| Contributors | xi |
| Preface | xiii |
| W. Keith Hall (1918-2001) | xv |
| George C.A. Schuit (1910-2001) | xix |
| Hydroformylation of Alkenes: An Industrial View of the Status and Importance | |
I. | Introduction | 1 |
II. | Fundamental Principles | 3 |
III. | Reaction Parameters, Mechanism, and Kinetics | 8 |
IV. | Commercial Applications | 16 |
A. | The Large-Scale Oxo Reaction | 16 |
B. | Economic Aspects | 18 |
C. | Other Hydroformylation Processes | 22 |
1. | Cobalt-catalyzed Processes | 22 |
2. | Rhodium-catalyzed Processes | 28 |
3. | Aqueous-Phase Processes | 33 |
V. | New Developments | 36 |
A. | New Ligands | 36 |
1. | Phosphines and Diphosphines | 36 |
2. | Water-Soluble Phosphines | 38 |
3. | New Phosphites | 40 |
4. | New P-N Ligands | 41 |
5. | Other Ligands | 41 |
B. | Central Atoms | 42 |
C. | Asymmetric Hydroformylation | 44 |
VI. | Conclusions and Forecasts | 48 |
| References | 53 |
| Hydrogen and Synthesis Gas by Steam- and CO[subscript 2] Reforming | |
I. | Synthesis Gas | 66 |
A. | Applications | 66 |
B. | Manufacture of Syngas | 68 |
1. | Syngas Technologies | 68 |
2. | Thermodynamics and Syngas Composition | 71 |
3. | Syngas for GTL Plants | 73 |
4. | Hydrogen for Fuel Cells | 75 |
II. | The Steam Reforming Process | 78 |
A. | The Reformer | 78 |
B. | Constraints of the Reforming Process | 80 |
C. | Catalyst and Reformer Performance | 82 |
D. | Sulfur Poisoning | 85 |
E. | Steam Reforming of Liquid Hydrocarbons | 86 |
F. | Carbon Formation | 87 |
1. | Various Routes | 87 |
2. | Carbon Limits | 91 |
3. | Metal Dusting | 96 |
III. | Catalysis of Steam Reforming | 96 |
A. | Reaction Rate | 96 |
1. | Kinetic Studies | 96 |
2. | Reaction Kinetics | 99 |
B. | Surface Characterization | 102 |
1. | Nickel surface area | 102 |
2. | Chemisorption of Hydrogen | 103 |
3. | Chemisorption of Sulfur | 104 |
4. | Adsorption of Nitrogen | 107 |
C. | Sintering | 109 |
D. | Activity Trends | 112 |
E. | Catalyst Promotion | 115 |
IV. | Reaction Mechanisms | 119 |
A. | Adsorption of Reactants | 119 |
1. | Methane | 119 |
2. | Carbon Monoxide | 120 |
3. | Carbon Dioxide | 121 |
4. | Steam | 122 |
5. | Hydrogen | 122 |
6. | Methane Activation in Methane-Hydrogen Mixtures | 123 |
B. | The Mechanism of Steam Reforming | 126 |
C. | Carbon Formation | 128 |
D. | Promotion | 130 |
V. | Conclusions | 132 |
| References | 133 |
| Oxide Solid Solutions As Catalysts | |
I. | Introduction | 142 |
A. | Background Concepts | 142 |
B. | The Correlation of Transition Metal Electron Configuration with Behavior in Chemisorption and Catalysis | 144 |
C. | Relevance of Research on Oxide Solid Solutions | 145 |
II. | Principles, Preparation and Characterization | 147 |
A. | Isovalent and Altervalent Ions in Oxide Solid Solutions | 147 |
B. | Preparation of Oxide Solid Solution Catalysts | 153 |
C. | Surface Composition and Surface Structure | 160 |
1. | Introduction | 160 |
2. | Thermodynamic Considerations | 161 |
3. | Experimental Studies | 163 |
D. | Supported Oxide Catalysts in Relation to Oxide Solid Solutions | 175 |
E. | Acidity and Basicity of Surfaces of Solid Solutions | 180 |
1. | Acidity, Basicity and Coordinative Unsaturation | 180 |
2. | Methods for Determining Acidity and Basicity of Surfaces | 182 |
3. | CO as a Selective Probe for Surface Cations in Solid Solutions | 185 |
4. | Acid Centers in Microporous Silicate and Aluminophosphate Solid Solutions | 188 |
F. | Reduced Solid Solutions | 192 |
1. | Formation of Supported Transition Metals | 192 |
2. | Extraction of Oxygen with Structure Retention | 196 |
III. | Catalysis | 199 |
A. | Introduction | 199 |
B. | Reactions of Small Molecules on MgO-Based Solid Solutions and Related Systems | 201 |
1. | N[subscript 2]O Decomposition as a Test Reaction | 201 |
2. | Surface Oxygen Species | 216 |
3. | CO Oxidation | 220 |
C. | Combustion of Hydrocarbons | 233 |
1. | Introduction | 233 |
2. | Perovskite-Based Catalysts | 234 |
3. | Hexa-aluminate-based Catalysts | 243 |
4. | Ceria-Zirconia | 249 |
D. | Selective Oxidation | 251 |
1. | Selective Oxidation of Alkenes | 251 |
2. | Selective Oxidation of Alkanes | 255 |
3. | Methane Coupling | 261 |
4. | Other Selective Oxidations | 272 |
E. | Acid-base Catalysis on Oxide Solid Solutions | 276 |
1. | Dehydration Reactions | 276 |
2. | Cracking and Isomerization of Hydrocarbons | 280 |
3. | Base-Catalyzed Reactions | 281 |
F. | Reactions Involving Hydrogen | 281 |
1. | General | 281 |
2. | Reactions on Supported Metals ex Oxide Solid Solutions | 282 |
IV. | Conclusion | 288 |
| References | 290 |
| Characterization of Oxide Surfaces and Zeolites by Carbon Monoxide as an IR Probe Molecule | |
I. | Introduction | 308 |
II. | Carbon Monoxide as a Probe Molecule | 312 |
A. | Interaction of CO with Oxide Surfaces | 312 |
1. | Electronic Structure of CO | 312 |
2. | Coordination of CO to Cationic Centers via its C Atom | 315 |
3. | Coordination of CO to Cationic Centers via its O Atom | 322 |
4. | CO in Bridging Positions | 323 |
5. | CO Bonded via Both Ends (tilted CO) | 324 |
6. | M[superscript n+] (CO)[subscript x] Species | 325 |
7. | Reactive Adsorption of CO | 327 |
B. | Factors influencing the C-O Fundamental Stretching Modes of M[superscript n+]-CO Species | 327 |
1. | Electrostatic Bonding | 329 |
2. | [sigma] Bonding | 332 |
3. | [pi] Bonding | 333 |
4. | Adsorbate-Adsorbate Interactions (Static and Dynamic Shifts) | 334 |
C. | Other Spectral Characteristics of Adsorbed CO | 336 |
1. | Combination Modes and Overtones | 336 |
2. | Species Absorbing in the Carbonyl Stretching Region | 338 |
3. | Isotopic Exchange | 340 |
4. | Intensity of the C-O Band | 344 |
D. | Practical Recommendations | 349 |
1. | Experimental Technique | 349 |
2. | Information from the IR Spectra of Adsorbed CO | 350 |
3. | How to Use CO as a Probe Molecule | 350 |
E. | Other Spectroscopic Methods using CO as a Probe Molecule | 352 |
1. | NMR Spectroscopy | 352 |
2. | EPR Spectroscopy | 353 |
3. | Thermochemical Methods | 353 |
4. | Other Techniques | 355 |
III. | IR Spectra of Surface Metal Carbonyls | 356 |
A. | Interaction of CO with Group 1 Cations | 356 |
1. | Adsorption of CO on Li[superscript +], Na[superscript +], K[superscript +], Rb[superscript +], and Cs[superscript +] Ions | 356 |
B. | Interaction of CO with group 2 cations | 365 |
1. | Adsorption of CO on Be[superscript 2+] ions | 365 |
2. | Adsorption of CO on Mg[superscript 2+] Ions | 365 |
3. | Adsorption of CO on Ca[superscript 2+], Sr[superscript 2+] and Ba[superscript 2+] Ions | 367 |
C. | Interaction of CO with Group 13 Cations | 371 |
1. | Adsorption of CO on Al[superscript 3+] Ions | 371 |
2. | Adsorption of CO on Cations of B, Ga, In, and Tl | 374 |
D. | Interaction of CO with Group 14 Cations | 375 |
1. | Adsorption of CO on Sn[superscript n+] and Pb[superscript n+] Ions | 375 |
E. | Interaction of CO with Group 11 cations | 376 |
1. | Adsorption of CO on Cu[superscript n+] Ions | 376 |
2. | Adsorption of CO on Ag[superscript +] Ions | 388 |
3. | Adsorption of CO on Au[superscript n+] Ions | 391 |
F. | Interaction of CO with Group 12 Cations | 395 |
1. | Adsorption of CO on Zn[superscript 2+] Ions | 395 |
G. | Interaction of CO with Group 3 Cations | 396 |
1. | Adsorption of CO on Sc, Y, and La Ions | 396 |
2. | Adsorption of CO on Ce[superscript n+] Ions and Ions of Other Lanthanides and Actinides | 398 |
H. | Interaction of CO with Group 4 Cations | 400 |
1. | Adsorption of CO on Ti[superscript n+] Ions | 400 |
2. | Adsorption of CO on Zr[superscript n+] Ions | 405 |
3. | Adsorption of CO on Hf[superscript 4+] Ions | 408 |
I. | Interaction of CO with Group 5 Cations | 408 |
1. | Adsorption of CO on V[superscript n+] Ions | 408 |
2. | Adsorption of CO on Nb[superscript n+] and Ta[superscript n+] Ions | 412 |
J. | Interaction of CO with Group 6 Cations | 412 |
1. | Adsorption of CO on Cr[superscript n+] Ions | 412 |
2. | Adsorption of CO on Mo[superscript n+] Ions | 419 |
3. | Adsorption of CO on W[superscript n+] Ions | 426 |
K. | Interaction of CO with Group 7 Cations | 428 |
1. | Adsorption of CO on Mn[superscript n+] Ions | 428 |
L. | Interaction of CO with Group 8-10 Cations | 430 |
1. | Adsorption of CO on Fe[superscript n+] Ions | 430 |
2. | Adsorption of CO on Co[superscript n+] Ions | 434 |
3. | Adsorption of CO on Ni[superscript n+] Ions | 443 |
4. | Adsorption of CO on Ru[superscript n+] Ions | 451 |
5. | Adsorption of CO on Rh[superscript n+] Ions | 462 |
6. | Adsorption of CO on Pd[superscript n+] Ions | 470 |
7. | Adsorption of CO on Os[superscript n+] Ions | 473 |
8. | Adsorption of CO on Ir[superscript n+] Ions | 475 |
9. | Adsorption of CO on Pt[superscript n+] ions | 476 |
IV. | Interaction of CO with OH Groups | 481 |
A. | General | 481 |
B. | Specific Samples | 485 |
1. | Zeolites and other microporous materials | 485 |
2. | Oxides | 489 |
V. | Conclusions | 489 |
VI. | Acknowledgments | 491 |
| References | 491 |
| Index | 513 |