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Nanomaterials in Catalysis

Philippe Serp (Editor), Karine Philippot (Editor), Gabor A. Somorjai (Foreword by), Bruno Chaudret (Foreword by)
ISBN: 978-3-527-33124-6
516 pages
February 2013
Nanomaterials in Catalysis (3527331247) cover image
Nanocatalysis has emerged as a field at the interface between homogeneous and heterogeneous catalysis and offers unique solutions to
the demanding requirements for catalyst improvement. Heterogeneous catalysis represents one of the oldest commercial applications of nanoscience and nanoparticles of metals, semiconductors, oxides, and other compounds have been widely used for important chemical reactions. The main focus of this fi eld is the development of well-defined catalysts, which may include both metal nanoparticles and a nanomaterial as the support. These nanocatalysts should display the benefits of both homogenous and heterogeneous catalysts, such as high efficiency and selectivity, stability and easy recovery/recycling. The concept of nanocatalysis is outlined in this book and, in particular, it provides a comprehensive overview of the science of colloidal nanoparticles. A broad range of topics, from the fundamentals to applications in catalysis, are covered, without excluding micelles, nanoparticles in ionic liquids, dendrimers, nanotubes, and nanooxides, as well as modeling, and the characterization of nanocatalysts, making it an indispensable reference for both researchers at universities and
professionals in industry.
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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

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Philippe Serp has been a Professor of Inorganic Chemistry at the Institute National Polytechnique de Toulouse (France) since 2005. His research interests in the Laboratory of Coordination Chemistry include the catalytic preparation of nanostructured catalytic materials,such as nanoparticles, nanotubes and nanowires, and the understanding of homogeneous catalytic reactions, fi elds in which he has published over 120 papers, including 7 review articles, 12 book chapters and 13 patents. He was the recipient of the Catalysis Division of the French Chemical Society Award in 2004, the APDF 'Celestino da Costa/Jean Perrin' award in 2005, and the Industrial Chemistry Division of the French Chemical Society Award in 2012.

Karine Philippot is Directrice de Recherche at CNRS in the Laboratory of Coordination Chemistry at Toulouse (France). Her research interests concern the development of synthetic methods based on organometallic chemistry to prepare metal nanoparticles and nanomaterials displaying well-controlled characteristics (size, composition and shape) and their application in colloidal or supported catalysis. She has published 93 papers including 1 review article, 4 book chapters and 4 patents.

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