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E-grāmata: Electron Microscopy in Heterogeneous Catalysis

(DuPont Experimental Station, Wilmington, Delaware, USA),
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Catalysis is one of the most important technologies in the industrial world, controlling more than 90% of industrial chemical processes and essential for large-scale production of plastics and fuel. Exploring the most common type of catalysis used in industry, Electron Microscopy in Heterogeneous Catalysis provides a coherent account of heterogeneous catalytic processes and catalyst surface structure at the atomic scale as elucidated by electron microscopy techniques.

The book addresses a number of issues that are fundamental to the understanding of heterogeneous catalysis by oxides and supported metals. The properties of a catalyst are governed by its microstructure and chemistry on an atomic scale, and electron microscopy methods are essential to directly analyze these properties. The book provides important information about active species, metastable-transient species, mechanisms of particle catalysis sintering, promoter-poisoning effects on an atomic scale, and catalyst support interactions on a microscale.

Recenzijas

"This book deals with in situ dynamic observation and analysis of heterogeneous catalysis using environmental cells (EC) in transmission (TEM) and scanning electron microscopes (SEM). In general, it is based on outstanding and unique works carried out by the authors themselves over the past three decades, who pioneered this key enabling area of materials science. It provides comprehensive and yet compact introductions to heterogeneous catalysis and electron microscopy and diffraction, followed by detailed descriptions of electron microscopy studies of oxide catalysis, zeolites, molecular sieves, supported small metal particles, and environmental catalysis. For those who are carrying out in situ dynamic studies of catalysis using EC in TEM and/or SEM, this book gives a state-of-the-art review of this field. More importantly, this book encourages those catalysis students and electron microscopists who are planning to perform in situ dynamic studies of catalysis." -Professor Hiroyasu Saka, Nagoya University, Japan

"P.L. Gai and E.D. Boyes have produced an authoritative text [ that is] indispensable if this is your subject." -P. Hawkes, Ultramicroscopy 101 (2004): 73-103

Preface xi
Acknowledgments xii
An introduction to heterogeneous catalysis
1(44)
Science and technology of catalysis
1(1)
Fundamental principles of catalysis: some basic definitions
2(3)
Electronic configurations and quantum theory
5(3)
Valence electrons: examples of common elements
7(1)
Chemical bonding
8(1)
Thermodynamic definitions relevant to catalysis and the role of electron microscopy
9(1)
Energy, enthalpy and entropy
9(1)
Structure and chemistry of carbons and hydrocarbons
10(1)
Catalysis and band theory
11(2)
pH scale, Lewis Bronsted acidity and basicity
12(1)
Band theory
12(1)
Some important structures of solid catalysts
13(5)
Metals and oxides
13(1)
Oxides
13(1)
ReO3
14(1)
Jahn--Teller distortion
15(1)
Titania (TiO2) system
15(1)
Rutile (TiO2) structure
15(1)
Anatase
15(1)
Layer structures
16(1)
Perovskites and pyrochlores
16(2)
Carbons as supports in catalysis and new forms of carbons with atomic scale building blocks
18(6)
Amorphous carbon, graphite, fullerene and carbon nanotubes (CNT)
18(2)
Nanotubes
20(1)
Carbons and catalytic reactions
20(2)
Choice and design of catalyst supports or carriers
22(1)
Carbon deposits
22(2)
Polymers
24(1)
Oxides and non-stoichiometry in catalysis and the unique role of electron microscopy
24(17)
Methods of accommodating non-stoichiometry
24(2)
Point defect models
26(1)
Larger deviations from stoichiometry
26(1)
Non-stoichiometry in metallic monoxides
27(2)
Defect elimination: crystallographic shear (CS)
29(1)
Background to earlier work
30(1)
Reaction mechanism
31(3)
Block structures
34(2)
Infinitely adaptive structures
36(1)
Vernier structures
37(2)
Coherent intergrowths
39(1)
Chemical twinning
40(1)
Novel glide shear mechanism in anion-deficient oxides
40(1)
Catalysis by oxides
41(1)
Non-stoichiometry in oxidation catalysis
41(1)
Extended defects and crystallographic shear
41(4)
Relevance to oxidation catalysis
41(1)
Distinction between shear mechanisms and defect structures
42(1)
Important issues in oxide catalysis and EM techniques
43(2)
Electron microscopy and diffraction in heterogeneous catalysis
45(37)
Background
45(4)
Imaging in the TEM
49(9)
Classification of some important defect structures and diffraction contrast in catalysis
49(3)
High-resolution transmission electron microscopy (HRTEM)
52(3)
Development of HRTEM
55(2)
Multi-slice HRTEM image simulations
57(1)
Surface-profile imaging in HRTEM
57(1)
Chemical composition analysis of catalysts in the EM
58(2)
X-ray spectroscopy in the electron microscope
59(1)
Electron energy loss spectroscopy
60(1)
Convergent (or focused) beam electron diffraction
61(1)
The development of in situ environmental-TEM (ETEM) under controlled reaction environments to probe catalysis at the atomic level
61(6)
Background to in situ ETEM
62(3)
In situ studies of dynamic oxidation catalysis in action under high gas pressures and at operating temperatures
65(1)
Recent advances in in situ atomic-resolution ETEM for probing gas-catalyst reactions at the atomic level
66(1)
Novel wet-ETEM development for nanoscale studies of liquid-catalyst reactions at operating temperatures
67(3)
Scanning EM (SEM), cathodoluminescence in catalysis and environmental SEM (ESEM)
70(5)
Recent advances in ultra high-resolution low-voltage FE SEM (HR-LVSEM) and extreme FESEM in catalysis
71(2)
Extreme FESEM
73(1)
Cathodoluminescence in catalysis
74(1)
Scanning transmission EM (STEM)---recent advances
75(2)
Z contrast and three-dimensional electron tomography
76(1)
Image processing
77(1)
Charge-coupled devices
77(1)
Other developments
78(1)
Reflection EM
78(1)
Electron holography
78(1)
Other surface techniques
78(1)
Parallel chemical studies and correlations with the catalyst microstructure
79(3)
Analysis and characterization of catalyst dispersion and surface areas
79(1)
Physical adsorption
80(1)
Chemisorption
81(1)
Comparison of surface areas with electron microscopy
81(1)
Electron microscopy studies of catalysis by oxides
82(59)
Single and mixed metal oxide systems: redox pathways and anion deficiency
82(1)
Single metal oxide catalysts: MoO3
83(1)
In situ direct observations of surface defect structures in catalysts under controlled reducing environments and methods for defect analysis
84(1)
Shear domains and crystallographic shear (CS) planes in catalytic reduction
85(8)
Do CS planes form at catalyst operating temperatures and how quickly do they form?
87(1)
Collapse in the catalyst's structure leading to the formation of CS planes
88(1)
Growth of surface defects: CS planes in catalytic reduction and climb of dislocations
89(2)
Direct observation of dynamic redox processes in C3H6:O2 (or air) mixtures: behaviour of surface defect structures
91(1)
Methanol oxidation over MoO3
91(1)
V2O5 catalysts
92(1)
Electron microscopy and defect thermodynamics: a new understanding of oxidation catalysis
93(5)
Development of thermodynamics of reacting catalysts based on EM
93(2)
New understanding of defect mechanisms in oxidation catalysis from dynamic electron microscopy
95(2)
Supersaturation leading to a modified mechanism for the formation of CS planes in oxides
97(1)
The role of defects in catalytic reactions
98(3)
Correlations of the catalyst microstructure with catalytic activity and selectivity
98(3)
Multi-component (practical) oxide catalysts
101(8)
Bismuth molybdate catalysts
101(1)
Review of crystal structures
102(2)
Experimental procedures
104(1)
Dynamic electron microscopy in controlled environments
104(5)
Iron molybdates in methanol oxidation reactions
109(1)
Vanadium phosphate (V--P--O) catalysts for butane oxidation technology: the elucidation of active sites by in situ electron microscopy
110(15)
Synthesis and characterization of VPO catalysts
113(12)
Examples of other mixed metal oxide systems
125(4)
Heteropolyacids
125(2)
Mixed metal amorphous and spinel phase oxidation catalysts derived from carbonates
127(1)
Ca--Mn--O perovskites
128(1)
Electronic structure of crystallites and dopant distributions by cathodoluminescence electron microscopy
129(2)
Sb--Sn oxide catalysts and Fe--Sb--O catalysts
129(2)
Zirconia (ZrO2)-based solid-acid catalysts and ceria (CeO2) systems
131(1)
The key role of electron microscopy in the discovery of novel reaction mechanisms in selective oxidation catalysis
131(4)
Stable silica-based ceramic oxide supports for catalysts: some recent developments
135(6)
Structural principles
136(2)
Nanostructure and microchemistry
138(1)
Stabilization mechanisms
139(2)
Catalysis by zeolites and molecular sieves
141(10)
Structures, acidity and uses of zeolites
141(3)
Shape-selective catalyst
143(1)
Silicalites and aluminophosphates
144(3)
Determining three-dimensional structures by ED and HRTEM: MALPO solid acid catalysts
147(4)
Catalysis by supported small metal particles
151(55)
Recent developments
151(1)
Facile versus structure-sensitive reactions
152(1)
Preparation and characterization of model and practical metallic catalysts
153(2)
Monometallics: single metals on amorphous alumina
153(1)
Model and practical (real-life) bimetallic systems
154(1)
Catalytic mechanisms on supported metals
155(7)
Single metal particles
155(1)
Ceramic surfaces
155(1)
Metal--ceramic interface interactions: wetting and interfacial energies
156(1)
Particle nucleation and sintering in supported metal catalysts
157(1)
Particle size distributions (PSD): measurement of dispersion of metal particles on supports
158(1)
Selective gas adsorption or chemisorption
159(1)
Particle migration model and its limitations
160(2)
Experimental studies by electron microscopy
162(4)
Sintering of Pt/alumina
162(3)
Re-dispersion phenomena
165(1)
Small particles in HRTEM
166(1)
Supported metal-particle catalysis
166(1)
Experimental and theoretical developments in small metal-particle catalysis using electron microscopy
167(4)
Detection and surface structure of very small particles by HRTEM
167(1)
Image contrast and visibility of supported small metal catalyst particles in HRTEM
167(1)
Examples of image simulations of supported small particles
168(1)
Theoretical procedures and corrections of spherical aberration
168(3)
Structure of small metal particles
171(4)
Single crystal particles and multiply twinned particles (MTP)
171(4)
EM studies of chemical interactions at metal--support interfaces
175(1)
Metal--support interactions
176(4)
Strong metal--support interactions (SMSI) and electronic structures: In situ atomic resolution ETEM
177(3)
In situ ETEM studies of metal--irreducible ceramic support interactions
180(8)
Copper/alumina systems in different gas environments
180(3)
Ag/alumina
183(1)
Pd/alumina and thermal sintering
184(4)
Methanol synthesis and oxidation reactions
188(1)
Monometallic nanocatalyst systems: copper nanocatalysts supported on silica (Cu/SiO2)
188(1)
Bimetallic or alloy systems: atomic structure and composition
189(16)
Cu--Pd alloy system: structure, phase stability and catalysis
189(3)
Diffuse scattering in essentially perfect B2 catalyst particles and Ewald sphere
192(2)
State of the active catalysts
194(3)
Cu--Ru system
197(3)
Promoted Pt catalysts in pollution control
200(1)
Different synthesis routes and HRTEM of bimetallic systems
201(1)
Wet-ETEM of catalyst-liquid reactions at operating temperatures: catalytic hydrogenation of nitriles in the liquid phase over novel bimetallic nanocatalysts and polymerization
202(3)
Fischer--Tropsch and Ziegler--Natta catalysts
205(1)
Environmental catalysis and catalyst design
206(15)
Perovskite-based catalysts for environmental pollution control: The role of electron microscopy
206(1)
High temperature superconducting cuprates (HTSC) as catalysts
207(6)
Lanthanum--copper-oxide-based systems
208(2)
Yttrium--barium--copper oxide systems (Y--Ba--Cu--O)
210(1)
Bismuth--copper--calcium based systems
210(3)
Hydrodesulfurization (HDS) catalysis
213(1)
Nanocatalysts in emission control, steam reforming, photocatalysis and fuel cell catalysis
214(3)
Nanocatalysts for alternatives to chlorofluorocarbons
217(1)
Concluding remarks
218(3)
References 221(9)
Index 230


P L Gai, DuPont, Central Research and Development, Wilmington, DE, USA and University of Delaware, Department of Materials Science and Engineering, Newark, USA, formerly at the University of Cambridge E D Boyes, DuPont, Central Research and Development, Wilmington, USA (and formerly University of Oxford).