Rioux Model Systems in Catalysis

Single Crystals to Supported Enzyme Mimics
1. Auflage 2009
ISBN: 978-0-387-98049-2
Verlag: Springer-Verlag
Format: PDF
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)

E-Book, Englisch, 526 Seiten

This book is an excellent compilation of cutting-edge research in heterogeneous catalysis and related disciplines - surface science, organometallic catalysis, and enzymatic catalysis. In 23 chapters by noted experts, the volume demonstrates varied approaches using model systems and their successes in understanding aspects of heterogeneous catalysis, both metal- and metal oxide-based catalysis in extended single crystal and nanostructured catalytic materials. To truly appreciate the astounding advances of modern heterogeneous catalysis, let us first consider the subject from a historical perspective. Heterogeneous catalysis had its beginnings in England and France with the work of scientists such as Humphrey Davy (1778-1829), Michael Faraday (1791-1867), and Paul Sabatier (1854-1941). Sabatier postulated that surface compounds, si- lar to those familiar in bulk to chemists, were the intermediate species leading to catalytic products. Sabatier proposed, for example, that NiH moieties on a Ni sur- 2 face were able to hydrogenate ethylene, whereas NiH was not. In the USA, Irving Langmuir concluded just the opposite, namely, that chemisorbed surface species are chemically bound to surfaces and are unlike known molecules. These chemisorbed species were the active participants in catalysis. The equilibrium between gas-phase molecules and adsorbed chemisorbed species (yielding an adsorption isotherm) produced a monolayer by simple site-filling kinetics.

Autoren/Hrsg.

Rioux, Robert

Inhaltsverzeichnis

1;Foreword;5
2;Preface;9
3;Contents;11
4;Contributors;14
5;Chapter 1;19
5.1;Catalytic Chemistry of Hydrocarbon Conversion Reactions on Metallic Single Crystals;19
5.1.1;1.1 Introduction;19
5.1.2;1.2 Chemistry of Acetylene Cyclotrimerization;21
5.1.3;1.3 Effect of Hydrogen Addition on the Benzene Formation Rate;27
5.1.4;1.4 Alkene and Alkyne Hydrogenation;33
5.1.4.1;1.4.1 Acetylene Hydrogenation;34
5.1.4.2;1.4.2 Ethylene Hydrogenation;37
5.1.5;1.5 Summary;40
6;Chapter 2;47
6.1;Structure, Characterization and Reactivity of Pt–Sn Surface Alloys;47
6.1.1;2.1 Introduction;47
6.1.2;2.2 Structure of Ordered Sn/Pt(111) and Sn/Pt(100) Surface Alloys;49
6.1.3;2.3 Other Related Surface Alloys;52
6.1.4;2.4 Chemisorption on Pt–Sn Surface Alloys;53
6.1.4.1;2.4.1 Diatomic Molecules (H2, O2, CO, and NO);53
6.1.4.1.1;2.4.1.1 Hydrogen Adsorption;55
6.1.5;2.5 Hydrocarbons;55
6.1.5.1;2.5.1 Alkanes;55
6.1.5.2;2.5.2 Alkenes;56
6.1.5.3;2.5.3 Dienes;58
6.1.5.4;2.5.4 Alkynes;58
6.1.5.5;2.5.5 Arenes;60
6.1.6;2.6 Small Oxygen-Containing Organic Molecules;61
6.1.7;2.7 Microreactor Studies of Catalysis over Pt–Sn Surface Alloys;62
6.1.7.1;2.7.1 Hydrogenation of Crotonaldehyde;62
6.1.7.2;2.7.2 Hydrogenation of Cyclohexanone;64
6.1.8;2.8 Summary;64
6.2;References;66
7;Chapter 3;69
7.1;Catalysis at Bimetallic Electrochemical Interfaces;69
7.1.1;3.1 Introduction;69
7.1.2;3.2 Bimetallic Surfaces;71
7.1.2.1;3.2.1 Preparation and UHV Characterization of Pt3M Bulk Alloys;71
7.1.2.2;3.2.2 Preparation and UHV Characterization of Surface Alloys and Thin Metal Films;74
7.1.2.2.1;3.2.2.1 Surface Alloys of Pd-Au;75
7.1.2.2.2;3.2.2.2 Pd Films on Pt;75
7.1.2.3;3.2.3 Characterization of Bimetallic Surfaces in Electrochemical Environments;76
7.1.2.3.1;3.2.3.1 Ex Situ Characterization of Pt3M Polycrystalline Surfaces;76
7.1.2.3.2;3.2.3.2 In Situ Characterization of Pt3Ni(hkl) Single-Crystal Surfaces;77
7.1.2.3.3;3.2.3.3 In Situ Characterization of Pd Thin Metal Films on Au(111) and Pt(111);79
7.1.3;3.3 Electrocatalysis on Well-Characterized Bimetallic Surfaces;79
7.1.3.1;3.3.1 Oxygen Reduction Reaction on Pt3.M;81
7.1.3.2;3.3.2 Hydrogen Oxidation Reaction on Au(111)-Pd and Pt(111)-Pd Overlayers;85
7.1.4;3.4 Summary;87
7.2;References;88
8;Chapter 4;92
8.1;Enantioselectivity on Naturally Chiral Metal Surfaces;92
8.1.1;4.1 Chirality and Enantioselectivity;92
8.1.2;4.2 Chiral Surfaces;94
8.1.3;4.3 Structure of Naturally Chiral Metal Surfaces;97
8.1.4;4.4 Enantiospecific Adsorption on Chiral Metal Surfaces;101
8.1.5;4.5 Enantioselective Surface Chemistry on Chiral Metal Surfaces;103
8.1.6;4.6 Enantiospecific Molecular Orientation on Chiral Surfaces;105
8.1.7;4.7 Synthesis of Naturally Chiral Surfaces;107
8.1.8;4.8 Conclusions;110
8.2;References;110
9;Chapter 5;113
9.1;Chiral Expression by Organic Architectures at Metal Surfaces: the Role of Both Adsorbate and Surface in Inducing Asymmetry;113
9.1.1;5.1 Introduction;113
9.1.2;5.2 Model Systems: (R,R)-Tartaric Acid on Cu(110);114
9.1.2.1;5.2.1 Hierarchical Chiral Expression: The (9 0,1 2) Phase;116
9.1.2.2;5.2.2 Point Chirality: Factors that Introduce Asymmetry in the (R,R)-Tartaric Acid Adsorbed Motif;116
9.1.2.3;5.2.4 Switching Space Group Chirality;118
9.1.2.4;5.2.5 Creation of Empty Chiral Channels Within Supramolecular Assemblies;121
9.1.3;5.3 Model Systems: R,R-Tartaric Acid on Ni(110);122
9.1.3.1;5.3.1 Chiral Transmission from Molecule to Surface;124
9.1.4;5.4 Model Systems: Succinic acid on Cu(110): The Adsorption of Achiral Molecules at Surfaces;124
9.1.4.1;5.4.1 Adsorption Induced Chirality: The (9 0, +1 1) and (9 0, 1 1) phases;125
9.1.4.2;5.4.2 The p(4.×.2) Organisation;125
9.1.5;5.5 Conclusions;128
9.2;References;129
10;Chapter 6;132
10.1;Role of C and P Sites on the Chemical Activity of Metal Carbides and Phosphides: From Clusters to Single-Crystal Surfaces;132
10.1.1;6.1 Introduction;132
10.1.2;6.2 Effects of Carbon/Metal Ratio on the Chemical Properties of Metal Carbides;134
10.1.3;6.3 Reaction of Oxygen with Metal Carbide Surfaces;136
10.1.4;6.4 Desulfurization Reactions on Metal Carbides and Phosphides;140
10.1.5;6.5 Conclusions;145
10.2;References;146
11;Chapter 7;148
11.1;Surface Reactions of Oxygen Containing Compounds on Metal Oxide (TiO2 and UO2) Single Crystals;148
11.1.1;7.1 Introduction;148
11.1.2;7.2 Structure of Rutile TiO2 and UO2 Surfaces;149
11.1.2.1;7.2.1 Rutile TiO2;149
11.1.2.2;7.2.2 Fluorite UO2;151
11.1.3;7.3 Defects on Single-Crystalline TiO2 and UO2 Surfaces;152
11.1.4;7.4 Catalytic Reactions on Uranium and Titanium-Oxide Surfaces;153
11.1.4.1;7.4.1 Dehydrogenation/Dehydration of Ethanol;153
11.1.4.2;7.4.2 Oxidation of CO, Formaldehyde, and Simple Alkenes on Uranium Oxides;157
11.1.4.3;7.4.3 Decomposition of Water at Point Defects on Single-Crystal UO2 Surfaces;158
11.1.4.4;7.4.4 Reaction of Aldehydes Over Titanium and Uranium Oxide Single-Crystal Surfaces;161
11.1.5;7.5 Photocatalysis on TiO2(110) Single Crystals;162
11.1.6;7.6 Conclusions;165
11.2;References;166
12;Chapter 8;170
12.1;Surface Science Studies of Strong Metal-Oxide Interactions on Model Catalysts;170
12.1.1;8.1 Introduction;170
12.1.2;8.2 Pd on TiO2 and the Formation of the SMSI State;171
12.1.3;8.3 Surface Chemistry of Pd Model Catalysts in the SMSI State;175
12.1.4;8.4 Pt on TiO2 and the Formation of the SMSI State;177
12.1.5;8.5 Structural Models for the SMSI State on Pd and Pt;178
12.1.6;8.6 Mechanisms of Encapsulation in the Formation of the SMSI State;183
12.1.7;8.7 Summary;186
12.2;References;186
13;Chapter 9;189
13.1;Surface Thermodynamics: Small Molecule Adsorption Calorimetry on Metal Single Crystals;189
13.1.1;9.1 Introduction;189
13.1.2;9.2 Experimental;190
13.1.3;9.3 Carbon Monoxide Adsorption on Pt, Ni, Rh and Fe;192
13.1.3.1;9.3.1 CO on Pt{211}, Pt{311} and Pt{411};192
13.1.3.2;9.3.2 CO on Ni{211};194
13.1.3.3;9.3.3 CO on Rh{100};195
13.1.3.4;9.3.4 CO on Fe{211};196
13.1.4;9.4 Oxygen Adsorption on Ni, Pt and Fe;198
13.1.4.1;9.4.1 O2 on Ni{211};198
13.1.4.2;9.4.2 O2 on Pt{111}, Pt{211} and Pt{411};201
13.1.4.3;9.4.3 O2 on Fe{211};202
13.1.5;9.5 Nitric Oxide Adsorption on Ni, Pt and Fe;204
13.1.5.1;9.5.1 NO on Clean and Oxygen-Covered Ni{211};204
13.1.5.2;9.5.2 NO on Pt{111}, Pt{211} and Pt{411};206
13.1.5.3;9.5.3 NO on Fe{211};208
13.1.6;9.6 Adsorption Thermodynamics and Pre-exponential Factor for Desorption;209
13.2;References;213
14;Chapter 10;216
14.1;Surface Femtochemistry*;216
14.1.1;10.1 Introduction;216
14.1.2;10.2 Experimental;219
14.1.2.1;10.2.1 Laser Induced Desorption;219
14.1.2.2;10.2.2 Sum-frequency Generation;220
14.1.2.3;10.2.3 Sample Preparation;221
14.1.3;10.3 Results and Discussion;223
14.1.3.1;10.3.1 Site-dependent Chemical Dynamics;223
14.1.3.2;10.3.2 Real-time Observation of Diffusion;226
14.1.4;10.4 Conclusions;231
14.2;References;232
15;Chapter 11;235
15.1;The Incorporation of Added Metal Atoms into Structures of Reaction Intermediates on Catalytic Metal Surfaces;235
15.1.1;11.1 Introduction;235
15.1.2;11.2 Oxygen-Induced Reconstructions on Metal Surfaces;238
15.1.3;11.3 Hydrogen-Induced Reconstructions on Metal Surfaces;244
15.1.4;11.4 Incorporation of Metal Adatoms into the Structures of Reaction Intermediates on Metal Surfaces;247
15.1.5;11.5 Effect of Incorporated Ni Adatoms on the Autocatalytic Decomposition of Formate and Acetate on Ni(110);254
15.1.6;11.6 Summary;257
15.2;References;259
16;Chapter 12;264
16.1;Chemical Bonding on Metal Surfaces;264
16.1.1;12.1 Introduction;264
16.1.2;12.2 Probing the Electronic Structure;265
16.1.3;12.3 Adsorbate Electronic Structure and Chemical Bonding;268
16.1.4;12.4 Radical Adsorption;271
16.1.5;12.5 Diatomic Molecules with Unsaturated p-Electron Systems;273
16.1.6;12.6 Unsaturated Hydrocarbons;277
16.1.7;12.7 Lone Pair Interactions and Bonding of Saturated Hydrocarbons;281
16.2;References;283
17;Chapter 13;286
17.1;From Molecular Insights to Novel Catalysts Formulation;286
17.1.1;13.1 Introduction;286
17.1.2;13.2 Steam Reforming: Background;288
17.1.3;13.3 DFT Studies: Carbon Chemistry on Ni Surfaces;290
17.1.4;13.4 Assessment of the Thermodynamic Stability of Alloys;293
17.1.5;13.5 Catalyst Synthesis, Characterization and Testing;296
17.1.6;13.6 Conclusions;300
17.2;References;300
18;Chapter 14;304
18.1;The Reactivity of Gas-Phase Metal Oxide Clusters: Systems for Understanding the Mechanisms of Heterogeneous Catalysts;304
18.1.1;14.1 Introduction;304
18.1.2;14.2 Formation and Composition of Metal Oxide Ions;307
18.1.3;14.3 New Insights into Heterogeneous Catalysis;307
18.1.3.1;14.3.1 Vanadium Oxides;307
18.1.3.2;14.3.2 Gold Oxides;310
18.1.3.3;14.3.3 Transition Metal Oxides;313
18.1.3.4;14.3.4 Iron Oxides;314
18.1.4;14.4 Periodic Trends in 3.d Transition Metal Oxide Reactivity;316
18.1.4.1;14.4.1 Cobalt Oxides;317
18.1.4.2;14.4.2 Nickel Oxides;318
18.1.4.3;14.4.3 Aluminum Oxides;320
18.1.4.4;14.4.4 Bimetallic Oxide Clusters;323
18.1.5;14.5 Conclusions;324
18.2;References;324
19;Chapter 15;329
19.1;Catalysis by Noble Metal Nanoparticles Supported on Thin-Oxide Films;329
19.1.1;15.1 Model Catalysis with Nanoparticles;329
19.1.2;15.2 Microstructure Changes of Nanoparticles;331
19.1.3;15.3 Epitaxial Thin Film Model Catalysts;332
19.1.3.1;15.3.1 Preparation and Nanoparticle Structure of Epitaxial Thin Film Model Catalysts;333
19.1.3.2;15.3.2 Applications of Epitaxially Grown Thin Film Model Catalysts;334
19.1.3.2.1;15.3.2.1 Restructuring of Rh–Al2O3 upon Oxidative and Reductive Treatments;334
19.1.3.2.2;15.3.2.2 Metal-support Interaction upon Hydrogen Reduction of Rh–Al2O3 and Rh–TiO2;336
19.1.3.3;15.3.3 Limitations of Epitaxial Thin Film Model Catalysts;337
19.1.4;15.4 Ultrahigh Vacuum Grown Model Catalysts;338
19.1.4.1;15.4.1 Preparation and Structure of UHV-grown Model Catalysts;338
19.1.4.2;15.4.2 Reactivity of UHV-grown Supported Model Catalysts;341
19.1.4.2.1;15.4.2.1 Ethylene and 1,3-Butadiene Hydrogenation;342
19.1.4.2.2;15.4.2.2 In situ Spectroscopy During Catalytic Reactions on UHV-grown Supported Model Catalysts;343
19.1.4.2.3;15.4.2.3 CO Hydrogenation;344
19.1.4.2.4;15.4.2.4 Methanol Oxidation;347
19.1.5;15.5 Conclusions;349
19.2;References;350
20;Chapter 16;354
20.1;Catalysis by Supported Size-Selected Clusters;354
20.1.1;16.1 Introduction;354
20.1.2;16.2 Brief Review of Methodology;355
20.1.3;16.3 Characterization;357
20.1.4;16.4 Reactivity;359
20.1.5;16.5 Future Experiments Involving Size-Selected Clusters;367
20.2;References;370
21;Chapter 17;375
21.1;Catalysis by Thin Oxide Films and Oxide Nanoparticles;375
21.1.1;17.1 Model Catalysis on Oxides;375
21.1.2;17.2 Thin-Film Model Oxide Catalysts;378
21.1.2.1;17.2.1 Preparation of Thin Oxide Films and Oxide Nanoparticles;378
21.1.2.2;17.2.2 Structure and Catalytic Activity of Thin Film Model Oxide Catalysts;379
21.1.2.2.1;17.2.2.1 Ga2O3;379
22;Chapter 18;403
22.1;Catalysis with Transition Metal Nanoparticles in Colloidal Solution: Heterogeneous or Homogeneous?;403
22.1.1;18.1 Introduction;403
22.1.2;18.2 Experimental Techniques to Determine Catalytic Nature of Colloidal Nanoparticles;405
22.1.3;18.3 Redox Reactions;406
22.1.3.1;18.3.1 Particle Size Dependence;406
22.1.3.2;18.3.2 Effect of Capping Material;408
22.1.3.3;18.3.3 Concentration Dependence of the Colloidal Nanoparticles;409
22.1.3.4;18.3.4 Particle Shape Dependence;409
22.1.3.4.1;18.3.4.1 Effect of Particle Shape on the Activity of the Reaction;409
22.1.3.5;18.3.5 Influence of Catalysis on the Stability of Particle Shape;410
22.1.4;18.4 Carbon–Carbon Bond Forming Reactions;412
22.1.4.1;18.4.1 Carbon–Carbon Bond Formation Reactions Catalyzedby Colloidal Nanoparticles;413
22.1.4.2;18.4.2 Influence of Catalysis on Particle stability;414
22.1.4.3;18.4.3 Investigations of Atomic Leaching from Colloidal Nanoparticle Catalysts;415
22.1.5;18.5 Summary;418
22.2;References;419
23;Chapter 19;423
23.1;Well-Defined Metallic and Bimetallic Clusters Supported on Oxides and Zeolites;423
23.1.1;19.1 Introduction;423
23.1.2;19.2 Mononuclear Metal Complexes Supported on Metal Oxides and Zeolites;424
23.1.2.1;19.2.1 Synthesis;425
23.1.2.2;19.2.2 Structural Characterization;426
23.1.2.3;19.2.3 Catalysis;431
23.1.3;19.3 Metal Clusters Supported on Metal Oxides and Zeolites;431
23.1.3.1;19.3.1 Synthesis;431
23.1.3.2;19.3.2 Structural Characterization;435
23.1.3.3;19.3.3 Catalysis;436
23.1.4;19.4 Bimetallic Clusters Supported on Metal Oxides and Zeolites;437
23.1.4.1;19.4.1 Synthesis;437
23.1.4.2;19.4.2 Structural Characterization;438
23.1.4.3;19.4.3 Catalysis;442
23.1.5;19.5 Concluding Remarks;443
23.2;References;443
24;Chapter 20;448
24.1;A Convergence of Homogeneous and Heterogeneous Catalysis: Immobilized Organometallic Catalysts;448
24.1.1;20.1 Introduction;448
24.1.2;20.2 Immobilized Polymerization Catalysts and Cocatalysts;449
24.1.3;20.3 Recyclability of Immobilized Polymerization Catalysts;454
24.1.4;20.4 Immobilized Palladium Catalysts: True Heterogeneous Catalysis?;457
24.1.5;20.5 Conclusions and Future Directions;460
24.2;References;460
25;Chapter 21;463
25.1;Single-Site Heterogeneous Catalysts: Innovations, Advantages, and Future Potential in Green Chemistry and Sustainable Technolog;463
25.1.1;21.1 Introduction;463
25.1.2;21.2 A High-Performance Selective Oxidation System for the Facile Production of Primary, Secondary, and Benzylic Alcohols U;465
25.1.3;21.3 One-Step Production of Niacin (Vitamin B3) and Other Nitrogen-Containing Pharmaceutical Chemicals;466
25.1.3.1;21.3.1 Selective Oxidation Of 3-Picoline to Nicotinic Acid;468
25.1.3.2;21.3.2 The Role of the Single-Site Solid Host;469
25.1.4;21.4 High-Performance Nonphosphine-based Single-Site Chiral Catalysts for the Production of Pharmaceutical Intermediates;469
25.1.5;21.5 Bimetallic and Trimetallic Nanocluster Catalysts for Single-Step, Solvent-Free Hydrogenations;472
25.1.5.1;21.5.1 Adipic Acid from Muconic Acid Using Atomically Engineered Single-Site Nanocluster Catalysts;473
25.1.5.2;21.5.2 Trimetallic Nanoparticle Single-Site Catalysts for the Single-Step Conversion of Dimethyl terephthalate to 1,4-Cyclo;474
25.1.5.3;21.5.3 Tin-Containing Nanoclusters for the Selective Hydrogenation of Cyclododecatriene to Cyclododecene;475
25.1.6;21.6 Summary and Future Outlook;477
25.2;References;477
26;Chapter 22;481
26.1;Molecular-Imprinted Metal Complexes for the Design of Catalytic Structures;481
26.1.1;22.1 Introduction;481
26.1.2;22.2 Principles of Molecular Imprinting;482
26.1.3;22.3 Molecular Imprinting of Metal Complexes in Bulk Polymers;485
26.1.4;22.4 Molecular-Imprinting of Rh Monomers onto SiO2 Surfaces;488
26.1.5;22.5 Surface Molecular Imprinting of Rh dimer on SiO2;491
26.1.6;22.6 Summary;495
26.2;References;495
27;Chapter 23;500
27.1;Heterogeneous Catalyst Design by Multiple Functional Group Positioning in Organic–Inorganic Materials: On the Route to Analogs ;500
27.1.1;23.1 Introduction;500
27.1.1.1;23.1.1 Cooperative Catalysis;501
27.1.2;23.2 Heterogeneous Cooperative Catalysis;503
27.1.2.1;23.2.1 Flexibility of Support;504
27.1.2.2;23.2.2 Functionality of Support;504
27.1.3;23.3 Randomly Distributed Bifunctional Catalysts;505
27.1.3.1;23.3.1 Acid/Thiol Catalysts;506
27.1.3.2;23.3.2 Amine/Urea Catalysts;507
27.1.3.3;23.3.3 Acid/Base Catalysts;509
27.1.4;23.4 Functional Group Positioning;511
27.1.4.1;23.4.1 Imprinting Approaches to Positioning;511
27.1.4.1.1;23.4.1.1 Covalent Imprinting;511
27.1.4.1.2;23.4.1.2 Noncovalent Imprinting;513
27.1.4.2;23.4.2 Other Approaches to Positioning;516
27.1.4.3;23.4.3 Future Directions;519
27.2;References;520
28;Index;522