V List of Contributors XI Preface XV Foreword XIX Symbols and Abbreviations XXI Part I Synthesis, Characterization, and Evaluation of Nanocatalysts in Ionic Liquids 1 1 Fe, Ru, and Os Nanoparticles 3 Madhu Kaushik, Yuting Feng, Nathaniel Boyce, and Audrey Moores 1.1 Introduction 3 1.2 Synthesis of Fe, Ru, and Os NPs in ILs 4 1.2.1 Synthesis via Reduction of Metal Precursors or Ligands 6 1.2.2 Synthesis via Decomposition of Metal Precursors 7 1.2.3 The Use of Additional Stabilizers and Functional ILs 8 1.3 Ionic Liquid Stabilization of Metal Nanoparticles 9 1.3.1 Ionic Liquid Properties 9 1.3.2 Molecular Aspects of Ionic Liquid Stabilization of Metal Nanoparticles 10 1.4 Applications of Ru, Fe, and Os Nanoparticles to Catalysis 11 1.4.1 Applications of Ru NPs in ILs to Catalysis 12 1.4.1.1 Hydrogenation of Olefins 12 1.4.1.2 Hydrogenation of Arenes 16 1.4.1.3 Other Types of Hydrogenations 17 1.4.1.4 Biomass Conversion 18 1.4.1.5 Miscellaneous Reactions 20 1.4.2 Applications of Fe Nanoparticles to Catalysis 20 1.5 Conclusion 21 Acknowledgments 21 References 21
VI 2 Co, Rh, and Ir Nanoparticles 25 Jackson D. Scholten and Muhammad I. Qadir 2.1 Introduction 25 2.2 Chemical Routes for the Synthesis of Metal NPs in ILs 26 2.2.1 Chemical Reduction 26 2.2.2 Thermal/Microwave Decomposition 29 2.3 Catalytic Application of Metal NPs in ILs 31 2.3.1 Hydrogenation Reaction 31 2.3.2 Miscellaneous Reactions 34 2.4 Conclusions 37 References 37 3 Ni and Pt Nanoparticles 41 Carla Weber Scheeren 3.1 Introduction 41 3.2 Synthesis and Characterization of Pt NPs in ILs 42 3.3 Catalytic Applications of Pt NPs in ILs 47 3.4 Synthesis and Characterization of Ni NPs in ILs 48 3.5 Catalytic Applications of Ni NPs in ILs 53 3.6 Summary and Conclusions 58 Symbols and Abbreviations 59 Characterization Methods 59 Ionic Liquids 59 References 59 4 Pd Nanoparticles for Coupling Reactions and Domino/Tandem Reactions 63 Anna M. Trzeciak 4.1 Introduction 63 4.2 Formation of Pd NPs in ILs 65 4.3 The Heck Coupling 68 4.4 The Suzuki Reaction 74 4.5 The Stille Coupling 75 4.6 The Sonogashira Coupling 76 4.7 Summary and Conclusions 78 Acknowledgments 79 References 79 5 Soluble Pd Nanoparticles for Catalytic Hydrogenation 83 Ran Zhang and Zhenshan Hou 5.1 Introduction 83 5.2 Synthesis of Pd Nanoparticles in ILs 85 5.2.1 Reduction of Pd NPs in ILs 86 5.2.2 Type of Metal Precursor 87
VII 5.2.3 Reducing Agents and Ionic Liquids 87 5.3 Pd Nanoparticles for Hydrogenation 88 5.3.1 Hydrogenation of Alkene, Alkynes, and Dienes 88 5.3.2 Hydrogenation of Aldehydes and Aromatic Nitro Compounds 90 5.3.3 Hydrogenation of Phenols 91 5.3.4 Hydrogenation of Ketones 91 5.3.5 Hydrogenation of Biomass 92 5.4 Summary and Conclusions 93 Ionic Liquid Abbreviations 93 References 94 6 Au, Ag, and Cu Nanostructures 97 Abhinandan Banerjee and Robert W. J. Scott 6.1 Introduction 97 6.2 Au NPs in the Presence of ILs 98 6.2.1 Early Examples and Chemical Synthesis Protocols 98 6.2.2 Advances in IL-Phase Au NP Synthesis: Physical Methods 102 6.2.3 Electrochemical Applications of AuNP/IL Composites 104 6.2.4 AuNP/IL Composites in Sensing 104 6.2.5 Miscellaneous Applications of AuNP/IL Composites 105 6.3 Catalytic Applications of AuNP/IL Composites 106 6.4 Ag NPs in the Presence of ILs 108 6.4.1 Novel Approaches for IL-Phase Synthesis of Ag NPs 108 6.4.2 IL-Phase Ag NPs for Sensors 110 6.4.3 Plasmonic Nanocatalysis with Ag NPs in ILs 111 6.4.4 Anti-pathogenic Applications of Ag NPs in ILs 112 6.5 Cu NPs in the Presence of ILs 113 6.5.1 Synthesis of IL-Phase Cu NPs for Miscellaneous Applications 113 6.5.2 Catalysis with IL-Phase Cu NPs 116 6.6 Summary and Conclusions 118 Acronyms 119 References 119 7 Bimetallic Nanoparticles in Ionic Liquids: Synthesis and Catalytic Applications 125 Isabelle Favier, Emmanuelle Teuma, and Montserrat Gómez 7.1 Introduction 125 7.2 Synthesis of Bimetallic Nanoparticles in Ionic Liquids 127 7.2.1 Bottom-Up Methodologies 127 7.2.1.1 Chemical Reduction 127 7.2.1.2 Thermal Decomposition 132 7.2.1.3 Electrochemical Methods 134 7.2.2 Top-Down Methodology 135
VIII 7.3 Applications in Catalysis 137 7.3.1 Reactions under Hydrogen Pressure: Hydrogenation Hydrogenolysis Dehalogenation 137 7.3.1.1 Hydrogenation Reactions 137 7.3.1.2 Hydrogenolysis Reactions 140 7.3.1.3 Dehalogenation Reactions 140 7.3.2 Oxidation 141 7.4 Summary and Outlook 143 Acknowledgments 144 References 144 8 Synthesis and Application of Metal Nanoparticle Catalysts in Ionic Liquid Media using Metal Carbonyl Complexes as Precursors 147 Raquel Marcos Esteban and Christoph Janiak 8.1 Introduction 147 8.2 Metal Carbonyls Synthesis, Structure, and Bonding 150 8.3 Metal Carbonyls for the Synthesis of Metal Nanoparticles (M-NPs) 152 8.3.1 Synthesis in Ionic Liquids 153 8.3.2 Synthesis in ILs with Deposition on Support 157 8.4 Catalytic Applications of Metal Nanoparticles from Metal Carbonyls in ILs 160 8.5 Conclusions 163 Acknowledgment 164 References 164 9 Top-Down Synthesis Methods for Nanoscale Catalysts 171 Tsukasa Torimoto, Tatsuya Kameyama, and Susumu Kuwabata 9.1 Introduction 171 9.2 Sputter Deposition of Metals in RTILs 172 9.2.1 Uniformly Dispersed Nanoparticles in RTILs via Sputter Deposition of a Single Element 172 9.2.2 Synthesis Mechanism of Nanoparticles via RTIL/Metal Sputtering 178 9.2.3 Preparation of Alloy Nanoparticles and Control of Their Composition 182 9.2.4 Sequential Sputter Deposition for Synthesizing Nanocomposite Particles 185 9.2.5 Film Preparation on the Surfaces of RTILs 186 9.2.6 Immobilization of Nanoparticles Sputter-Deposited in RTILs 187 9.2.7 Application/Plasmonic Materials 189 9.2.8 Application/Photoluminescence Materials 192 9.2.9 Application/Electrocatalysts 192 9.2.10 Application/Catalysts for Organic Syntheses 195
IX 9.3 Thermal Vapor Deposition on RTILs for Preparation of Metal Nanoparticles 196 9.4 Laser-Induced Downsizing and Ablation of Materials 197 9.5 Preparation of Single Crystals by Vapor Deposition onto RTILs 199 9.6 Conclusion 202 References 203 10 Electrochemical Preparation of Metal Nanoparticles in Ionic Liquids 207 Yasushi Katayama 10.1 Introduction 207 10.2 Basics of Electrodeposition 208 10.3 Electrodeposition of Silver and Formation of Silver Nanoparticles in Ionic Liquids 210 10.4 Electrochemical Formation of the Nanoparticles of Various Metals 215 10.4.1 Iron, Cobalt, and Nickel 215 10.4.2 Palladium 218 10.4.3 Gold 220 10.4.4 Platinum 222 10.5 Summary and Conclusions 225 References 227 Part II Perspectives for Application of Nanocatalysts in Ionic Liquids 231 11 Tailoring Biomass Conversions using Ionic Liquid Immobilized Metal Nanoparticles 233 Srinidhi Narayanan, Jiaguang Zhang, and Ning Yan 11.1 Introduction 233 11.2 Cellulose 234 11.3 Lignin 238 11.4 Fatty Acid and Its Derivatives 241 11.5 Other Biomass Substrates 243 11.6 Conclusion 245 References 245 12 Nanoparticles on Supported Ionic Liquid Phases Opportunities for Application in Catalysis 249 Pedro Migowski, Kylie L. Luska, and Walter Leitner 12.1 Introduction 249 12.2 Synthesis of Supported Ionic Liquid Phases (SILPs) 250 12.3 Nanoparticles Immobilized onto Supported Ionic Liquid Phases (NPs@SILPs) 252 12.3.1 Nanoparticles Supported onto Physisorbed SILPs 254
X 12.3.2 Nanoparticles Supported onto Chemisorbed SILPs 255 12.4 Catalytic Applications of NPs@SILPs 256 12.4.1 C C Coupling 257 12.4.1.1 Nonfunctionalized ILs 257 12.4.1.2 Functionalized ILs 259 12.4.2 Hydrogenation 262 12.4.2.1 Nonfunctionalized ILs 262 12.4.2.2 Functionalized ILs 264 12.5 Summary and Conclusions 268 Acknowledgments 269 References 269 13 Photovoltaic, Photocatalytic Application, and Water Splitting 275 Adriano F. Feil, Heberton Wender, and Renato V. Gonçalves 13.1 Introduction 275 13.2 Photovoltaic Cells 276 13.2.1 Working Principles of a DSSC 276 13.2.2 ILs in Photovoltaic Cells 277 13.3 Photocatalytic Processes 281 13.3.1 Principles of Photocatalysis 281 13.3.2 ILs in Photocatalysis 282 13.4 Water Splitting 285 13.4.1 Principles of Photocatalytic and Photoelectrochemical Water Splitting 286 13.4.2 Nanostructured Semiconductor for Photocatalytic WS Reaction 287 13.4.3 Nanostructured Semiconductor for the PEC WS Reaction 289 13.5 Summary and Conclusions 291 References 292 Index 295