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E-grāmata: Surface Science: Foundations of Catalysis and Nanoscience

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Kurt W. Kolasinski (Queen Mary, University of London, UK)

Formāts: PDF+DRM
Izdošanas datums: 24-Oct-2019
Izdevniecība: John Wiley & Sons Inc
Valoda: eng
ISBN-13: 9781119546689

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Formāts: PDF+DRM
Izdošanas datums: 24-Oct-2019
Izdevniecība: John Wiley & Sons Inc
Valoda: eng
ISBN-13: 9781119546689

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An updated fourth edition of the text that provides an understanding of chemical transformations and the formation of structures at surfaces

The revised and enhanced fourth edition of Surface Science covers all the essential techniques and phenomena that are relevant to the field. The text elucidates the structural, dynamical, thermodynamic and kinetic principles concentrating on gas/solid and liquid/solid interfaces. These principles allow for an understanding of how and why chemical transformations occur at surfaces. The author (a noted expert on in the field) combines the required chemistry, physics and mathematics to create a text that is accessible and comprehensive.

The fourth edition incorporates new end-of-chapter exercises, the solutions to which are available on-line to demonstrate how problem solving that is relevant to surface science should be performed. Each chapter begins with simple principles and builds to more advanced ones. The advanced topics provide material beyond the introductory level and highlight some frontier areas of study. This updated new edition:

Contains an expanded treatment of STM and AFM as well as super-resolution microscopy
Reviews advances in the theoretical basis of catalysis and the use of activity descriptors for rational catalyst design
Extends the discussion of two-dimensional solids to reflect remarkable advances in their growth and characterization
Delves deeper into the surface science of electrochemistry and charge transfer reactions
Updates the “Frontiers and Challenges” sections at the end of each chapter as well as the list of references

Written for students, researchers and professionals, the fourth edition of Surface Science offers a revitalized text that contains the tools and a set of principles for understanding the field.

Instructor support material, solutions and PPTs of figures, are available at http://booksupport.wiley.com

Preface

Supplementary Material

xvii

Introduction

(10)

I.1 Heterogeneous catalysis

(1)

I.2 Why surfaces?

(1)

I.3 Where are surfaces, interfaces, and nanoscale objects important?

(1)

I.3.1 Making bread from air: ammonia synthesis

(1)

I.3.2 Gas-to-liquids: fischer-tropsch synthesis, C1 chemistry and artificial photosynthesis

(1)

I.3.3 Clean propulsion: three-way catalyst, lithium ion batteries, fuel cells

(1)

I.3.4 Water splitting: oxygen and hydrogen evolution reactions (OER and HER)

(1)

I.4 Semiconductor processing and nanotechnology

(2)

I.5 Other areas of relevance

(1)

I.6 Structure of the book

(1)

I.7 Further reading

(1)

References

(2)

1 Surface and Adsorbate Structure

(50)

1.1 Clean surface structure

(17)

1.1.1 Ideal flat surfaces

(3)

1.1.2 High-index and vicinal planes

(1)

1.1.3 Faceted surfaces

(1)

1.1.4 Bimetallic surfaces

(1)

1.1.5 Oxide and compound semiconductor surfaces

(2)

1.1.6 The Carbon family: Diamond, Graphite, Graphene, Fullerenes, and Carbon Nanotubes

(4)

1.1.7 Two-dimensional solids (2D solids)

(2)

1.1.8 Advanced topic: stacked two-dimensional materials and Moire superlattices

(2)

1.1.9 Porous solids

(1)

1.2 Reconstruction and adsorbate structure

(9)

1.2.1 Implications of surface heterogeneity for adsorbates

(1)

1.2.2 Clean surface reconstructions

(1)

1.2.3 Adsorbate-induced reconstructions

(4)

1.2.4 Islands

(1)

1.2.5 Chiral surfaces

(2)

1.3 Band structure of solids

(12)

1.3.1 Bulk electronic states

(1)

1.3.2 Metals, semiconductors, and insulators

(4)

1.3.3 Energy levels at metal interfaces

(1)

1.3.4 Energy levels at metal-semiconductor interfaces

(3)

1.3.5 Surface electronic states

(2)

1.3.6 Size effects in nanoscale systems

(1)

1.4 The vibrations of solids

(3)

1.4.1 Bulk systems

(2)

1.4.2 Nanoscale systems

(1)

1.5 Summary of important concepts

(1)

1.6 Frontiers and challenges

(1)

1.7 Further reading

(1)

1.8 Exercises

(3)

References

(4)

2 Experimental Probes and Techniques

(70)

2.1 Ultrahigh vacuum

(2)

2.1.1 The need for UHV

(1)

2.1.2 Attaining UHV

(1)

2.2 Light and electron sources

(5)

2.2.1 Types of lasers

(1)

2.2.2 Atomic lamps

(3)

2.2.3 Synchrotrons

(1)

2.2.4 Free electron laser (FEL)

(1)

2.2.5 Electron guns

(1)

2.3 Molecular beams

(5)

2.3.1 Knudsen molecular beams

(1)

2.3.2 Free jets

(2)

2.3.3 Comparison of Knudsen and supersonic beams

(2)

2.4 Scanning probe techniques

(14)

2.4.1 Scanning tunnelling microscopy (STM)

(4)

2.4.2 Scanning tunnelling spectroscopy (STS)

(2)

2.4.3 Scanning electrochemical microscopy (SECM)

(1)

2.4.4 Atomic force microscopy (AFM)

(4)

2.4.5 Near-field optical microscopy (NSOM)

(3)

2.5 Low-energy electron diffraction (LEED)

(7)

2.6 Electron Spectroscopy

(15)

2.6.1 X-ray photoelectron spectroscopy (XPS)

(5)

2.6.2 Ultraviolet photoelectron spectroscopy (UPS)

(5)

2.6.3 Auger electron spectroscopy (AES)

104

(4)

2.6.4 Photoelectron microscopy

108

(1)

2.7 Vibrational spectroscopy

109

(8)

2.7.1 IR spectroscopy

110

(5)

2.7.2 Electron energy loss spectroscopy (EELS)

115

(2)

2.8 Second harmonic and sum frequency generation

117

(2)

2.9 Summary of important concepts

119

(1)

2.10 Frontiers and challenges

120

(1)

2.11 Further reading

120

(1)

2.12 Exercises

121

(4)

References

125

(6)

3 Chemisorption, Physisorption, and Dynamics

131

(74)

3.1 Types of interactions

131

(2)

3.2 Binding sites and diffusion

133

(3)

3.3 Physisorption

136

(2)

3.4 Non-dissociative chemisorption

138

(7)

3.4.1 Theoretical treatment of chemisorption

138

(3)

3.4.2 The Blyholder model of CO chemisorption on a metal

141

(2)

3.4.3 Molecular oxygen chemisorption

143

(1)

3.4.4 The binding of ethene

144

(1)

3.5 Dissociative chemisorption: H2 on a simple metal

145

(2)

3.6 What determines the reactivity of metals?

147

(3)

3.7 Atoms and molecules incident on a surface

150

(12)

3.7.1 Scattering channels

150

(2)

3.7.2 Non-activated adsorption

152

(3)

3.7.3 Hard-cube model

155

(2)

3.7.4 Activated adsorption

157

(1)

3.7.5 Direct versus precursor-mediated adsorption

158

(4)

3.8 Microscopic reversibility in ad/desorption phenomena

162

(5)

3.9 The influence of individual degrees of freedom on adsorption and desorption

167

(2)

3.9.1 Energy exchange

167

(1)

3.9.2 PES topography and the relative efficacy of energetic components

168

(1)

3.10 Translations, corrugation, surface-atom motions

169

(5)

3.10.1 Effects on adsorption

169

(2)

3.10.2 Connecting adsorption and desorption with microscopic reversibility

171

(2)

3.10.3 Normal energy scaling

173

(1)

3.11 Rotations and adsorption

174

(2)

3.11.1 Non-activated adsorption

174

(2)

3.11.2 Activated adsorption

176

(1)

3.12 Vibrations and adsorption

176

(1)

3.13 Competitive adsorption and collision-induced processes

177

(3)

3.13.1 High energy collisions

179

(1)

3.14 Classification of reaction mechanisms

180

(3)

3.14.1 Langmuir-Hinshelwood mechanism

180

(2)

3.14.2 Eley-Rideal mechanism

182

(1)

3.14.3 Hot atom mechanism

183

(2)

3.15 Measurement of sticking coefficients

185

(3)

3.16 Summary of important concepts

188

(1)

3.17 Frontiers and challenges

189

(1)

3.18 Further reading

189

(1)

3.19 Exercises

190

(7)

References

197

(8)

4 Thermodynamics and Kinetics of Adsorption and Desorption

205

(54)

4.1 Thermodynamics of ad/desorption

205

(8)

4.1.1 Single-particle versus distribution-averaged quantities

205

(2)

4.1.2 Binding energies and activation barriers

207

(2)

4.1.3 Thermodynamic quantities

209

(1)

4.1.4 Some definitions

210

(1)

4.1.5 Absorption enthalpy

211

(2)

4.2 Adsorption isotherms from thermodynamics

213

(5)

4.2.1 Adsorbate chemical potential and activity

216

(2)

4.3 Lateral interactions

218

(1)

4.4 Rate of desorption

219

(12)

4.4.1 First-order desorption

219

(1)

4.4.2 Transition state theory treatment of first-order desorption

220

(4)

4.4.3 Thermodynamic treatment of first-order desorption

224

(3)

4.4.4 Adsorption entropy

227

(2)

4.4.5 Configurational entropy

229

(1)

4.4.6 Non-first-order desorption

230

(1)

4.5 Kinetics of adsorption

231

(7)

4.5.1 CTST approach to adsorption kinetics

231

(1)

4.5.2 Langmuirian adsorption: non-dissociative adsorption

231

(3)

4.5.3 Langmuirian adsorption: dissociative adsorption

234

(1)

4.5.4 Dissociative Langmuirian adsorption with lateral interactions

235

(1)

4.5.5 Precursor-mediated adsorption

236

(2)

4.6 Adsorption isotherms from kinetics

238

(3)

4.6.1 Langmuir isotherm

238

(1)

4.6.2 Classification of adsorption isotherms

239

(2)

4.6.3 Thermodynamic measurements via isotherms

241

(1)

4.7 Temperature programmed desorption (TPD)

241

(8)

4.7.1 The basis of TPD

241

(2)

4.7.2 Qualitative analysis of TPD spectra

243

(3)

4.7.3 Quantitative analysis of TPD Spectra

246

(3)

4.8 Summary of important concepts

249

(1)

4.9 Frontiers and challenges

250

(1)

4.10 Further reading

250

(1)

4.11 Exercises

250

(6)

References

256

(3)

5 Liquid Interfaces

259

(44)

5.1 Structure of the liquid/solid interface

259

(5)

5.1.1 The Structure of the water/solid interface

261

(3)

5.2 Surface energy and surface tension

264

(6)

5.2.1 Liquid surfaces

264

(3)

5.2.2 Curved interfaces

267

(1)

5.2.3 Surface melting and surface crystallization

268

(1)

5.2.4 Capillary waves

269

(1)

5.3 Liquid films

270

(2)

5.3.1 Liquid-on-solid films

270

(2)

5.4 Langmuir films

272

(2)

5.5 Langmuir-Blodgett films

274

(5)

5.5.1 Capillary condensation and meniscus formation

275

(2)

5.5.2 Vertical deposition

277

(1)

5.5.3 Horizontal lifting (Schaefer's Method)

278

(1)

5.6 Self-assembled monolayers (SAMs)

279

(6)

5.6.1 Thermodynamics of self-assembly

280

(1)

5.6.2 Amphiphiles and bonding interactions

281

(1)

5.6.3 Mechanism of SAM formation

282

(3)

5.7 Thermodynamics of liquid interfaces

285

(4)

5.7.1 The Gibbs model

285

(2)

5.7.2 Surface excess

287

(1)

5.7.3 Interfacial enthalpy and internal, Helmholtz and Gibbs surface energies

287

(1)

5.7.4 Gibbs adsorption isotherm

288

(1)

5.8 Electrified and charged interfaces

289

(5)

5.8.1 Surface charge and potential

289

(3)

5.8.2 Relating work functions to the electrochemical series

292

(2)

5.9 Summary of important concepts

294

(1)

5.10 Frontiers and challenges

295

(1)

5.11 Exercises

295

(3)

5.12 Further reading

298

(1)

References

298

(5)

6 Heterogeneous Catalysis

303

(52)

6.1 The prominence of heterogeneous reactions

303

(2)

6.2 How to choose a catalyst

305

(3)

6.3 Sabatier analysis and optimal catalyst selection

308

(2)

6.4 Measurement of surface kinetics and reaction mechanisms

310

(4)

6.5 Haber-Bosch process

314

(5)

6.6 From microscopic kinetics to catalysis

319

(8)

6.6.1 Reaction kinetics

319

(1)

6.6.2 Kinetic analysis using De Donder relations

320

(1)

6.6.3 Counting sites in surface kinetics

321

(2)

6.6.4 Definition of the rate determining step (RDS)

323

(1)

6.6.5 Microkinetic analysis of ammonia synthesis

324

(3)

6.7 Fischer-Tropsch synthesis and related chemistry

327

(4)

6.7.1 Steam reforming

327

(1)

6.7.2 Water gas shift reaction

327

(1)

6.7.3 Methanol synthesis

328

(1)

6.7.4 Fischer-Tropsch synthesis

328

(3)

6.8 The three-way automotive catalyst

331

(3)

6.9 Promoters

334

(1)

6.10 Poisons

335

(1)

6.11 Bimetallic and bifunctional catalysts

336

(2)

6.12 Rate oscillations and spatiotemporal pattern formation

338

(2)

6.12.1 Advanced topic: cluster assembled catalysts

339

(1)

6.13 Electrocatalysis

340

(5)

6.13.1 Hydrogen evolution reaction (HER) and H2 oxidation reaction (HOR)

341

(1)

6.13.2 Oxygen evolution reaction (OER) and O2 reduction reaction (ORR)

342

(2)

6.13.3 Advanced topic: water splitting in photosystem II

344

(1)

6.14 Summary of important concepts

345

(1)

6.15 Frontiers and challenges

346

(1)

6.16 Further reading

347

(1)

6.17 Exercises

348

(2)

References

350

(5)

7 Growth and Epitaxy

355

(62)

7.1 Stress and strain

355

(3)

7.2 Types of interfaces

358

(2)

7.2.1 Strain relief

358

(2)

7.3 Surface energy, surface tension and strain energy

360

(2)

7.4 Growth modes

362

(6)

7.4.1 Solid-on-solid growth

362

(2)

7.4.2 Strain in solid-on-solid growth

364

(1)

7.4.3 Ostwald ripening

365

(1)

7.4.4 Equilibrium overlayer structure and growth mode

366

(2)

7.5 Nucleation theory

368

(3)

7.5.1 Cloud formation: heterogeneous versus homogeneous nucleation

370

(1)

7.6 Growth away from equilibrium

371

(4)

7.6.1 Thermodynamics versus dynamics

371

(1)

7.6.2 Non-equilibrium growth modes

372

(3)

7.7 Techniques for growing layers

375

(10)

7.7.1 Molecular beam epitaxy (MBE)

375

(3)

7.7.2 Chemical vapour deposition (CVD)

378

(4)

7.7.3 Atomic layer deposition (ALD)

382

(1)

7.7.4 Ablation techniques

382

(1)

7.7.5 Growth on liquid metals

383

(1)

7.7.6 van der Waals epitaxy

383

(2)

7.8 Catalytic growth of nanotubes and nanowires

385

(4)

7.9 Etching

389

(16)

7.9.1 Classification of etching

390

(3)

7.9.2 Etch morphologies

393

(1)

7.9.3 Porous solid formation

394

(2)

7.9.4 Silicon etching in aqueous fluoride solutions

396

(3)

7.9.5 Selective area growth and etching

399

(2)

7.9.6 Atomic layer etching (ALE)

401

(3)

7.9.7 Coal gasification and graphite etching

404

(1)

7.10 Summary of important concepts

405

(1)

7.11 Frontiers and challenges

406

(1)

7.12 Further reading

407

(1)

7.13 Exercises

407

(3)

References

410

(7)

8 Laser and Non-thermal Chemistry: Photon and Electron Stimulated Chemistry and Atom Manipulation

417

(64)

8.1 Photon excitation of surfaces

418

(12)

8.1.1 Light absorption by condensed matter

418

(1)

8.1.2 Lattice heating

419

(4)

8.1.3 Advanced topic: temporal evolution of electronic excitations

423

(5)

8.1.4 Summary of laser excitations

428

(1)

8.1.5 Plasmon excitation

428

(2)

8.2 Mechanisms of electron and photon stimulated processes

430

(7)

8.2.1 Direct versus substrate mediated processes

430

(1)

8.2.2 Gas phase photochemistry

431

(2)

8.2.3 Gas phase electron stimulated chemistry

433

(1)

8.2.4 MGR and Antoniewicz models of DIET

434

(2)

8.2.5 Desorption induced by ultrafast excitation

436

(1)

8.3 Photon and electron induced chemistry at surfaces

437

(13)

8.3.1 Thermal desorption, reaction, and diffusion

437

(2)

8.3.2 Stimulated desorption/reaction

439

(6)

8.3.3 Ablation

445

(5)

8.4 Charge transfer and electrochemistry

450

(14)

8.4.1 Homogeneous electron transfer

452

(3)

8.4.2 Corrections to and improvements on Marcus theory

455

(1)

8.4.3 Heterogeneous electron transfer

455

(3)

8.4.4 Current flow at a metal electrode

458

(2)

8.4.5 Advanced topic: semiconductor photoelectrodes and the Gratzel photovoltaic cell

460

(4)

8.5 Tip- induced process: mechanisms of atom manipulation

464

(5)

8.5.1 Electric field effects

464

(1)

8.5.2 Tip-induced ESD

464

(2)

8.5.3 Vibrational ladder climbing

466

(1)

8.5.4 Pushing

467

(1)

8.5.5 Pulling

468

(1)

8.5.6 Atom manipulation by covalent forces

468

(1)

8.6 Summary of important concepts

469

(1)

8.7 Frontiers and challenges

470

(1)

8.8 Further reading

470

(1)

8.9 Exercises

471

(3)

References

474

(7)

Appendix A Abbreviations and Prefixes

481

(4)

Appendix B Symbols

485

(4)

Appendix C Useful Mathematical Expressions

489

(4)

Index

493

Kurt W. Kolasinski, PhD, is Professor of Physical Chemistry at West Chester University. His research concentrates on the study of dynamical processes at the surfaces of metals and semiconductors with a special emphasis on structure formation and laser-surface interactions. He is responsible for teaching Theoretical and Experimental Physical Chemistry as well as Surface Science.

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E-grāmata: Surface Science: Foundations of Catalysis and Nanoscience

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