Nanoparticles in Catalysis
Advances in Synthesis and Applications

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:

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.

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 Ru₁₃D_n, 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

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.