Edited by rising stars in the community, the team of prominent expert authors provides here authoritative first–hand information on the fundamental principles of nanomaterials, as well as their application in catalysis. As a result, the book defines the concepts of nanocatalysis and gives a comprehensive overview of the science of colloidal nanoparticles in particular. Chapters cover micelles, nanoparticles in ionic liquids, dendrimers, nanotubes, nanooxides as well as microreactors, modeling, and characterization of nanocatalysts. An indispensable reference for both researchers at universities and professionals in industry. INDICE: Foreword XI Preface XIII List of Contributors XVII 1 Concepts in Nanocatalysis 1 Karine Philippot and Philippe Serp 1.1 Introduction 1 1.2 The Impact of the Intrinsic Properties of Nanomaterials on Catalysis 5 1.2.1 Metallic Nanoparticles 6 1.2.2 Metal Oxide Nanoparticles 9 1.2.3 Carbon Nanoparticles 12 1.3 How can Nanocatalyst Properties be Tailored? 15 1.3.1 Size, Shape and Surface Chemistry of Nanoparticles 15 1.3.2 Assembling Strategies to Control Active Site Location 20 1.4 Nanocatalysis: Applications in Chemical Industry 23 1.4.1 Fuel Cells 25 1.4.2 Nanostructured Exhaust Catalysts 28 1.4.3 Gas Sensors 31 1.4.4 Photocatalysis 34 1.4.5 Enantioselective Catalysis 38 1.5 Conclusions and Perspectives 40 References 42 2 Metallic Nanoparticles in Neat Water for Catalytic Applications 55 Audrey Denicourt–Nowicki and Alain Roucoux 2.1 Introduction 55 2.2 Synthesis of Nanoparticles in Water: The State of The Art 56 2.3 Water–Soluble Protective Agents and their use in Nanocatalysis 59 2.3.1 Electrosteric Stabilization by Surfactants 60 2.3.2 Steric Stabilization by Cyclodextrins 67 2.3.2.1 Hydrogenation Reactions 68 2.3.2.2 Carbon–Carbon Coupling Reactions 73 2.3.3 Steric Stabilization by Polymers and Derivatives 77 2.3.4 Steric Stabilization by Ligands 83 2.4 Conclusion and Perspectives 88 References 89 3 Catalysis by Dendrimer–Stabilized and Dendrimer–Encapsulated Late–Transition–Metal Nanoparticles 97 Didier Astruc, Abdou Diallo, and Catia Ornelas 3.1 Introduction 97 3.2 Synthesis 98 3.3 Homogeneous Catalysis with DENs Generated from PAMAM and PPI Dendrimers 102 3.3.1 Olefin and Nitroarene Hydrogenation 102 3.3.2 PdNP–Catalyzed Carbon–Carbon Cross Coupling 104 3.3.3 Heterobimetallic Catalysts 104 3.4 Highly Efficient ‘click’–Dendrimer–Encapsulated and Stabilized Pd Nanoparticle Pre–Catalysts 106 3.5 Heterogeneous Catalysis 111 3.6 Electrocatalysis 112 3.7 Conclusion and Outlook 113 References 114 4 Nanostructured Metal Particles for Catalysts and Energy–Related Materials 123 Helmut B€onnemann, Guram Khelashvili, Josef Hormes, Timma–Joshua Kühn, and Wolf–J€urgen Richter 4.1 General Survey 123 4.2 Nanostructured Clusters and Colloids as Catalyst Precursors 128 4.2.1 Selected Applications in Energy–Related Processes 128 4.2.1.1 Size–Selective Fischer–Tropsch Nanocatalysts 128 4.2.1.2 Nanocatalysts for Fuel Cell Devices 131 4.2.1.3 Partial Methane Oxidation with NO 139 4.2.2 Nanocatalysts for Specific Organic Reactions 140 4.3 Nanostructured Materials in Energy–Related Processes 142 4.3.1 Nanomaterials for High–Performance Solar Cells 142 4.3.2 Nanocomposites for Batteries 145 4.3.3 Applications for Energy and Hydrogen Storage 148 4.3.3.1 Nano for Hydrogen Production 149 4.3.3.2 Nano for Hydrogen Storage 150 4.4 Characterization of Nanostructured Metallic Catalyst Precursors and their Interaction with Coatings and Supports Using X–ray Absorption Spectroscopy 154 4.4.1 X–ray Absorption Spectroscopy (XANES and EXAFS) as an Analytical Tool for Nanostructures 156 4.4.2 The Electronic and Geometric Properties of Monometallic Systems 161 4.4.3 The Geometric and Electronic Structure of Bimetallic Systems 168 4.4.4 The Specific Interaction of Metallic Nanoparticles with Coatings and Supports 173 4.4.5 Resonant Elastic and Inelastic X–ray Scattering: Site and/or Valency Specific Spectroscopy 178 References 183 5 Metallic Nanoparticles in Ionic Liquids – Applications in Catalysis 203 Isabelle Favier, David Madec, and Montserrat Gómez 5.1 Introduction 203 5.2 Interactions between Ionic Liquids and Metallic Nanoparticles 204 5.2.1 Stabilization Modes of Metallic Nanoparticles by Ionic Liquids 206 5.2.1.1 DLVO Theory: Anionic Stabilization Mode 206 5.2.1.2 Steric Stabilization Mode 207 5.2.1.3 Cationic Stabilization Mode 207 5.2.1.4 Anionic and Cationic Stabilization Mode 209 5.2.1.5 Interactions of Ionic Liquids with Metal Oxide Nanoparticles (MONPs) 209 5.2.2 Effect of Ionic Liquids on the Structures of Metallic Nanoparticles 210 5.3 Catalytic Applications 213 5.3.1 Metallic Nanoparticles of Block p 213 5.3.2 Metallic Nanoparticles of Block d and f 213 5.3.2.1 Early Transition Metals and Block f Metals 213 5.3.2.2 Metallic Nanoparticles of Groups 8–9 214 5.3.2.3 Metallic Nanoparticles of Group 10 222 5.3.2.4 Metallic Nanoparticles of Group 11 232 5.3.2.5 Metallic Nanoparticles of Group 12 235 5.4 Conclusions 235 References 236 6 Supported Ionic Liquid Thin Film Technology 251 Judith Scholz and Marco Haumann 6.1 Introduction 251 6.1.1 Supported Ionic Liquid Phase (SILP) 252 6.1.2 Solid Catalysts with Ionic Liquid Layers (SCILL) 253 6.1.3 Ionic Liquid as Surface Modifier 253 6.2 Nanoparticle Catalysis with Supported Ionic Liquids 254 6.2.1 Nanoparticles in SILP Systems (nano–SILP) 254 6.2.2 Nanoparticles in SCILL Systems (nano–SCILL) 260 6.2.3 Nanoparticles in IL Surface Modified Systems 264 6.2.3.1 Surface–Modified Ordered Meso–Porous Silica 265 6.2.3.2 Surface Modified Nanocrystalline Metal Oxides 266 6.2.3.3 IL–Functionalized Highly Cross–Linked Polymers as Support 267 6.2.3.4 Natural Clays with IL–Functionalization 268 6.2.3.5 Carbon Nanotubes 269 6.2.3.6 Miscellaneous Supports 270 6.3 Benefits for Synthesis and Processes 272 6.4 Conclusion 273 References 273 7 Nanostructured Materials Synthesis in Supercritical Fluids for Catalysis Applications 281 Samuel Marre and Cyril Aymonier 7.1 Introduction: Properties of Supercritical Fluids 281 7.2 Synthesis of Nanopowders as Nanocatalysts in SCFs 286 7.3 Synthesis of Supported Nanoparticles as Nanocatalysts in SCFs 292 7.3.1 Kinetically–Controlled SFCD Process (K–SFCD) 292 7.3.2 Thermodynamically–Controlled SFCD Process (T–SFCD) 293 7.4 Supercritical Microfluidic Synthesis of Nanocrystals 297 7.4.1 Supercritical Microreactors 299 7.4.2 Nanocrystals Synthesis in SCmF 300 7.5 Conclusion 302 References 303 8 Recovery of Metallic Nanoparticles 311 Inge Geukens and Dirk E. De Vos 8.1 Introduction 311 8.2 Immobilization on a Solid Support 311 8.3 Multiple Phases 314 8.4 Precipitation and Redispersion 317 8.4.1 Centrifugation 317 8.4.2 Adjustment of the Stabilization Conditions 318 8.5 Magnetic Separation 320 8.6 Filtration 322 8.7 Conclusions 324 References 324 9 Carbon Nanotubes and Related Carbonaceous Structures 331 Dang Sheng Su 9.1 Introduction 331 9.2 Carbon Nanotubes as Nanosupport 333 9.3 Purification and Functionalization 334 9.3.1 CNT Purification 334 9.3.2 CNT Functionalization 335 9.3.2.1 Functionalization of CNTs by Wet Chemical Methods 336 9.3.2.2 Functionalization of CNTs by Gas–Phase Reactions 338 9.4 Preparation of CNT–Supported Catalysts 340 9.4.1 Growing Metal Nanoparticles Directly on the CNT Surface 340 9.4.2 Anchoring Pre–Formed Nanoparticles on CNTs 341 9.4.3 Selective Preparation of Catalysts on CNTs 342 9.4.3.1 Selective Placing of Metal Catalysts Inside CNTs 343 9.4.3.2 Selective Placing of Metal Catalyst Outside CNTs 344 9.4.4 Localizing the Catalyst Particles Supported on CNTs 345 9.5 Applications of CNT–Supported Catalysts 346 9.5.1 Liquid–Phase Reactions 346 9.5.1.1 Hydrogenation 346 9.5.1.2 Oxidation 348 9.5.2 Gas–Phase Reactions 349 9.5.2.1 Fischer–Tropsch Synthesis 349 9.5.2.2 Ammonia Decomposition 350 9.5.3 Electrocatalysis 352 9.5.4 Photocatalysis 354 9.6 Other Related Carbonaceous Materials 356 9.6.1 Graphene and Graphene Oxide 356 9.6.2 Carbon Nanofibers 358 9.6.3 Mesoporous Carbon 360 9.7 Summary 361 References 362 10 Nano–oxides 375 Vasile Hulea and Emil Dumitriu 10.1 Introduction 375 10.2 Synthesis and Characterization of Nano–oxides 376 10.2.1 Design of Metal Oxide Nanoparticles 376 10.2.2 Size–Dependent Oxide Properties 380 10.3 Catalytic Applications of Nano–oxides 381 10.3.1 Nano–oxides as Active Phases for Catalytic Applications 381 10.3.1.1 Catalytic Behavior Related to the Characteristics of Nanoparticles 381 10.3.1.2 Catalysis by Unsupported Oxide Nanoparticles 388 10.3.1.3 Catalysis by Supported Oxide Nanoparticles 391 10.3.1.4 Oxide Nanocatalysts for Green Chemistry 395 10.3.2 Nano–oxides as Supports for Active Phases 396 10.4 Conclusions and Perspectives 402 References 403 11 Confinement Effects in Nanosupports 415 Xiulian Pan and Xinhe Bao 11.1 Introduction 415 11.2 Confinement Effects in Carbon Nanotubes 416 11.2.1 Spatial Restriction of the Carbon Nanotube Channels 417 11.2.2 Adsorption Inside Carbon Nanotubes 419 11.2.3 Diffusion Inside Carbon Nanotubes 421 11.2.4 Interaction of Confined Materials with the Graphene Layers of Carbon Nanotubes 423 11.3 Metal Catalyst–Free Chemical Reactions inside Carbon Nanotubes 428 11.4 Catalytic Reactions over Metal Particles Confined Inside Carbon Nanotubes 430 11.4.1 Liquid–Phase Catalytic Reactions 430 11.4.2 Gas–Phase Catalytic Reactions 432 11.5 Summary 436 References 437 12 In Silico Nanocatalysis with Transition Metal Particles: Where Are We Now? 443 Iann C. Gerber and Romuald Poteau 12.1 Introduction 443 12.2 Surface Chemistry and Chemistry on Facets of Nanoparticles: Is it the Same? 446 12.2.1 The Experimental Evidence: Size and Shape Matter 446 12.2.2 Can this Diversity of Observations be Rationalized by Theoretical Insights? 448 12.2.3 Structural and Chemical Bonding Knowledge: A Mandatory Prerequisite 448 12.2.3.1 Silver 449 12.2.3.2 Iron 450 12.2.3.3 Platinum 450 12.3 Electronic and Geometric Factors that Determine the Reactivity of Metal Surfaces 451 12.3.1 Introduction 451 12.3.2 Special Sites 451 12.3.3 The Electronic Structure Effect in Heterogeneous Catalysis: The d–Band Model 452 12.3.4 Descriptors and Predictive Studies 455 12.3.5 Density Functional Theory in Surface Chemistry and Nanocatalysis: Limitations and Challenges 456 12.3.6 Difference between Bulk, Surface and Nanoparticles from a Theoretical Point of View 457 12.4 Theoretical Studies of Multistep Pathways 460 12.4.1 Methods 460 12.4.2 Ammonia Synthesis 462 12.4.3 Oxidation 463 12.4.3.1 Styrene 463 12.4.3.2 Propylene 464 12.4.3.3 Aerobic Phenylethanol Oxidation in Aqueous Solution 465 12.4.4 Dissociation 466 12.4.4.1 Carbon Monoxide 466 12.4.4.2 Methane Steam Reforming 468 12.5 Conclusion 470 References 471 Index 483
- ISBN: 978-3-527-33124-6
- Editorial: Wiley VCH
- Encuadernacion: Cartoné
- Páginas: 516
- Fecha Publicación: 10/01/2013
- Nº Volúmenes: 1
- Idioma: Inglés