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In the past ten years the study of the mechanisms of chemical transformations on metal surfaces has advanced appreciably. Today complex reaction networks can be unraveled by combining several spectroscopies, derived principally from the practice of ultrahigh-vacuum surface physics. Of paramount importance in this field is the combination of mass spectrometric methods for the identification of reaction products with spectroscopies which help identify surface-bound reactive intermediates. This quasi-monograph highlights the progress in this field with studies which clearly exemplify such research and at the same time provide more general understanding of chemical reactivity at surfaces. This book was constructed to be a resource to all scientists interested in the chemical reactivity of metals, including those whose primary interest may lie in fields outside surface reactivity. The book is'intended to be an advanced case study text, not a "review" in the standard sense. Each chapter develops principles and illustrates the use of experimental methods. Consequently, more attention is given to experimentation than normally found in journal articles or review articles. My intent in organizing these chapters was to make this field accessible to professionals and graduate students in the fields of chemistry, material science, and physics. Even so, we hope that experts in the field of surface reactivity will also find these chapters informative. After the introduction (Chap. 1) the book consists of chapters on the mechanism of selective oxidation by silver (Chap. 2 by R.1. Madix and J.T.
List of contents
1. Introduction.- References.- 2. The Problem of Heterogeneously Catalyzed Partial Oxidation: Model Studies on Single Crystal Surfaces.- 2.1 Modes of Oxygen Chemisorption on Metal Surfaces.- 2.2 Reactions of Molecularly Chemisorbed Oxygen.- 2.3 Reactions of Atomically Chemisorbed Oxygen.- 2.4 Conclusion.- References.- 3. Desulfurization Reactions Induced by Transition Metal Surfaces.- 3.1 Background.- 3.2 The Reactions of Thiols on Transition-Metal Surfaces.- 3.3 Desulfurization of Cyclic Sulfur-Containing Molecules.- 3.4 Conclusions.- References and Notes.- 4. Tricyclisation and Heterocyclisation Reactions of Ethyne over Well-Defined Palladium Surfaces.- 4.1 Background.- 4.2 Mechanistic Studies of Ethyne Tricyclisation.- 4.3 Studies at High Pressures.- 4.4 The Effects of Promoters, Poisons and Other Coadsorbed Species.- 4.5 The Structure and Bonding of Ethyne Chemisorbed on Transition Metal Surfaces.- 4.6 Why is Tricyclisation so Specific to Palladium and Why is the (111) Plane so Strongly Favoured?.- 4.7 Other Cyclisation Reactions.- 4.8 Conclusions.- References.- 5. Model Organic Rearrangements on Aluminum Surfaces.- 5.1 Background.- 5.2 Carbon-Halogen Bond Cleavage.- 5.3 Integrated Desorption Mass Spectrometry.- 5.4 Alkyl Surface Chemistry.- 5.5 Etching of Aluminum Surfaces with Alkyl Halides.- 5.6 Model and Real Systems: A Comparison.- 5.7 Aluminum Surfaces vs. Aluminum Compounds: A Summary.- 5.8 Conclusion.- References and Notes.- 6. The Adsorption of Hydrogen at Copper Surfaces: A Model System for the Study of Activated Adsorption.- 6.1 Introductory Remarks.- 6.2 A One-Dimensional Description: The Translational Degree of Freedom.- 6.3 A Two-Dimensional Description: The Translational and Vibrational Degrees of Freedom.- 6.4 A Multidimensional Description: The Degrees of Freedom Including Translation, Vibration, Rotation, Molecular Orientation, and Impact Parameter.- 6.5 Summary.- References.- 7. Kinetics and Dynamics of Alkane Activation on Transition Metal Surfaces.- 7.1 Background.- 7.2 Trapping-Mediated Dissociative Chemisorption.- 7.3 Direct Dissociative Chemisorption.- References.
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"Professor Madix and the individual authors are to be congratulated in putting together a casebook which will serve as an introduction to scientists in related fields as well as a guidebook for practitioners of surface science." Journal of the American Chemical Society
