Kolasinski, K W

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Surface ScienceFoundations of Catalysis and NanoscienceKurt W. KolasinskiQueen Mary, University of London, UKJOHN WILEY 8t SONS, LTDContentsIntroductionHeterogeneous catalysisWhy surfaces?Where are heterogeneous reactions important?Haber-Bosch processFischer-Tropsch chemistryThreeway catalystSemiconductor processing and nanotechnologyOther areas of relevanceStructure of the bookReferencesI	Surface structure1.1 Clean surface structure1 .1 .1 Ideal flat surfaces1 .1 .2 High-index and vicinal planes1 .1 .3 Faceted surfaces1 .1 .4 Bimetallic surfaces1 .2 Reconstruction and adsorbate structure1.2.1 Implications of surface heterogeneity for adsorbates1.2.2 Clean surface reconstructions1 .2 .3 Adsorbate-induced reconstructions1 .2 .4 Islands1 .3 Band structure of solids1 .3 .1 Bulk electronic states1 .3 .2 Metals, semiconductors and insulators1 .3 .3 Energy levels at metal interfaces1 .3 .4 Energy levels at metal-semiconductor interfaces1 .3 .5 Surface electronic states1 .4 The vibrations of solids1.5 Summary of important conceptsExercisesFurther readingReferencesvi CONTENTS2 Experimental probes of surface and adsorbate structure 312.1 Scanning probe techniques 312.1 .1 Scanning tunnelling microscopy 322.1 .2 Scanning tunnelling spectroscopy 372.1 .3 Atomic force microscopy 382.1 .4 Near-field scanning optical microscopy (NSOM) 422.2 Low-energy electron diffraction 452.3 Electron spectroscopy 532.3 .1 X-ray photoelectron spectroscopy 532.3 .2 Ultraviolet photoelectron spectroscopy 582.3 .3 Auger electron spectroscopy 642.3 .4 Photoelectron microscopy 662.4 Vibrational spectroscopy 682.4 .1 Infrared spectroscopy 722.4 .2 Electron energy loss spectroscopy 762.5 Other surface analytical techniques 782.6 Summary of important concepts 78Exercises 79Further reading 81References 823 Chemisorption, physisorption and dynamics 853.1 Types of interactions 853.2 Binding sites and diffusion 863 .3 Physisorption 913 .4 Nondissociative chemisorption 923.4 .1 Theoretical treatment of chemisorption 923.4 .2 The Blyholder model of CO chemisorption on a metal 963 .4 .3 Molecular oxygen chemisorption 993 .4.4 The binding of ethene 1003 .5 Dissociative chemisorption: Hz on a simple metal 1023.6 What determines the reactivity of metals? 1033.7 Atoms and molecules incident on a surface 1073 .7 .1 Scattering channels 1073.7.2 Nonactivated adsorption 1093.7 .3 Hard-cube model 1123.7 .4 Activated adsorption 1143.7 .5 Direct and precursor-mediated adsorption 1173 .8 Microscopic reversibility in ad/desorption phenomena 1203 .9 The influence of individual degrees of freedom on adsorption and desorption 1263.9 .1 Energy exchange 1263.9 .2 Potential energy surface topography and the relative efficacy of energeticcomponents 1273.10 Translations, corrugation and surface atom motions 1283.10.1 Effects on adsorption 1283.10.2 Connecting adsorption and desorption with microscopic reversibility 1313.10.3 Normal energy scaling 1333.11 Rotations and adsorption 1355 .1	Measurement of surface kinetics and reaction mechanisms 2075 .2 Haber-Bosch process 2114 Thermodynamics and kinetics of surface processes 1634.1 Thermodynamics of ad/desorption 1634.1 .1 Binding energies and activation barriers 1634.1 .2 Thermodynamic quantities 1654.1 .3 Some definitions 1664.1 .4 Heat of adsorption 1674.2 Adsorption isotherms: thermodynamics approach 1684.3 Lateral interactions 1704.4 Rate of desorption 1734.4 .1 First-order desorption 1734.4 .2 Transition-state-theory treatment of first-order desorption 1754.4 .3 Thermodynamic treatment of first-order desorption 1794.4 .4 Non-first-order desorption 1814.5 Kinetics of adsorption 1834.5 .1 The conventional transition-state theory 1834.5 .2 Langmuirian adsorption : nondissociative adsorption 1834.5 .3 Langmuirian adsorption : dissociative adsorption 1874.5 .4 Dissociative Langmuirian adsorption with lateral interactions 1874.5 .5 Precursor-mediated adsorption 1884.6 Adsorption isotherms: kinetics approach 1924.6 .1 Langmuir isotherm 1924.6 .2 Thermodynamic measurements via isotherms 1924.7 Temperature-programmed desorption 1934.7 .1 The basis of temperature-programmed desorption 1934.7 .2 Qualitative analysis of temperature-programmed desorption spectra 1954.7 .3 Quantitative analysis of temperature-programmed desorption spectra 1984.8 Summary of important concepts 201Exercises 202Further reading 205References 2055 Complex surface reactions : catalysis and etching 207CONTENTS vii3.11 .1 Nonactivated adsorption 1353.11 .2 Activated adsorption 1373.12 Vibrations and adsorption 1383.13 Competitive adsorption and collision-induced processes 1383.14 Classification of reaction mechanisms 1423 .14.1 Langmuir-Hinshelwood mechanism 1423 .14.2 Eley-Rideal mechanism 1433 .14.3 Hot-atom mechanism 1453.15 Measurement of sticking coefficients 1463.16 Summary of important concepts 147Exercises 149Further reading 155References 156A.1	Fundamental constants, conversion factors and prefixesA.1 .1 Fundamental constants287287viii CONTENTS5.3 From microscopic kinetics to catalysis 2165 .4 Fischer-Tropsch synthesis and related chemistry 2195.5 The threeway automotive catalyst 2245.6 Promoters 2275.7 Poisons 2285.8 Rate oscillations and spatiotemporal pattern formation 2305.9 Etching 2335.9 .1 Coal gasification and graphite etching 2335 .9 .2 Silicon etching in aqueous fluoride solutions 2345.9 .3 Selective area growth and etching 2375.10 Summary of important concepts 241Exercises 242Further reading 244References 2456 Growth and epitaxy 2496.1 Stress and strain 2496.2 Types of interfaces 2516.3 Surface energy and surface tension 2526.3 .1 Liquid surfaces 2526.3 .2 Solid surfaces 2546.4 Growth modes 2556.4.1 Liquid-on-solid growth 2556.4.2 Solid-on-solid growth 2576.4 .3 Strain in solid-on-solid growth 2586.5 Growth away from equilibrium 2626.5 .1 Thermodynamics versus kinetics 2626.5 .2 Nonequilibrium growth modes 2636.6 Techniques for growing layers 2666.6.1 Molecular beam epitaxy 2676.6.2 Chemical vapour deposition 2676.6 .3 Ablation techniques 2686.7 Langmuir films 2706.8 Langmuir-Blodgett films 2726.8 .1 Meniscus formation 2726.8.2 Vertical deposition 2736.8 .3 Horizontal lifting (Shaefer's method) 2756.9 Self-assembled monolayers 2756.9 .1 Amphiphiles and bonding interactions 2766.9.2 Mechanism of self-assembled monolayer formation 2776.9 .3 Self-assembly in inorganic thin films 2816.10 Summary of important concepts 281Exercises 282Further reading 283References 284Appendix A 287A.1 .2	Conversion factorsA.1 .3 PrefixesAppendix BB.1 AbbreviationsAppendix CAppendix DCONTENTS ix287288289289293299299D.1 Useful mathematical expressionsIndex 301Symbols 293C.1 .1 Kisliuk model of precursor-mediated adsorption 296C.1 .2 Symbols commonly used in subscripts and superscripts 297C.1 .3 Mathematical symbols 297C.1 .4 Chemical notation 297

Surface science: foundations of catalysis and nanoscience

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