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 РАМАМ
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 Bönnemann, Curam Khelashvili, Josef Hormes, Timma-
Joshua Kühn, and Wolf-Jürgen 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 SCμlF ................ 300
7.5 Conclusion ............................................ 302
References ................................................. 303
8 Recovery of Metallic Nanoparticles ......................... 311
Inge Ceukens 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
Lann С. 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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