Bond G.C. Metal-catalysed reactions of hydrocarbons (New York, 2005). - ОГЛАВЛЕНИЕ / CONTENTS
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ОбложкаBond G.C. Metal-catalysed reactions of hydrocarbons. - New York: Springer Science, 2005. - xxi, 666 p.: ill. - (Fundamental and applied catalysis). - Bibliogr. at the end of the chapters. - Ind.: p.657-666. - ISBN 0-387-24141-8
 

Место хранения: 031 | Институт катализа им. Г.К.Борескова CO РАН | Новосибирск

Оглавление / Contents
 
CHAPTER 1  METALS AND ALLOYS
1.1  The Metallic State ......................................... 2
     1.1.1  Characteristic Properties ........................... 2
     1.1.2  Theories of the Metallic State ...................... 9
1.2  The Metallic Surface ...................................... 14
     1.2.1  Methods of Preparation ............................. 14
     1.2.2  Structure of Metallic Surfaces ..................... 16
     1.2.3  Theoretical Descriptions of the Metal Surface ...... 22
1.3  Alloys .................................................... 24
     1.3.1  The Formation of Alloys ............................ 24
     1.3.2  Electronic Properties of Alloys and Theoretical
            Models ............................................. 27
     1.3.3  The Composition of Alloy Surfaces .................. 29
     References ................................................ 31

CHAPTER 2  SMALL METAL PARTICLES AND SUPPORTED METAL
CATALYSTS
2.1  Introduction .............................................. 36
     2.1.1  Microscopic Metals ................................. 36
     2.1.2  Instability of Small Metal Particles ............... 38
2.2  Preparation of Unsupported Metal Particles ................ 39
2.3  Supported Metal Catalysts ................................. 40
     2.3.1  Scope .............................................. 40
     2.3.2  Methods of Preparation ............................. 41
2.4  Measurement of the Size and Shape of Small Metal
     Particles ................................................. 47
     2.4.1  Introduction: Sites, Models, and Size
            Distributions ...................................... 47
     2.4.2  Physical Methods for Characterising Small Metal
            Particles .......................................... 52
     2.4.3  Measurement of Dispersion by Selective Gas-
            Chemisorption ...................................... 58
2.5  Properties of Small Metal Particles ....................... 60
     2.5.1  Variation of Physical Properties with Size:
            Introduction ....................................... 60
     2.5.2  Structure .......................................... 63
     2.5.3  Energetic Properties ............................... 65
     2.5.4  Electronic Properties .............................. 66
     2.5.5  Theoretical Methods ................................ 67
     2.5.6  Conclusions ........................................ 68
2.6  Metal-Support Interactions ................................ 69
     2.6.1  Causes and Mechanisms .............................. 69
     2.6.2  Particle Size Effects and Metal-Support
            Interactions: Summary .............................. 74
2.7  Promoters and Selective Poisons ........................... 75
2.8  Sintering and Redispersion ................................ 77
     References ................................................ 78

CHAPTER 3  CHEMISORPTION AND REACTIONS OF HYDROGEN
3.1  The Interaction of Hydrogen with Metals ................... 94
3.2  Chemisorption of Hydrogen on Unsupported Metals and
     Alloys .................................................... 97
     3.2.1  Introduction ....................................... 97
     3.2.2  The Process of Chemisorption ...................... 100
     3.2.3  The Chemisorbed State: Geometric Aspects .......... 102
     3.2.4  The Chemisorbed State: Energetic Aspects .......... 108
3.3  Chemisorption of Hydrogen on Supported Metals ............ 114
     3.3.1  Introduction: Determination of Metal Dispersion ... 114
     3.3.2  Characterisation of Chemisorbed Hydrogen .......... 124
     3.3.3  Theoretical Approaches ............................ 129
     3.3.4  Hydrogen Spillover ................................ 132
     3.3.5  The "Strong Metal-Support Interaction" ............ 137
3.4  Reactions of Hydrogen .................................... 140
     References ............................................... 142

CHAPTER 4  THE CHEMISORPTION OF HYDROCARBONS
4.1  Introduction ............................................. 154
     4.1.1  Types of Alkane ................................... 154
     4.1.2  Types of Unsaturated Hydrocarbon .................. 154
     4.1.3  The Literature .................................... 155
4.2  The Chemisorption of Hydrocarbons: An Overview ........... 156
4.3  The Techniques ........................................... 158
4.4  Identification of Adsorbed Hydrocarbon Species ........... 161
     4.4.1  The Catalogue - or 'The Organometallic Zoo' ....... 161
     4.4.2  The π and di-σ Forms of Chemisorbed Alkenes ...... 169
4.5  Structures and Properties of Chemisorbed Hydrocarbons .... 176
     4.5.1  Detailed Structures of Chemisorbed Alkenes ........ 176
     4.5.2  Structures of Chemisorbed Ethyne .................. 178
     4.5.3  Structures of Chemisorbed Benzene ................. 178
     4.5.4  Heats of Adsorption ............................... 180
     4.5.5  Characterisation by Other Spectroscopic Methods ... 186
     4.5.6  C6 Molecules ...................................... 186
4.6  Thermal Decomposition of Chemisorbed Hydrocarbons ........ 186
4.7  Theoretical Approaches ................................... 190
4.8  Chemisorption of Alkanes ................................. 196
4.9  The Final Stage: Carbonaceous Deposits ................... 197
     References ............................................... 198

CHAPTER 5  INTRODUCTION TO THE CATALYSIS OF HYDROCARBON
           REACTIONS
5.1  The Essential Nature of Catalysis ........................ 210
     5.1.1  A Brief History of Catalysis ...................... 210
     5.1.2  How Catalysts Act ................................. 211
     5.1.3  The Catalytic Cycle ............................... 213
5.2  The Formulation of Kinetic Expressions ................... 214
     5.2.1  Mass Transport versus Kinetic Control ............. 214
     5.2.2  The Purpose of Kinetic Measurements ............... 215
     5.2.3  Measurement and Expression of Rates of Reaction ... 216
     5.2.4  The Langmuir-Hinshelwood Formalism ................ 218
     5.2.5  Effect of Temperature on Rate and Rate Constant ... 221
     5.2.6  Selectivity ....................................... 223
     5.2.7  Kinetic modelling ................................. 225
5.3  The Concept of Reaction Mechanism ........................ 227
5.4  The Idea of the Active Centre ............................ 229
5.5  The Use of Bimetallic Catalysts .......................... 234
5.6  The Phenomenon of 'Compensation' ......................... 239
5.7  The Temkin Equation: Assumptions and Implications ........ 246
5.8  Techniques ............................................... 247
     5.8.1  Reactors .......................................... 247
     5.8.2  Use of Stable and Radioactive Isotopes ............ 249
     References ............................................... 251

CHAPTER 6  EXCHANGE OF ALKANES WITH DEUTERIUM
6.1  Introduction ............................................. 257
6.2  Equilibration of Linear and Branched Alkanes with
     Deuterium ................................................ 260
     6.2.1  Methane ........................................... 260
     6.2.2  Ethane and Higher Linear Alkanes .................. 267
     6.2.3  Higher Linear Alkanes ............................. 271
     6.2.4  Branched Alkanes .................................. 273
6.3  Equilibration of Cycloalkanes with Deuterium ............. 275
6.4  Interalkane Exchange ..................................... 285
6.5  Conclusions .............................................. 285
     References ............................................... 287

CHAPTER 7  HYDROGENATION OF ALKENES AND RELATED PROCESSES
7.1  Introduction ............................................. 292
7.2  Hydrogenation of Ethene and Propene ...................... 297
     7.2.1  Kinetics of Hydrogenation ......................... 297
     7.2.2  Structure Sensitivity ............................. 303
     7.2.3  Ethene Hydrogenation on Bimetallic Catalysts ...... 306
     7.2.4  Reactions of Ethene and of Propene with
            Deuterium ......................................... 307
     7.2.5  Reactions on Single Crystal Surfaces .............. 319
     7.2.6  The Reaction Mechanism: Microkinetic Analysis,
            Monte Carlo Simulation, and Multiple Steady
            States ............................................ 321
     7.2.7  Catalysis by Hydrogen Spillover and the
            Reactivity of Hydrogen Bronzes .................... 325
7.3  Reactions of the Butenes with Hydrogen and with
     Deuterium ................................................ 328
     7.3.1  Then-Butenes ...................................... 328
     7.3.2  The Single Turnover Approach ...................... 333
     7.3.3  Isobutene ......................................... 334
     7.3.4  Exchange Reactions between Alkenes ................ 335
7.4  Reactions of Higher Alkenes with Hydrogen and with
     Deuterium ................................................ 336
7.5  Hydrogenation of Cycloalkenes ............................ 338
     7.5.1  Cyclohexene ....................................... 338
     7.5.2  Other Cycloalkenes ................................ 339
     7.5.3  Substituted Cycloalkenes: Stereochemical
            Factors ........................................... 340
     References ............................................... 348

CHAPTER 8  HYDROGENATION OF ALKADIENES AND POLYENES
8.1  Introduction ............................................. 357
     8.1.1  Types of Unsaturation ............................. 357
     8.1.2  Practical Applications of Selective
            Hydrogenation: Outline of Mechanisms .............. 359
8.2  Hydrogenation of 1,2-Alkadienes (Allenes) ................ 360
     8.2.1  Hydrogenation of Propadiene ....................... 360
     8.2.2  Hydrogenation of Substituted 1,2-Alkadienes ....... 362
     8.2.3  Hydrogenation of Cumulenes ........................ 365
8.3  Hydrogenation of 1,3-Butadiene ........................... 365
     8.3.1  General Characteristics of Butadiene
            Hydrogenation ..................................... 365
     8.3.2  Chemisorbed States of 1,3-Butadiene ............... 366
     8.3.3  Hydrogenation of 1,3-Butadiene on Single Crystal
            Surfaces .......................................... 367
     8.3.4  Hydrogenation of 1,3-Butadiene on Supported
            and Unsupported Metals ............................ 368
     8.3.5  The Reaction of 1,3-Butadiene with Deuterium:
            Reaction Mechanisms ............................... 375
     8.3.6  Hydrogenation of 1,3-Butadiene by  Bimetallic
            Catalysts ......................................... 379
8.4  Hydrogenation of Higher Alkadienes ....................... 382
     8.4.1  Linear Alkadienes ................................. 382
     8.4.2  Branched Alkadienes ............................... 386
     8.4.3  Cycloalkadienes ................................... 388
     References ............................................... 390

CHAPTER 9  HYDROGENATION OF ALKYNES
9.1  Introduction ............................................. 395
     9.1.1  The Scope of the Literature ....................... 395
     9.1.2  Industrial Applications of Alkyne Hydrogenation ... 396
     9.1.3  The Chemisorbed State of Alkynes .................. 397
     9.1.4  The Origin of Selectivity in Alkyne
            Hydrogenation ..................................... 398
     9.1.5  Interpretation of Results: Some Preliminary
            Comments .......................................... 399
9.2  Hydrogenation of Ethyne: 1, In Static Systems ............ 400
     9.2.1  Introduction ...................................... 400
     9.2.2  Kinetic Parameters ................................ 401
     9.2.3  The Formation of Benzene from Ethyne .............. 407
     9.2.4  The Reaction of Ethyne with Deuterium ............. 407
9.3  Hydrogenation of Ethyne: 2, in Dynamic System with
     Added Ethene ............................................. 411
     9.3.1  Kinetics and Selectivity .......................... 411
     9.3.2  Mechanisms and Modelling .......................... 415
     9.3.3  Oligomerisation ................................... 417
     9.3.4  Gaseous Promoters ................................. 417
9.4  Use of Bimetallic Catalysts for Ethyne Hydrogenation ..... 418
9.5  Hydrogenation of Higher Alkynes .......................... 421
     9.5.1  Propyne ........................................... 421
     9.5.2  The Butynes ....................................... 422
     9.5.3  Alkyl-Substituted Alkynes Having More Than Four
            Carbon Atoms ...................................... 426
     9.5.4  Aryl-Substituted Alkynes .......................... 428
     9.5.5  Multiply-Unsaturated Molecules .................... 429
9.6  Conclusion ............................................... 430
     References ............................................... 431

CHAPTER 10 HYDROGENATION OF THE AROMATIC RING
10.1 Introduction ............................................. 438
     10.1.1 Scope ............................................. 438
     10.1.2 Industrial Applications of Benzene
            Hydrogenation ..................................... 439
10.2 Kinetics and Mechanism of Aromatic Ring Hydrogenation .... 440
     10.2.1 Introduction: Early Work .......................... 440
     10.2.2 Kinetics of Aromatic Ring Hydrogenation ........... 441
     10.2.3 Rate Expressions and Reaction Mechanisms .......... 446
     10.2.4 Temperature-Inversion of Rates .................... 448
     10.2.5 Hydrogenation of Benzene Over Bimetallic
            Catalysts ......................................... 450
     10.2.6 Exchange of Aromatic Hydrocarbons with
            Deuterium ......................................... 453
     10.2.7 Hydrogenation of Benzene to Cyclohexene ........... 457
10.3 Hydrogenation of Alkyl-Substituted Benzenes .............. 458
     10.3.1 Kinetic Parameters ................................ 458
     10.3.2 Stereochemistry of the Hydrogenation of Alkyl-
            Substituted Benzenes .............................. 460
10.4 Hydrogenation of Multiple Aromatic Ring Systems .......... 461
     10.4.1 Polyphenyls ....................................... 461
     10.4.2 Fused Aromatic Rings: (1) Naphthalene ............. 461
     10.4.3 Fused Aromatic Rings: (2) Multiple Fused Rings .... 466
     References ............................................... 468

CHAPTER 11 HYDROGENATION OF SMALL ALICYCLIC RINGS
11.1 Introduction ............................................. 473
11.2 Hydrogenation and Hydrogenolysis of Cyclopropane ......... 477
     11.2.1 Kinetics .......................................... 477
     11.2.2 The Reaction of Cyclopropane with Deuterium ....... 481
     11.2.3 Reaction Mechanisms ............................... 482
11.3 Hydrogenation of Alkylcyclopropanes ...................... 484
     11.3.1 Mono-alkylcyclopropanes ........................... 484
     11.3.2 Poly-alkylcyclopropanes ........................... 488
     11.3.3 The Cyclopropane Ring in More Complex
            Hydrocarbons ...................................... 490
11.4 Hydrogenation of Cyclopropanes Having Other Unsaturated
     Groups ................................................... 491
11.5 Hydrogenation of Alkylcyclobutanes and Related
     Molecules ................................................ 494
     References ............................................... 499

CHAPTER 12 DEHYDROGENATION OF ALKANES
12.1 Introduction ............................................. 501
12.2 Dehydrogenation of Acyclic Alkanes ....................... 504
     12.2.1 Introduction: Alkane Chemisorption ................ 504
     12.2.2 Supported Platinum and Platinum-Tin Catalysts ..... 505
     12.2.3 Other Metals and Modifiers ........................ 507
     12.2.4 Kinetics and Mechanism ............................ 508
12.3 Dehydrogenation of Cycloalkanes .......................... 509
     12.3.1 Overview .......................................... 509
     12.3.2 Reaction on Pure Metals ........................... 510
     12.3.3 Reaction on Bimetallic Catalysts .................. 512
12.4 The Chemisorption of Hydrogen on Platinum ................ 514
12.5 The Formation, Structure, and Function of Carbonaceous
     Deposits ................................................. 516
12.6 The Homologation of Methane .............................. 519
     References ............................................... 520

CHAPTER 13 REACTIONS OF THE LOWER ALKANES WITH HYDROGEN
13.1 Introduction ............................................. 526
     13.1.1 A Short Philosophical Digression .................. 526
     13.1.2 Alkane Hydrogenolysis: General Characteristics .... 527
     13.1.3 Problems in Studying Reaction Kinetics ............ 528
     13.1.4 Ways of Expressing Product Composition ............ 530
13.2 Hydrogenolysis of the Lower Alkanes on Single Metal
     Catalysts: Rates, Kinetics, and Mechanisms ............... 531
     13.2.1 The Beginning ..................................... 531
     13.2.2 Kinetic Parameters ................................ 531
     13.2.3 Mechanisms and Kinetic Formulations ............... 540
     13.2.4 A Generalised Model for Alkane Hydrogenolysis ..... 549
     13.2.5 Alkane Hydrogenolysis on Metals Other than
            Platinum .......................................... 552
13.3 Structure-Sensitivity of Rates of Alkane
     Hydrogenolysis ........................................... 552
13.4 Selectivity of Product Formation in Alkane
     Hydrogenolysis ........................................... 555
13.5 Mechanisms Based on Product Selectivities ................ 562
13.6 Hydrogenolysis of Alkanes on Ruthenium Catalysts ......... 565
13.7 Effects of Additives and the Strong Metal-Support
     Interaction on Alkane Hydrogenolysis ..................... 569
13.8 Hydrogenolysis of Alkanes on Bimetallic Catalysts ........ 574
     13.8.1 Introduction ...................................... 574
     13.8.2 Metals of Groups 8 to 10 plus Group 11 ............ 575
     13.8.3 Metals of Groups 8 to 10 plus Groups 13 or 14 ..... 578
     13.8.4 Platinum and Iridium plus Zirconium, Molybdenum,
            and Rhenium ....................................... 579
     13.8.5 Bimetallic Catalysts of Metals of Groups 8 to
            10 ................................................ 583
13.9 Apologia ................................................. 583
     References ............................................... 583
     14.2.3 Reactions of Linear Alkanes with Hydrogen ......... 602
     14.2.4 Reactions of Branched Alkanes with Hydrogen ....... 609
     14.2.5 Reactions of Cyclic Alkanes with Hydrogen ......... 616
     14.2.6 The Environment of the Active Site: Effect of
            'Carbon' .......................................... 621

CHAPTER 14 REACTIONS OF HIGHER ALKANES WITH HYDROGEN
14.1 Introduction: Petroleum Reforming and Reactions of
     Higher Alkanes with Hydrogen.............................. 592
     14.1.1 The Scope of This Chapter ......................... 592
     14.1.2 Bifunctional Catalysis: Principles of Petroleum
            Reforming .......................... .............. 592
     14.1.3 Reactions of the Higher Alkanes with Hydrogen ..... 596
     14.1.4 The Scope and Limitations of the Literature ....... 597
     14.1.5 The Principal Themes .............................. 598
14.2 Reactions of Higher Alkanes with Hydrogen: Rates and
     Product Selectivities .................................... 599
     14.2.1 Activities of Pure Metals ......................... 599
     14.2.2 Effect of Varying Conversion ...................... 601
14.3 Mechanisms of Alkane Transformations ..................... 624
     14.3.1 A General Overview ................................ 624
     14.3.2 Mechanisms of Skeletal Isomerisation .............. 625
     14.3.3 Dehydrocyclisation ................................ 628
14.4 Structure-Sensitivity .................................... 629
     14.4.1 Reactions on Single-Crystal Surfaces .............. 629
     14.4.2 Particle-Size Effects with Supported Metals ....... 630
14.5 Modification of the Active Centre ........................ 634
     14.5.1 Introduction ...................................... 634
     14.5.2 Metal Particles in Zeolites ....................... 634
     14.5.3 Platinum-Rhenium Catalysts ........................ 635
     14.5.4 Modification by Elements of Groups 14 and 15 and
            Some Others ....................................... 637
     14.5.5 Other Bimetallic Catalysts ........................ 639
     14.5.6 The Role of Sulfur ................................ 643
     14.5.7 Metal-Support Interactions ........................ 644
     References ............................................... 647

INDEX ......................................................... 657


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