Nanoparticles in Catalysis

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.

• Foreword xiii1 New Trends in the Design of Metal Nanoparticles and Derived Nanomaterials for Catalysis 1Alain Roucoux and Karine Philippot1.1 Nanocatalysis: Position, Interests, and Perspectives 11.2 Metal Nanoparticles: What Is New? 41.3 Conclusions and Perspectives 8References 92 Introduction to Dynamic Catalysis and the Interface Between Molecular and Heterogeneous Catalysts 13Alexey S. Galushko, Alexey S. Kashin, Dmitry B. Eremin, Mikhail V. Polynski, Evgeniy O. Pentsak, Victor M. Chernyshev, and Valentine P. Ananikov2.1 Introduction 132.2 Dynamic Catalysis 142.3 Interface Between Molecular and Heterogeneous Catalysts 172.3.1 Direct Observation of Nanoparticle Evolution by Electron Microscopy 172.3.2 Through the Interface – Detection of Molecular Species by Mass Spectrometry 192.3.3 Pervasiveness of Nanoparticles and the Problem of Catalytic Contamination 222.3.4 Computational Modeling of Dynamic Catalytic Systems 242.3.4.1 Equilibrium of Leaching and Recapture 242.3.4.2 Modeling Leaching, Recapture, and Transformations in Solution 252.3.5 Nanoparticle Catalysis in Solvent-Free and Solid-State Organic Reactions 272.3.6 Applications of the Mercury Test and Other Poisoning Techniques in the Nanoparticle Catalysis Studies 302.3.6.1 Catalyst Poisoning Techniques and Typical Poisons 302.3.6.2 Mercury Test 312.3.6.3 Fundamental Limitations of the Catalyst Poisoning Techniques for Dynamic Systems 332.4 Summary and Conclusions 34References 36Part I Nanoparticles in Solution 433 Metal Nanoparticles in Water: A Relevant Toolbox for Green Catalysis 45Audrey Denicourt-Nowicki, Natalia Mordvinova, and Alain Roucoux3.1 Introduction 453.2 Protection by Ligands 463.2.1 Hydrogenation Reactions 463.2.1.1 Phosphorous Ligands 463.2.1.2 Nitrogenated Ligands 473.2.1.3 Carbon Ligands 493.2.2 Suzuki–Miyaura Coupling Reactions 503.2.2.1 Nitrogenated Ligands 503.2.2.2 Carbonaceous and Phosphorous Ligands 513.3 Stabilization by Surfactants 513.3.1 Hydrogenation Reactions 523.3.2 Oxidation Reactions 563.3.3 Other Reactions 573.4 Stabilization by Polymers 583.4.1 Hydrogenation Reactions 583.4.2 Carbon–Carbon Coupling Reactions 643.4.3 Oxidation Reactions 663.5 Conclusions and Perspectives 67References 684 Organometallic Metal Nanoparticles for Catalysis 73M. Rosa Axet and Karine Philippot4.1 Introduction 734.2 Interests of the Organometallic Approach to Study Stabilizer Effect on Metal Surface Properties 744.3 Application of Organometallic Nanoparticles as Catalysts for Hydrogenation Reactions 784.3.1 Metal Nanoparticles Stabilized with Phosphorus Ligands 784.3.2 Metal Nanoparticles Stabilized with N-Heterocyclic Carbenes 804.3.3 Metal Nanoparticles Stabilized with Zwitterionic Ligands 824.3.4 Metal Nanoparticles Stabilized with Fullerenes 824.3.5 Metal Nanoparticles Stabilized with Carboxylic Acids 844.3.6 Metal Nanoparticles Stabilized with Miscellaneous Ligands 864.3.7 Bimetallic Nanoparticles 884.3.8 Supported Nanoparticles 904.4 Conclusions 94References 955 Metal Nanoparticles in Polyols: Bottom-up and Top-down Syntheses and Catalytic Applications 99Trung Dang-Bao, Isabelle Favier, and Montserrat Gómez5.1 Introduction 995.2 Bottom-up Approach: Colloidal Synthesis in Polyols 1005.2.1 Ethylene Glycol and Poly(ethylene glycol) 1005.2.2 Glycerol 1055.2.3 Carbohydrates 1085.3 Top-down Approach: Sputtering in Polyols 1135.4 Summary and Conclusions 117Acknowledgments 118References 1186 Catalytic Properties of Metal Nanoparticles Confined in Ionic Liquids 123Muhammad I. Qadir, Nathália M. Simon, and Jairton Dupont6.1 Introduction 1236.2 Stabilization of Metal Nanoparticles in ILs 1246.3 Synthesis of Soluble Metal Nanoparticles in ILs 1256.4 Catalytic Application of NPs in ILs 1266.4.1 Catalytic Hydrogenation of Aromatic Compounds 1276.4.2 Coupling Reactions in ILs 1306.4.3 Hydroformylation in ILs 1326.4.4 Fischer–Tropsch Synthesis in ILs 1336.4.5 Catalytic Carbon Dioxide Hydrogenation in ILs 1336.5 Conclusions 134Acknowledgments 135References 135Part II Supported Nanoparticles 1397 Nanocellulose in Catalysis: A Renewable Support Toward Enhanced Nanocatalysis 141Tony Jin and Audrey Moores7.1 Introduction 1417.2 Nanocellulose-Based Catalyst Design and Synthesis 1437.2.1 Synthesis of Suspendable, CNC-Based Nanocatalysts 1447.2.1.1 Unmodified CNCs as a Support for Metal NPs 1447.2.1.2 Functionalized CNCs as a Support for Metal NPs 1457.2.2 Nanocellulose-Based Solid Supports for Metal NPs 1467.2.2.1 CNC-Embedded Supports 1467.2.2.2 Functionalized CNFs as a Support for Metal NPs 1477.2.2.3 Use of CNCs as a Source for Carbon Supports 1477.3 Organic Transformations Catalyzed by Metal NP/nanocellulose Hybrids 1487.3.1 C–C Coupling Reactions 1487.3.2 Reduction Reactions 1517.4 Conclusions 154References 1548 Magnetically Recoverable Nanoparticle Catalysts 159Liane M. Rossi, Camila P. Ferraz, Jhonatan L. Fiorio, and Lucas L. R. Vono8.1 Introduction 1598.2 Magnetic Support Material 1618.2.1 Magnetite Coated with Silica 1638.2.2 Magnetite Coated with Ceria, Titania, and Other Oxides 1658.2.3 Magnetite Coated with Carbon-Based Materials 1668.3 Preparation of Magnetically Recoverable Metal Nanoparticle Catalysts 1678.3.1 Immobilization of Metal Precursors Before Reduction 1678.3.2 Decomposition of Organometallic Precursors 1708.3.3 Immobilization of Colloidal Nanoparticles 1728.3.4 Influence of Ligands on Catalytic Properties 1738.4 Summary and Conclusions 176References 1769 Synthesis of MOF-Supported Nanoparticles and Their Interest in Catalysis 183Guowu Zhan and Hua C. Zeng9.1 Introduction 1839.2 General Synthetic Methodologies 1859.2.1 Catalytic Properties of Metal Nanoparticles 1859.2.2 Synthetic Strategies of Metal Nanoparticles 1879.2.2.1 Wet Chemical Reduction Method 1879.2.2.2 Metal Vapor Condensation/Deposition Method 1879.2.2.3 Electrochemical Method 1889.2.2.4 Biosynthesis Method 1889.2.3 Catalytic Activity and Catalytic Sites of MOFs 1889.2.4 Porosity of MOFs for Catalysis Applications 1899.2.5 Synthetic Strategies of MOFs 1909.2.5.1 Electrochemical Method 1919.2.5.2 Sonochemical Method 1919.2.5.3 Microwave Irradiation Method 1929.2.5.4 Mechanochemical Method 1929.2.5.5 Synthesis of MOFs in Green Solvents 1929.2.5.6 Microemulsion Method 1939.2.5.7 Transformation from Solid Matters to MOFs 1939.2.6 Integration Methods of MNPs with MOFs 1949.2.6.1 Preformation of MNPs and Growth of MOFs 1959.2.6.2 Incorporation of Metal Precursors Followed by in Situ Reduction 1979.2.6.3 One-pot Integration of MOFs and MNPs 1999.3 Architectural Designs and Catalytic Applications of MNP/MOF Nanocomposites 2009.3.1 Zero-Dimensional MNP/MOF Nanocomposites 2019.3.2 One-Dimensional MNP/MOF Nanocomposites 2019.3.3 Two-Dimensional MNP/MOF Nanocomposites 2039.3.4 Three-Dimensional MNP/MOF Nanocomposites 2039.3.5 Other Representative Structures of MNP/MOF Composites 2059.3.5.1 Core–Shell/Yolk–Shell Nanostructures 2059.3.5.2 Sandwich-like Nanostructures 2069.3.5.3 Formation of Nanoreactors with a Central Cavity 2089.4 Summary and Conclusions 208References 21010 Silica-Supported Nanoparticles as Heterogeneous Catalysts 215Mahak Dhiman, Baljeet Singh, and Vivek Polshettiwar10.1 Introduction 21510.2 Deposition Methods of Metal NPs 21610.2.1 Wet Impregnation Method 21610.2.2 Deposition–Precipitation Method 21710.2.3 Colloidal Immobilization Method 21810.2.4 Solid-State Grinding Method 21910.2.5 Postsynthetic Grafting Method 22010.3 Application of Silica-Supported NPs in Catalysis 22110.3.1 Oxidation Reactions 22110.3.1.1 CO Oxidation 22110.3.1.2 Alcohol Oxidation 22210.3.1.3 Hydrolysis of Silane 22410.3.2 Hydrogenation Reactions 22610.3.3 Carbon–Carbon (C–C) Coupling Reactions 23010.4 Conclusion 234References 235Part III Application 23911 CO2 Hydrogenation to Oxygenated Chemicals Over Supported Nanoparticle Catalysts: Opportunities and Challenges 241Qiming Sun, Zhenhua Zhang, and Ning Yan11.1 Introduction 24111.2 CO2 Hydrogenation into Formic Acid 24211.3 CO2 Hydrogenation to Methanol 24711.4 CO2 Hydrogenation to Dimethyl Ether 25011.5 Perspectives and Conclusion 252Acknowledgment 253References 25312 Rebirth of Ruthenium-Based Nanomaterials for the Hydrogen Evolution Reaction 257Nuria Romero, Jordi Creus, Jordi García-Antón, Roger Bofill, and Xavier Sala12.1 Introduction 25712.2 Relevant Figures of Merit 25812.3 Factors Ruling the Performance of Ru-Based NPs in HER Electrocatalysis 26112.3.1 Surface Composition 26212.3.2 Phase Structure and Degree of Crystallinity 26512.3.3 Influence of the C Matrix or the C-Based Support 26612.3.4 Influence of Heteroatoms 27012.3.4.1 Phosphorous 27012.3.4.2 Metals and Semimetals 27212.4 Factors Ruling the Performance of Ru-Based NPs in HER Photocatalysis 27212.5 Summary and Conclusions 274Acknowledgments 275References 27513 Nanocatalytic Architecture for the Selective Dehydrogenation of Formic Acid 279Ismail B. Baguc, Gulsah S. Kanberoglu, Mehmet Yurderi, Ahmet Bulut, Metin Celebi, Murat Kaya, and Mehmet Zahmakiran13.1 Introduction 27913.2 Monometallic Palladium-Based Nanocatalysts 28213.3 Bimetallic Palladium-Based Nanocatalysts 28613.3.1 Bimetallic Pd-Containing Nanocatalysts in the Physical Mixture Form 28613.3.2 Bimetallic Pd-Containing Nanocatalysts in the Alloy Structure 28713.3.3 Bimetallic Pd-Containing Nanocatalysts in the Core@Shell Structure 29113.3.4 Trimetallic Pd-Containing Nanocatalysts 29413.3.5 Other Pd-Free Nanocatalysts 29713.4 Summary and Conclusions 301Acknowledgments 302References 302Part IV Activation and Theory 30714 Magnetically Induced Nanocatalysis for Intermittent Energy Storage: Review of the Current Status and Prospects 309Julien Marbaix, Nicolas Mille, Julian Carrey, Katerina Soulantica, and Bruno Chaudret14.1 Introduction 30914.2 General Context and Historical Aspects 31014.3 Characteristics of the Nanocatalysts Used in Magnetic Hyperthermia 31214.3.1 Metal Oxide Nanomaterials 31214.3.2 Iron (0) Nanoparticles 31214.3.3 Iron Carbide Fe(C) Nanomaterials 31214.3.4 Bimetallic FeNi Nanoparticles 31314.3.5 Bimetallic FeCo Nanoparticles 31314.3.6 CoNi Nanoparticles 31414.4 Catalytic Applications in Liquid Solution and Gas Phase 31414.4.1 Gas-Phase Catalysis 31414.4.1.1 Catalysis Activated by Magnetically Heated Micro- and Macroscaled Materials 31414.4.1.2 Catalysis Activated by Magnetic Heating of Nanoparticles 31614.4.2 Catalytic Reactions in Solution 31814.5 Perspectives 32214.5.1 Stability of the Catalytic Bed During Catalysis by Magnetic Heating 32214.5.2 Thermal Management and Process Chemistry Using Magnetic Heating for Catalytic Applications 32214.6 Perspective of the Integration for Renewable Energy Use 32314.6.1 Interest of Power to Gas and Catalysis Using Magnetic Heating for Renewable Energy Use 32314.6.2 Energy Efficiency and Environmental Considerations of Catalysis by Magnetic Heating 32414.7 Conclusion 326References 32715 Sabatier Principle and Surface Properties of Small Ruthenium Nanoparticles and Clusters: Case Studies 331Iker del Rosal and Romuald Poteau15.1 Introduction 33115.2 C–H Activation and H/D Isotopic Exchange in Amino Acids and Derivatives 33315.2.1 Reference Activation and Dissociation Energies 33315.2.2 H/D Exchange Mechanism 33415.2.3 Bare Cluster 33615.2.4 Ru13D19 33815.2.5 Ru13Dn, n = 6–17 33815.2.6 Short Discussion 33815.3 Hydrogen Evolution Reaction 34015.3.1 Introduction 34015.3.2 4-Phenylpyridine-Protected RuNPs 34115.3.3 Optimal Ligands for the HER? 34415.4 Summary 34615.5 Computational Details 347Acknowledgments 348References 348Index 353

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