Following introductory chapters on environmental photocatalysis, water splitting, and applications in synthetic chemistry, further chapters focus on the synthesis and design of photocatalysts, solar energy conversion, and such environmental aspects as the removal of water pollutants, photocatalytic conversion of CO2. Besides metal oxide-based photocatalysts, the authors cover other relevant material classes including carbon-based nanomaterials and novel hybrid materials. Chapters on mechanistic aspects, computational modeling of photocatalysis and Challenges and perspectives of solar reactor design for industrial applications complete this unique survey of the subject.
With its in-depth discussions ranging from a comprehensive understanding to the engineering of materials and applied devices, this is an invaluable resource for a range of disciplines.
Table of Contents
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
