metal Materials for Electrocatalytic CO 2 Conversion 61
Zhiqi Huang and Qingfeng Hua
4.1 Introduction 61
4.2 CO-Producing Metals 62
4.2.1 Au-Based Electrocatalysts 62
4.2.2 Ag-Based Electrocatalysts 66
4.2.3 Pd-Based Electrocatalysts 68
4.2.4 Zn-Based Electrocatalysts 70
4.3 HCOOH-Producing Metals 72
4.3.1 Sn-Based Electrocatalysts 72
4.3.2 Bi-Based Electrocatalysts 76
4.3.3 In-Based Electrocatalysts 78
References 80
5 Organic–Inorganic Hybrid Materials for CO 2 Photo/Electro-Conversion 93
Peilei He
5.1 Hybrid Materials for Photocatalytic CO 2 Reduction Reaction (co 2 Rr) 93
5.1.1 Photocatalytic CO 2 RR on p-type Semiconductor/Molecule Catalysts 93
5.1.2 Photocatalytic CO 2 RR on Carbon Nitride (C 3 N 4)-supported Molecular Catalysts 95
5.1.3 Photocatalytic CO 2 RR on Polyoxometalates (POMs)-based Catalysts 97
5.2 Hybrid Materials for Electrochemical CO 2 RR 98
5.2.1 Electrochemical CO 2 RR on Carbon-supported Molecular Catalysts 98
5.2.2 Electrochemical CO 2 RR on TiO 2 -based Hybrid Materials 103
5.3 Hybrid Materials for Photoelectrochemical (PEC) CO 2 RR 104
5.4 Challenge and Opportunity 106
References 107
6 Metal–Organic Framework Materials for CO 2 Photo-/Electro-Conversion 111
Bingqing Yao, Xiaoya Cui, and Zhicheng Zhang
6.1 Introduction 111
6.2 Photocatalysis 112
6.2.1 MOFs with Photoactive Organic Ligands 113
6.2.2 MOFs with Photoactive Metal Nodes 116
6.2.3 MOF-Based Hybrid System 117
6.3 Electrocatalysis 119
6.3.1 MOFs with Active Sites at Organic Ligands 120
6.3.2 MOFs with Active Sites at Metal Nodes 121
6.3.3 MOF-Based Hybrid System 125
6.4 Photoelectrocatalysis 128
6.5 Conclusion and Outlook 129
Acknowledgment 130
References 130
7 Covalent Organic Frameworks for CO 2 Photo/Electro-Conversion 137
Ting He
7.1 Introduction 137
7.2 COFs for Photocatalytic CO 2 Reduction 138
7.2.1 Imine-Linked COFs 138
7.2.2 Ketoenamine COFs 141
7.2.3 Carbon–Carbon Double Bond-Linked COFs 145
7.2.4 Dioxin-Linked COFs 147
7.2.5 Azine-Linked and Hydrazone-Linked COFs 147
7.3 COFs for Electrocatalytic CO 2 Reduction 148
7.3.1 Porphyrin-Based COFs 148
7.3.2 Phthalocyanine-Based COFs 151
7.3.3 Other COFs 152
7.4 Challenges and Perspectives 152
References 154
8 Single/Dual-Atom Catalysts for CO 2 Photo/Electro-Conversion 157
Honghui Ou and Yao Wang
8.1 Introduction 157
8.2 Synthetic Methods of Single/Dual-Atom Catalysts 158
8.2.1 Single-Atom Photocatalysts 158
8.2.2 Dual-Atom Photocatalysts 160
8.2.3 Single-Atom Electro-Catalysts 162
8.2.4 Dual-Atom Electro-Catalysts 164
8.3 CO 2 Photo-Conversion 165
8.4 CO 2 Electro-Conversion 169
8.5 Summary and Perspective 171
References 172
9 Homogeneous Catalytic CO 2 Photo/Electro-Conversion 177
Zhenguo Guo and Houjuan Yang
9.1 Introduction 177
9.2 Homogeneous Catalytic CO 2 Electro-Conversion 177
9.2.1 The Structure Homogeneous Electrocatalytic CO 2 Reduction System 177
9.2.2 Products in Homogeneous Electrocatalytic CO 2 Reduction 178
9.2.3 Characterizing the Performance of Molecular Electrocatalysts 178
9.2.3.1 Selectivity 178
9.2.3.2 Activity 178
9.2.3.3 Overpotential (η) 179
9.2.3.4 Stability 179
9.2.4 Catalysts for Homogeneous Electrocatalytic CO 2 Reduction 179
9.3 Homogeneous Photocatalytic CO 2 Reduction 180
9.3.1 Mechanism of Homogeneous Photocatalytic CO 2 Reduction 180
9.3.2 Characterizing the Performance of Photocatalysis 181
9.3.3 Photosensitizers Used in Homogeneous Photocatalytic CO 2 Reduction 181
9.3.4 Sacrificial Electron Donors in Homogeneous Photocatalytic CO 2 Reduction 181
9.3.5 Catalysts Used in Homogeneous Photocatalytic CO 2 Reduction 182
9.4 Summary and Perspective 186
Acknowledgments 187
References 187
10 High-Entropy Alloys for CO 2 Photo/Electro-Conversion 189
Fengqi Wang, Pei Liu, and Yuchen Qin
10.1 Introduction 189
10.2 Reaction Pathways and Evaluation Parameters of Electrochemical Co 2 Rr 191
10.2.1 Reaction Pathways of CO 2 RR 191
10.2.2 Evaluation Parameters of Electrochemical CO 2 RR 192
10.2.2.1 Faraday Efficiency 192
10.2.2.2 Current Density 193
10.2.2.3 Turnover Number (TON) 194
10.2.2.4 Turnover Frequency (TOF) 194
10.2.2.5 Overpotential 194
10.3 Characteristics and Synthesis of HEAs 194
10.3.1 Characteristics of HEAs 194
10.3.1.1 The Cocktail Effect 194
10.3.1.2 The Sluggish Diffusion Effect 195
10.3.1.3 The High-entropy Effect 195
10.3.1.4 The Lattice Distortion Effect 195
10.3.1.5 The Phase Structure 196
10.3.2 Synthesis of HEAs 196
10.3.2.1 Top-Down Method 196
10.3.2.2 Down–Top Method 198
10.4 High-Entropy Alloys for CO 2 RR 199
10.5 Summary and Outlook 204
References 205
11 Semiconductor Composite Materials for Photocatalytic CO 2 Reduction 215
Shengyao Wang and Bo Jiang
11.1 Introduction 215
11.2 TiO 2 -Based Composite Photocatalysts 216
11.2.1 Mixed-Phase TiO 2 Composites 217
11.2.2 Metal-Modified TiO 2 218
11.2.3 Nonmetallic-Modified TiO 2 219
11.2.4 Organic Photosensitizer-Modified TiO 2 219
11.2.5 Composited TiO 2 Catalyst 220
11.3 Metal Oxides/Hydroxides-Based Composite Photocatalysts 222
11.3.1 Binary Metal Oxide 222
11.3.2 Ternary Metal Oxide 222
11.3.3 Oxide Perovskite 224
11.3.4 Transition Metal Hydroxide 224
11.3.5 Layered Double Hydroxides (LDHs) 226
11.4 Metal Chalcogenides/Nitrides-Based Composite Photocatalysts 226
11.4.1 Metal Chalcogenides-Based Composite Photocatalysts 227
11.4.2 Metal Nitrides-Based Composite Photocatalysts 228
11.5 c 3 N 4 -Based composite Photocatalysts 229
11.5.1 Change the Morphology and Structure 230
11.5.2 Doped Elements and Other Structural Units 231
11.5.3 Influence of Cocatalyst 232
11.5.4 Constructing Heterojunction 233
11.6 MOFs-Derived Composite Photocatalysts 233
11.6.1 Tunable Frame Structure 234
11.6.2 High Specific Surface Area Enhances CO 2 Adsorption 234
11.6.3 MOFs-Derived Composite Photocatalysts 234
11.7 Nonmetal-Based Composite Photocatalysts 236
11.7.1 Graphene Oxide-Based Composite Photocatalysts 236
11.7.2 SiC-Based Composite Photocatalysts 237
11.7.3 BN-Based Composite Photocatalysts 237
11.7.4 Black Phosphorus-Based Composite Photocatalysts 238
11.7.5 COFs-Based Composite Photocatalysts 239
11.7.6 CMPs-Based Composite Photocatalysts 240
11.8 Conclusions and Perspectives 240
References 242
12 Carbon-Based Materials for CO 2 Photo/Electro-Conversion 251
Qing Qin and Lei Dai
12.1 Advances of Carbon-Based Materials 251
12.1.1 Heteroatom-Doped Carbon 251
12.1.2 Metal-Based Carbon Composites 252
12.1.3 Carbon–Carbon Composites 253
12.1.4 Pore Construction 254
12.2 Background of CO 2 Conversion 255
12.3 EC CO 2 Conversion 256
12.3.1 Heteroatom-Doped Carbon in EC CO 2 Conversion 257
12.3.2 Metal-Modified Carbon Materials in EC CO 2 Conversion 259
12.3.3 Carbon–Carbon Composites in EC CO 2 Conversion 261
12.3.4 Pore Engineering in EC CO 2 Conversion 262
12.4 PC CO 2 Reduction 264
12.4.1 Heteroatom-Doped Carbon in PC CO 2 Conversion 265
12.4.2 Metal-Based/Carbon Nanocomposites in PC CO 2 Conversion 266
12.4.3 Carbon–Carbon Composites in PC CO 2 Conversion 268
12.5 Carbon-Based Materials in PEC CO 2 Reduction 269
12.6 Challenge and Opportunity 270
References 272
13 Metal–CO 2 Batteries: Novel Routes for CO 2 Utilization 283
Xiangyu Zhang and Le Yu
13.1 Introduction 283
13.2 The Mechanism for Metal–CO 2 Electrochemistry 284
13.2.1 Discharge/Charge Mechanisms of Li–CO 2 Batteries 284
13.2.1.1 Discharge Mechanisms of Pure Li–CO 2 Batteries 284
13.2.1.2 Charge Mechanisms of Pure Li–CO 2 Batteries 285
13.2.2 Discharge/Charge Mechanisms of Zn–CO 2 Batteries 286
13.3 The Electrocatalysts for Metal–CO 2 Batteries 286
13.3.1 Carbonaceous Materials 286
13.3.2 Noble Metal-based Materials and Transition Metal-based Materials 287
13.4 The Electrolytes for Metal–CO 2 Batteries 290
13.4.1 Nonaqueous Aprotic Liquid Electrolytes for Pure Li–CO 2 Electrochemistry 290
13.4.2 Solid-State Electrolytes for Pure Li–CO 2 Electrochemistry 290
13.5 Conclusion and Outlook 292
References 293
14 CO 2 Conversion into Long-Chain Compounds 297
Tingting Zheng and Chuan Xia
14.1 Introduction 297
14.2 Photobiochemical Synthesis (PBS) 299
14.2.1 Principles in Designing the PBS System 299
14.2.2 Multicarbon Compounds Produced from PBS 301
14.2.3 Challenges and Prospects for PBS 304
14.3 Microbial Electrosynthesis (MES) 306
14.3.1 Extracellular Electron Transfer (EET) 306
14.3.2 Approaches to Optimize MES 309
14.3.2.1 Metabolic Pathways 309
14.3.2.2 Metabolic Engineering 309
14.3.2.3 Culture 311
14.3.2.4 Biocathode 312
14.3.3 Multicarbon Products Derived from MES 313
14.3.4 The Status Quo and Challenges of MES 316
14.4 Decoupling Biotic and Abiotic Processes 318
14.5 Conclusions and Perspectives 322
References 324
15 Conclusions and Perspectives 335
Haiqing Wang
15.1 New CO 2 RR Catalyst 335
15.2 New CO 2 RR Mechanism 336
15.3 Industrial CO 2 RR Perspectives 337
Index 339
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