CO2 Conversion and Utilization: Photocatalytic and Electrochemical Methods and Applications

CO2 Conversion and Utilization Comprehensive overview of current development of various catalysts in CO2 conversion and utilization through photocatalytic and electrochemical methods CO2 Conversion and Utilization systematically summarizes the development of CO2 photo- and electro-conversion and utilization, especially the reaction mechanism, engineering and technology of testing, and preparation methods and physicochemical properties of various catalytic materials. The rational design and preparation of catalysts, development of characterization technologies, and in-depth understanding of catalytic mechanisms are systematically discussed. In particular, the various parameters influencing the photocatalytic and electrochemical CO2 reduction are emphasized. The underlying challenges and perspectives for the future development of efficient catalysts for CO2 reduction to specific chemicals and fuels are discussed at the end of the text. Written by a highly qualified author with significant experience in the field, CO2 Conversion and Utilization includes information on: Measurement systems and parameters for CO2 photo/electro-conversion, CO2 photo/electro-conversion mechanism, and Cu-based and Cu-free metal materials for electrocatalytic CO2 reduction Organic-inorganic, metal organic framework, and covalent organic framework hybrid materials for CO2 photo/electro-conversion Single/dual-atom catalysts, homogeneous catalysts, and high-entropy alloys for CO2 photo/electro-conversion Semiconductor composite and carbon-based materials for photocatalytic CO2 reduction, novel routes for CO2 utilization via metal-CO2 batteries, and CO2 conversion into long-chain compounds Providing comprehensive coverage of the subject, CO2 Conversion and Utilization is of high interest for scientific researchers as well as engineers and technicians in industry, including but not limited to photochemists, electrochemists, environmental chemists, catalytic chemists, chemists in industry, and inorganic chemists.

Table of Contents:
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