Springer Handbook of Advanced Catalyst Characterization

Description

Co-edited by world-renowned scientists in the field of catalysis, this book contains the cutting-edge in situ and operando spectroscopy characterization techniques operating under reaction conditions to determine a materials’ bulk, surface, and solution complex and their applications in the field of catalysis with emphasis on solid catalysts in powder form since such catalyst are relevant for industrial applications. The handbook covers from widely-used to cutting-edge techniques. The handbook is written for a broad audience of students and professionals who want to pursue the full capabilities available by the current state-of-the-art in characterization to fully understand how their catalysts really operate and guide the rational design of advanced catalysts. Individuals involved in catalysis research will be interested in this handbook because it contains a catalogue of cutting-edge methods employed in characterization of catalysts.  These techniques find wide use in applications such as petroleum refining, chemical manufacture, natural gas conversion, pollution control, transportation, power generation, pharmaceuticals and food processing.  fdsfds Preface Editors´ Introduction References Contents About the Editors Contributors Part I: Vibrational Spectroscopy 1 Infrared (IR) Spectroscopy 1.1 Introduction 1.2 Principles of Vibrational Spectroscopy 1.3 Experimental Techniques 1.4 The Bulk Characterization of Solid Catalysts by Infrared Spectroscopy 1.4.1 IR Absorption Spectra of Crystalline Nonconducting Solids 1.4.2 IR Absorption Spectra of Amorphous Solids 1.4.3 IR Characterization of Spent Catalysts 1.4.4 Infrared Detection of Impurities in Catalysts 1.4.5 Application of Skeletal IR Spectroscopy in the Characterization of Unsupported and Supported Metal Nanoparticles 1.4.6 Revealing the State of Oxidation of Catalysts by Skeletal IR Spectroscopy 1.5 Surface Characterization of Catalysts by IR Spectroscopy 1.5.1 The Infrared Spectra of Pure Catalyst Powders Line-Base Slope and Light Scattering The Cutoff The Bulk Vibration Overtones Spectra of Surface or Bulk Impurities The IR Spectra of the Surface Hydroxyl Groups Absorptions Due to Surface Metal-Oxygen ``Double´´ Bonds Absorptions by Surface Metal-Oxygen-Metal Bridges 1.5.2 The IR Spectra of Adsorbed Probe Molecules IR Spectra of Basic Probes for Surface Acidity Characterization IR Spectra of Acidic Probes for Surface Basicity Characterization IR Spectra of Adsorbed Carbon Monoxide for Metallic/Cationic Sites Characterization 1.6 Application of IR Spectroscopy to the Study of the Mechanisms of Heterogeneous Catalysis 1.7 Conclusions References 2 Case Studies: Infrared (IR) Spectroscopy 2.1 The FT-IR Experimental Setups 2.2 Case Study 1: Formation of Cu Nitrates on Cu-CHA Catalyst by Operando FT-IR 2.2.1 The Catalyst 2.2.2 Effect of Temperature on the NO/O2 Reactivity on Cu-CHA Operando FT-IR Spectroscopy at Fixed Temperature Operando FT-IR Spectroscopy at Variable Temperature 2.2.3 Interpretation of the Bands 2.2.4 In Situ FT-IR Spectroscopy Monitoring Nitrates Formation with Isotopic Labelled 15NO 2.3 Case Study 2: Dynamic Behavior of Pt-Hydrides on a Pt/Al2O3 Catalyst 2.3.1 The Catalyst 2.3.2 Pt-Hydride Species as a Function of the H2 Concentration In Situ FT-IR Spectroscopy in Transmission Mode Operando FT-IR Spectroscopy in Transmission Mode Operando FT-IR Spectroscopy in DRIFT Mode 2.3.3 Explaining the Dynamic Behavior of the Pt-H Species 2.3.4 The Behavior of the Pt-Hydrides During a Hydrogenation Reaction 2.4 Conclusions References 3 Reflection Absorption Infrared Spectroscopy 3.1 Introduction 3.2 Case Studies 3.2.1 Hydrocarbons on Metallic and Single-Atom Alloy Surfaces 3.2.2 Adsorption of Methanol on Palladium 3.2.3 CO2 Activation on a ZrO2 Film 3.2.4 CO on Metallic, Bimetallic, and Single-Atom Alloy (SAA) Surfaces 3.3 Conclusion References 4 Raman Spectroscopy 4.1 Introduction 4.2 Description of Raman Method 4.2.1 Theory of Raman Scattering 4.2.2 Benefits of Raman Spectroscopy for Characterization of Catalysts 4.2.3 Limitations of Raman Spectroscopy for Characterization of Catalysts 4.2.4 Comparison of Method to Other Techniques: Pros and Cons 4.3 Description of General Raman System to Conduct Characterization of Catalysts 4.3.1 Excitation Source 4.3.2 Sample Illumination and Light Collection System 4.3.3 Sample Holder 4.3.4 Detection System 4.4 New Instrumental Advances in Raman Spectroscopy 4.4.1 Avoidance of Fluorescence Effect 4.4.2 Increase Sensitivity 4.4.3 Increase Spatial Resolution 4.5 Description of Reaction Cells for In Situ and Operando Raman Studies 4.6 Chronology of Application of Raman Spectroscopy to Catalysis 4.6.1 Early Ambient Conditions and In Situ Condition 4.6.2 Reaction Conditions: In Situ/Operando Measurement 4.7 Time-Resolved Raman Spectroscopy 4.8 Spatial-Resolved Raman Spectroscopy: Microscopy 4.9 Modulation Excitation Raman Spectroscopy 4.10 Applications of Raman Spectroscopy to Catalyst Synthesis 4.11 Applications of Raman Spectroscopy Study to Catalyst Treatments 4.12 Applications of Raman Spectroscopy to Catalyst Structure-Activity Relationships 4.13 Combining Raman Spectroscopy with Other Techniques (Multimodal) 4.14 Summary References 5 Case Studies: Raman Spectroscopy 5.1 Introduction 5.2 In Situ Raman Spectroscopy 5.3 Case Studies on the Application of Operando Raman Spectroscopy to Heterogeneous Catalysts 5.3.1 Case Studies Case Study 1: The Three Generations of Characterization of Zirconia-Supported Vanadium Oxide Catalysts Case Study 2: Operando Raman Spectroscopy and Density Functional Theory-Based Vibrational Assignment Case Study 3: Recent Studies on the Operando Raman Spectroscopy Identification of Coke During Heterogeneously Catalyzed Reacti... 5.4 Present Challenges and Future Recourse References 6 Ultraviolet (UV) Raman Spectroscopy 6.1 Introduction 6.2 Description of Raman Spectroscopy 6.2.1 Raman Scattering Theory 6.2.2 Benefits and Limitations for Catalyst Characterization 6.3 UV Raman Instrumentation 6.4 New Instrument Advances 6.5 Reaction Cells 6.6 Chronology of Application to Catalysis 6.7 Time Resolution 6.8 Spatial Resolution 6.9 Applications of UV Raman 6.9.1 Silica/Zeolite Synthesis 6.9.2 Thermal, Oxidation, and Reduction Treatments 6.9.3 Catalyst Deactivation by Coke Formation 6.9.4 Speciation of Titania 6.9.5 Supported Vanadium Oxide 6.9.6 Ceria Support 6.10 Multimodal Operation 6.11 Conclusions and Future Outlook References 7 Surface Enhanced Raman Spectroscopy (SERS) 7.1 Introduction 7.2 Raman Scattering 7.3 Surface-Enhanced Raman Scattering (SERS) 7.3.1 The Electromagnetic Effect in SERS 7.3.2 Chemical Mechanism (CT) 7.4 Surface-Enhanced Resonance Raman Scattering (SERRS) 7.5 Surface Selection Rules 7.6 SERS Active Substrates 7.6.1 Metallic Nanoparticles 7.6.2 Highly Ordered Substrates 7.6.3 Hybrid Materials 7.7 Tip-Enhanced Raman Scattering 7.8 SERS Imaging 7.9 SERS Applications in Catalysis 7.10 Conclusions References 8 Nanoscale Raman Spectroscopy 8.1 Short Introduction to TERS 8.2 Theoretical Background of Plasmon-Induced Catalysis 8.2.1 Thermal Effects 8.3 Nanoscale Spectroscopic Investigation of Catalyzed Reactions 8.4 Nanoscale Catalytic Reactions with Plasmon Contribution 8.4.1 pNTP and pATP Dimerization to DMAB and Other Azo Bridge Containing Molecules 8.4.2 Triple Bond Formation 8.4.3 (De)Protonation of Pyridine 8.4.4 Miscellaneous: Bond Cleavages 8.5 Electrochemical Processes Using EC-AFM-TERS and EC-STM-TERS 8.5.1 Reversible Redox Reaction of Nile Blue 8.5.2 Protonation Reactions 8.5.3 Cleavage of Water 8.5.4 Manipulating Phthalocyanine 8.6 Catalytic Reactions Without Plasmon Contribution 8.6.1 Porphyrin and Phthalocyanine: NO, CO, O, O2 Complexation 8.6.2 Bimetallic Substrates: Oxidation on Au/Pd and Au/Pt Surfaces 8.6.3 Cis-Trans Isomerization Around an Azo Bridge 8.7 Conclusion References 9 Operando Electrochemical Raman Spectroscopy 9.1 Introduction 9.2 Raman Spectroscopy 9.2.1 Basic Principle 9.2.2 Instrumentation 9.3 Surface-Enhanced Raman Spectroscopy 9.3.1 Surface-Enhanced Raman Spectroscopy 9.3.2 SERS Substrates and Fabrication 9.3.3 Extensions of SERS 9.4 Operando Electrochemical Raman Spectroscopy in Electrocatalysis 9.4.1 Coupling Raman Spectroscopy and Electrochemistry 9.4.2 Central Topics in Electrocatalysis 9.4.3 Case Studies on Electrocatalytic Energy Conversion Water Electrolysis: OERS and SECM The Oxygen Reduction Reaction (ORR): OERS and SHINERS The Carbon Dioxide Reduction Reaction (CO2RR): OERS and SERS 9.5 Experiences from a Practical Point of View 9.6 Conclusion References 10 Sum Frequency Generation (SFG) Spectroscopy 10.1 Introduction to Sum Frequency Generation (SFG) Spectroscopy 10.2 SFG Theory 10.2.1 SFG Signal Intensity and Lineshape 10.3 SFG Instrumentation and Operation Modes 10.4 Applications of SFG Spectroscopy and Selected Case Studies 10.4.1 SFG Spectroscopy on Metal Surfaces SFG Spectroscopy on Metal Single Crystals SFG Spectroscopy on Supported Metal Nanoparticles 10.4.2 SFG Spectroscopy on Oxide Surfaces 10.4.3 SFG Spectroscopy on Polymer and Biomaterial Interfaces 10.4.4 SFG Spectroscopy of Water and Ice Layers 10.5 Synopsis References Part II: Electron and Photoelectron Spectroscopy 11 Ultraviolet-Visible (UV-Vis) Spectroscopy 11.1 Basic Principles of Ultraviolet-Visible Spectroscopy 11.2 The Spectrometer and Related Accessories 11.2.1 The UV-Vis Spectrometer 11.2.2 Sample Preparation, Mode of Measuring, and Catalytic Reactors Transmission Spectroscopy Diffuse Reflectance Spectroscopy Fiber Optics Spectroscopy Micro-Spectroscopy 11.3 Probe Molecule UV-Vis Spectroscopy 11.4 Coupling UV-Vis Spectroscopy with Other Analytical Methods 11.5 Complementing Data Interpretation with Density Functional Theory 11.6 Application of Chemometrics and Multivariate Analyses 11.7 Selected Applications of UV-Vis Spectroscopy in the Field of Catalysis 11.7.1 Heterogeneous Catalysis 11.7.2 Homogeneous Catalysis 11.7.3 Electrocatalysis 11.7.4 Photocatalysis 11.8 Conclusions and Outlook References 12 Case Studies: Ultraviolet-Visible (UV-Vis) Spectroscopy 12.1 Introduction 12.2 NH3-SCR Over Supported Vanadium/Copper Catalysts 12.3 Dehydrogenation of Propane Over Supported Catalysts 12.4 Electroreduction of CO2 Over Molecular Catalysts 12.5 Methanol to Olefin (MTO) Process Over Zeolite Catalysts 12.6 Conclusions and Remarks References 13 Fluorescence Microscopy 13.1 Introduction 13.2 Reactivity and Heterogeneity of Individual Particles 13.3 Restructuring and Switching 13.4 Super-resolution Mapping of Catalytic Activities at the Single to Subparticle Level 13.5 Scalable Parallel Screening of Catalyst Activities 13.6 Spatial and Temporal Catalysis Cooperativity Within and Between Nanoparticles 13.7 Conclusion References 14 Photoluminescence (PL) Spectroscopy 14.1 Introduction 14.2 Basic Principles of Photoluminescence 14.2.1 Absorption Spectrum, Franck-Condon Principle, and Vibration Structure 14.2.2 The Fate of Electronic Excitation Energy Excitation, Emission (Fluorescence), and Stokes Shift Excited Triplet State, Intersystem Crossing, Phosphorescence, and Selection Rules Vibrational Deactivation and Internal Conversion Radiative Processes on Semiconducting Catalyst: Effect of the Adsorption of Various Reactant Molecules Upon the Radiative Proc... 14.3 Practical Aspects of Photoluminescence 14.3.1 Instrumentation 14.3.2 Sample Preparation 14.3.3 Spectral Parameters to Identify Photoluminescence Sites 14.3.4 Wavelength and Spectral Shape 14.3.5 Quantum Efficiency 14.3.6 Lifetimes and the Stern-Volmer Expression 14.3.7 Energy Transfer and Migration 14.3.8 Ultrafast Time-Resolved PL Spectroscopy 14.3.9 Relevance of Photoluminescence to Surface Phenomena 14.4 Characterization of Catalytically Active Sites by In Situ Photoluminescence Spectroscopy 14.4.1 Ti-Oxide Single-Site Containing Samples 14.4.2 V-Oxide Single-Site Containing Samples 14.4.3 Mo-Oxide Single-Site Containing Samples 14.4.4 Carbon Containing Samples 14.5 Characterization of Acidic and Basic Sites by Means of Luminescent Probe Molecules and In Situ Photoluminescence Spectros... 14.6 In Situ Photoluminescence Studies of Photocatalytic Processes Involving Inorganic and Organic Semiconductor Photocatalyti... 14.7 Effect of Temperature on Photoluminescence Spectra 14.8 Effect of Magnetic Fields on Photoluminescence Spectra 14.9 Conclusions and Outlook References 15 Case Studies: Photoluminescence (PL) Spectroscopy 15.1 Investigation of Charge Carrier Dynamics in Photocatalysts 15.1.1 Time-Resolved PL Studies of Pure and Doped TiO2 Nanoparticles 15.1.2 PL Studies of Reactant Interactions with TiO2 Nanoparticles 15.1.3 PL Investigation of Charge Carrier Separation in g-C3N4 Heterojunctions 15.2 Investigation of Photocatalytic Reactions Promoted by Supported Transition Metal Ions 15.2.1 NO Photo-Reduction by CO on Mo6+/SiO2 15.2.2 Photo-PROX Reaction on Visible Light Responsive Cr6+-MCM-41 References 16 Near Ambient Pressure (NAP) X-Ray Photoelectron Spectroscopy (XPS) 16.1 Introduction 16.2 Technical Issues 16.3 Applications of NAP-XPS 16.3.1 CO Oxidation 16.3.2 CO2 Hydrogenation and Methanol Synthesis 16.3.3 Methane Activation and Conversion 16.4 Conclusion References 17 Case Studies: Near Ambient Pressure (NAP) X-Ray Photoelectron Spectroscopy (XPS) 17.1 Case Study: Monitoring Catalyst Preparation and Formation of Active Catalytic Sites 17.2 Case Study: Tracking Adsorbate on Catalyst Formed Under Catalytic Conditions 17.3 Case Studies: Observing Compositional Restructuring of a Catalyst Driven by a Reaction 17.4 Summary References Part III: Electron Microscopy 18 Scanning Electron Microscopy (SEM) 18.1 Introduction 18.2 Instrumental Considerations 18.2.1 Origin of Signals Used for Image Formation in SEM 18.2.2 Types of Detectors Used in SEM Secondary Electron Detectors Backscattered Electron Detectors Transmitted Electron Detectors in the SEM 18.2.3 Choice of Operating Voltage 18.2.4 What Determines Image Resolution 18.2.5 Quantifying Resolution in SEM 18.2.6 Correlating SEM Data with XRD 18.2.7 Applying Bias to the Specimen to Enhance Resolution 18.2.8 Performing SEM in a STEM for Imaging the Location of Single Atoms 18.2.9 Performing STEM in an SEM for Improved Resolution 18.2.10 Elemental Analysis via EDS and WDS 18.2.11 Electron Backscatter Diffraction (EBSD) 18.3 Applications of SEM to the Study of Heterogeneous Catalysts 18.3.1 Study of Surface Facets in Nanoparticles 18.3.2 Determining Location of Nanoparticles, Within the Pores or on the External Surface? 18.3.3 Confinement of Pt in Mesoporous Silica to Improve Sinter Resistance 18.3.4 Electron Backscatter Diffraction to Determine Facet Orientation in Cu Catalysts for CO2 Electroreduction 18.3.5 Interaction of Plasmonic Ag Nanoparticles with High-Energy Sites on TiO2 Studied via SEM-EBSD 18.3.6 In Situ Study of Ag-Cu Catalysts for Ethylene Epoxidation 18.3.7 In Situ Imaging and Spectroscopy of Liquids in an SEM 18.3.8 Imaging the Formation of Graphene Layers During In Situ Growth 18.4 Perspective References 19 High Pressure Transmission Electron Microscopy (TEM) 19.1 General Principles 19.1.1 Why High-Pressure Transmission Electron Microscopy? 19.1.2 Basic Principles of TEM and STEM Modes with a Standard Instrument 19.2 Environmental Transmission Electron Microscopes (ETEM) 19.2.1 General Setup for ETEM 19.2.2 Advantages and Drawbacks of ETEM 19.3 Environmental Holder 19.3.1 General Setup for Environmental Holder Use 19.3.2 Advantages and Disadvantages of Environmental Holders 19.4 Detection Systems for Imaging and Spectroscopy with ETEM and Environmental Holders 19.4.1 General Overview of EDS and EELS 19.4.2 Considerations for EDS, EELS, Imaging, and Diffraction with In Situ Experiments 19.5 Examples of ETEM Applications 19.5.1 Oxidation and Reduction Effect on Dealloyed Nanoporous Gold [42] 19.5.2 Change of the Crystal Structure of Au Nanoparticles and Adsorption of CO Molecules [48] 19.5.3 In Situ Manipulation of the Active Au-TiO2 Interface with Atomic Precision During CO Oxidation [51] 19.6 Examples of Environmental Holder Applications 19.6.1 Ostwald Ripening and Particle Migration and Coalescence (PMC) Phenomena [55] 19.6.2 Structural Dynamics of Nanoparticles Revealed by a Combination of In Situ TEM and XAFS [57] 19.6.3 Visualization of Nanoparticle Growth [60] 19.6.4 Direct Observation of Kirkendall Effect in Nanoparticles with a Liquid-Heating In Situ Holder [63] 19.6.5 Photoelectrocatalysis for the Generation of H2 19.6.6 Structural Evolution During Photocorrosion of Ni/NiO Core/Shell Co-Catalyst on TiO2 [74, 75] 19.7 Common Questions That Users Should Ask Themselves Before Starting an In Situ Experiment 19.8 Future Perspective for In Situ TEM at High Pressures References 20 STEM High Angle Annular Dark-Field Imaging 20.1 Introduction 20.1.1 Image Formation in STEM 20.1.2 Forming an Electron Probe 20.1.3 Electron-Matter Interactions and HAADF Image Formation 20.2 Some Case Studies of STEM-HAADF Imaging for Catalyst Research 20.2.1 STEM Imaging of Supported Metal Catalysts Gold-on-Oxide Supports for Low-Temperature CO Oxidation Matching Different Forms of Gold to Different Catalytic Reactions Supported Bimetallic Au-Pd Catalysts 20.2.2 STEM-HAADF Imaging of Supported Metal Oxide Catalysts: The WOx/ZrO2 Solid Acid Catalyst 20.2.3 STEM-HAADF Imaging of Bulk Mixed Oxide Catalysts Introduction to M1 and M2 Catalysts Confirming the M1 and M2 Structures with STEM-HAADF Imaging STEM-HAADF Studies of Lateral Surfaces STEM-HAADF Studies of Dynamic Catalyst Structures 20.3 ``Gentle´´ STEM-HAADF Imaging 20.3.1 Low-Voltage STEM Imaging of Catalysts Comprised of Beam-Sensitive 2D-Layered Materials or Nanostructured Carbon Direct Identification of MNx Species in Carbon-Based Electrocatalysts Identification of Active Structures in 2D MoS2-Based Catalysts 20.3.2 Low-Dose STEM-HAADF Imaging of Zeolite-Type Materials 20.4 3D Imaging of Catalysts via STEM-HAADF 20.4.1 STEM-HAADF Tomography 20.4.2 Depth Sectioning with Through-Focal STEM-HAADF Imaging 20.4.3 Quantitative STEM-HAADF Imaging 20.4.4 Comparison of 3D STEM-HAADF Imaging Methods 20.5 STEM-HAADF Imaging of Catalysts in a More Realistic Working Environment 20.6 Summary References 21 Case Studies: Aberration Corrected High-Angle Annular Dark-Field (AC-HAADF) Microscopy 21.1 Case Studies of Molybdenum Carbide-Supported Metal Catalysts 21.1.1 Supported Pt/α-MoC Catalyst for Low-Temperature Aqueous-Phase Reforming of Methanol (APRM) 21.1.2 Supported Au/α-MoC Catalyst for Low-Temperature WGS Reaction 21.1.3 α-MoC-Supported Light Transition Metal Catalysts: Ni/α-MoC and (Co-Ni)/α-MoC 21.2 Conclusions and Perspectives References Part IV: Particle Scattering 22 Low Energy Ion Scattering (LEIS) Spectroscopy 22.1 Introduction 22.2 Descriptions of LEIS 22.2.1 Fundamentals 22.2.2 Quantification 22.2.3 Depth Information 22.2.4 Pretreatments 22.3 Application of LEIS to Heterogeneous Catalysts 22.3.1 Dispersion of the Active Component 22.3.2 Surface Compositions of Supported Bimetal Catalysts 22.3.3 Catalytically Active Surface Sites 22.3.4 Nanocatalysts with Core-Shell Structures 22.3.5 Strong Metal-Support Interaction 22.3.6 Other Applications 22.4 Summary and Outlook References 23 Case Studies: Low Energy Ion Scattering (LEIS) Spectroscopy 23.1 Case Study: LEIS Surface Analysis of Photocatalysts 23.2 Case Study: LEIS Surface Analysis of Bulk Mixed Metal Oxide Catalysts 23.3 Case Study: LEIS Surface Analysis of Supported Metal Oxide Catalysts 23.4 Case Study: LEIS Surface Analysis of Isotopically 18O-16O Exchanged Bulk Metal Catalysts 23.5 Summary/Conclusions References 24 Neutron Scattering (NS) Spectroscopy 24.1 Introduction 24.2 Theory of Neutron Scattering 24.2.1 Properties of Neutrons and Neutron Sources 24.2.2 How Neutron Scattering Works 24.2.3 Instrumentation 24.2.4 Modeling 24.3 Pros and Cons of Neutron Scattering for Catalysis Research 24.4 Inelastic Neutron Spectroscopy (INS) 24.4.1 Basic Principles of INS 24.4.2 Application of INS to Heterogeneous Catalysis 24.5 Quasi-Elastic Neutron Scattering (QENS) 24.5.1 Basic Principles of QENS 24.5.2 Application of QENS to Heterogeneous Catalysis 24.6 Neutron Diffraction (ND) 24.6.1 Basic Principles of ND 24.6.2 Application of ND to Heterogeneous Catalysis 24.7 Other Neutron Scattering Techniques for Heterogeneous Catalysis 24.8 Summary References Part V: X-Ray Methods 25 X-Ray Diffraction (XRD) 25.1 Introduction 25.2 Physics of XRD 25.2.1 Sources of X-Rays 25.2.2 XRD 25.3 Crystalline Solids and XRD 25.4 Understanding X-Ray Diffractograms 25.5 Toward In Situ and Operando XRD Characterization of Catalysts 25.6 Case Studies Highlighting In Situ/Operando XRD in Catalyst Characterization 25.6.1 A Tailored Multifunctional Catalyst for Ultraefficient Styrene Production Under a Cyclic Redox Scheme 25.6.2 In Situ Studies of the Active Sites for the Water-Gas Shift (WGS) Reaction Over Cu-CeO2 Catalysts:Complex Interaction B... 25.6.3 Combined In Situ X-Ray Powder Diffractometry/Raman Spectroscopy of Iron Carbide and Carbon Species Evolution in Fe(-Na-... 25.7 Limitations of XRD 25.8 Outlook References 26 Case Studies: Crystallography as a Tool for Studying Methanol Conversion in Zeolites 26.1 Introduction 26.2 MTH Conversion 26.3 Diffraction for Zeolite Characterization 26.4 Organic Molecules Adsorbed in Zeolites 26.5 Catalysts ``Postmortem´´ 26.6 In Situ Studies on Zeolites 26.7 Operando Catalytic Studies 26.8 Time- and Space-Resolved Operando Studies 26.9 Perspective References 27 X-Ray Absorption Spectroscopy (XAS): XANES and EXAFS 27.1 Introduction 27.2 Recent Technical Developments for Operando XAS Studies of Catalysts and Catalysis: The Induction of Highly Time-Resolved,... 27.2.1 Fast, Single-Shot, Fluorescence-Yield XAS Using a Passivated Implanted Planar Silicon (PIPS) Diode Detector [36] 27.3 Recent Selected Examples of Advanced Operando XAS 27.3.1 Advances in Spatially Resolved Operando XAS: From Single Metal Nanoparticles to Reactors and from Two- to Three- to Fou... One-Dimensional Spatial Investigation of Reactor Beds ``Nano-focus´´ XAS: Toward Interrogating Single Supported Nanoparticles 27.3.2 Operando XAS in Two and Three Dimensions Quantifying Changes in Iron Speciation in LiFePO4 Battery Materials Using XAS Imaging Operando Computed Tomography (CT) XANES of Structure and Speciation in Pt Cathodes in a PEM Fuel Cell 27.3.3 XAS on the Microseconds Timescale: Investigating Mechanisms of Photocatalysis 27.3.4 Electrochemistry/Catalysis: Novel Approaches to Combining XAFS with Electrochemical Techniques and Cells The Importance of Pd Hydride Phases and Pd-Based PEMFC Fuel Cells [99] The Role of Iron Dopants in Cobalt-Based Perovskite Catalysts in the Oxygen Evolution Reaction (OER) The Nature, Stability, and Reversibility of Active Iron Phases Under Conditions of Hydrogen Evolution (HER) 27.3.5 Combined XAS and Photo-Electro-Catalysis 27.3.6 Operando XAS Goes Soft 27.3.7 Operando Studies Using Laboratory XAS Instruments 27.4 Checks, Balances, and Outlook 27.5 Conclusions References 28 Time-Resolved X-Ray Absorption Spectroscopy (XAS) 28.1 Basic Concepts of X-Ray Spectroscopy 28.1.1 Interaction of X-Rays with Matter 28.1.2 The EXAFS Equation 28.2 The X-Ray Absorption Experiment 28.2.1 The X-Ray Source Synchrotron Radiation Sources Lab-Based X-Ray Absorption Spectroscopy Free Electron Lasers Soft Versus Hard X-Rays 28.2.2 Spectral Versus Time Resolution 28.2.3 Spatially Resolved X-Ray Absorption Spectroscopy 28.2.4 Choosing the Correct Experimental Mode 28.3 X-Ray Absorption Spectroscopy in Catalysis 28.4 Showcases from the Field of Heterogeneous Catalysis 28.4.1 Automotive Catalysis 28.4.2 Hydrogenation Catalysis 28.4.3 Electrocatalysis 28.4.4 Photocatalysis 28.5 Toward Ultrafast X-Ray Spectroscopy of Catalysts 28.6 Conclusions and Outlook References 29 Case Studies: Time-Resolved X-Ray Absorption Spectroscopy (XAS) 29.1 Introduction 29.2 Multivariate Curve Resolution with Alternating Least Square (MCR-ALS) Analysis 29.2.1 Basic Concepts 29.2.2 Rank Determination of Matrix D 29.2.3 Initial Estimates 29.2.4 Limitations: Deviation of the Bilinearity Model for Evolutionary Data Set Recorded in Temperature 29.2.5 Limitations: Rank Deficiency by Existing Correlated Data 29.3 How Time Resolution Can Give Insights on ``Birth, Life, and Death´´ of Solid Catalysts 29.3.1 Preparation of Catalysts: From Solution Processes to Solid-State Reactions Solution Preparation of Colloidal Particles Synthesis of Supported Catalysts Active-Phase Dispersion: Particle Size and Particle Density Metal Distribution: Formation of Undesirable Phases and Interaction with the Support Metal Distribution Within Bimetallic Particles 29.3.2 Catalysts in Operation: From Active Phases to Spent Catalysts Insights of Catalyst Structure and Composition vs Activity: A Lever for Process Optimization Catalyst Deactivation and Regeneration 29.4 Conclusion References 30 X-Ray Absorption Spectroscopy (XAS): Surface Structural Determination of Alloy Nanoparticles 30.1 Introduction 30.2 Surface XAS of Alloy Metal Nanoparticle Catalysts: Basic Approach 30.3 Case Study 1: Incomplete Formation of a Pt3Cr Surface Alloy 30.4 Case Study 2: Identification of the Evolution of the Core-Shell Structures 30.5 Case Study 3: Identification of Bimetallic Alloy Compositions Suitable for Determination of Electronic Changes by XANES o... 30.6 Summary References 31 Case Studies: Mapping Using X-Ray Absorption Spectroscopy (XAS) and Scattering Methods 31.1 Introduction 31.2 X-Ray Scattering-Based Imaging 31.3 X-Ray Absorption Spectroscopy-Based Imaging 31.4 X-Ray Coherent Diffraction Imaging 31.5 Conclusions References 32 X-Ray Microscopy and Tomography 32.1 Introduction 32.1.1 A Brief Overview of X-Ray Microscopy and Tomography 32.1.2 Limitations of Integral or Conventional Catalyst Characterization 32.1.3 Advantages of Spatially Resolved Catalyst Characterization 32.1.4 The Role of Hard X-Ray Microscopy and Tomography in Catalysis 32.2 Motivation and Scope of This Chapter 32.2.1 The Target Audience 32.2.2 The Learning Curve in XRM and X-Ray CT 32.2.3 Summary: Aims and Objectives 32.3 Characteristics of X-Ray Imaging Methods 32.3.1 Laboratory X-Ray Sources and Synchrotron Light Sources Characteristics of Synchrotron Radiation 32.3.2 Imaging in 2D vs. Tomography in 3D Principles of X-Ray Tomography Principles of Tomographic Reconstruction Common Tomographic Reconstruction Algorithms Scientific Resources for Tomography Data Image Data Outputs in 2D and 3D 32.3.3 Scanning Probe Imaging vs. Full-Field Imaging Full-Field Imaging Scanning Probe Imaging 32.3.4 Spatial Resolution and Length Scale Relevance of Spatial Resolution in Heterogeneous Catalysis 32.4 XRM in Catalysis: Molecular Information in Two and Three Dimensions 32.4.1 X-Ray Imaging Contrast Modes Absorption Contrast Imaging Fluorescence Contrast Imaging Energy-Resolved XAS Imaging Diffraction Contrast Imaging Phase Contrast Imaging 32.4.2 Comparing Hard XRM and X-Ray CT to Other Microscopies 32.5 Notable Current and Developing Hard X-Ray Imaging Methods 32.5.1 Advanced XANES Tomography 32.5.2 X-Ray Ptychographic Microscopy and Tomography 32.5.3 Toward In Situ and Operando Tomography 32.5.4 Fourth-Generation and Diffraction-Limited Synchrotron Radiation Sources 32.6 Conclusions and Outlook References 33 X-Ray Absorption Spectroscopy (XAS) Combined with Other Spectroscopic Techniques 33.1 Introduction 33.2 Examples 33.2.1 Study Case 1: XAS Combined with DRIFTS and MS 33.2.2 Study Case 2: XAS Combined with DRIFTS and MS 33.2.3 Study Case 3: XAS Combined with Transmission FT-IR and X-Ray Diffraction 33.3 Summary References Part VI: Magnetic Resonances 34 High-Field Nuclear Magnetic Resonance (NMR) Spectroscopy 34.1 A Brief Introduction of NMR for Catalyst Characterization 34.2 High-Field NMR and Quadrupolar Nuclei 34.3 High-Field 27Al MAS NMR 34.4 Vanadium Oxide Characterization 34.5 Energy Storage 34.6 Low-Natural Abundance, Low-Gamma Nuclei 34.7 Outlook References 35 Nuclear Magnetic Resonance (NMR): Modern Methods 35.1 Introduction 35.2 NMR of Catalyst Support Surfaces 35.3 HF NMR of Supported Catalysts 35.4 HF NMR of Zeolites 35.4.1 Framework Structure 35.4.2 Acidity 35.5 HF NMR for MOFs 35.5.1 Introduction 35.5.2 NMR of Pristine MOFs Metal Centers Organic Linkers 35.5.3 Multivariate Metal-Organic Framework Mixed Linkers Mixed Metals in the Framework Additional Metal Centers 35.5.4 NMR of Guest Molecules 35.6 Summary References 36 Nuclear Magnetic Resonance (NMR): Physisorbed Xenon for Porosity 36.1 Introduction 36.2 Hyperpolarized Xenon 36.3 Generalities 36.4 Zeolites 36.4.1 Zeolites with Only One Type of Pore. Influence of the Structure Experimental Results Determination of the Mean Free Path [33, 34] Influence of High Pressure Influence of Temperature Chemical Shift Anisotropy 36.4.2 Complex Structures and Mixtures of Zeolites Zeolites with Complex Structures Mixtures of Zeolites and with other Catalysts. Influence of the Structural Defects Kinetics of Zeolite Crystallization 36.4.3 Influence of Strong Adsorption Sites Theory Influence of Cations Alkali-Metal Cations Divalent and Trivalent Cations with d0 Electronic Structure Cations with dx Electronic Structure (x > 0) 36.4.4 Encumberment of Pores Nonframework Aluminum Poisoning of Catalysts: Coking 36.5 Other Microporous Materials 36.5.1 Polymers 36.5.2 Clays 36.5.3 Some Other Applications Heteropolyoxometalate Salts Porous Molecular Crystals Industry Archaeology Biosensors 36.6 Supported Metals 36.7 Mesoporous Solids 36.8 Electric Field Gradient (EFG) in Porous Solids: 131Xe NMR 36.9 Metal-Organic Framework (MOF) 36.9.1 Non-flexible MOFs 36.9.2 Flexible MOFs 36.10 Carbon Materials 36.11 Heterogeneous Catalysis 36.11.1 Chemical Properties of Some Solid Catalysts 36.11.2 Chemical Kinetics 36.11.3 Diffusion 36.12 Theory: Modeling of Xenon Adsorption, Diffusion and Chemical Shift 36.12.1 Xe Atom-Surface Interaction, δa 36.12.2 Lennard-Jones Potential Curves 36.12.3 Other Modelings 36.13 Conclusion 36.14 Symbols References 37 Magnetic Resonance Imaging (MRI) 37.1 Introduction 37.2 The MRI Technique 37.3 Homogeneous Versus Heterogeneous Catalysis 37.4 MRI/MRS of Operating Catalysts and Reactors 37.4.1 Liquid-Solid Processes 37.4.2 Gas-Liquid-Solid Processes 37.4.3 Gas-Solid Processes 37.4.4 Signal Enhancement in Reactions Involving H2 37.5 MRI Thermometry of Operating Catalysts and Reactors 37.6 Conclusions and Outlook References 38 Electron Paramagnetic Resonance (EPR) 38.1 Introduction 38.1.1 Theory 38.1.2 Hardware 38.1.3 Data Analysis 38.2 Strategies for In Situ EPR Studies 38.2.1 Spin Trapping 38.2.2 Spin Labeling and Isotopic Substitution 38.2.3 Metals and Free Radicals 38.2.4 Electrochemistry and EPR 38.3 The Future of In Situ EPR References 39 Case Studies: Time-Resolved Electron Paramagnetic Resonance (EPR) 39.1 Introduction 39.2 Opportunities and Challenges in In Situ EPR of Transition Metal Centers 39.3 Information from Analysis of EPR Spectra 39.4 Information from Time-Resolved EPR Spectral Intensity During In Situ Measurements 39.4.1 Cu-Zeolite 39.4.2 Vanadium in a Keggin-Type Polyoxometalate on Titania 39.5 Discussion 39.6 Conclusion References Part VII: Transient and Thermal Methods 40 Temporal Analysis of Product (TAP) 40.1 Introduction 40.2 Basic Experimental Concepts 40.2.1 Instrument Configuration 40.2.2 Experimental Concepts, Distinctions 40.3 Theoretical Tools for Extracting Kinetic Information from the Pulse Response 40.3.1 Collisions in a Diffusion Reactor 40.3.2 Reactor Transport: The Standard Diffusion Curve Active Zone Configurations Uniformity of the Gas and Solid in the Kinetic Measurement 40.3.3 Numerical Solution to Diffusion/Reaction Systems 40.3.4 Model-Free Analysis of Pulse Response Data Primary Analysis: Moment-Based Quantities Shekhtman Reactivities Time-Dependent Analysis of Rate and Concentration 40.4 Experimental Studies of TAP Catalyst Characterization 40.4.1 Coverage-Dependent Sticking Coefficients 40.4.2 Active Site Titration at Working Temperatures Titrating Sites with Irreversibly Adsorbing Species Screening Multiple Active Site Mixtures Heat of Adsorption, Counting Sites Where Adsorption Is Reversible 40.4.3 Mechanistic Features Adsorption Mechanism Competitive and Inhibited Adsorption Mars van Krevelen Mechanism General Reaction Model Analysis 40.4.4 Role of Dynamic Surface Species in Reaction Mechanism, Lifetime of Fast Surface Intermediates 40.4.5 The Pressure Gap 40.5 Conclusion References 41 Steady-State Isotopic Transient Kinetic Analysis (SSITKA) 41.1 Introduction 41.2 SSITKA Principle 41.3 SSITKA Modeling 41.3.1 Single Pool First-Order Irreversible Reaction 41.3.2 Multiple Pools in Series for a First-Order Irreversible Reaction 41.3.3 Multiple Pools in Parallel for a First-Order Irreversible Reaction 41.3.4 Reversible Reactions 41.4 Complicating Factors 41.4.1 Gas Phase Hold-Up, Readsorption, and Chromatographic Effect 41.5 Reactivity Distributions 41.5.1 Fitting to Exponential Functions (Parametric Approach) 41.5.2 Inverse Laplace Transform (ILT) Method 41.5.3 Tikhonov-Fredholm (T-F) Method 41.6 Reactors and Isotope Effects 41.7 Experimental Setup 41.8 Combination of SSITKA with Spectroscopic Methods 41.8.1 SSITKA-FTIR 41.8.2 SSITKA-Neutron Scattering 41.9 Other Considerations and Recent Developments 41.10 Applications 41.10.1 Discriminate Between Different Reaction Mechanisms 41.11 Examples of the Use of SSITKA 41.11.1 CO Hydrogenation on Al2O3-Supported Co Catalysts 41.11.2 The Use of Multicomponent SSITKA to Obtain Kinetic Parameters for Higher Hydrocarbons in CO Hydrogenation [8] 41.11.3 Surface Species and Mechanistic Studies by Combination of SSITKA and Kinetic Isotope Effect 41.11.4 Combing DFT and Transient and Steady-State Modeling to Study Reaction Mechanism of CO Hydrogenation 41.12 Examples of Combining SSITKA-DRIFT for WGS 41.13 Further Reading References 42 Modulation Excitation Spectroscopy (MES) 42.1 Introduction 42.2 Modulation and Phase-Sensitive Detection 42.3 Use and Interpretation of Phase-Resolved Data 42.4 Summary and Outlook References 43 Case Study 1: Modulation Excitation Spectroscopy (MES) 43.1 Introduction 43.2 State-of-the-Art Spectroscopic Studies on Selective Catalytic Reduction 43.3 Beyond the Steady-State: Advantages of Modulated Excitation 43.3.1 Amplification of Weak Signals and Resolution of Peaks 43.3.2 Discrimination Between Active and Responsive Sites 43.3.3 Detection of Intermediates Species 43.4 Considerations on the Selection of Modulation Experiment 43.5 Summary References 44 Case Study 2: Modulation Excitation Spectroscopy (MES) 44.1 Introduction 44.1.1 Biocatalyzed Kinetic Resolution of Racemic Profens with Lipases 44.1.2 Mechanism of the Enzymatic Kinetic Resolution of Racemic Profens 44.1.3 Experimental Evidences of the Acyl-Enzyme Intermediate 44.2 Experimental Setup 44.2.1 Materials 44.2.2 Attenuate Total Reflection Infrared Spectroscopy 44.2.3 Isotopic Exchange H-D of the Enzymes with D2O 44.2.4 MES Experiments 44.2.5 MCR-ALS Procedure 44.3 Results 44.3.1 Effect of the Nature of the Liquid Environment in the Secondary Structure of Lipases 44.3.2 MES-PSD Approach for the Molecular Recognition of an Acyl-Enzyme Intermediate 44.4 Conclusions and Future Perspectives References 45 Temperature-Programmed (TP) Techniques 45.1 Introduction 45.2 Description of Temperature-Programmed Methods 45.2.1 Theory 45.2.2 Benefits from Characterization of Catalysts 45.2.3 Limitations of Temperature-Programmed Techniques 45.2.4 Comparison of Method to Other Techniques 45.3 Description of Temperature-Programmed Instruments 45.3.1 Single Crystals 45.3.2 Powders 45.3.3 History 45.4 Applications to Catalyst Structure-Activity Relationships: Methods and Case Studies 45.4.1 Thermogravimetric Analysis (TGA) and Differential Thermogravimetric Analysis (DTG) 45.4.2 Temperature-Programmed Decomposition Thermal Decomposition of Silver Carbonate (Ag2CO3) Thermal Decomposition of Ammonium Metavanadate (NH4VO3) 45.4.3 Temperature-Programmed Oxidation (TPO) and Differential TPO 45.4.4 Temperature-Programmed Reduction (TPR) H2-TPR CO-TPR 45.4.5 Temperature-Programmed Desorption (TPD) NH3-TPD O2-TPD 45.4.6 Temperature-Programmed Surface Reaction (TPSR) Number and Types of Surface Sites (Ns) Supported Metal Oxide Catalysts Bulk Oxide Catalysts Bulk V2O5 Bulk MoO3 Bulk Nb2O5 Bulk TeO2 Bulk Mixed Oxides Bulk Fe2(MoO4)3 Mixed Oxide Source of Oxygen Involved in Oxidation Reactions Supported Metal Oxide Catalysts Bulk Mixed Oxide Catalysts Reaction Mechanisms Water-Gas Shift (WGS) Reaction (CO + H2O H2 + CO2) Selective Oxidation of C3H6 to C3H4O (Acrolein) Selective Catalytic Reduction (SCR) of NO with NH3 45.5 Summary/Conclusion/Future Outlook References 46 Calorimetry Techniques 46.1 Introduction 46.1.1 Operation Modes in Calorimetry Temperature Range Measurement Under Pressure Heating Rate Effective Sample Volume Sensitivity 46.1.2 General Calorimetry Applications Specific Heat Measurements Measurement of Reaction Heats 46.1.3 Measurement of Heats of Interactions 46.2 Differential Scanning Calorimetry (DSC) 46.2.1 Heat Flux DSC 46.2.2 Power Compensated DSC 46.2.3 Calvet DSC 46.2.4 Catalytic Applications of DSC and Coupled DSC/TGA Unit 46.3 Calorimetry-Volumetry (Gas Adsorption Calorimetry) 46.4 Liquid Phase Calorimetry 46.4.1 Titration Calorimetry Determination of Effective Acid-Base Properties Determination of Heat of Adsorption 46.4.2 Immersion Calorimetry 46.4.3 Reaction Calorimetry Isothermal Reaction Calorimeters Heat-Flow Reaction Calorimeter Heat-Balance Reaction Calorimeter Power-Compensation Reaction Calorimeter Peltier Reaction Calorimeter Isoperibolic Differential Reaction Calorimeter 46.5 Single Crystal Adsorption Calorimetry (SCAC) 46.6 Conclusions References 47 Case Study: Calorimetry 47.1 Introduction 47.2 Strength and Surface Density of Acid/Base Sites 47.3 Interaction of Reactants with the Surface 47.4 Turnover Frequencies 47.5 Transient Catalyst Behavior 47.6 Elucidating a Reaction Mechanism 47.7 Summary References Part VIII: Soft Operando 48 Chemometrics and Process Control 48.1 Why Chemometrics? 48.2 Mechanistic Methods 48.2.1 Basics of Mechanistic Methods 48.2.2 Workflow of Peak Integration Case 1: Carbonate Selectivity in CO2 Utilization 48.2.3 Workflow of Spectral Hard Modeling Case 2: Continuous Lithiation Reaction 48.2.4 Workflow of Univariate Calibration Case 2: Continued 48.3 Statistical Methods 48.3.1 Basics of Statistical Methods 48.3.2 Workflow of PLS Calibration Case 3: Nutrients, Metabolites, and Cell Parameters in Mammalian Cell Culture 48.4 Conclusion References Index