Adsorption and Catalysis on Transition Metals and Their Oxides

ISBN-13: 9783642738890 / Angielski / Miękka / 2011 / 445 str.

Vsevolod F. Kiselev; Oleg V. Krylov

Opis

This book deals with adsorption and catalysis on the surface of transition elements and their compounds, many of which are in teresting because of their particular electronic structure. The authors have worked through a vast body of experimental evi dence on the structure and properties of surfaces of transition metals and relevant oxides. Consideration is given mostly to simple (as opposed to mixed) oxides of transition elements, to common metals and to the adsorption of simple gases. A great deal of attention is paid to the nature of active surface sites responsible for chemisorption and catalytic transformations. The description relies mainly on the simplified ligand-field theory, which, however, proves quite satisfactory for predicting the adsorptive and catalytic activity of species. In many cases simple systems were explored with the aid of novel techniques, and it is only for such systems that the mechanism of the ele mentary act of adsorption and catalysis can be given adequate treatment. The present monograph has emerged from our earlier work in Russian, which appeared in the Khimiya Publishing House (Mos cow) in 1981. This English edition has, however, been revised completely to broaden its scope and to include more recent a chievements. For fruitful discussions the authors are grateful to A.A."

Spis treści

1. Introduction.- 2. The Electronic Structure of Transition-Metal Atoms.- 2.1 The Principles of the Crystal-Field and Ligand-Field Theories.- 2.2 Experimental Techniques for Investigating the Surface Compounds and Transition-Metal Atoms in Solids.- 2.2.1 Optical Spectra.- 2.2.2 Photoelectron and Auger Spectra.- 2.2.3 Low-Energy Electron Diffraction (LEED).- 2.2.4 Vacuum Tunneling Spectroscopy.- 2.2.5 Magnetic Techniques.- 2.2.6 EPR Spectra.- 2.2.7 Nuclear Magnetic Resonance.- 2.2.8 Mössbauer Spectroscopy.- 2.2.9 Vibration Spectroscopy.- 3. The Surfaces of Transition-Metal Oxides.- 3.1 Surface Atoms of Transition Metals in Dilute Oxide Systems.- 3.1.1 The NiO-MgO System.- 3.1.2 The CoO-MgO System.- 3.1.3 The Cr2O3-Al2O3 System.- 3.1.4 Spinel Formation.- 3.1.5 The CrOX-SiO2 System.- 3.1.6 The MoOX-Al2O3 and MoOX-MgO Systems.- 3.1.7 The VOX-Al2O3, VOX-MgO, and VOX-SiO2 Systems.- 3.1.8 The Co0X MoOY-Al2O3 System.- 3.1.9 The Ti3+-TiO2 System.- 3.2 Transition-Metal Atoms in Zeolites.- 3.3 The Surface of Simple Transition-Metal Oxide.- 3.3.1 Chromium Oxide.- 3.3.2 Molybdenum Oxide.- 3.4 The Surfaces of Some Complex Oxide Systems.- 3.4.1 Bismuth Molybdate.- 3.4.2 Molybdates of Other Metals.- 3.4.3 Magnetic and Ferroelectric Semiconductors and Dielectrics.- 3.5 Energy Levels of Transition-Element Ions in the Bulk and on the Surface of Their Oxides.- 3.5.1 Electrophysical Data.- 3.5.2 Optical Methods.- 3.5.3 Photoelectron Spectroscopy.- 4. Adsorption and Catalysis on Oxides of Transition Metals.- 4.1 Application of the Crystal-Field and Ligand-Field Theories to Adsorptive and Catalytic Phenomena.- 4.2 Symmetry and Reactivity of Coordinated and Adsorbed Molecules.- 4.3 Energy Levels of Adsorbed Molecules in the Band Structure of Oxides and Complexes of Transition Elements.- 4.4 Adsorption of Oxygen on Oxides.- 4.5 Adsorption of Olefins on Oxides.- 4.5.1 Ethylene.- 4.5.2 Propylene.- 4.5.3 Butylene.- 4.6 Adsorption of Carbon Monoxide by Oxides.- 4.6.1 Carbonyl Structures.- 4.6.2 Carbonates and Carboxylates.- 4.7 Adsorption and Catalysis on the Diluted and the Supported Oxide Systems.- 4.8 Catalysis by Zeolites Containing Ions of Transition Elements.- 4.9 Adsorption and Catalysis on Magnetic and Ferroelectric Oxides.- 5. The Surface of the Transition Metals.- 5.1 The Band Structure of the Transition Metals.- 5.2 The Surface Orbitals of the Transition Metals.- 5.3 The Real Surface of Pure Metals.- 5.4 The Surface of Alloys.- 5.5 Supported Metals.- 5.6 Small Metallic Clusters.- 6. Adsorption and Catalysis on the Transition Metals.- 6.1 The Adsorptive Complexes on the Surface of Transition Metals.- 6.2 The Energy Levels of Adsorbed Particles on Metallic Surfaces.- 6.3 Adsorption of Hydrogen on Pure Metals.- 6.4 Adsorption of Oxygen on Pure Metals.- 6.4.1 Two-Dimensional Layers of Adsorbed Oxygen on Transition Metals.- 6.4.2 Initial Steps of the Oxidation of Transition Metals.- 6.4.3 Surface Levels of Adsorbed Oxygen.- 6.4.4 Oxygen Adsorption on Silver.- 6.5 Adsorption of Carbon Monoxide on Metals.- 6.5.1 The Structure of Surface Carbonyls.- 6.5.2 Structure of Adsorbed Layers of CO on Transition Metals.- 6.5.3 Surface Levels of Adsorbed CO on Transition Metals.- 6.6 Adsorption and Catalysis on Alloys.- 6.7 Adsorption and Catalysis on Supported Metals.- 7. Conclusion.- References.