Visible-Light-Active Photocatalysis

Preface xvii Part I Visible-Light Active Photocatalysis – Research and Technological Advancements 1 1 Research Frontiers in Solar Light Harvesting 3 Srabanti Ghosh 1.1 Introduction 3 1.2 Visible-Light-Driven Photocatalysis for Environmental Protection 4 1.3 Photocatalysis forWater Splitting 8 1.4 Photocatalysis for Organic Transformations 11 1.5 Mechanistic Studies of Visible-Light-Active Photocatalysis 13 1.6 Summary 14 References 15 2 Recent Advances on Photocatalysis forWater Detoxification and CO2 Reduction 27 Carlotta Raviola and Stefano Protti 2.1 Introduction 27 2.2 Photocatalysts for Environmental Remediation and CO2 Reduction 30 2.3 Photoreactors for Solar Degradation of Organic Pollutants and CO2 Reduction 38 2.4 Conclusion 44 Acknowledgment 44 References 45 3 Fundamentals of PhotocatalyticWater Splitting (Hydrogen and Oxygen Evolution) 53 Sanjib Shyamal, Paramita Hajra, Harahari Mandal, Aparajita Bera, Debasis Sariket, and Chinmoy Bhattacharya 3.1 Introduction 53 3.2 Strategy for Development of Photocatalyst Systems forWater Splitting 54 3.3 Electrochemistry of Semiconductors at the Electrolyte Interface 56 3.4 Effect of Light at the Semiconductor–Electrolyte Interface 58 3.5 Conversion and Storage of Sunlight 62 3.6 Electrolysis and Photoelectrolysis 63 3.7 Development of Photocatalysts for Solar-DrivenWater Splitting 65 3.8 Approaches to Develop Visible-Light-AbsorbingMetal Oxides 66 3.9 Conclusions 68 References 68 4 Photoredox Catalytic Activation of Carbon—Halogen Bonds: C—H Functionalization Reactions under Visible Light 75 Javier I. Bardagi and Indrajit Ghosh 4.1 Introduction 75 4.2 Activation of Alkyl Halides 77 4.3 Activation of Aryl Halides 91 4.4 Factors That Determine the Carbon–Halogen Bond Activation of Aryl Halides 108 4.5 Factors That Determine the Yields of the C—H Arylated Products 109 4.6 Achievements and Challenges Ahead 109 4.7 Conclusion 110 References 110 Part II Design and Developments of Visible Light Active Photocatalysis 115 5 Black TiO2: The New-Generation Photocatalyst 117 Sanjay Gopal Ullattil, Soumya B. Narendranath, and Pradeepan Periyat 5.1 Introduction 117 5.2 Designing Black TiO2 Nanostructures 118 5.3 Black TiO2 as Photocatalyst 122 5.4 Conclusions 123 References 123 6 Effect of Modification of TiO2 with Metal Nanoparticles on Its Photocatalytic Properties Studied by Time-Resolved Microwave Conductivity 129 Hynd Remita,María GuadalupeMéndezMedrano, and Christophe Colbeau-Justin 6.1 Introduction 129 6.2 Deposition of Metal Nanoparticles by Radiolysis and by Photodeposition Method 130 6.3 Electronic Properties Studied Time-Resolved Microwave Conductivity 132 6.4 Modification of TiO2 with Au Nanoparticles 138 6.5 Modification of TiO2 with Bi Clusters 144 6.6 Surface Modification of TiO2 with Bimetallic Nanoparticles 146 6.7 The Effect of Metal Cluster Deposition Route on Structure and Photocatalytic Activity of Mono- and Bimetallic Nanoparticles Supported on TiO2 155 6.8 Summary 156 References 157 7 Glassy Photocatalysts: New Trend in Solar Photocatalysis 165 Bharat B. Kale,Manjiri A. Mahadadalkar, and Ashwini P. Bhirud 7.1 Introduction 165 7.2 Fundamentals of H2S Splitting 166 7.3 Designing the Assembly for H2S Splitting 168 7.4 Chalcogenide Photocatalysts 170 7.5 Limitations of Powder Photocatalysts 170 7.6 Glassy Photocatalyst: Innovative Approach 171 7.7 General Methods for Glasses Preparation 172 7.8 Color of the Glass – Bandgap Engineering by Growth of 7.9 CdS–Glass Nanocomposite 174 7.10 Bi2S3–Glass Nanocomposite 178 7.11 Ag3PO4–Glass Nanocomposite 179 7.12 Summary 183 Acknowledgments 184 References 184 8 Recent Developments in Heterostructure-Based Catalysts for Water Splitting 191 J. A. SavioMoniz 8.1 Introduction 191 8.2 Visible-Light-Responsive Junctions 195 8.3 Visible-Light-Driven Photocatalyst/OEC Junctions 207 8.4 Observation of Charge Carrier Kinetics in Heterojunction Structure 209 8.5 Conclusions 215 References 216 9 Conducting Polymers Nanostructures for Solar-Light Harvesting 227 Srabanti Ghosh, Hynd Remita, and Rajendra N. Basu 9.1 Introduction 227 9.2 Conducting Polymers as Organic Semiconductor 228 9.3 Conducting Polymer-Based Nanostructured Materials 231 9.4 Synthesis of Conducting Polymer Nanostructures 231 9.5 Applications of Conducting Polymer 233 9.6 Conclusion 245 References 246 Part III Visible Light Active Photocatalysis for Solar Energy Conversion and Environmental Protection 253 10 Sensitization of TiO2 by Dyes: A Way to Extend the Range of Photocatalytic Activity of TiO2 to the Visible Region 255 Marta I. Litter, Enrique San Román, the late María A. Grela, Jorge M. Meichtry, and Hernán B. Rodríguez 10.1 Introduction 255 10.2 Mechanisms Involved in theUse of Dye-Modified TiO2 Materials for Transformation of Pollutants and Hydrogen Production under Visible Irradiation 256 10.3 Use of Dye-Modified TiO2 Materials for Energy Conversion in Dye-Sensitized Solar Cells 260 10.4 Self-Sensitized Degradation of Dye Pollutants 262 10.5 Use of Dye-Modified TiO2 for Visible-Light-Assisted Degradation of Colorless Pollutants 265 10.6 Water Splitting and Hydrogen Production using Dye-Modified TiO2 Photocatalysts under Visible Light 269 10.7 Conclusions 270 Acknowledgement 271 References 271 11 Advances in the Development of Novel Photocatalysts for Detoxification 283 Ciara Byrne,Michael Nolan, Swagata Banerjee, Honey John, Sheethu Jose, Pradeepan Periyat, and Suresh C. Pillai 11.1 Introduction 283 11.2 Theoretical Studies of Photocatalysis 285 11.3 Metal-Doped Photocatalysts for Detoxification 296 11.4 Graphene-TiO2 Composites for Detoxification 299 11.5 Commercial Applications of Photocatalysis in Environmental Detoxification 303 11.6 Conclusions 313 References 313 12 Metal-Free Organic Semiconductors for Visible-Light-Active Photocatalytic Water Splitting 329 S. T. Nishanthi, Battula Venugopala Rao, and Kamalakannan Kailasam 12.1 Introduction 329 12.2 Organic Semiconductors for PhotocatalyticWater Splitting and Emergence of Graphitic Carbon Nitrides 331 12.3 Graphitic Carbon Nitrides for PhotocatalyticWater Splitting 332 12.4 Novel Materials 349 12.5 Conclusions and Perspectives 351 References 352 13 Solar Photochemical Splitting ofWater 365 Srinivasa Rao Lingampalli and C. N. R. Rao 13.1 Introduction 365 13.2 PhotocatalyticWater Splitting 366 13.3 OverallWater Splitting 371 13.4 Oxidation ofWater 376 13.5 Reduction ofWater 380 13.6 Coupled Reactions 386 13.7 Summary and Outlook 387 Acknowledgments 387 References 387 14 Recent Developments on Visible-Light Photoredox Catalysis by Organic Dyes for Organic Synthesis 393 Shounak Ray, Partha Kumar Samanta, and Papu Biswas 14.1 Introduction 393 14.2 General Mechanism 393 14.3 Recent Application of Organic Dyes as Visible-Light Photoredox Catalysts 396 14.4 Conclusion 415 Abbreviations 415 References 415 15 Visible-Light Heterogeneous Catalysts for Photocatalytic CO2 Reduction 421 Sanyasinaidu Boddu, S.T. Nishanthi, and Kamalakannan Kailasam 15.1 Introduction 421 15.2 Basic Principles of Photocatalytic CO2 Reduction 422 15.3 Inorganic Semiconductors 424 15.4 Organic Semiconductors 430 15.5 Semiconductor Heterojunctions 436 15.6 Conclusion and Perspectives 437 References 438 Part IV Mechanistic Studies of Visible Light Active Photocatalysis 447 16 Band-gap Engineering of Photocatalysts: Surface Modification versus Doping 449 Ewa Kowalska, ZhishunWei, and Marcin Janczarek 16.1 Introduction 449 16.2 Doping 451 16.3 Surface Modification 458 16.4 Heterojunctions 468 16.5 Z-Scheme 470 16.6 Hybrid Nanostructures 471 16.7 Summary 473 References 473 17 Roles of the Active Species Generated during Photocatalysis 485 Mats Jonsson 17.1 Introduction 485 17.2 Mechanism of Photocatalysis in TiO2/Water Systems 486 17.3 Active Species Generated at the Catalyst/Water Interface 486 17.4 Oxidative Degradation of Solutes Present in the Aqueous Phase 490 17.5 Impact of H2O2 on Oxidative Degradation of Solutes Present in the Aqueous Phase 492 17.6 The Role of Common Anions Present in the Aqueous Phase 493 17.7 Summary of Active Species Present in Heterogeneous Photocatalysis in Water 494 References 495 18 Visible-Light-Active Photocatalysis: Nanostructured Catalyst Design,Mechanisms, and Applications 499 Ramachandran Vasant Kumar andMichael Coto 18.1 Introduction 499 18.2 Historical Background 499 18.3 Basic Concepts 501 18.4 Structure of TiO2 504 18.5 Photocatalytic Reactions 506 18.6 Physical Architectures of TiO2 507 18.7 Visible-Light Photocatalysis 509 18.8 Ion Doping and Ion Implantation 510 18.9 Dye Sensitization 513 18.10 Noble Metal Loading 514 18.11 Coupled Semiconductors 518 18.12 Carbon–TiO2 Composites 518 18.13 Alternatives to TiO2 520 18.14 Conclusions 521 References 522 Part V Challenges and Perspectives of Visible Light Active Photocatalysis for Large Scale Applications 527 19 Quantum Dynamics Effects in Photocatalysis 529 Abdulrahiman Nijamudheen and Alexey V. Akimov 19.1 Introduction 529 19.2 Computational Approaches to Model Adiabatic Processes in Photocatalysis 531 19.3 Computational Approaches to Model Nonadiabatic Effects in Photocatalysis 532 19.4 Quantum Tunneling in Adiabatic and Nonadiabatic Dynamics 535 19.5 The Mechanisms of Organic Reactions Catalyzed by Semiconductor Photocatalysts 541 19.5.1 Methanol Photooxidation on Semiconductor Surfaces 541 19.5.2 Water-Splitting Reactions on Semiconductor Surfaces 544 19.5.3 Carbon Oxide Redox Reactions on Semiconductor Surfaces 546 19.6 Conclusions and Outlook 547 References 549 20 An Overview of Solar Photocatalytic Reactor Designs and Their Broader Impact on the Environment 567 Justin D. Glover, Adam C. Hartley, Reid A.Windmiller, Naoma S. Nelsen, and Joel E. Boyd 20.1 Introduction 567 20.2 Materials 568 20.3 Slurry-Style Photocatalysis 569 20.4 Deposited Photocatalysts 569 20.5 Applications 570 20.6 Conclusion 577 References 577 21 Conclusions and FutureWork 585 Srabanti Ghosh Index 589