Advances in Catalysis

by Bruce C. Gates (Editor), Helmut Knoezinger (Editor), Friederike C. Jentoft (Editor)

Overview

Catalysis is the acceleration of a chemical reaction by a catalyst, a substance that notably affects the rate of a chemical reaction without itself being consumed or altered.

Since 1948, Advances in Catalysis has filled the gap between the papers that report on and the textbooks that teach in the diverse areas of catalysis research. The editors of and contributors to Advances in Catalysis are dedicated to recording progress in this area.

Product Details

ISBN-13:	9780123877734
Publisher:	Elsevier Science
Publication date:	11/23/2011
Series:	ISSN , #54
Sold by:	Barnes & Noble
Format:	eBook
Pages:	352
File size:	8 MB

Table of Contents

	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

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"This volume of Advances in Catalysis consists of important contributions covering three different topics: homogeneous catalysis, heterogeneous catalysis, and chemical reactor engineering. The content is of current interest and would be useful to those working in catalysis, process development, and specific areas of the reactions discussed."—Catal Lett (2012) Vol. 142 pages 397–398

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