About the Editors ............................................ XIII
List of Contributors ........................................... XV
1 Zeolites in Catalysis ........................................ 1
Stephen H. Brown
1.1 Introduction ............................................ 1
1.1.1 The Environmental Benefits of Zeolite-enabled
Processes ........................................ 2
1.2 General Process Considerations .......................... 5
1.3 Zeolite Fundamentals .................................... 6
1.3.1 Other Properties ................................. 7
1.3.2 Number of Acid Sites ............................. 8
1.3.3 Acid Strength .................................... 8
1.4 Reaction Mechanisms ..................................... 8
1.4.1 Hydrocarbon Cracking ............................. 8
1.4.2 Oligomerization and Alkylation .................. 12
1.4.3 Isomerization ................................... 14
1.4.4 Transalkylation of Aromatics .................... 15
1.4.5 Hydrogen Transfer or Conjunct Polymerization .... 18
1.5 Mass Transport and Diffusion ........................... 21
1.6 Zeolite Shape Selectivity .............................. 22
1.6.1 Mass Transport Discrimination of Product
Molecules ....................................... 22
1.6.2 Molecular Sieving ............................... 23
1.6.3 Molecular Orientation ........................... 23
1.6.4 Transition State Stabilization .................. 25
1.6.5 Organic Reaction Centers ........................ 26
1.7 Counter Ion Mobility ................................... 29
1.8 Conclusions ............................................ 29
References .................................................. 29
2 Sol-Gel Sulfonic Acid Silicas as Catalysts .................. 37
Adam F. Lee and Karen Wilson
2.1 Introduction ........................................... 37
2.2 Preparation of Meso-structured Silica Sulfonic Acid
Catalysts .............................................. 38
2.2.1 Templating Methods .............................. 38
2.2.1.1 Cationic/Anionic Templates ............. 38
2.2.1.2 Neutral Templates ...................... 39
2.2.2 Organically Functionalized Silica ............... 39
2.2.2.1 Characterization ....................... 40
2.2.2.2 Grafting Methods ....................... 42
2.2.2.3 Direct Preparation Methods ............. 43
2.2.3 Acid Strength of Sulfonic Acid Catalysts ........ 44
2.2.3.1 Phenyl- Versus Propylsulfonic Acids .... 45
2.2.4 Fine Tuning the Catalytic Activity of Sulfonic
Acid Silicas .................................... 46
2.2.4.1 Cooperative Effects .................... 46
2.2.4.2 Effect of Spectator Groups ............. 48
2.3 Application in Organic Transformations ................. 49
2.3.1 Condensation and Esterification ................. 49
2.3.2 Electrophilic Aromatic Substitution ............. 51
2.3.3 Miscellaneous Reactions ......................... 52
2.4 Conclusions and Future Prospects ....................... 53
References ............................................. 55
3 Applications of Environmentally Friendly TiO2
Photocatalysts in Green Chemistry: Environmental
Purification and Clean Energy Production Under Solar Light
Irradiation ................................................. 59
Masaya Matsuoka and Masakazu Anpo
3.1 Introduction ........................................... 59
3.2 Principles of Photocatalysis ........................... 61
3.3 Application of Photocatalysts in Green Chemistry:
Solar Energy Conversion and Environmental Protection ... 62
3.3.1 Water Splitting to Produce Pure Hydrogen as
Clean Fuel ...................................... 62
3.3.2 Photocatalytic Reduction of CO2 with H2O
(Artificial Photosynthesis) ..................... 64
3.3.3 Direct Photocatalytic Decomposition of NO into
N2 and O2 ....................................... 67
3.3.4 Application to the Purification of Air
Polluted with Various Organic Compounds ......... 70
3.3.5 Application to the Purification of Water
Polluted with Toxic Compounds Such as Dioxins ... 71
3.3.6 Superhydrophilic Properties of TiO2 Thin Films
and Their Application in Self-cleaning
Materials ....................................... 72
3.4 Development of Visible Light-responsive TiO2
Photocatalysts ......................................... 73
3.4.1 Modification of the Electronic State of TiO2
by Applying an Advanced Metal Ion Implantation
Method .......................................... 73
3.4.2 Design of Visible Light-responsive Ti/Zeolite
Catalysts by Applying an Advanced Metal Ion
Implantation Method ............................. 75
3.4.3 Preparation of Visible Light-responsive TiO2
Thin-film Photocatalysts by an RF Magnetron
Sputtering Deposition Method .................... 76
3.5 Conclusion ............................................. 79
References ............................................. 79
4 Nanoparticles in Green Catalysis ............................ 81
Mazaahir Kidwai
4.1 Introduction ........................................... 81
4.2 Advanced Catalysis by Gold Nanoparticles ............... 81
4.3 Nickel Nanoparticles: a Versatile Green Catalyst ....... 85
4.4 Copper Nanoparticles: an Efficient Catalyst ............ 87
4.5 Bimetallic Nanoparticles in a Variety of Reactions ..... 89
References .................................................. 91
5 'Heterogreeneous Chemistry' ................................. 93
Heiko Jacobsen
5.1 Introduction ........................................... 93
5.2 'Heterogreeneous Catalysis' ............................ 96
5.2.1 An Exemplarily Reaction - Catalysts for
Hydrogen Production from Biomass-Derived
Hydrocarbons .................................... 97
5.2.2 Transportation Fuels from Biomass - Catalytic
Processing of Biomass-derived Reactants ........ 100
5.2.3 Diesel Fuels from Biomass - Heterogreeneous
Processes for Biodiesel Production ............. 103
5.2.4 Other Heterogreeneous Aspects of Catalysis ..... 106
5.2.4.1 Solid and Solid Acid Catalysts ........ 106
5.2.4.2 Recycling Catalysts ................... 107
5.2.4.3 One-pot Catalysis ..................... 108
5.2.4.4 Photocatalysis ........................ 108
5.3 Solvents for Green Catalysis .......................... 108
5.3.1 Heterogreeneous Solvent Systems ................ 109
5.3.2 Solvent-free'Heterogreeneous Chemistry' ........ 112
5.4 Conclusion and Outlook ................................ 113
References ............................................ 114
6 Single-site Heterogeneous Catalysts via Surface-bound
Organometallic and Inorganic Complexes ..................... 117
Christophe Copéret
6.1 Introduction .......................................... 117
6.2 Generalities .......................................... 117
6.3 Hydrogenation and Hydrosilylation ..................... 119
6.3.1 Hydrogenation .................................. 119
6.3.2 Hydrosilylation ................................ 123
6.4 Metathesis and Homologation Processes of Alkenes ...... 124
6.4.1 Alkene Metathesis .............................. 124
6.4.1.1 Silica-supported Catalysts ............ 124
6.4.1.2 Alumina-supported Catalysts ........... 127
6.4.2 Other Alkene Homologation Processes ............ 128
6.4.2.1 Direct Conversion of Ethene into
Propene ............................... 128
6.4.2.2 Cyclization of Dienes ................. 129
6.5 Metathesis, Dimerization, Trimerization and Other
Reactions Involving Alkynes ........................... 129
6.5.1 Alkyne Metathesis .............................. 129
6.5.2 Dimerization and Trimerization of Alkynes ...... 130
6.5.3 Hydroamination of Alkynes ...................... 131
6.6 Lewis Acid-catalyzed Reactions ........................ 131
6.6.1 Silica-supported Group 4 Metals ................ 131
6.6.1.1 Reduction of Ketones Through
Hydrogen Transfer ..................... 133
6.6.1.2 Transesterification of Esters ......... 134
6.6.2 Silica-supported Group 3 Metals and
Lanthanides .................................... 134
6.7 Oxidation ............................................. 135
6.7.1 Single-site Titanium Species ................... 135
6.7.2 Single-site Zirconium Species .................. 137
6.7.3 Single-site Vanadium Species ................... 137
6.7.4 Single-site Tantalum Species ................... 137
6.7.5 Single-site Group 6 Species .................... 138
6.7.6 Single-site Iron Species ....................... 139
6.7.7 Single-site Cobalt Species ..................... 141
6.8 Alkane Homologation ................................... 141
6.8.1 Alkane Hydrogenolysis .......................... 141
6.8.2 Alkane Metathesis .............................. 143
6.8.3 Alkane Cross-metathesis ........................ 146
References ................................................. 146
7 Sustainable Heterogeneous Acid Catalysis by Heteropoly
Acids ...................................................... 153
Ivan Kozhevnikov
7.1 Introduction .......................................... 153
7.2 Development of HPA Catalysts Possessing High Thermal
Stability ............................................. 156
7.3 Modification of HPA Catalysts to Enhance Coke
Combustion ............................................ 157
7.3.1 Propene Oligomerization ........................ 158
7.3.2 Friedel-Crafts Acylation ....................... 159
7.1 Inhibition of Coke Formation on HPA Catalysts ......... 161
7.5 Reactions in Supercritical Fluids ..................... 163
7.6 Cascade Reactions Using Multifunctional HPA
Catalysts ............................................. 165
7.6.1 Synthesis of MIBK .............................. 166
7.6.2 Hydrogenolysis of Glycerol to Propanediol ...... 167
7.6.3 Synthesis of Menthol from Citronellal .......... 170
7.7 Conclusion ............................................ 172
References ............................................ 172
8 The Kinetics of TiO2-based Solar Cells Sensitized by Metal
Complexes .................................................. 153
Anthony G. Fitch, Don Walker, and Nathan S. Lewis
8.1 Introduction .......................................... 175
8.2 History ............................................... 176
8.3 DSSC Design ........................................... 177
8.4 Function of the DSSC .................................. 178
8.5 Performance of a DSSC ................................. 179
8.6 Kinetics Processes .................................... 180
8.7 Charge Injection ...................................... 181
8.8 Recombination to the Dye .............................. 184
8.9 Regeneration .......................................... 187
8.10 Conclusion ............................................ 190
References ................................................. 192
9 Automotive Emission Control: Past, Present and Future ...... 197
Robert J. Farrauto and Jeffrey Hoke
9.1 Introduction .......................................... 197
9.2 The First Oxidation Catalysts (1975-80) ............... 198
9.2.1 Pollution Abatement Reactions for Gasoline-
Fueled Engines ................................. 198
9.2.2 Catalyst Materials ............................. 199
9.2.3 Carriers ....................................... 201
9.3 Three-Way Catalysis (1980-present) .................... 202
9.3.1 Three-Way Catalysis ............................ 202
9.3.2 Oxygen or Lambda Sensor ........................ 203
9.3.3 Oxygen Storage Component ....................... 203
9.3.4 Further Improvements in TWC .................... 204
9.4 Diesel Catalysis ...................................... 206
9.4.1 Controlling Diesel Emissions ................... 206
9.4.2 Diesel Emissions ............................... 207
9.4.3 Diesel Oxidation Catalysts (DOCs): the Past .... 208
9.5 Diesel Emission Control: the Future ................... 210
9.5.1 Catalytic Solutions for the Existing Diesel
1С Engine ...................................... 210
9.5.2 The Homogeneous Charge Compression Ignition
Engine (HCCI) and Advanced Engine Technology ... 213
9.6 Fuel Cells and the Hydrogen Economy for
Transportation Applications: the Future ............... 217
9.6.1 The Fuel Cell .................................. 217
9.6.2 Fuel Cells for Transportation .................. 218
9.6.3 The Hydrogen Service Station ................... 219
9.7 Conclusions ........................................... 220
References ............................................ 220
10 Heterogeneous Catalysis for Hydrogen Production ............ 223
Morgan S. Scott and Hicham Idriss
10.1 Introduction .......................................... 223
10.1.1 Renewable Energy ............................... 224
10.1.2 Hydrogen ....................................... 225
10.1.3 Hydrogen from Ethanol Decomposition ............ 226
10.1.4 Catalytic Oxidation ............................ 228
10.1.5 Steam Reforming ................................ 228
10.1.6 Dry Reforming .................................. 229
10.1.7 Water Gas Shift Reaction (WGSR) ................ 229
10.1.8 Catalytic Reforming of Methane ................. 230
10.1.9 Thermodynamics ................................. 230
10.2 Catalysis ............................................. 231
10.2.1 The Noble Metals Pd and Rh ..................... 232
10.2.2 Structure and Properties of Cerium Dioxide ..... 233
10.2.3 Noble Metal/Ceria Catalysts .................... 235
10.2.4 Adsorption of Ethanol .......................... 236
10.2.5 Adsorption of Water ............................ 236
10.2.6 Adsorption of Carbon Oxides .................... 237
10.2.7 Hydrides ....................................... 237
10.3 Catalytic Decomposition of Ethanol .................... 238
10.3.1 Ethanol on Metal Oxides ........................ 238
10.3.2 Ethanol on a Noble Metal/Ceria Surface ......... 239
10.3.3 Catalytic Oxidation of Ethanol ................. 242
10.3.4 Catalytic Reforming of Ethanol ................. 243
10.4 Conclusions ........................................... 244
References ............................................ 245
11 High-Throughput Screening of Catalyst Libraries for
Emissions Control .......................................... 247
Stephen Cypes, Joel Cizeron, Alfred Hagemeyer, and
Anthony Volpe
11.1 Introduction .......................................... 247
11.1.1 Introduction to High-Throughput Heterogeneous
Catalysis ...................................... 247
11.1.2 The Hierarchical Workflow in Heterogeneous
Catalysis ...................................... 248
11.1.3 Applications to Green Chemistry ................ 249
11.2 Experimental Techniques and Equipment ................. 250
11.2.1 Overview of Hardware and Methodologies for
Combinatorial Heterogeneous Catalysis .......... 250
11.2.2 Experimental High-Throughput Workflow for
Low-Temperature CO Oxidation and VOC
Combustion ..................................... 259
11.2.2.1 Primary Synthesis Methods ............. 260
11.2.2.2 Secondary Synthesis Methods .................. 260
11.2.2.3 IR Thermography Reactor ............... 261
11.2.2.4 Multi-Channel Fixed-bed Reactor ....... 263
11.2.3 Experimental High-Throughput Workflow for NOx
Abatement ...................................... 263
11.2.3.1 Primary Synthesis Methods ............. 263
11.2.3.2 Primary Screening Methods ............. 263
11.2.3.3 Data Analysis for NOx Abatement from
SMS ................................... 264
11.2.3.1 Low-Temperature CO Oxidation and VOC
Combustion ............................ 265
11.4 NOx Abatement ......................................... 273
11.5 Conclusion ............................................ 277
11.5.1 Application of High-Throughput Screening to
Emissions Control .............................. 277
11.5.2 Future Trends in Combinatorial Catalysis ....... 278
References ................................................. 278
12 Catalytic Conversion of High-Moisture Biomass to
Synthetic Natural Gas in Supercritical Water ............... 281
Frédéric Vogel
12.1 Introduction .......................................... 281
12.1.1 Heterogeneous Catalysis in Hydrothermal
Medium at the Origin of Life? .................. 281
12.1.2 Biomethane - a Green and Sustainable Fuel ...... 282
12.1.3 Energetic Potentials ........................... 283
12.1.4 Nutrient Cycles ................................ 284
12.2 Survey of Different Technologies for the Production
of Methane from Carbonaceous Feedstocks ............... 285
12.2.1 Anaerobic Digestion ............................ 285
12.2.2 Thermal Processes .............................. 286
12.3 Water as Solvent and Reactant ......................... 288
12.3.1 Solubility of Organic compounds and Gases ...... 289
12.3.2 Solubility of Salts ............................ 290
12.4 The Role of Heterogeneous Catalysis ................... 290
12.4.1 Experimental Methods ........................... 290
12.4.2 Thermodynamic Stability of Methane under
Hydrothermal Conditions ........................ 291
12.4.3 Main Reactions of Biomass Gasification ......... 293
12.4.4 Homogeneous, Non-catalyzed Pathways in Hot
Compressed Water ............................... 294
12.4.5 Heterogeneously Catalyzed Pathways in Hot
Compressed Water ............................... 297
12.4.6 Active Metals Suited to Hydrothermal
Conditions ..................................... 298
12.4.6.1 Methanation and Steam Reforming
Catalysts ............................. 299
12.4.6.2 Nickel ................................ 302
12.4.6.3 Ruthenium ............................. 305
12.4.7 Catalyst Supports Suited to Hydrothermal
Conditions ..................................... 306
12.4.8 Deactivation Mechanisms in a Hydrothermal
Environment .................................... 312
12.4.8.1 Coke Formation ........................ 312
12.4.8.2 Sintering ............................. 314
12.4.8.3 Poisoning ............................. 314
12.5 Continuous Catalytic Hydrothermal Process for the
Production of Methane ................................. 315
12.5.1 Overview of Processes .......................... 315
12.5.2 PSI's Catalytic Hydrothermal Gasification
Process ........................................ 315
12.5.2.1 Continuous Salt Precipitation and
Separation ............................ 316
12.5.2.2 Status ................................ 318
12.6 Summary and Conclusions ............................... 318
12.7 Outlook for Future Developments ....................... 319
12.7.1 A Self-sustaining Biomass Vision (SunCHem) ..... 319
References ................................................. 320
Index ......................................................... 325
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