Encyclopedia of Interfacial Chemistry: Surface Science and Electrochemistry (Vol 1 - Vol 7)

9780128098943v1_WEB Front Cover ENCYCLOPEDIA OF INTERFACIAL CHEMISTRY: SURFACE SCIENCE AND ELECTROCHEMISTRY ENCYCLOPEDIA OF INTERFACIAL CHEMISTRY:SURFACE SCIENCE AND ELECTROCHEMISTRY Copyright EDITORIAL BOARD PREFACE References CONTRIBUTORS TO VOLUME 1 CONTENTS OF VOLUME 1 PERMISSION ACKNOWLEDGMENTS A Review on In Situ Sum Frequency Generation Vibrational Spectroscopy Studies of Liquid–Solid Interfaces in Electrochemical ... Introduction: The Significance of Probing Electrified Interfaces for Renewable Energy Production and Storage Basic Concepts of SFGVS for Studies of Electrified Solid–Liquid Interfaces Probing Solid–Liquid Interfaces Under Reaction Condition Li-Ion Batteries Fuel Cells Conclusions and Remarks Acknowledgments References Ambient Pressure X-Ray Photoelectron Spectroscopy Introduction X-Ray Photoelectron Spectroscopy Ambient Pressure X-Ray Photoelectron Spectroscopy Examples of APXPS Applications Solid–Vapor Interface Catalytic methanol steam reforming Mapping the surface potential of a working electrochemical cell Vapor–Liquid Interface Ion distribution at the vapor–liquid water interface Methanol distribution at the vapor–liquid interface of aerosol particles Solid–Liquid Interface Pt electrode species in KF solution Ion distribution at the hematite–liquid water interface Summary Acknowledgment References Further Reading Angle-Resolved Photoelectron Spectroscopy at Surfaces With High-Order Harmonic Generation Introduction Experimental Development Overview Photon Energy Range Energy and Time Resolution Photon Flux and Repetition Rate Band Mapping Theory for Time-Dependent Photoemission Processes Surfaces Investigated by HHG-Based PES Adsorbates Two-Dimensional and Layered Materials Metals Semiconductors Oxides and Strongly Correlated Materials Summary Acknowledgments References Further Reading Atomic Scale STM Imaging of Alloy Surfaces With Chemical Resolution Introduction Experimental and Theoretical Background STM Imaging With Atomic and Chemical Resolution Macroscopic Tip Effects Local Tip Effects Alloyed Surfaces Structural Properties of Alloyed Surfaces Chemical Properties of Alloyed Surfaces Technical and Experimental Limitations Tip Effects Tunneling Conditions Homogeneity Bulk Contribution Concluding Remark Acknowledgment References Further Reading Relevant Website Cyclic Voltammetry Introduction Processes Controlled by the Rate of Mass Transport Complex Mechanims Cyclic Voltammetry in the Presence of Adsorption Processes Coadsorption Phenomena Cyclic Voltammetry of Platinum Single Crystal Electrodes. Voltammetry as a Surface Sensitive Characterization Technique Fit of Voltammetric Peaks to Adsorption Peaks Ideally Polarizable Electrodes Kinetic Effects in the Adsorption Pseudocapacity Oxidation of Small Organic Molecules Concluding Remarks Acknowledgment Further Reading Differential Capacitance Measurements on Passive Films Introduction SC/El. Interface C-SC/El. Interface a-SC/El. Interface Admittance Equations for a-SC/El. Junction Thick Films With Variable DOS Thin Films Variable DOS Conclusions References EIS Technique in Passivity Studies: Determination of the Dielectric Properties of Passive Films Introduction Theory Exponential Resistivity Distributions: Young Model Power-Law Distributions Application to Nb2O5 and to Al2O3 Nb2O5 Oxide Layer Al2O3 Oxide Layer Oxide Layer as an Electrode Conclusions References Further Reading Electrochemical Scanning Tunneling Microscopy Introduction Scanning Tunneling Microscopy The Principle of Electron Tunneling Tunneling Through an Electrolyte Instrumental Aspects Control of the tip position Electrochemical STM setup Potentiostatic, potentiodynamic, and spectroscopic detection methods Sample Preparation Flame annealing Electrochemical etching and annealing UHV-EC transfer Tip preparation Case Studies Anion Adsorption Chloride and iodide adsorption on Cu(111) Corrosive Surface Compound Formation Metal Underpotential Deposition Molecular Ordering The Tip as Tool References Electron Paramagnetic Resonance Spectroscopy at Surfaces Introduction Basic Experimental Considerations CW EPR Spectroscopy on Solid Surfaces Paramagnetic Species With S=½ Physical Interpretation of g- and Hyperfine-Matrix Components Impact of Rotational Dynamics on CW EPR Spectra Pulsed Spectroscopic Techniques: Hyperfine Interactions as an Introductory Example Conclusion Acknowledgment References Ellipsometry in Passive Films Passive Films and Ellipsometry Reflection of Polarized Light Reflection Coefficient Ellipsometry and Differential Reflectance Apparatus Thickness of the Passive Oxide Film Under Quasi-stationary State Transient Change in Thickness of Passive Oxide Films Spectroscopic Ellipsometry Microscopic Measurement by Ellipsometry Summary References Further Reading Relevant Websites Experimental Methods in Interfacial and Surface Chemistry References Field Ion and Field Desorption Microscopy: Surface Chemistry Applications Overview Principles of FIM Operation Basics of the Field Desorption Microcopy Surface Science Applications Surface Physics and Material Science Surface Chemistry Fluctuation-induced effects Li-FDM Applications Probe-Hole Ion Analysis Summary and Future Perspective References High-Speed Electrochemical STM Introduction Piezoelectric Scanner and its Feedback Circuit Height Feedback Hybrid Mode Preamplifier and its Stability Preamplifier Noise Bipotentiostat Tunneling Current and Work Function Examples Conclusion Further Reading Acknowledgments References How to Probe Structure, Kinetics, and Dynamics at Complex Interfaces In Situ and Operando by Optical Spectroscopy Why “In Situ”? Scope of This Chapter Overview Over In Situ and Operando Spectroscopic Techniques Absorption Spectroscopy UV/VIS General principles What is special at interfaces? Applications IR General principles What is special at interfaces? Applications Techniques Exploiting Polarization of Light Ellipsometry General principles Applications Polarization Modulation General principles Applications Techniques Based on Excitation and Emission Raman General principles What is special at interfaces? Applications PL General principles What is special at interfaces? Applications SFG General principles Applications Summary Acknowledgments References Further Reading Imaging Chemical Reactions One Molecule at a Time Introduction Basics of Scanning Probe Techniques Scanning Tunneling Microscopy Atomic Force Microscopy Benefits and Drawbacks of Single Molecule Imaging by STM Delivery of Reactants Imaging Elemental Steps in Surface Reactions Molecular Adsorption Reactive Systems—Understanding What You See Same area imaging Bias- and tunneling current-dependent imaging Scanning tunneling spectroscopy22 Tip-induced manipulation Simulation of STM images Inelastic electron tunneling spectroscopy Adsorbate Motion Rotational dynamics Surface diffusion Formation of Surface Intermediates Imaging Complex Reactions Future Directions and Challenges High Pressure and Condensed Phase Studies Combined Molecular Beam Scattering and Scanning Tunneling Microscopy Adsorbate Structure Imaging with Functionalized Scanning Probes Combining Scanning Probe Techniques with Vibrational Spectroscopies Acknowledgments References Impedance Spectroscopy Applied to the Study of Electrocatalytic Processes Introduction Introduction to EIS Simple Electrosorption Reaction Electrosorption of One Species With Subsequent Desorption Volmer–Heyrovsky Mechanism The Volmer–Heyrovsky–Tafel Mechanism Influence of Mass Transfer Faradaic Reaction Involving Two Adsorbed Species Faradaic Reaction Involving Three or More Adsorbed Species Oxygen Reduction Reaction, ORR Oxidation of CO and Simple Aliphatic Alcohols Oxidation of CO Oxidation of Aliphatic Alcohols Conclusions References In Situ Photoelectron Spectroscopy Introduction Physical Principles of Photoelectron Spectroscopy History and Development Terminology for XPS, UPS, and PES Inverse PES for Unoccupied States Strengths and Weaknesses Ex Situ, In Situ, and Operando Spectroscopy Criterion for Necessity of In Situ Studies Beyond Mere Surface Sensitivity Between UHV and Ambient Pressure ESCA Chemistry Versus VB Physics Fermi Level Simulation of Spectra Binding Energy Versus Work Function Versus Electrochemical Potentials Further Applications of in Situ XPS In Situ Oxidation Organic Films on Metals Wear and Friction Correlation of Electronic Structure and Transport Properties Gas Sensors Heterogeneous Catalysis Lithium and Other Alkaline Ion Insertion and Intercalation High-Temperature Electrochemistry Water and Wet Samples Photoelectrochemistry Biological Samples Soot Oxidation and Atmospheric Chemistry X-Ray Standing Wave Spectroscopy References Further Reading Relevant Websites In Situ Probing of Adsorbates at Electrochemical Interfaces With Vibrational Sum Frequency Spectroscopy Introduction Electrochemical VSFG Spectroscopy Experimental Geometries VSFG Spectroscopy Data Analysis Adsorbates at the EC Interface Water Structure at the Gold–Aqueous Solution Interface Reaction Precursor for Formic Acid Electrochemical Oxidation on Pt(100) Future Directions Further Reading In Situ Real-Time Low-Energy Electron Microscopy Introduction The Microscope Contrast Mechanisms Applications Nucleation and Growth of Diindenoperylene Thin Films on Au(100) Single Crystals Further Reading Ion Conductance Probe Microscopy—Molecular Resolution Introduction SICM for Electrochemical Sensors SICM for Surface-Charge Mapping SICM for Nanopore-Based Sensors SICM for Picking Contents of Living Cells Acknowledgments References Further Reading Micro-Spectroscopy to Interrogate Solid Catalysts at Work Introduction Setting the Scene On the Nature of the Active Site Zeolites Supported metal nanoparticles The Catalytic Process The Partnership Between Catalyst Structure and Composition, Diffusion, and Reactivity Structure and Composition of a Catalytic Solid Diffusion Reactivity of a Single-Catalyst Particle in Space and Time Diffraction-Limited Micro-Spectroscopy: Far-Field Approaches Diffraction-Unlimited Micro-Spectroscopy: Near-Field and Wide-Field Approaches Concluding Remarks and Look Into the Future Acknowledgments References Online Chromatographic Detection Introduction Analysis of a Liquid Phase Analysis of a Headspace Other Methods for Online Detection and Their Combination with Chromatography References On-Line Inductively Coupled Plasma Spectrometry in Electrochemistry: Basic Principles and Applications Introduction Basic Operational Principles Inductively Coupled Plasma Optical Emission Spectrometry Inductively Coupled Plasma Mass Spectrometry Comparison Between ICP-OES and ICP-MS for On-Line Analysis in Electrochemistry Theoretical and Practical Basis of Dissolution Products Quantification Coupling ICPs to Electrochemistry Stationary Flow Cell-Based Techniques Scanning Flow Cell-Based Techniques Probes in Conventional Electrochemical Cells Final Remarks Acknowledgments References Further Reading Operando Scanning Probe Microscopy, Surface X-Ray Diffraction, and Optical Microscopy for Catalysis Studies Introduction Bridging the Pressure Gap High-Pressure SPM Instrumentation Requirements for Operando SPM Design of the ReactorSTM Design of the ReactorAFM High-Pressure SXRD Instrumentation Design of the ReactorSXRD Combination of High-Pressure SPM With High-Pressure SXRD High-Pressure Optical Microscopy Instrumentation Catalytic Systems Investigated Under High-Pressure Conditions CO Oxidation on Pd(100) CO Oxidation on Pd Nanoparticles CO Oxidation on Rh(111) NO Reduction on Pt(110) Chlorine Production on RuO2(110)/Ru(0001) Conclusions and Outlook Acknowledgments References Perspectives of Advanced Ion Beam Analysis of Electrochemically Active Surfaces Introduction High-Resolution Ion Beam Analytical Techniques SIMS Isotopic Exchange Tracer Diffusion Measurements Low Energy Ion Scattering (LEIS) The Challenges References Further Reading Photocurrent Spectroscopy in Passivity Studies Introduction Semiconductor/Electrolyte Junctions Under Illumination: The Gärtner–Butler Model PCS Location of Ufb and Eg Determination in c-Semiconductor/Electrolyte Junction Passive Film/Electrolyte Interface Under Illumination Electronic Properties of Disordered Passive Films Optical Gap in Amorphous Materials Amorphous Film/Electrolyte Junction Under Illumination Photoemission Phenomena at the Metal/Passive Film Interface Band Gap and Oxide Film Composition Binary Crystalline Oxides Ternary Crystalline Oxides Amorphous Oxide Films Correlation for Hydroxides and Oxihydroxide Films Modeling of Photoelectrochemical Behavior of Layered Oxide Films References Photoelectron Diffraction Introduction: Basic Principles XPD: Applications PhD: Applications Concluding Remarks and Comparison With Other Structural Techniques References Further Reading Photoemission Tomography: Valence Band Photoemission as a Quantitative Method for Investigating Molecular Films Introduction The Plane Wave Final State Approximation Multilayer Molecular Films Real Space Orbital Reconstruction Molecular Orientations in Heterogeneous Monolayers Site-Specific UPS, k-Space Deconvolution beyond the Energy Resolution Quantifying Charge Transfer on Metals and Dielectrics Conclusions and Outlook Acknowledgments References Porous Electrodes in Bioelectrochemistry Typical Components of Porous Enzymatic Electrodes Current Collectors Catalyst Layer Support materials Enzymes Binders Mediators Comparison of Enzymatic Electrode Performances Conclusions References Further Reading Quartz Crystal Nanobalance Measurements in Electrocatalysis Principle of the Operation of the EQCN Factors Affecting the EQCN Response Presence of Mass Rigidly Attached to the Quartz Surface Immersion of the Quartz Crystal in a Solution Stresses Effect of Interactions at the Crystal/Solution Interface Effect of Surface Roughness Viscoelastic Effects Nonuniform Mass Distribution over the Resonator Surface Changes in Temperature, Hydrostatic Pressure and Physical Parameters of the Resonator Components Calibration of the EQCN Ways of the EQCN Data Analysis Impedance Measurements Examples of Using the EQCN for Electrocatalysis Concluding Remarks Acknowledgments References Further Reading Reflectance Anisotropy Spectroscopy RAS: A Brief Introduction Experimental Applications of RAS Surfaces of Metals and Semiconductors Organic and New Carbon-Based Materials Investigation in Liquids References Rotating Disk and Ring–Disk Electrodes Introduction RDEs and RRDEs—Practical Aspects Design Measurements With RDEs Measurements With RRDEs Theory Fluid Flow Under a Rotating Disk Stationary Concentration Profiles and Currents at RDEs Digital Simulation of the RRDE System Charge transfer effects Mass transfer effects IR-drop-related effects Concluding Remarks References Scanning Electrochemical Microscopy for Bioimaging Introduction SECM Instrumentation and Scanning Modes SECM Operation Modes SECM and Complementary Techniques SECM Imaging of Biomolecules at Biointerface as Biosensors SECM Imaging of Live Cells SECM Imaging of Animal Tissues Further Reading Relevant Websites Scanning Electrochemical Microscopy in the AC-Mode Introduction AC High-Frequency (HF) Feedback Mode Applied Either on the Probe or the Substrate AC (Impedance) Feedback Mode Applied on the Probe AC-SECM Generation/Collection Mode Conclusions References Further Reading Scanning Ion Conductance Microscopy—Morphology and Mechanics Introduction The Current-Distance Dependence Instrumental Equipment Scanning and Operating Modes Performances Applications References Further Reading Shell-Isolated Nanoparticles-Enhanced Raman Spectroscopy Introduction Basic Principles of SHINERS Technique Preparation of SHINs Characterization of SHINs Application of SHINERS in Electrochemical Surface Science In Situ Monitoring of Pyridine Behaviors at Au(hkl) Electrode Surfaces by SHINERS Technique Real-Time Research of the Growth Process of Benzotriazole Film at Single Crystal Cu(hkl) and Polycrystalline Cu(poly) Elect ... Real-Time Monitoring of the Electrooxidation Processes of Au(hkl) Electrodes In Situ Research of the Adsorption and Hydrogenation Behavior of Ethyl Pyruvate (EP) at Pt(hkl) Electrode Surfaces by SHINERS The Quantitative Analysis of Temporal Changes by SHINERS Technique Summary and Prospective References Further Reading Spectroelectrochemistry Applied to Electrocatalytic Processes Introduction IR Spectroelectrochemistry Surface-Enhanced Raman Scattering Outlook and Concluding Remarks References Further Readings Structural Investigations by Means of Directional Elastic Peak Electron Spectroscopy Introduction Experimental Results and Discussion Summary Acknowledgments References Sum Frequency Generation Spectroscopy and Second Harmonics Generation Introduction SFG Theory Basics Signal Intensity, Lineshape, and Molecular Concentrations SFG Instrumentation and Modes of Operation Surfaces and Interfaces Suitable for SFG Spectroscopy SFG Cells for Different Applications Case Studies SFG at Solid–(UHV/Gas/Air) Interfaces Single crystals Thin films UHV-grown and wet-chemically prepared supported nanoparticles SFG at Solid–Liquid Interfaces Conclusions References Surface Characterization by Ion Scattering Spectroscopy Composition Analysis Binary Collision Charge Exchange Scattering Cross Section Equipment Standards Surface Composition Subsurface Composition Surface Structure Shadow Cone Polar Scan Azimuthal Scan Summary References Surface X-Ray Diffraction Under Gases Introduction Sensitivity of X-Rays to Chemisorbed Gases Adsorption Under UHV and Atmospheric Pressures Batch and Flow Reactors CO Oxidation on Pt(110): Metal and Oxide Reactivity Gas-Induced Faceting Surface Steps Conclusions Acknowledgment References Surface-Enhanced Infrared Absorption Spectroscopy Introduction Enhancement Phenomena Metal Film Preparation Methods Surface Selection Rule Measurement Cell and Spectra Acquisition Composition, Coverage, and Orientation of Adsorbed Molecules Prism Shape and Material Applications Further Reading Time-Resolved Photoelectron Spectroscopy Introduction Light Sources and the Dynamic Phenomena at Various Timescales Basics in TRPES Techniques Examples of the TRPES Experiments Two-Photon Photoemission Spectroscopy Time- and Angle-Resolved Photoemission Spectroscopy With HHG Lasers Time-Resolved X-Ray Photoelectron Spectroscopy With Laser and Synchrotron Radiation Sequential Ambient Pressure XPS Measurement of an Irreversible Process Space-Charge Effect References Further Reading Time-Resolved Photoemission Electron Microscopy Introduction Technical Aspects of Photoemission Electron Microscopy (PEEM) Electron Optics Detector Electron Energy Analyzer Contrast Mechanisms and Lateral Resolution Time-Resolved PEEM Sub-Nanosecond Dynamics of Remagnetization Processes Experimental aspects Example Femtosecond Time-Resolved PEEM Experimental aspects Example 1: plasmon dynamics Example 2: excited state dynamics in molecular films Example 3: electron transport on a semiconductor surface Ultrafast Momentum Microscope Towards Attosecond Time-Resolved PEEM References Further Reading Relevant Websites Trapped Ion Electron Diffraction of Metal Cluster Ions Introduction TIED Technique Theoretical Background GED Experimental Setup Data Reduction Candidate Structures Structures of Metal Cluster Ions: A Few Examples Ag55+/−: The Icosahedron The 2D–3D Transition in Gold Cluster Anions: Au11−—Au13− Correlation of Bulk and Gas Phase Cluster Structures: M55− Discussion Conclusion Acknowledgments References Further Reading UHV Surface Preparation Methods Introduction Why Do We Need UHV? Preparation of the Surfaces of Bulk Materials in UHV Heating and Chemical Treatment Ion Bombardment Cleavage in UHV Preparation of Thin Films Metal Films Oxide Films Summary References X-Ray Photoelectron Spectroscopy in Electrochemistry Research Introduction Electrochemistry X-Ray Photoelectron Spectroscopy Preparation and Transfer XPS in Electrochemistry Research XPS Studies on Double Layer Formation XPS Studies on Passive Layer Formation XPS Studies on Nonaqueous EC Systems XPS Studies on EC Intercalation Processes XPS of Liquids XPS studies of ILs Quasi in situ EC XPS studies on EC systems containing IL electrolytes In situ EC XPS studies on EC systems containing IL electrolytes Acknowledgments References X-Ray Photoelectron Spectroscopy for Investigation of Heterogeneous Catalytic Process Introduction Gas Phase Acetoxylation at Pd-Based Catalysts Introducing the Third Dimension in XPS Nanostructured Catalysts Looking Into the Future Further Reading Catalyst Electronic Surface Structure Under Gas and Liquid Environments The Characterization of the Catalytic Gas/Solid Interface: CO Oxidation Over Au Untangle the Complexity at Electrified Interfaces by PES: From Free Photoelectrons in Vacuum Till Bulk Liquid Mechanistic Insights Into the Oxygen Evolution Reaction From In Situ Photoemission and Absorption Spectroscopy Toward a Unified Theory of the Oxygen Evolution Reaction Development in Ambient Pressure X-ray Photoemission Spectroscopy to Study PEM Electrodes Reactivity of Pt- and Ir-Based Electrocatalysts in OER Investigated by AP-XPS Conclusions Acknowledgments References Surface Science Approach to Catalyst Preparation Using Thin Oxide Films as Substrates Introduction Model Studies of Supported Metal Catalyst Preparation Surface Science Approach to Supported Catalyst Preparation Using Thin Oxide Films as Supports Concluding Remarks Acknowledgment References Surface Science at the Dawn of the 21st Century: From UHV to Ambient Conditions in Gas and Liquid Environments Surface Structure and Modifications Under Ambient Pressure: A Case Study With Copper Surfaces High-Pressure Scanning Tunneling Microscopy Structure of Low-Index Cu Surfaces in the Presence of CO Cu(111) Cu(100) Cu(110) Use of Complementary Spectroscopy Techniques Infrared Reflection Absorption Spectroscopy X-Ray Photoelectron Spectroscopy Use of Complementary Theory Effects of Other Reactant Gases (CO2 and Methanol) Final Remarks Acknowledgments References The Dynamic Structure of Model Catalyst Surfaces Under Ambient Conditions Introduction Thin Film Oxides Reductive Reconstruction of Copper Oxide Thin Films CO Oxidation on Copper and Mixed CuTiOx Model Catalysts Nanoparticle Oxide/Metal Interfaces Water-Gas Shift Reaction (WGSR) Methanol Synthesis Porous Thin Film Oxides on Metal Substrates Two-Dimensional Zeolite Models Chemistry at the Interface Between 2D-Zeolites and Metal Substrates Interaction of Molecules With Zeolite Nanosheets Summary References The Initial Steps of Hydrogen–Metal Reactions: The GdH2 as a Model System Introduction Hydride Development on Single-Crystal Gd(0001)/W(110) Islands Hydride Development on “Real-Life” Oxide-Coated Polycrystalline Gd General Description The Development of the Submicron “Small Family” The Initial Formation of Growth Centers (GCs) Summary Computational Details for the DFT Calculations References Theoretical Treatment of Surfaces in Equilibrium with Gases Introduction Modeling Molecule Surface Interaction Density Functional Theory Benchmarking XC Functionals for Metal Surface Adsorption Reactions Surface Reconstruction at Reaction Condition First-Principles Atomistic Thermodynamics RuO2(110) surface structures at different oxygen chemical potential Adsorbates induced metal surface reconstruction Hydrogen adsorption induced reconstruction of metal clusters Combining with Global Optimization Methods Extension of First-Principles Atomistic Thermodynamics to Solid–Aqueous Interface Conclusion References Thin-Film Growth and Oxidation of Surfaces Under Relevant Pressure Conditions Introduction Surface Science Methods for In Situ Investigations Ambient Pressure X-Ray Photoelectron and X-Ray Absorption Spectroscopies Surface X-Ray Diffraction Infrared Spectroscopy Other Techniques Time Resolution Examples Oxidation of Platinum Nanoparticles Atomic Layer Deposition From Tetrakis(dimethylamido) Metal Ligands Conclusions References Further Reading 9780128098943v2_WEB Front Cover ENCYCLOPEDIA OF INTERFACIAL CHEMISTRY: SURFACE SCIENCE AND ELECTROCHEMISTRY ENCYCLOPEDIA OF INTERFACIAL CHEMISTRY:SURFACE SCIENCE AND ELECTROCHEMISTRY Copyright EDITORIAL BOARD PREFACE References CONTRIBUTORS TO VOLUME 2 CONTENTS OF VOLUME 2 PERMISSION ACKNOWLEDGMENTS Adsorption and Reaction of Unsaturated Hydrocarbons on Sn/Pt Alloys Introduction Structure of Surface Alloys of Sn/Pt Geometric (Ensemble) Effects and Ligand (Electronic) Effects in Alloy Surface Chemistry and Catalysis Alkenes (Olefins) Ethene (Ethylene, C2H4) Propene (Propylene, C3H6) and Butene (Butylene, C4H8) Isomers Cyclopentene (C5H8) Cyclohexene (C6H10) Dienes Butadiene (C4H6) 1,3-Cyclohexadiene (C6H8) Aromatics Benzene (C6H6) Alkynes Ethyne (Acetylene, C2H2) Propyne (Methylacetylene, C3H2) Crotonaldehyde (CH3CHCHCHO), an α,β-Unsaturated Aldehyde Further Reading Adsorption of Organic Molecules on Silicon Surfaces: Dynamics, Kinetics, and Control Introduction Dynamics Kinetics Control Summary Acknowledgment References Further Reading Aerobic Alcohol Oxidation on Nanoporous Gold: Toward a Mechanistic Understanding of the Reactivity Aerobic Oxidation of Alcohols as a Way to “Greener” Chemical Industry Activation of Molecular Oxygen and the Catalytic Activity of np-Au Aerobic Oxidation of Alcohols on Gold Summary and Outlook References Further Reading An Approach to Structure-Sensitive Desorption Dynamics Introduction Energy Partitioning in Desorption Approach to the Transition State Intermediate N2O in DeNOx Off-Normal N2 Emission Swing Desorption Potential Energy Surface Inappropriate Use of Detailed Balance Principle in Desorption Dynamics Further Reading Atomic-Scale Friction Introduction Atomic Friction Models Graphene Lubrication Friction on Exfoliated, Thermal, or CVD Graphene Layer Dependence of Graphene Environmental Influence of Graphene Friction Substrate Influence on Graphene IL Lubrication ILs at Charged Surfaces Controlled Electrochemical Environment Conclusion Acknowledgments References Atomic Structures of Surfaces and Interfaces Surface X-ray Diffraction (SXRD) Low Energy Electron Diffraction (LEED) Photoelectron Diffraction (PED) Further Methods References Desorption Kinetics Introduction Observation Desorption Rate Spatial Distribution References Further Reading Direct Observation of Hydrogen-Atom Relay Reactions Using Low-temperature Scanning Tunneling Microscopy Introduction Formation of One-Dimensional Water–Hydroxyl Chain Complexes Structure of H2O–(OH)2 Chain Complex Direct Observation of Hydrogen-Atom Relay Reactions Voltage, Current, and Spatial Dependence of the Hydrogen-Atom Relay Reaction Reaction Pathway of the Hydrogen-Atom Relay Reaction Within H2O–(OH)2 Summary References Direct Observation of Hydrogen-Bond Exchange Reaction in a Water Dimer Using Low-Temperature Scanning Tunneling Microscopy Introduction Water Dimer on a Cu(110) Surface Current and Voltage Dependence of the Donor–Acceptor Interchange Mechanism of the H-bond Exchange Reaction Impact of Local Environments on the Hydrogen-Bond Interchange Reaction Summary References Exploring the Organic–Inorganic Interface With a Scanning Tunneling Microscope Introduction Phthalocyanine Assemblies on Surfaces Flat Terraces of Noble Metals Dielectric Buffer Layers Molecular thin films NaCl Graphene Prestructured Template Surfaces Reconstructed surfaces Vicinal surfaces Electronic templates Graphene moiré superstructure Electronic Properties Frontier Orbitals Negative Differential Conductance (NDC) Vibrational Quanta Chemical Reactions at the Single-Phthalocyanine Level Configurational Changes Metalation Demetalation Depopulation of a Molecular Orbital by Pyrrolic-H Abstraction Electron Transport Across Single-Phthalocyanine Junctions Acknowledgment References Further Reading From Langmuir to Ertl: The “Nobel” History of the Surface Science Approach to Heterogeneous Catalysis Introduction The Term Catalysis The Action of a Catalyst Adsorption Reaction Mechanisms Active Sites The Turning Point of Modern Catalysis Research Direct Imaging of Surfaces and Reactions The Surface Science Approach References Further Reading Relevant Websites Fundamentally Understanding Fischer–Tropsch Synthesis Introduction Syngas-Related Reactions FT Reaction Mechanism Reaction Regime and Catalyst Surface Science and Spectroscopic Studies in FT Synthesis Time-Resolved Chemical Transient Kinetic Analysis In Situ Scanning Tunneling Microscope Electron Tomography Combined Techniques Summary References Further Reading Relevant Websites Hematite, Its Stable Surface Terminations and Their Reactivity Toward Water Hematite: Bulk Structure and Properties Hematite Surfaces Fe2O3(001) Fe2O3(012) Molecular Water Adsorption on Hematite Surfaces Role of Surface Defects Relation to Other Materials References Further Reading Relevant Websites Hot-Electron-Mediated Surface Chemistry Introduction: Hot Electrons Generated During Surface Reactions Detection of Hot Electrons Under Surface Reactions Influence of Hot Electrons on Surface Reactions Influence of Hot Electrons and Surface Plasmons on Surface Reactions Concluding Remarks Acknowledgment References Further Reading In or Out of Control? Electron Spin Polarization in Spin-Orbit-Influenced Systems Introduction Experimental k-Dependent Spin Polarization q-Dependent Spin Polarization Conclusions Acknowledgments References Influence of Defects on Adsorption—Model Studies With Stepped Surfaces Introduction Basic Concepts and Notations Miller Indexes and Relative Notation Structure Insensitivity and Structure Sensitivity Deviating Physical Properties at the Steps Adsorption of Simple Molecules Hydrogen Adsorption CO Adsorption CO adsorption at “highly reactive” substrates CO adsorption at “less reactive” substrates NO and NO2 Adsorption NO and NO2 adsorption at stepped Au surf 9780128098943v1_WEB Front Cover ENCYCLOPEDIA OF INTERFACIAL CHEMISTRY: SURFACE SCIENCE AND ELECTROCHEMISTRY ENCYCLOPEDIA OF INTERFACIAL CHEMISTRY:SURFACE SCIENCE AND ELECTROCHEMISTRY Copyright EDITORIAL BOARD PREFACE References CONTRIBUTORS TO VOLUME 1 CONTENTS OF VOLUME 1 PERMISSION ACKNOWLEDGMENTS A Review on In Situ Sum Frequency Generation Vibrational Spectroscopy Studies of Liquid–Solid Interfaces in Electrochemical ... Introduction: The Significance of Probing Electrified Interfaces for Renewable Energy Production and Storage Basic Concepts of SFGVS for Studies of Electrified Solid–Liquid Interfaces Probing Solid–Liquid Interfaces Under Reaction Condition Li-Ion Batteries Fuel Cells Conclusions and Remarks Acknowledgments References Ambient Pressure X-Ray Photoelectron Spectroscopy Introduction X-Ray Photoelectron Spectroscopy Ambient Pressure X-Ray Photoelectron Spectroscopy Examples of APXPS Applications Solid–Vapor Interface Catalytic methanol steam reforming Mapping the surface potential of a working electrochemical cell Vapor–Liquid Interface Ion distribution at the vapor–liquid water interface Methanol distribution at the vapor–liquid interface of aerosol particles Solid–Liquid Interface Pt electrode species in KF solution Ion distribution at the hematite–liquid water interface Summary Acknowledgment References Further Reading Angle-Resolved Photoelectron Spectroscopy at Surfaces With High-Order Harmonic Generation Introduction Experimental Development Overview Photon Energy Range Energy and Time Resolution Photon Flux and Repetition Rate Band Mapping Theory for Time-Dependent Photoemission Processes Surfaces Investigated by HHG-Based PES Adsorbates Two-Dimensional and Layered Materials Metals Semiconductors Oxides and Strongly Correlated Materials Summary Acknowledgments References Further Reading Atomic Scale STM Imaging of Alloy Surfaces With Chemical Resolution Introduction Experimental and Theoretical Background STM Imaging With Atomic and Chemical Resolution Macroscopic Tip Effects Local Tip Effects Alloyed Surfaces Structural Properties of Alloyed Surfaces Chemical Properties of Alloyed Surfaces Technical and Experimental Limitations Tip Effects Tunneling Conditions Homogeneity Bulk Contribution Concluding Remark Acknowledgment References Further Reading Relevant Website Cyclic Voltammetry Introduction Processes Controlled by the Rate of Mass Transport Complex Mechanims Cyclic Voltammetry in the Presence of Adsorption Processes Coadsorption Phenomena Cyclic Voltammetry of Platinum Single Crystal Electrodes. Voltammetry as a Surface Sensitive Characterization Technique Fit of Voltammetric Peaks to Adsorption Peaks Ideally Polarizable Electrodes Kinetic Effects in the Adsorption Pseudocapacity Oxidation of Small Organic Molecules Concluding Remarks Acknowledgment Further Reading Differential Capacitance Measurements on Passive Films Introduction SC/El. Interface C-SC/El. Interface a-SC/El. Interface Admittance Equations for a-SC/El. Junction Thick Films With Variable DOS Thin Films Variable DOS Conclusions References EIS Technique in Passivity Studies: Determination of the Dielectric Properties of Passive Films Introduction Theory Exponential Resistivity Distributions: Young Model Power-Law Distributions Application to Nb2O5 and to Al2O3 Nb2O5 Oxide Layer Al2O3 Oxide Layer Oxide Layer as an Electrode Conclusions References Further Reading Electrochemical Scanning Tunneling Microscopy Introduction Scanning Tunneling Microscopy The Principle of Electron Tunneling Tunneling Through an Electrolyte Instrumental Aspects Control of the tip position Electrochemical STM setup Potentiostatic, potentiodynamic, and spectroscopic detection methods Sample Preparation Flame annealing Electrochemical etching and annealing UHV-EC transfer Tip preparation Case Studies Anion Adsorption Chloride and iodide adsorption on Cu(111) Corrosive Surface Compound Formation Metal Underpotential Deposition Molecular Ordering The Tip as Tool References Electron Paramagnetic Resonance Spectroscopy at Surfaces Introduction Basic Experimental Considerations CW EPR Spectroscopy on Solid Surfaces Paramagnetic Species With S=1⁄2 Physical Interpretation of g- and Hyperfine-Matrix Components Impact of Rotational Dynamics on CW EPR Spectra Pulsed Spectroscopic Techniques: Hyperfine Interactions as an Introductory Example Conclusion Acknowledgment References Ellipsometry in Passive Films Passive Films and Ellipsometry Reflection of Polarized Light Reflection Coefficient Ellipsometry and Differential Reflectance Apparatus Thickness of the Passive Oxide Film Under Quasi-stationary State Transient Change in Thickness of Passive Oxide Films Spectroscopic Ellipsometry Microscopic Measurement by Ellipsometry Summary References Further Reading Relevant Websites Experimental Methods in Interfacial and Surface Chemistry References Field Ion and Field Desorption Microscopy: Surface Chemistry Applications Overview Principles of FIM Operation Basics of the Field Desorption Microcopy Surface Science Applications Surface Physics and Material Science Surface Chemistry Fluctuation-induced effects Li-FDM Applications Probe-Hole Ion Analysis Summary and Future Perspective References High-Speed Electrochemical STM Introduction Piezoelectric Scanner and its Feedback Circuit Height Feedback Hybrid Mode Preamplifier and its Stability Preamplifier Noise Bipotentiostat Tunneling Current and Work Function Examples Conclusion Further Reading Acknowledgments References How to Probe Structure, Kinetics, and Dynamics at Complex Interfaces In Situ and Operando by Optical Spectroscopy Why “In Situ”? Scope of This Chapter Overview Over In Situ and Operando Spectroscopic Techniques Absorption Spectroscopy UV/VIS General principles What is special at interfaces? Applications IR General principles What is special at interfaces? Applications Techniques Exploiting Polarization of Light Ellipsometry General principles Applications Polarization Modulation General principles Applications Techniques Based on Excitation and Emission Raman General principles What is special at interfaces? Applications PL General principles What is special at interfaces? Applications SFG General principles Applications Summary Acknowledgments References Further Reading Imaging Chemical Reactions One Molecule at a Time Introduction Basics of Scanning Probe Techniques Scanning Tunneling Microscopy Atomic Force Microscopy Benefits and Drawbacks of Single Molecule Imaging by STM Delivery of Reactants Imaging Elemental Steps in Surface Reactions Molecular Adsorption Reactive Systems—Understanding What You See Same area imaging Bias- and tunneling current-dependent imaging Scanning tunneling spectroscopy22 Tip-induced manipulation Simulation of STM images Inelastic electron tunneling spectroscopy Adsorbate Motion Rotational dynamics Surface diffusion Formation of Surface Intermediates Imaging Complex Reactions Future Directions and Challenges High Pressure and Condensed Phase Studies Combined Molecular Beam Scattering and Scanning Tunneling Microscopy Adsorbate Structure Imaging with Functionalized Scanning Probes Combining Scanning Probe Techniques with Vibrational Spectroscopies Acknowledgments References Impedance Spectroscopy Applied to the Study of Electrocatalytic Processes Introduction Introduction to EIS Simple Electrosorption Reaction Electrosorption of One Species With Subsequent Desorption Volmer–Heyrovsky Mechanism The Volmer–Heyrovsky–Tafel Mechanism Influence of Mass Transfer Faradaic Reaction Involving Two Adsorbed Species Faradaic Reaction Involving Three or More Adsorbed Species Oxygen Reduction Reaction, ORR Oxidation of CO and Simple Aliphatic Alcohols Oxidation of CO Oxidation of Aliphatic Alcohols Conclusions References In Situ Photoelectron Spectroscopy Introduction Physical Principles of Photoelectron Spectroscopy History and Development Terminology for XPS, UPS, and PES Inverse PES for Unoccupied States Strengths and Weaknesses Ex Situ, In Situ, and Operando Spectroscopy Criterion for Necessity of In Situ Studies Beyond Mere Surface Sensitivity Between UHV and Ambient Pressure ESCA Chemistry Versus VB Physics Fermi Level Simulation of Spectra Binding Energy Versus Work Function Versus Electrochemical Potentials Further Applications of in Situ XPS In Situ Oxidation Organic Films on Metals Wear and Friction Correlation of Electronic Structure and Transport Properties Gas Sensors Heterogeneous Catalysis Lithium and Other Alkaline Ion Insertion and Intercalation High-Temperature Electrochemistry Water and Wet Samples Photoelectrochemistry Biological Samples Soot Oxidation and Atmospheric Chemistry X-Ray Standing Wave Spectroscopy References Further Reading Relevant Websites In Situ Probing of Adsorbates at Electrochemical Interfaces With Vibrational Sum Frequency Spectroscopy Introduction Electrochemical VSFG Spectroscopy Experimental Geometries VSFG Spectroscopy Data Analysis Adsorbates at the EC Interface Water Structure at the Gold–Aqueous Solution Interface Reaction Precursor for Formic Acid Electrochemical Oxidation on Pt(100) Future Directions Further Reading In Situ Real-Time Low-Energy Electron Microscopy Introduction The Microscope Contrast Mechanisms Applications Nucleation and Growth of Diindenoperylene Thin Films on Au(100) Single Crystals Further Reading Ion Conductance Probe Microscopy—Molecular Resolution Introduction SICM for Electrochemical Sensors SICM for Surface-Charge Mapping SICM for Nanopore-Based Sensors SICM for Picking Contents of Living Cells Acknowledgments References Further Reading Micro-Spectroscopy to Interrogate Solid Catalysts at Work Introduction Setting the Scene On the Nature of the Active Site Zeolites Supported metal nanoparticles The Catalytic Process The Partnership Between Catalyst Structure and Composition, Diffusion, and Reactivity Structure and Composition of a Catalytic Solid Diffusion Reactivity of a Single-Catalyst Particle in Space and Time Diffraction-Limited Micro-Spectroscopy: Far-Field Approaches Diffraction-Unlimited Micro-Spectroscopy: Near-Field and Wide-Field Approaches Concluding Remarks and Look Into the Future Acknowledgments References Online Chromatographic Detection Introduction Analysis of a Liquid Phase Analysis of a Headspace Other Methods for Online Detection and Their Combination with Chromatography References On-Line Inductively Coupled Plasma Spectrometry in Electrochemistry: Basic Principles and Applications Introduction Basic Operational Principles Inductively Coupled Plasma Optical Emission Spectrometry Inductively Coupled Plasma Mass Spectrometry Comparison Between ICP-OES and ICP-MS for On-Line Analysis in Electrochemistry Theoretical and Practical Basis of Dissolution Products Quantification Coupling ICPs to Electrochemistry Stationary Flow Cell-Based Techniques Scanning Flow Cell-Based Techniques Probes in Conventional Electrochemical Cells Final Remarks Acknowledgments References Further Reading Operando Scanning Probe Microscopy, Surface X-Ray Diffraction, and Optical Microscopy for Catalysis Studies Introduction Bridging the Pressure Gap High-Pressure SPM Instrumentation Requirements for Operando SPM Design of the ReactorSTM Design of the ReactorAFM High-Pressure SXRD Instrumentation Design of the ReactorSXRD Combination of High-Pressure SPM With High-Pressure SXRD High-Pressure Optical Microscopy Instrumentation Catalytic Systems Investigated Under High-Pressure Conditions CO Oxidation on Pd(100) CO Oxidation on Pd Nanoparticles CO Oxidation on Rh(111) NO Reduction on Pt(110) Chlorine Production on RuO2(110)/Ru(0001) Conclusions and Outlook Acknowledgments References Perspectives of Advanced Ion Beam Analysis of Electrochemically Active Surfaces Introduction High-Resolution Ion Beam Analytical Techniques SIMS Isotopic Exchange Tracer Diffusion Measurements Low Energy Ion Scattering (LEIS) The Challenges References Further Reading Photocurrent Spectroscopy in Passivity Studies Introduction Semiconductor/Electrolyte Junctions Under Illumination: The Gärtner–Butler Model PCS Location of Ufb and Eg Determination in c-Semiconductor/Electrolyte Junction Passive Film/Electrolyte Interface Under Illumination Electronic Properties of Disordered Passive Films Optical Gap in Amorphous Materials Amorphous Film/Electrolyte Junction Under Illumination Photoemission Phenomena at the Metal/Passive Film Interface Band Gap and Oxide Film Composition Binary Crystalline Oxides Ternary Crystalline Oxides Amorphous Oxide Films Correlation for Hydroxides and Oxihydroxide Films Modeling of Photoelectrochemical Behavior of Layered Oxide Films References Photoelectron Diffraction Introduction: Basic Principles XPD: Applications PhD: Applications Concluding Remarks and Comparison With Other Structural Techniques References Further Reading Photoemission Tomography: Valence Band Photoemission as a Quantitative Method for Investigating Molecular Films Introduction The Plane Wave Final State Approximation Multilayer Molecular Films Real Space Orbital Reconstruction Molecular Orientations in Heterogeneous Monolayers Site-Specific UPS, k-Space Deconvolution beyond the Energy Resolution Quantifying Charge Transfer on Metals and Dielectrics Conclusions and Outlook Acknowledgments References Porous Electrodes in Bioelectrochemistry Typical Components of Porous Enzymatic Electrodes Current Collectors Catalyst Layer Support materials Enzymes Binders Mediators Comparison of Enzymatic Electrode Performances Conclusions References Further Reading Quartz Crystal Nanobalance Measurements in Electrocatalysis Principle of the Operation of the EQCN Factors Affecting the EQCN Response Presence of Mass Rigidly Attached to the Quartz Surface Immersion of the Quartz Crystal in a Solution Stresses Effect of Interactions at the Crystal/Solution Interface Effect of Surface Roughness Viscoelastic Effects Nonuniform Mass Distribution over the Resonator Surface Changes in Temperature, Hydrostatic Pressure and Physical Parameters of the Resonator Components Calibration of the EQCN Ways of the EQCN Data Analysis Impedance Measurements Examples of Using the EQCN for Electrocatalysis Concluding Remarks Acknowledgments References Further Reading Reflectance Anisotropy Spectroscopy RAS: A Brief Introduction Experimental Applications of RAS Surfaces of Metals and Semiconductors Organic and New Carbon-Based Materials Investigation in Liquids References Rotating Disk and Ring–Disk Electrodes Introduction RDEs and RRDEs—Practical Aspects Design Measurements With RDEs Measurements With RRDEs Theory Fluid Flow Under a Rotating Disk Stationary Concentration Profiles and Currents at RDEs Digital Simulation of the RRDE System Charge transfer effects Mass transfer effects IR-drop-related effects Concluding Remarks References Scanning Electrochemical Microscopy for Bioimaging Introduction SECM Instrumentation and Scanning Modes SECM Operation Modes SECM and Complementary Techniques SECM Imaging of Biomolecules at Biointerface as Biosensors SECM Imaging of Live Cells SECM Imaging of Animal Tissues Further Reading Relevant Websites Scanning Electrochemical Microscopy in the AC-Mode Introduction AC High-Frequency (HF) Feedback Mode Applied Either on the Probe or the Substrate AC (Impedance) Feedback Mode Applied on the Probe AC-SECM Generation/Collection Mode Conclusions References Further Reading Scanning Ion Conductance Microscopy—Morphology and Mechanics Introduction The Current-Distance Dependence Instrumental Equipment Scanning and Operating Modes Performances Applications References Further Reading Shell-Isolated Nanoparticles-Enhanced Raman Spectroscopy Introduction Basic Principles of SHINERS Technique Preparation of SHINs Characterization of SHINs Application of SHINERS in Electrochemical Surface Science In Situ Monitoring of Pyridine Behaviors at Au(hkl) Electrode Surfaces by SHINERS Technique Real-Time Research of the Growth Process of Benzotriazole Film at Single Crystal Cu(hkl) and Polycrystalline Cu(poly) Elect ... Real-Time Monitoring of the Electrooxidation Processes of Au(hkl) Electrodes In Situ Research of the Adsorption and Hydrogenation Behavior of Ethyl Pyruvate (EP) at Pt(hkl) Electrode Surfaces by SHINERS The Quantitative Analysis of Temporal Changes by SHINERS Technique Summary and Prospective References Further Reading Spectroelectrochemistry Applied to Electrocatalytic Processes Introduction IR Spectroelectrochemistry Surface-Enhanced Raman Scattering Outlook and Concluding Remarks References Further Readings Structural Investigations by Means of Directional Elastic Peak Electron Spectroscopy Introduction Experimental Results and Discussion Summary Acknowledgments References Sum Frequency Generation Spectroscopy and Second Harmonics Generation Introduction SFG Theory Basics Signal Intensity, Lineshape, and Molecular Concentrations SFG Instrumentation and Modes of Operation Surfaces and Interfaces Suitable for SFG Spectroscopy SFG Cells for Different Applications Case Studies SFG at Solid–(UHV/Gas/Air) Interfaces Single crystals Thin films UHV-grown and wet-chemically prepared supported nanoparticles SFG at Solid–Liquid Interfaces Conclusions References Surface Characterization by Ion Scattering Spectroscopy Composition Analysis Binary Collision Charge Exchange Scattering Cross Section Equipment Standards Surface Composition Subsurface Composition Surface Structure Shadow Cone Polar Scan Azimuthal Scan Summary References Surface X-Ray Diffraction Under Gases Introduction Sensitivity of X-Rays to Chemisorbed Gases Adsorption Under UHV and Atmospheric Pressures Batch and Flow Reactors CO Oxidation on Pt(110): Metal and Oxide Reactivity Gas-Induced Faceting Surface Steps Conclusions Acknowledgment References Surface-Enhanced Infrared Absorption Spectroscopy Introduction Enhancement Phenomena Metal Film Preparation Methods Surface Selection Rule Measurement Cell and Spectra Acquisition Composition, Coverage, and Orientation of Adsorbed Molecules Prism Shape and Material Applications Further Reading Time-Resolved Photoelectron Spectroscopy Introduction Light Sources and the Dynamic Phenomena at Various Timescales Basics in TRPES Techniques Examples of the TRPES Experiments Two-Photon Photoemission Spectroscopy Time- and Angle-Resolved Photoemission Spectroscopy With HHG Lasers Time-Resolved X-Ray Photoelectron Spectroscopy With Laser and Synchrotron Radiation Sequential Ambient Pressure XPS Measurement of an Irreversible Process Space-Charge Effect References Further Reading Time-Resolved Photoemission Electron Microscopy Introduction Technical Aspects of Photoemission Electron Microscopy (PEEM) Electron Optics Detector Electron Energy Analyzer Contrast Mechanisms and Lateral Resolution Time-Resolved PEEM Sub-Nanosecond Dynamics of Remagnetization Processes Experimental aspects Example Femtosecond Time-Resolved PEEM Experimental aspects Example 1: plasmon dynamics Example 2: excited state dynamics in molecular films Example 3: electron transport on a semiconductor surface Ultrafast Momentum Microscope Towards Attosecond Time-Resolved PEEM References Further Reading Relevant Websites Trapped Ion Electron Diffraction of Metal Cluster Ions Introduction TIED Technique Theoretical Background GED Experimental Setup Data Reduction Candidate Structures Structures of Metal Cluster Ions: A Few Examples Ag55+/−: The Icosahedron The 2D–3D Transition in Gold Cluster Anions: Au11−—Au13− Correlation of Bulk and Gas Phase Cluster Structures: M55− Discussion Conclusion Acknowledgments References Further Reading UHV Surface Preparation Methods Introduction Why Do We Need UHV? Preparation of the Surfaces of Bulk Materials in UHV Heating and Chemical Treatment Ion Bombardment Cleavage in UHV Preparation of Thin Films Metal Films Oxide Films Summary References X-Ray Photoelectron Spectroscopy in Electrochemistry Research Introduction Electrochemistry X-Ray Photoelectron Spectroscopy Preparation and Transfer XPS in Electrochemistry Research XPS Studies on Double Layer Formation XPS Studies on Passive Layer Formation XPS Studies on Nonaqueous EC Systems XPS Studies on EC Intercalation Processes XPS of Liquids XPS studies of ILs Quasi in situ EC XPS studies on EC systems containing IL electrolytes In situ EC XPS studies on EC systems containing IL electrolytes Acknowledgments References X-Ray Photoelectron Spectroscopy for Investigation of Heterogeneous Catalytic Process Introduction Gas Phase Acetoxylation at Pd-Based Catalysts Introducing the Third Dimension in XPS Nanostructured Catalysts Looking Into the Future Further Reading Catalyst Electronic Surface Structure Under Gas and Liquid Environments The Characterization of the Catalytic Gas/Solid Interface: CO Oxidation Over Au Untangle the Complexity at Electrified Interfaces by PES: From Free Photoelectrons in Vacuum Till Bulk Liquid Mechanistic Insights Into the Oxygen Evolution Reaction From In Situ Photoemission and Absorption Spectroscopy Toward a Unified Theory of the Oxygen Evolution Reaction Development in Ambient Pressure X-ray Photoemission Spectroscopy to Study PEM Electrodes Reactivity of Pt- and Ir-Based Electrocatalysts in OER Investigated by AP-XPS Conclusions Acknowledgments References Surface Science Approach to Catalyst Preparation Using Thin Oxide Films as Substrates Introduction Model Studies of Supported Metal Catalyst Preparation Surface Science Approach to Supported Catalyst Preparation Using Thin Oxide Films as Supports Concluding Remarks Acknowledgment References Surface Science at the Dawn of the 21st Century: From UHV to Ambient Conditions in Gas and Liquid Environments Surface Structure and Modifications Under Ambient Pressure: A Case Study With Copper Surfaces High-Pressure Scanning Tunneling Microscopy Structure of Low-Index Cu Surfaces in the Presence of CO Cu(111) Cu(100) Cu(110) Use of Complementary Spectroscopy Techniques Infrared Reflection Absorption Spectroscopy X-Ray Photoelectron Spectroscopy Use of Complementary Theory Effects of Other Reactant Gases (CO2 and Methanol) Final Remarks Acknowledgments References The Dynamic Structure of Model Catalyst Surfaces Under Ambient Conditions Introduction Thin Film Oxides Reductive Reconstruction of Copper Oxide Thin Films CO Oxidation on Copper and Mixed CuTiOx Model Catalysts Nanoparticle Oxide/Metal Interfaces Water-Gas Shift Reaction (WGSR) Methanol Synthesis Porous Thin Film Oxides on Metal Substrates Two-Dimensional Zeolite Models Chemistry at the Interface Between 2D-Zeolites and Metal Substrates Interaction of Molecules With Zeolite Nanosheets Summary References The Initial Steps of Hydrogen–Metal Reactions: The GdH2 as a Model System Introduction Hydride Development on Single-Crystal Gd(0001)/W(110) Islands Hydride Development on “Real-Life” Oxide-Coated Polycrystalline Gd General Description The Development of the Submicron “Small Family” The Initial Formation of Growth Centers (GCs) Summary Computational Details for the DFT Calculations References Theoretical Treatment of Surfaces in Equilibrium with Gases Introduction Modeling Molecule Surface Interaction Density Functional Theory Benchmarking XC Functionals for Metal Surface Adsorption Reactions Surface Reconstruction at Reaction Condition First-Principles Atomistic Thermodynamics RuO2(110) surface structures at different oxygen chemical potential Adsorbates induced metal surface reconstruction Hydrogen adsorption induced reconstruction of metal clusters Combining with Global Optimization Methods Extension of First-Principles Atomistic Thermodynamics to Solid–Aqueous Interface Conclusion References Thin-Film Growth and Oxidation of Surfaces Under Relevant Pressure Conditions Introduction Surface Science Methods for In Situ Investigations Ambient Pressure X-Ray Photoelectron and X-Ray Absorption Spectroscopies Surface X-Ray Diffraction Infrared Spectroscopy Other Techniques Time Resolution Examples Oxidation of Platinum Nanoparticles Atomic Layer Deposition From Tetrakis(dimethylamido) Metal Ligands Conclusions References Further Reading 9780128098943v2_WEB Front Cover ENCYCLOPEDIA OF INTERFACIAL CHEMISTRY: SURFACE SCIENCE AND ELECTROCHEMISTRY ENCYCLOPEDIA OF INTERFACIAL CHEMISTRY:SURFACE SCIENCE AND ELECTROCHEMISTRY Copyright EDITORIAL BOARD PREFACE References CONTRIBUTORS TO VOLUME 2 CONTENTS OF VOLUME 2 PERMISSION ACKNOWLEDGMENTS Adsorption and Reaction of Unsaturated Hydrocarbons on Sn/Pt Alloys Introduction Structure of Surface Alloys of Sn/Pt Geometric (Ensemble) Effects and Ligand (Electronic) Effects in Alloy Surface Chemistry and Catalysis Alkenes (Olefins) Ethene (Ethylene, C2H4) Propene (Propylene, C3H6) and Butene (Butylene, C4H8) Isomers Cyclopentene (C5H8) Cyclohexene (C6H10) Dienes Butadiene (C4H6) 1,3-Cyclohexadiene (C6H8) Aromatics Benzene (C6H6) Alkynes Ethyne (Acetylene, C2H2) Propyne (Methylacetylene, C3H2) Crotonaldehyde (CH3CHCHCHO), an α,β-Unsaturated Aldehyde Further Reading Adsorption of Organic Molecules on Silicon Surfaces: Dynamics, Kinetics, and Control Introduction Dynamics Kinetics Control Summary Acknowledgment References Further Reading Aerobic Alcohol Oxidation on Nanoporous Gold: Toward a Mechanistic Understanding of the Reactivity Aerobic Oxidation of Alcohols as a Way to “Greener” Chemical Industry Activation of Molecular Oxygen and the Catalytic Activity of np-Au Aerobic Oxidation of Alcohols on Gold Summary and Outlook References Further Reading An Approach to Structure-Sensitive Desorption Dynamics Introduction Energy Partitioning in Desorption Approach to the Transition State Intermediate N2O in DeNOx Off-Normal N2 Emission Swing Desorption Potential Energy Surface Inappropriate Use of Detailed Balance Principle in Desorption Dynamics Further Reading Atomic-Scale Friction Introduction Atomic Friction Models Graphene Lubrication Friction on Exfoliated, Thermal, or CVD Graphene Layer Dependence of Graphene Environmental Influence of Graphene Friction Substrate Influence on Graphene IL Lubrication ILs at Charged Surfaces Controlled Electrochemical Environment Conclusion Acknowledgments References Atomic Structures of Surfaces and Interfaces Surface X-ray Diffraction (SXRD) Low Energy Electron Diffraction (LEED) Photoelectron Diffraction (PED) Further Methods References Desorption Kinetics Introduction Observation Desorption Rate Spatial Distribution References Further Reading Direct Observation of Hydrogen-Atom Relay Reactions Using Low-temperature Scanning Tunneling Microscopy Introduction Formation of One-Dimensional Water–Hydroxyl Chain Complexes Structure of H2O–(OH)2 Chain Complex Direct Observation of Hydrogen-Atom Relay Reactions Voltage, Current, and Spatial Dependence of the Hydrogen-Atom Relay Reaction Reaction Pathway of the Hydrogen-Atom Relay Reaction Within H2O–(OH)2 Summary References Direct Observation of Hydrogen-Bond Exchange Reaction in a Water Dimer Using Low-Temperature Scanning Tunneling Microscopy Introduction Water Dimer on a Cu(110) Surface Current and Voltage Dependence of the Donor–Acceptor Interchange Mechanism of the H-bond Exchange Reaction Impact of Local Environments on the Hydrogen-Bond Interchange Reaction Summary References Exploring the Organic–Inorganic Interface With a Scanning Tunneling Microscope Introduction Phthalocyanine Assemblies on Surfaces Flat Terraces of Noble Metals Dielectric Buffer Layers Molecular thin films NaCl Graphene Prestructured Template Surfaces Reconstructed surfaces Vicinal surfaces Electronic templates Graphene moiré superstructure Electronic Properties Frontier Orbitals Negative Differential Conductance (NDC) Vibrational Quanta Chemical Reactions at the Single-Phthalocyanine Level Configurational Changes Metalation Demetalation Depopulation of a Molecular Orbital by Pyrrolic-H Abstraction Electron Transport Across Single-Phthalocyanine Junctions Acknowledgment References Further Reading From Langmuir to Ertl: The “Nobel” History of the Surface Science Approach to Heterogeneous Catalysis Introduction The Term Catalysis The Action of a Catalyst Adsorption Reaction Mechanisms Active Sites The Turning Point of Modern Catalysis Research Direct Imaging of Surfaces and Reactions The Surface Science Approach References Further Reading Relevant Websites Fundamentally Understanding Fischer–Tropsch Synthesis Introduction Syngas-Related Reactions FT Reaction Mechanism Reaction Regime and Catalyst Surface Science and Spectroscopic Studies in FT Synthesis Time-Resolved Chemical Transient Kinetic Analysis In Situ Scanning Tunneling Microscope Electron Tomography Combined Techniques Summary References Further Reading Relevant Websites Hematite, Its Stable Surface Terminations and Their Reactivity Toward Water Hematite: Bulk Structure and Properties Hematite Surfaces Fe2O3(001) Fe2O3(012) Molecular Water Adsorption on Hematite Surfaces Role of Surface Defects Relation to Other Materials References Further Reading Relevant Websites Hot-Electron-Mediated Surface Chemistry Introduction: Hot Electrons Generated During Surface Reactions Detection of Hot Electrons Under Surface Reactions Influence of Hot Electrons on Surface Reactions Influence of Hot Electrons and Surface Plasmons on Surface Reactions Concluding Remarks Acknowledgment References Further Reading In or Out of Control? Electron Spin Polarization in Spin-Orbit-Influenced Systems Introduction Experimental k-Dependent Spin Polarization q-Dependent Spin Polarization Conclusions Acknowledgments References Influence of Defects on Adsorption—Model Studies With Stepped Surfaces Introduction Basic Concepts and Notations Miller Indexes and Relative Notation Structure Insensitivity and Structure Sensitivity Deviating Physical Properties at the Steps Adsorption of Simple Molecules Hydrogen Adsorption CO Adsorption CO adsorption at “highly reactive” substrates CO adsorption at “less reactive” substrates NO and NO2 Adsorption NO and NO2 adsorption at stepped Au su