Nanoparticles in Catalysis: Advances in Synthesis and Applications

Nanoparticles in Catalysis Discover an essential overview of recent advances and trends in nanoparticle catalysis Catalysis in the presence of metal nanoparticles is an important and rapidly developing research field at the frontier of homogeneous and heterogeneous catalysis. In Nanoparticles in Catalysis, accomplished chemists and authors Karine Philippot and Alain Roucoux deliver a comprehensive guide to the key aspects of nanoparticle catalysis, ranging from synthesis, activation methodology, characterization, and theoretical modeling, to application in important catalytic reactions, like hydrogen production and biomass conversion. The book offers readers a review of modern and efficient tools for the synthesis of nanoparticles in solution or onto supports. It emphasizes the application of metal nanoparticles in important catalytic reactions and includes chapters on activation methodology and supported nanoclusters. Written by an international team of leading voices in the field, Nanoparticles in Catalysis is an indispensable resource for researchers and professionals in academia and industry alike. Readers will also benefit from the inclusion of: A thorough introduction to New Trends in the Design of Metal Nanoparticles and Derived Nanomaterials for Catalysis An exploration of Dynamic Catalysis and the Interface Between Molecular and Heterogeneous Catalysts A practical discussion of Metal Nanoparticles in Water: A Relevant Toolbox for Green Catalysis Organometallic Metal Nanoparticles for Catalysis A concise treatment of the opportunities and challenges of CO2 Hydrogenation to Oxygenated Chemicals Over Supported Nanoparticle Catalysts Perfect for catalytic, organic, inorganic, and physical chemists, Nanoparticles in Catalysis will also earn a place in the libraries of chemists working with organometallics and materials scientists seeking a one-stop resource with expert knowledge on the synthesis and characterization of nanoparticle catalysis.

Table of Contents:
Foreword xiii 1 New Trends in the Design of Metal Nanoparticles and Derived Nanomaterials for Catalysis 1 Alain Roucoux and Karine Philippot 1.1 Nanocatalysis: Position, Interests, and Perspectives 1 1.2 Metal Nanoparticles: What Is New? 4 1.3 Conclusions and Perspectives 8 References 9 2 Introduction to Dynamic Catalysis and the Interface Between Molecular and Heterogeneous Catalysts 13 Alexey S. Galushko, Alexey S. Kashin, Dmitry B. Eremin, Mikhail V. Polynski, Evgeniy O. Pentsak, Victor M. Chernyshev, and Valentine P. Ananikov 2.1 Introduction 13 2.2 Dynamic Catalysis 14 2.3 Interface Between Molecular and Heterogeneous Catalysts 17 2.3.1 Direct Observation of Nanoparticle Evolution by Electron Microscopy 17 2.3.2 Through the Interface – Detection of Molecular Species by Mass Spectrometry 19 2.3.3 Pervasiveness of Nanoparticles and the Problem of Catalytic Contamination 22 2.3.4 Computational Modeling of Dynamic Catalytic Systems 24 2.3.4.1 Equilibrium of Leaching and Recapture 24 2.3.4.2 Modeling Leaching, Recapture, and Transformations in Solution 25 2.3.5 Nanoparticle Catalysis in Solvent-Free and Solid-State Organic Reactions 27 2.3.6 Applications of the Mercury Test and Other Poisoning Techniques in the Nanoparticle Catalysis Studies 30 2.3.6.1 Catalyst Poisoning Techniques and Typical Poisons 30 2.3.6.2 Mercury Test 31 2.3.6.3 Fundamental Limitations of the Catalyst Poisoning Techniques for Dynamic Systems 33 2.4 Summary and Conclusions 34 References 36 Part I Nanoparticles in Solution 43 3 Metal Nanoparticles in Water: A Relevant Toolbox for Green Catalysis 45 Audrey Denicourt-Nowicki, Natalia Mordvinova, and Alain Roucoux 3.1 Introduction 45 3.2 Protection by Ligands 46 3.2.1 Hydrogenation Reactions 46 3.2.1.1 Phosphorous Ligands 46 3.2.1.2 Nitrogenated Ligands 47 3.2.1.3 Carbon Ligands 49 3.2.2 Suzuki–Miyaura Coupling Reactions 50 3.2.2.1 Nitrogenated Ligands 50 3.2.2.2 Carbonaceous and Phosphorous Ligands 51 3.3 Stabilization by Surfactants 51 3.3.1 Hydrogenation Reactions 52 3.3.2 Oxidation Reactions 56 3.3.3 Other Reactions 57 3.4 Stabilization by Polymers 58 3.4.1 Hydrogenation Reactions 58 3.4.2 Carbon–Carbon Coupling Reactions 64 3.4.3 Oxidation Reactions 66 3.5 Conclusions and Perspectives 67 References 68 4 Organometallic Metal Nanoparticles for Catalysis 73 M. Rosa Axet and Karine Philippot 4.1 Introduction 73 4.2 Interests of the Organometallic Approach to Study Stabilizer Effect on Metal Surface Properties 74 4.3 Application of Organometallic Nanoparticles as Catalysts for Hydrogenation Reactions 78 4.3.1 Metal Nanoparticles Stabilized with Phosphorus Ligands 78 4.3.2 Metal Nanoparticles Stabilized with N-Heterocyclic Carbenes 80 4.3.3 Metal Nanoparticles Stabilized with Zwitterionic Ligands 82 4.3.4 Metal Nanoparticles Stabilized with Fullerenes 82 4.3.5 Metal Nanoparticles Stabilized with Carboxylic Acids 84 4.3.6 Metal Nanoparticles Stabilized with Miscellaneous Ligands 86 4.3.7 Bimetallic Nanoparticles 88 4.3.8 Supported Nanoparticles 90 4.4 Conclusions 94 References 95 5 Metal Nanoparticles in Polyols: Bottom-up and Top-down Syntheses and Catalytic Applications 99 Trung Dang-Bao, Isabelle Favier, and Montserrat Gómez 5.1 Introduction 99 5.2 Bottom-up Approach: Colloidal Synthesis in Polyols 100 5.2.1 Ethylene Glycol and Poly(ethylene glycol) 100 5.2.2 Glycerol 105 5.2.3 Carbohydrates 108 5.3 Top-down Approach: Sputtering in Polyols 113 5.4 Summary and Conclusions 117 Acknowledgments 118 References 118 6 Catalytic Properties of Metal Nanoparticles Confined in Ionic Liquids 123 Muhammad I. Qadir, Nathália M. Simon, and Jairton Dupont 6.1 Introduction 123 6.2 Stabilization of Metal Nanoparticles in ILs 124 6.3 Synthesis of Soluble Metal Nanoparticles in ILs 125 6.4 Catalytic Application of NPs in ILs 126 6.4.1 Catalytic Hydrogenation of Aromatic Compounds 127 6.4.2 Coupling Reactions in ILs 130 6.4.3 Hydroformylation in ILs 132 6.4.4 Fischer–Tropsch Synthesis in ILs 133 6.4.5 Catalytic Carbon Dioxide Hydrogenation in ILs 133 6.5 Conclusions 134 Acknowledgments 135 References 135 Part II Supported Nanoparticles 139 7 Nanocellulose in Catalysis: A Renewable Support Toward Enhanced Nanocatalysis 141 Tony Jin and Audrey Moores 7.1 Introduction 141 7.2 Nanocellulose-Based Catalyst Design and Synthesis 143 7.2.1 Synthesis of Suspendable, CNC-Based Nanocatalysts 144 7.2.1.1 Unmodified CNCs as a Support for Metal NPs 144 7.2.1.2 Functionalized CNCs as a Support for Metal NPs 145 7.2.2 Nanocellulose-Based Solid Supports for Metal NPs 146 7.2.2.1 CNC-Embedded Supports 146 7.2.2.2 Functionalized CNFs as a Support for Metal NPs 147 7.2.2.3 Use of CNCs as a Source for Carbon Supports 147 7.3 Organic Transformations Catalyzed by Metal NP/nanocellulose Hybrids 148 7.3.1 C–C Coupling Reactions 148 7.3.2 Reduction Reactions 151 7.4 Conclusions 154 References 154 8 Magnetically Recoverable Nanoparticle Catalysts 159 Liane M. Rossi, Camila P. Ferraz, Jhonatan L. Fiorio, and Lucas L. R. Vono 8.1 Introduction 159 8.2 Magnetic Support Material 161 8.2.1 Magnetite Coated with Silica 163 8.2.2 Magnetite Coated with Ceria, Titania, and Other Oxides 165 8.2.3 Magnetite Coated with Carbon-Based Materials 166 8.3 Preparation of Magnetically Recoverable Metal Nanoparticle Catalysts 167 8.3.1 Immobilization of Metal Precursors Before Reduction 167 8.3.2 Decomposition of Organometallic Precursors 170 8.3.3 Immobilization of Colloidal Nanoparticles 172 8.3.4 Influence of Ligands on Catalytic Properties 173 8.4 Summary and Conclusions 176 References 176 9 Synthesis of MOF-Supported Nanoparticles and Their Interest in Catalysis 183 Guowu Zhan and Hua C. Zeng 9.1 Introduction 183 9.2 General Synthetic Methodologies 185 9.2.1 Catalytic Properties of Metal Nanoparticles 185 9.2.2 Synthetic Strategies of Metal Nanoparticles 187 9.2.2.1 Wet Chemical Reduction Method 187 9.2.2.2 Metal Vapor Condensation/Deposition Method 187 9.2.2.3 Electrochemical Method 188 9.2.2.4 Biosynthesis Method 188 9.2.3 Catalytic Activity and Catalytic Sites of MOFs 188 9.2.4 Porosity of MOFs for Catalysis Applications 189 9.2.5 Synthetic Strategies of MOFs 190 9.2.5.1 Electrochemical Method 191 9.2.5.2 Sonochemical Method 191 9.2.5.3 Microwave Irradiation Method 192 9.2.5.4 Mechanochemical Method 192 9.2.5.5 Synthesis of MOFs in Green Solvents 192 9.2.5.6 Microemulsion Method 193 9.2.5.7 Transformation from Solid Matters to MOFs 193 9.2.6 Integration Methods of MNPs with MOFs 194 9.2.6.1 Preformation of MNPs and Growth of MOFs 195 9.2.6.2 Incorporation of Metal Precursors Followed by in Situ Reduction 197 9.2.6.3 One-pot Integration of MOFs and MNPs 199 9.3 Architectural Designs and Catalytic Applications of MNP/MOF Nanocomposites 200 9.3.1 Zero-Dimensional MNP/MOF Nanocomposites 201 9.3.2 One-Dimensional MNP/MOF Nanocomposites 201 9.3.3 Two-Dimensional MNP/MOF Nanocomposites 203 9.3.4 Three-Dimensional MNP/MOF Nanocomposites 203 9.3.5 Other Representative Structures of MNP/MOF Composites 205 9.3.5.1 Core–Shell/Yolk–Shell Nanostructures 205 9.3.5.2 Sandwich-like Nanostructures 206 9.3.5.3 Formation of Nanoreactors with a Central Cavity 208 9.4 Summary and Conclusions 208 References 210 10 Silica-Supported Nanoparticles as Heterogeneous Catalysts 215 Mahak Dhiman, Baljeet Singh, and Vivek Polshettiwar 10.1 Introduction 215 10.2 Deposition Methods of Metal NPs 216 10.2.1 Wet Impregnation Method 216 10.2.2 Deposition–Precipitation Method 217 10.2.3 Colloidal Immobilization Method 218 10.2.4 Solid-State Grinding Method 219 10.2.5 Postsynthetic Grafting Method 220 10.3 Application of Silica-Supported NPs in Catalysis 221 10.3.1 Oxidation Reactions 221 10.3.1.1 CO Oxidation 221 10.3.1.2 Alcohol Oxidation 222 10.3.1.3 Hydrolysis of Silane 224 10.3.2 Hydrogenation Reactions 226 10.3.3 Carbon–Carbon (C–C) Coupling Reactions 230 10.4 Conclusion 234 References 235 Part III Application 239 11 CO2 Hydrogenation to Oxygenated Chemicals Over Supported Nanoparticle Catalysts: Opportunities and Challenges 241 Qiming Sun, Zhenhua Zhang, and Ning Yan 11.1 Introduction 241 11.2 CO2 Hydrogenation into Formic Acid 242 11.3 CO2 Hydrogenation to Methanol 247 11.4 CO2 Hydrogenation to Dimethyl Ether 250 11.5 Perspectives and Conclusion 252 Acknowledgment 253 References 253 12 Rebirth of Ruthenium-Based Nanomaterials for the Hydrogen Evolution Reaction 257 Nuria Romero, Jordi Creus, Jordi García-Antón, Roger Bofill, and Xavier Sala 12.1 Introduction 257 12.2 Relevant Figures of Merit 258 12.3 Factors Ruling the Performance of Ru-Based NPs in HER Electrocatalysis 261 12.3.1 Surface Composition 262 12.3.2 Phase Structure and Degree of Crystallinity 265 12.3.3 Influence of the C Matrix or the C-Based Support 266 12.3.4 Influence of Heteroatoms 270 12.3.4.1 Phosphorous 270 12.3.4.2 Metals and Semimetals 272 12.4 Factors Ruling the Performance of Ru-Based NPs in HER Photocatalysis 272 12.5 Summary and Conclusions 274 Acknowledgments 275 References 275 13 Nanocatalytic Architecture for the Selective Dehydrogenation of Formic Acid 279 Ismail B. Baguc, Gulsah S. Kanberoglu, Mehmet Yurderi, Ahmet Bulut, Metin Celebi, Murat Kaya, and Mehmet Zahmakiran 13.1 Introduction 279 13.2 Monometallic Palladium-Based Nanocatalysts 282 13.3 Bimetallic Palladium-Based Nanocatalysts 286 13.3.1 Bimetallic Pd-Containing Nanocatalysts in the Physical Mixture Form 286 13.3.2 Bimetallic Pd-Containing Nanocatalysts in the Alloy Structure 287 13.3.3 Bimetallic Pd-Containing Nanocatalysts in the Core@Shell Structure 291 13.3.4 Trimetallic Pd-Containing Nanocatalysts 294 13.3.5 Other Pd-Free Nanocatalysts 297 13.4 Summary and Conclusions 301 Acknowledgments 302 References 302 Part IV Activation and Theory 307 14 Magnetically Induced Nanocatalysis for Intermittent Energy Storage: Review of the Current Status and Prospects 309 Julien Marbaix, Nicolas Mille, Julian Carrey, Katerina Soulantica, and Bruno Chaudret 14.1 Introduction 309 14.2 General Context and Historical Aspects 310 14.3 Characteristics of the Nanocatalysts Used in Magnetic Hyperthermia 312 14.3.1 Metal Oxide Nanomaterials 312 14.3.2 Iron (0) Nanoparticles 312 14.3.3 Iron Carbide Fe(C) Nanomaterials 312 14.3.4 Bimetallic FeNi Nanoparticles 313 14.3.5 Bimetallic FeCo Nanoparticles 313 14.3.6 CoNi Nanoparticles 314 14.4 Catalytic Applications in Liquid Solution and Gas Phase 314 14.4.1 Gas-Phase Catalysis 314 14.4.1.1 Catalysis Activated by Magnetically Heated Micro- and Macroscaled Materials 314 14.4.1.2 Catalysis Activated by Magnetic Heating of Nanoparticles 316 14.4.2 Catalytic Reactions in Solution 318 14.5 Perspectives 322 14.5.1 Stability of the Catalytic Bed During Catalysis by Magnetic Heating 322 14.5.2 Thermal Management and Process Chemistry Using Magnetic Heating for Catalytic Applications 322 14.6 Perspective of the Integration for Renewable Energy Use 323 14.6.1 Interest of Power to Gas and Catalysis Using Magnetic Heating for Renewable Energy Use 323 14.6.2 Energy Efficiency and Environmental Considerations of Catalysis by Magnetic Heating 324 14.7 Conclusion 326 References 327 15 Sabatier Principle and Surface Properties of Small Ruthenium Nanoparticles and Clusters: Case Studies 331 Iker del Rosal and Romuald Poteau 15.1 Introduction 331 15.2 C–H Activation and H/D Isotopic Exchange in Amino Acids and Derivatives 333 15.2.1 Reference Activation and Dissociation Energies 333 15.2.2 H/D Exchange Mechanism 334 15.2.3 Bare Cluster 336 15.2.4 Ru13D19 338 15.2.5 Ru13Dn, n = 6–17 338 15.2.6 Short Discussion 338 15.3 Hydrogen Evolution Reaction 340 15.3.1 Introduction 340 15.3.2 4-Phenylpyridine-Protected RuNPs 341 15.3.3 Optimal Ligands for the HER? 344 15.4 Summary 346 15.5 Computational Details 347 Acknowledgments 348 References 348 Index 353

About the Author :
Karine Philippot is Senior Researcher at CNRS and Head of the Engineering of Metal Nanoparticles group at the Laboratory of Coordination Chemistry of Toulouse in France. Her research focus is on the synthesis of metal nanoparticles and derived nanomaterials by applying molecular chemistry concepts, for their application in colloidal or supported catalysis and energy. Alain Roucoux is Full Professor at the École Nationale Supérieure de Chimie de Rennes and Head of the Nanocatalysis group at the Institut des Sciences Chimiques de Rennes in France. His research area concerns the synthesis of nanoparticles in water and their application in polyphasic catalysis.