Contents to Volume 1 ........................................... XI
11 Oxidation Reactions over Supported Metal Oxide Catalysts:
Molecular/Electronic Structure-Activity/Selectivity
Relationships ............................................. 487
Israel E. Wachs and Taejin Kim
11.1 Overview ............................................ 487
11.2 Introduction ........................................ 487
11.3 Monolayer Surface Coverage .......................... 488
11.4 Molecular and Electronic Structures ................. 490
11.5 Number of Exposed Catalytic Active Sites (Ns) ....... 491
11.6 Surface Reactivity .................................. 492
11.7 Steady-State Reactivity (TOF) ....................... 493
11.8 Number of Participating Catalytic Active Sites in
Oxidation Reactions ................................. 494
11.9 Role of Surface Acid Sites on Oxidation Reactions ... 495
11.10 Other Supported MOx Redox Active and Acidic
Systems ............................................. 496
11.11 Conclusions ......................................... 496
References ................................................ 497
12 Vanadium Phosphate Catalysts .............................. 499
Johnathan K. Bartley, Nicholas F. Dummer, and Graham
J. Hutchings
12.1 Introduction ........................................ 499
12.2 The Active Catalyst ................................. 500
12.2.1 The Oxidation State of the Catalyst ......... 502
12.2.2 The Phosphorus-to-Vanadium Ratio of the
Catalyst .................................... 504
12.2.3 The Role of Amorphous Material .............. 505
12.2.4 The Disordered Plane ........................ 507
12.2.5 Acid-Base Properties ........................ 507
12.3 Preparation of VPP Precursors ....................... 508
12.3.1 The Preparation of Novel Vanadium
Phosphates .................................. 513
12.4 Activation of the Catalyst Precursors ............... 514
12.4.1 Activation Procedures ....................... 514
12.4.2 Structural Transformations during
Activation .................................. 517
12.5 Promoted Catalysts .................................. 519
12.6 Mechanism of n-Butane Partial Oxidation ............. 524
12.6.1 Consecutive Alkenyl Mechanism ............... 524
12.6.2 Consecutive Alkoxide Mechanism .............. 527
12.6.3 Concerted Mechanism ......................... 529
12.6.4 Redox Couple Mechanism ...................... 530
12.7 Concluding Comments ................................. 530
References .......................................... 531
13 Heterogeneous Catalysis by Uranium Oxides ................. 539
Stuart H. Taylor
13.1 Introduction ........................................ 539
13.2 Structure of Uranium Oxides ......................... 540
13.3 Historical Uses of Uranium Oxides as Catalysts ...... 543
13.4 Catalysis by Uranium Oxides ......................... 547
13.4.1 Total Oxidation ............................. 547
13.4.2 Selective Oxidation ......................... 528
13.4.3 Reduction ................................... 554
13.4.4 Steam Reforming ............................. 556
13.5 Conclusions ......................................... 558
References .......................................... 559
14 Heteropolyoxometallate Catalysts for Partial Oxidation .... 561
Jacques С. Védrine and Jean-Marc M. Millet
14.1 Introduction ........................................ 561
14.2 History of Polyoxometallates ........................ 565
14.3 Properties and Applications of Polyoxometallates .... 566
14.4 Catalytic Applications in Partial Oxidation
Reactions ........................................... 568
14.4.1 Oxidation with Molecular Oxygen ............. 570
14.4.2 Oxidation by Hydrogen Peroxide .............. 575
14.5 Characterization: Redox and Acid-Base Properties .... 578
14.5.1 IR Spectroscopy ............................. 581
14.5.2 Photoacoustic Spectroscopy .................. 582
14.5.3 UV-Visible Spectroscopy ..................... 583
14.5.4 Nuclear Magnetic Resonance Spectroscopy ..... 583
14.5.5 Electron Spin Resonance (ESR)
Spectroscopy ................................ 584
14.5.6 Electrochemistry of Keggin Heteropoly
Compounds ................................... 585
14.5.7 Thermal Analysis ............................ 586
14.5.8 Microcalorimetry of Acid or Basic Probe
Adsorption .................................. 586
14.6 Conclusions and Perspectives in Polyoxometallate
Application in Heterogeneous Oxidation Catalysis .... 587
References .......................................... 589
15 Alkane Dehydrogenation over Vanadium and Chromium
Oxides .................................................... 595
S. Dauid Jackson, Peter C. Stair, Lynn F. Cladden, and
James McGregor
15.1 Introduction ........................................ 595
15.2 Commercial LPG Dehydrogenation Process .............. 596
15.3 Lummus/Houdry CATOFIN® Process ...................... 596
15.4 Chromia ............................................. 596
15.5 Vanadia ............................................. 601
15.6 Conclusions ......................................... 610
References ................................................ 610
16 Properties, Synthesis and Applications of Highly
Dispersed Metal Oxide Catalysts ........................... 613
Juncheng Ни, Lifang Chen, and Ryan Richards
16.1 Introduction ........................................ 613
16.2 Properties .......................................... 614
16.2.1 Structure and Bonding ....................... 614
16.2.2 Defects ..................................... 616
16.2.3 Acid-Base Properties of Metal Oxides ........ 617
16.2 A Redox Property of Metal Oxides ................... 619
16.3 Synthesis ........................................... 619
16.3.1 Sol-Gel Technique ........................... 620
16.3.1.1 Hydrolysis and Condensation of
Metal Alkoxides .................... 622
16.3.1.2 Solvent Removal and Drying ........ 623
16.3.2 Co-precipitation Methods .................... 627
16.3.2.1 Co-precipitation from Aqueous
Solution at Low Temperature ....... 628
16.3.2.2 Sonochemical Co-precipitation ..... 630
16.3.2.3 Microwave-Assisted
Co-precipitation .................. 631
16.3.3 Solvothermal Technique ...................... 633
16.3.4 Micro-Emulsion Technique .................... 636
16.3.5 Combustion Methods .......................... 638
16.3.6 Others ...................................... 639
16.3.6.1 Vapor Condensation Methods ........ 639
16.3.6.2 Spray Pyrolysis ................... 640
16.3.6.3 Templated/Surface Derivatized
Nanoparticles ..................... 640
16.4 Applications in Catalysis ........................... 641
16.4.1 Oxygenation of Alkanes ...................... 641
16.4.2 Biodiesel Production ........................ 643
16.4.3 Methanol Adsorption and Decomposition ....... 645
16.4.4 Destructive Adsorption of Chlorocarbons ..... 649
16.4.5 Alkene Metathesis ........................... 650
16.4.6 Claisen-Schmidt Condensation ................ 652
16.5 Conclusions ......................................... 653
References .......................................... 654
17 Preparation of Superacidic Metal Oxides and Their
Catalytic Action .......................................... 665
Kazushi Arata
17.1 Introduction ........................................ 665
17.2 Preparation ......................................... 669
17.2.1 Sulfated Metal Oxides of Zr, Sn, Ti, Fe,
Hf, Si, and Al .............................. 669
17.2.1.1 Preparation of Zirconia Gel ....... 669
17.2.1.2 Preparation of Stannia Gel ........ 669
17.2.1.3 Preparation of H4TiO4 ............. 670
17.2.1.4 Preparation of Fe(OH)3 ............ 670
17.2.1.5 Preparation of Hf(OH)4 ............ 670
17.2.1.6 Sulfation, Calcination, and
Catalytic Action .................. 670
17.2.1.7 Preparation of Sulfated Silica .... 671
17.2.1.8 Preparation of Sulfated Alumina ... 671
17.2.1.9 Property and Characterization ..... 671
17.2.1.10 One-Step Method for Preparation
of SO4/ZrO2 ....................... 672
17.2.1.11 Commercial Gels for Preparation
of SO4/ZrO2 and SO4/SnO2 ........... 672
17.2.1.12 Effect of Drying and Calcination
Temperatures on the Catalytic
Activity of SO4/ZrO2 .............. 673
17.2.2 Tungstated, Molybdated, and Borated Metal
Oxides ...................................... 674
17.2.2.1 Preparation of WO3/ZrO2 and
MoO3/ZrO2 ......................... 674
17.2.2.2 Preparation of WO3/SnO2,
WO3/TiO2, and WO3/Fe2O3 ............ 674
17.2.2.3 Preparation of B2O3/ZrO2 ........... 674
17.2.2.4 Property and Characterization ..... 675
17.3 Determination of Acid Strength ...................... 675
17.3.1 Hammett Indicators .......................... 676
17.3.2 Test Reactions .............................. 677
17.3.3 Temperature-Programmed Desorption (TPD) ..... 677
17.3.4 Temperature-Programmed Reaction (TPRa) ...... 678
17.3.5 Ar-TPD ...................................... 678
17.3.6 Ar- Adsorption .............................. 680
17 4 Nature of Acid Sites ................................ 682
17.5 Isomerization of Butane Catalyzed by Sulfated
Zirconia ............................................ 685
17.6 Isomerization of Cycloalkanes ....................... 686
17.7 Structure of Sulfated Zirconia ...................... 687
17.8 Promoting Effect .................................... 689
17.8.1 Effect of Addition of Metals to Sulfated
Zirconia on the Catalytic Activity .......... 689
17.8.2 Effect of Mechanical Mixing of Pt-Added
Zirconia on the Catalytic Activity .......... 690
17.9 Friedel-Crafts Acylation of Aromatics ............... 692
17.10 Ceramic Acid ........................................ 695
17.10.1 Tungstated Stannia .......................... 696
17.10.2 Tungstated Alumina .......................... 697
17.11 Application to Sensors and Photocatalysis ........... 698
References .......................................... 698
18 Titanium Silicalite-1 ..................................... 705
Mario G. Clerici
18.1 Synthesis and Characterization ...................... 706
18.2 Hydroxylation of Alkanes ............................ 707
18.2.1 Titanium Silicalite-1 ....................... 708
18.2.2 Other Ti-Zeolites ........................... 712
18.3 Hydroxylation of Aromatic Compounds ................. 712
18.3.1 Hydroxylation of Phenol ..................... 713
18.3.1.1 Titanium Silicalite-1 ............. 713
18.3.1.2 Other Ti-Zeolites ................. 715
18.3.2 Hydroxylation of Benzene .................... 716
18.3.3 Oxidation of Substituted Benzenes ........... 717
18.4 Oxidation of Olefinic Compounds ..................... 717
18.4.1 Epoxidation of Simple Olefins ............... 717
18.4.1.1 Titanium Silicalite-1 ............. 718
18.4.1.2 Other Ti-Zeolites ................. 722
18.4.2 Epoxidation of Unsaturated Alcohols ......... 724
18.4.3 Epoxidation of Allyl Chloride and other
Substituted Olefins ......................... 726
18.4.4 Epoxidation with Solvolysis/Rearrangement
of Intermediate Epoxide ..................... 726
18.5 Oxidation of Alcohol and Other Oxygenated
Compounds ........................................... 727
18.6 Ammoximation of Carbonyl Compounds .................. 730
18.7 Oxidation of N-Compounds ............................ 732
18.8 Oxidation of S-Compounds ............................ 734
18.9 Industrial Processes Catalyzed by TS-1 .............. 734
18.9.1 Hydroxylation of Phenol to Catechol and
Hydroquinone ................................ 734
18.9.2 Salt-Free Production of Cyclohexanone
Oxime ....................................... 734
18.9.3 Propene Oxide Synthesis (HPPO) .............. 735
18.10 Problems in the Use of H2O2 and Possible
Solutions ........................................... 736
18.10.1 Direct Synthesis of Hydrogen Peroxide ....... 737
18.10.2 In Situ Production of Hydrogen Peroxide ..... 737
18.10.3 Process Integration ......................... 738
18.10.4 Miscellanea ................................. 739
18.11 Adsorption, Active Species and Oxidation
Mechanisms .......................................... 740
18.11.1 Adsorption and Catalytic Performances ....... 740
18.11.2 The Structure of Ti-OOH Species ............. 742
18.11.3 Reactive Intermediates and Oxidation
Mechanisms .................................. 743
18.11.4 Proposal for a General Mechanistic Scheme ... 746
18.12 Conclusions ......................................... 748
References .......................................... 749
19 Oxide Materials in Photocatalytic Processes ............... 755
Richard P.K. Wells
19.1 Introduction ........................................ 755
19.2 Basic Principles of Heterogeneous Photocatalysis .... 756
19.3 Traditional Photocatalysts .......................... 757
19.4 Improving Photocatalytic Activity ................... 760
19.4.1 Visible Light Sensitization by Adsorption
of Organic and Inorganic Dyes ............... 760
19.4.2 Visible Light Sensitization by Anion
Doping ...................................... 760
19.4.3 Visible Light Sensitization by Metal Ion
Implantation Techniques ..................... 761
19.4.4 Physical Methods to Enhance Photocatalytic
Activity .................................... 763
19.4.5 Potential-Assisted Photocatalysis ........... 766
19.5 Conclusions ......................................... 766
References .......................................... 767
20 Catalytic Ammoxidation of Hydrocarbons on Mixed Oxides .... 771
Fabrizio Cavani, Gabriele Centi, and Philippe Marion
20.1 Introduction ........................................ 771
20.2 Propene Ammoxidation to Acrylonitrile ............... 775
20.3 Propane Ammoxidation to Acrylonitrile ............... 778
20.3.1 Mo/V/Te/Sb/(Nb)/O Catalysts ................. 782
20.3.2 Rutile-Type Antimonate Catalysts ............ 786
20.4 Alkylaromatic Ammoxidation .......................... 791
20.4.1 Alkylbenzenes and Substituted
Alkylbenzenes ............................... 791
20.4.2 Alkylaromatics Containing Hetero-Groups ..... 795
20.4.3 Ammonolysis vs Ammoxidation ................. 796
20.5 Ammoxidation of Unconventional Molecules ............ 797
20.5.1 The Ammoxidation of C4 Hydrocarbons ......... 797
20.5.2 The Ammoxidation of Cyclohexanol and
Cyclohexanone ............................... 800
20.5.3 The Ammoxidation of Cyclohexane and
n-Hexane .................................... 802
20.5.4 The Ammoxidation of Benzene ................. 805
20.5.5 Ammoxidation of C2 Hydrocarbons ............. 807
20.5.6 Conclusions on the Ammoxidation of
Unconventional Molecules .................... 808
20.6 Use of Other Oxidants for Ammoxidation Reactions .... 810
20.7 Conclusions ......................................... 810
References ................................................ 811
21 Base Catalysis with Metal Oxides .......................... 819
Khalaf AlGhamdi, Justin S. J. Hargreaves, and S. David
Jackson
21.1 Introduction ........................................ 819
21.2 Catalysts and Catalytic Processes ................... 825
21.2.1 Alkali Metal Oxides ......................... 826
21.2.2 Alkaline Earth Metal Oxides ................. 830
21.2.3 Hydrotalcites ............................... 835
21.2.4 Rare Earth Oxides ........................... 836
21.2.5 Basic Zeolites .............................. 837
21.2.6 Zirconia Superbases ......................... 837
21.3 Outlook ............................................. 838
References ................................................ 840
Index ......................................................... 845
|
