Edited by

Michel Che and Jacques C. Vedrine

Characterization of Solid Materials and

Heterogeneous Catalysts

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Edited by Michel Che and Jacques C. Védrine

Characterization of Solid Materials andHeterogeneous Catalysts

From Structure to Surface Reactivity

The Editors

Prof. Dr. Ing. Michel CheInstitut Universitaire de France andUniversité Pierre et Marie CurieLaboratoire de Réactivité de Surface4, Place Jussieu75252 Paris Cedex 05France

Prof. Dr. Ing. Jacques C. VédrineUniversité Pierre et Marie CurieLaboratoire de Réactivité de Surface4, Place Jussieu75252 Paris Cedex 05France

Please cite this document as follows:M. Che, J. C. Védrine: Characterization of SolidMaterials and Heterogeneous Catalysts - FromStructure to Surface Reactivity, Page(s). 2012.Copyright Wiley-VCH Verlag GmbH & Co. KGaA.Reproduced with permission.

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All rights reserved (including those of translationinto other languages). No part of this book may bereproduced in any form – by photoprinting, micro-film, or any other means – nor transmitted or trans-lated into a machine language without writtenpermission from the publishers. Registered names,trademarks, etc. used in this book, even when notspecifically marked as such, are not to be consideredunprotected by law.

Composition Thomson Digital, Noida, IndiaPrinting and Binding Strauss GmbH, MörlenbachCover Design Design Formgeber, Eppelheim

Printed in the Federal Republic of GermanyPrinted on acid-free paper

Print ISBN: 978-3-527-32687-7ePub ISBN: 978-3-527-64533-6ePdf ISBN: 978-3-527-64534-3mobi ISBN: 978-3-527-64535-0oBook ISBN: 978-3-527-64532-9oBook ISBN:

For our mentor Dr. Boris Imelik, and our Families

Contents

About the Editors XXVIIList of Contributors XXIX

Preface XXXVMichel Che and Jacques C. VédrineGeneral Introduction XXXIXMichel Che and Jacques C. Védrine

Overview on Physical Techniques for InvestigatingModel Solid Catalysts LIIIGerhard ErtlOverview on Physical Techniques for InvestigatingPorous Catalysts LXIIIJohn Meurig Thomas

Part One Molecular/Local Spectroscopies 1

1 Infrared Spectroscopy 3Frédéric Thibault-Starzyk and Françoise Maugé

1.1 Introduction 31.2 Principles of IR Spectroscopy and Basic Knowledge for Its Use 31.2.1 IR Light 31.2.2 Matter–Radiation Interaction 41.2.3 Spectrometry, Interferometry 41.2.4 Limitations of and Problems with the Fourier Transform 61.3 Experimental Considerations 71.3.1 Technical Aspects of the Fourier Transform 71.3.2 Practical Implementation 81.3.2.1 Transmission Experiments, Quantitative Aspects 81.3.2.2 Diffuse Reflection 91.4 Use of IR Spectroscopy to Characterize Solids 111.4.1 IR Spectrum and Structure of a Solid 11

VII

1.4.1.1 The Example of Zeolites 111.4.1.2 Substitution of Metals in the Structure of Zeolites 131.4.2 Activation: Cleaning the Sample to Observe Surface Sites 131.4.2.1 Experimental Aspects 131.4.2.2 Activation – Cleaning the Sample to Observe Surface Sites 141.4.3 The Spectrum of OH Groups 171.4.3.1 OH Groups on Alumina 181.4.3.2 OH Groups in Zeolites 181.4.4 Characterization of Acidity with Probe Molecules 201.4.4.1 Brønsted Sites: Hydrogen Bonding and IR Spectroscopy 211.4.4.2 Molecular Probes for Lewis Acidity 241.4.4.3 Common Probe Molecules for Acidity 241.4.5 Characterization of Basicity with Probe Molecules 321.4.5.1 CO2 as a Probe for Basic Sites 321.4.5.2 Protic Molecules 331.4.5.3 Methanol 331.4.6 Probes for Supported Metal Catalysts 341.4.7 Probes for Sulfide Catalysts 361.4.8 Quantitative Analysis by Coupling IR Spectroscopy with Gravimetry 381.5 Application to Surface Reactivity: Operando Spectroscopy 391.5.1 Experimental Setup for Operando IR Spectroscopy and Reactions

Conditions 401.5.2 Examples of Operando IR Measurements 401.6 Conclusion 45

References 45

2 Raman and UV-Raman Spectroscopies 49Fengtao Fan, Zhaochi Feng, and Can Li

2.1 Introduction 492.1.1 Raman Spectroscopy 492.1.2 FT-Raman Spectroscopy 512.1.3 UV Raman Spectroscopy 532.1.4 Resonance Raman Spectroscopy 532.2 Characterization of Active Sites and Phase Structure ofMetal Oxides 552.2.1 Identification of the Active Species on Metal Oxides 552.2.2 Phase Transformation in the Surface Region of Metal Oxides 562.3 Characterization of Surface Metal Oxide Species on Supported

Metal Oxides 592.4 Electron–Phonon Coupling in Nanostructured Materials 632.5 Characterization of sp2 Carbon Materials 642.6 Characterization of Transition Metal-Containing Microporous

and Mesoporous Materials 672.6.1 Identification of the Isolated Quadrivalent Transition Metal

Sites in Microporous and Mesoporous Materials 672.6.2 Identification of the Isolated Trivalent Transition Metal Sites

in Microporous and Mesoporous Materials 69

VIII Contents

2.6.3 Identification of Extra-Framework Active Sites in Microporousand Mesoporous Materials 71

2.7 Synthesis Mechanisms of Molecular Sieves 732.7.1 Assembling Zeolites from Prefabricated Units 732.7.2 Assembling Fe-ZSM-5 fromActive Centers and Silicate Building Units 742.7.3 A Real-Time Probing for the Crystallization Process: In Situ

Raman Spectroscopy 762.8 Conclusions 80

References 81

3 Electronic Spectroscopy: Ultra Violet-visible and Near IRSpectroscopies 89Friederike C. Jentoft

3.1 Introduction and Overview 893.1.1 Scope 893.1.2 History 893.1.3 Overview 913.2 UV–vis–NIR Spectra 933.2.1 Spectra Representation 933.2.1.1 Spectral Position of Absorption Features 933.2.1.2 Intensity of Absorption Features 933.2.2 Spectra Processing 983.2.3 Transitions in Molecular Species 993.2.3.1 Selection Rules 993.2.3.2 Individual Molecules 993.2.3.3 Composite Species: Metal Complexes 1013.2.4 Transitions in Extended Solid Structures 1043.2.4.1 Bandgaps 1043.2.4.2 Metallic Colloids: Localized Surface Plasmon Resonance 1063.2.5 Quantitative Analysis 1073.3 Experimental Considerations 1083.3.1 Instrumentation: Spectrometers, Sources, and Detectors 1083.3.1.1 Overview of Essential Instrument Components 1083.3.1.2 Instrument Selection Criteria for Measurements of Solids 1103.3.2 Optical Configuration and Cells for Controlled

Environments 1103.3.2.1 Transmission Mode 1113.3.2.2 Cells for Use in Transmission Mode 1113.3.2.3 Diffuse Reflection Mode: Integrating Spheres 1123.3.2.4 Cells for Use with Integrating Spheres 1133.3.2.5 Diffuse Reflection Mode: Mirror Optics 1153.3.2.6 Cells for Use with Mirror Optics Attachment 1163.3.2.7 Diffuse Reflection Mode: Fiber-Optic Probes 1173.3.2.8 Cells for Use with Fiber-Optic Probes 1183.3.2.9 Combination of UV–vis–NIR with Other Techniques 1193.4 Formation and Alteration of Solids 120

Contents IX

3.4.1 Precursor Analysis 1203.4.2 Solid Formation 1213.4.3 Characterization of Solids 1223.4.3.1 Isomorphous Substitution of Framework Cations in Zeolites 1233.4.3.2 Ion Exchange in Zeolites 1243.4.3.3 Dispersion of Supported Metal Oxide Species 1253.4.3.4 Bandgap Determination in Semiconductors 1253.4.3.5 Spatially Resolved Spectroscopy of Specimens with Compositional

Variation on the Millimeter Scale 1273.4.3.6 Spatially Resolved Spectroscopy of Specimens with Compositional

Variation on the Micrometer Scale 1273.4.4 Probing of Surface Properties 1293.4.5 Dynamic Experiments 1293.4.5.1 Dehydration 1293.5 Surface Reactivity and Catalysis 1303.5.1 Oxidation State and Coordination Changes 1303.5.1.1 Oxidation State of Transition Metals in Supported MOx

Moieties or Solid Solutions 1303.5.1.2 Supported Metals: Oxidation State and Particle Size

and Shape 1313.5.2 Hydrocarbon Species on Surfaces 1333.5.2.1 Reference Spectra 1333.5.2.2 Surface Hydrocarbon Pool Under Reaction

Conditions 1373.5.2.3 Deactivation and Regeneration 1383.6 Conclusions 139

References 140

4 Photoluminescence Spectroscopy 149Masaya Matsuoka, Masakazu Saito, and Masakazu Anpo

4.1 Introduction 1494.2 Basic Principles of Photoluminescence 1504.3 General Aspects of Photoluminescence Measurements 1534.3.1 Steady-State Photoluminescence Measurements 1534.3.2 Time-Resolved Photoluminescence Measurements 1544.4 Characterization of Catalysts by Photoluminescence and

Time-Resolved Photoluminescence Spectroscopy 1564.4.1 In Situ Photoluminescence of Microcrystalline MgO 1564.4.2 In Situ Photoluminescence of Bulk TiO2 Photocatalysts 1594.4.3 In Situ Photoluminescence of Highly Dispersed Transition Metal

Ions and Oxides 1634.4.3.1 V-Containing BEA Zeolite Catalysts 1634.4.3.2 Ag+/MFI Catalysts 1654.5 Investigations of the Dynamics of Photocatalysis by Time-Resolved

Photoluminescence Spectroscopy 165

X Contents

4.5.1 Dynamics of Photocatalytic Reactions on TiO2

Photocatalysts 1664.5.2 Dynamics of Photocatalytic Reactions on Highly Dispersed

Transition Metal Ion and Oxide Catalysts 1694.5.2.1 Cu+/Zeolite Catalysts 1694.5.2.2 Ti Oxide/Zeolite Catalysts 1754.5.2.3 Mo Oxide/SiO2 Catalysts 1774.6 Conclusion 182

References 182

5 Neutron Scattering 185Hervé Jobic

5.1 Introduction 1855.2 Introduction to the Theory 1865.2.1 Properties of Neutrons 1865.2.2 Scattering Cross-Sections 1875.2.3 Coherent and Incoherent Scattering 1885.3 Experimental 1905.4 Structure 1925.5 Dynamics 1945.5.1 Vibrational Spectroscopy 1955.5.2 Diffusive Motions 1975.5.2.1 Neutron Spin-Echo Technique 1985.5.2.2 Rotational Motion 2015.5.2.3 Translational Motion 2025.6 Conclusion 208

References 208

6 Sum Frequency Generation and Infrared Reflection AbsorptionSpectroscopy 211Karin Föttinger, Christian Weilach, and Günther Rupprechter

6.1 Introduction 2116.2 Theoretical Background of SFG 2136.2.1 SFG Signal Intensity and Selection Rules 2156.2.2 Surface Concentration (Coverage) and SFG Signal Intensity 2166.3 Spectrometer Setup 2176.3.1 Modes of Operation 2186.4 Case Studies 2216.4.1 Metal Single-Crystal Surfaces 2216.4.2 Bimetallic Surfaces 2286.4.3 Oxide Surfaces 2336.4.4 Metal Nanoparticles on Oxide Surfaces 2406.5 Conclusion 245

References 245

Contents XI

7 Infra Red Reflection Absorption Spectroscopy and PolarisationModulation-IRRAS 255Christophe Méthivier and Claire-Marie Pradier

7.1 Introduction 2557.1.1 Some History 2567.2 Principle of IRAS 2587.3 Principle of PM-IRAS 2617.4 Applications of IRAS and PM-IRAS 2637.4.1 Formation of Self-Assembled Monolayers 2637.4.2 Adsorption of Organic Small Molecules and Chirality 2667.4.3 Monitoring Surface Reactivity and Catalysis 2687.4.3.1 Oxidation of CO on Ru 2687.4.3.2 CO hydrogenation on Ru 2707.4.3.3 Vinyl Acetate Synthesis Reaction on Pd 2707.4.3.4 Oxidation of NH3 and reduction of N2O by NH3 on Cu 2727.4.3.5 Decomposition of Methanol on Pd 2757.4.3.6 Dissociation of NO on Rh 2757.4.3.7 Reactivity/Storage of NO on Metal and Oxide Surfaces 2777.4.4 Surface Functionalization and Elaboration of Sensors 2817.4.5 PM-IRAS in the Liquid Phase 2827.5 Conclusion 285

References 286

8 Nuclear Magnetic Resonance Spectroscopy 289Lynn F. Gladden, Michal Lutecki, and James McGregor

8.1 Introduction and Historical Perspective 2898.2 Theory 2918.2.1 Basic Principles of NMR 2918.2.1.1 Zeeman Interaction 2928.2.1.2 Dipolar Interaction 2928.2.1.3 Chemical Shift Interaction 2938.2.1.4 Quadrupolar Interaction 2938.2.1.5 Indirect Electron Coupled Interaction 2948.2.2 Relaxation Times 2948.2.3 Application of Magnetic Field Gradients 2958.2.3.1 Magnetic Resonance Imaging 2958.2.3.2 Measuring Flow and Diffusion 2968.3 Popular NMR Techniques for Studying Solids 2978.3.1 General Techniques for Bulk and Surface Characterization 2988.3.2 Studying Quadrupolar Systems with I > 1/2 2998.3.3 Techniques for Measuring Heteronuclear Dipolar Couplings 3008.4 Characterization of Heterogeneous Catalysts 3028.4.1 Silica- and Alumina-Containing Materials 3038.4.1.1 Pure Silicas and Aluminas 3038.4.1.2 Zeolites and Aluminosilicates 304

XII Contents

8.4.2 Vanadium-Containing Materials 3058.4.3 Surface Acidity and Basicity 3068.5 Porosity, Adsorption, and Transport Processes 3088.5.1 Porosity 3088.5.1.1 129Xe NMR 3088.5.1.2 T1 and T2 Relaxometry 3098.5.1.3 Magnetic Resonance Imaging 3108.5.2 Adsorption 3118.5.3 Diffusion 3128.6 ‘‘In Situ’’ NMR 3138.6.1 Experimental Apparatus 3148.6.1.1 Batch Conditions 3148.6.1.2 Flow Conditions 3158.6.2 Applications 3178.6.2.1 Batch Conditions 3178.6.2.2 Flow Conditions 3228.6.2.3 Coupling with a Second Technique 3258.7 Towards ‘‘Operando’’ Studies 3298.8 Conclusion and Outlook 331

References 332

9 Electron Paramagnetic Resonance Spectroscopy 343Piotr Pietrzyk, Zbigniew Sojka, and Elio Giamello

9.1 Introduction 3439.1.1 Interaction of Matter with a Magnetic Field 3439.1.2 Experimental Approaches in EPR 3449.2 Principles of EPR 3459.2.1 The Zeeman Effect and the Resonance Phenomenon 3469.2.2 Spin Resonance and Spin Relaxation 3489.3 Electron–Nucleus Hyperfine Interaction 3509.3.1 The Hydrogen Atom (S ¼ 1/2 and I¼ 1/2) 3539.3.2 Hyperfine Interaction in Polynuclear Systems 3559.4 Experimental Background 3569.5 Anisotropy of Magnetic Interactions in EPR: the g, A, and D

Tensors 3599.5.1 The g Tensor 3619.5.2 The A Tensor 3629.5.3 The Electron–Electron Interactions in S > 1/2 Systems: The D

Tensor 3639.5.4 The Spin-Hamiltonian 3669.6 EPR Spectra and the Solid State: Single Crystal Versus Powders 3669.6.1 Powder EPR Spectra 3679.7 Guidelines to Interpretation of EPR Spectra 3689.7.1 Classification of EPR Spectra and Determination of Spectral

Parameters 368

Contents XIII

9.7.2 Unusual Spectral Features and Puzzling Lineshapes 3729.7.3 Dynamic Lineshape Effects and Partially Averaged Signals 3769.8 Computer Simulation of Powder Spectra 3789.9 Molecular Interpretation of Parameters 3809.9.1 g-Tensor 3809.9.2 Hyperfine Tensor 3839.10 Quantum Chemical Calculations of Magnetic

Parameters 3869.11 Advanced EPR Techniques 3889.11.1 Electron Spin Echo-Based Techniques 3889.12 Characteristics of EPR Techniques in Application to Catalysis

and Surfaces 3899.12.1 Distinction Between Surface and Bulk Species 3909.12.2 Poorly Resolved Spectra – Multifrequency Approach 3929.12.3 Overlapping Signals 3949.12.4 Strain Broadening and Smearing of Features with High

Angular Anisotropy 3959.12.5 Use of Probe Molecules and Spin Labels 3969.13 Interfacial and Surface Charge-Transfer Processes 3989.14 In Situ and Operando EPR Techniques 3999.15 Conclusions and Prospects 403

References 403

10 Mössbauer Spectroscopy 407Lorenzo Stievano and Friedrich E. Wagner

10.1 Introduction 40710.2 The Mössbauer Effect 40910.3 Radiation Source 41110.4 Mössbauer Absorbers 41410.5 Hyperfine Interactions 41410.5.1 Electric Monopole Interaction 41510.5.2 Magnetic Dipole Interaction 41710.5.3 Electric Quadrupole Interaction 41910.6 Experimental Setups 42110.6.1 Transmission Mössbauer Spectroscopy 42110.6.2 Surface-Sensitive Mössbauer Spectroscopy 42210.6.3 Emission Mössbauer Spectroscopy 42310.7 Evaluation of Experimental Data 42410.7.1 Spectra Folding 42410.7.2 Spectra Fitting 42410.8 Theoretical Calculation of Mössbauer Parameters 42610.9 Common Mössbauer-Active Transitions 42710.9.1 The 14.4keV Mössbauer Transition of 57Fe 42710.9.2 The 89.4 keV Mössbauer Transition of 99Ru 42910.9.3 The 23.9 keV Mössbauer Transition of 119Sn 430

XIV Contents

10.9.4 The 37.1 keV Mössbauer Transition of 121Sb 43210.9.5 The 73.0 keV Mössbauer Transition of 193Ir 43210.9.6 The 77.3 keV Mössbauer Transition of 197Au 43310.10 Survey of Applications of the Mössbauer Effect in the

Study of Catalytic Materials 43410.10.1 197Au Mössbauer Spectroscopy in the Study of Gold

Catalysts 43510.10.1.1 Electronic Properties: Au/Al2O3 Oxidation Catalysts 43510.10.1.2 Determination of Chemical Composition: Supported

AuPd Alloys 43610.10.1.3 Determination of Lamb–Mössbauer f-Factors for Quantitative

Analyses: Au/Activated Carbon Catalysts for the Hydrochlorinationof Acetylene 437

10.10.1.4 Identification of Surface Species: Gold Nanoparticles Embeddedin Mylar 438

10.10.2 57Fe Mössbauer Spectroscopic Study of Iron-Containing Catalysts 43910.10.2.1 Superparamagnetism and the Determination of Particle Sizes:

Fe/C Catalysts for CO Hydrogenation 44010.10.2.2 In Situ Measurements: Iron-Based Fischer–Tropsch Catalysts 44310.10.2.3 Emission Mössbauer Spectroscopy: Cobalt-Based Fischer–Tropsch

Catalysts 44410.10.3 119Sn Mössbauer Study of Bimetallic Tin-Containing Catalysts 44610.11 Conclusion 447

References 448

11 Low Energy Ion Scattering and Secondary Ion Mass Spectrometry 453Norbert Kruse and Sergey Chenakin

11.1 Introduction 45311.2 Secondary Ion Mass Spectrometry 45711.2.1 Basic Principles 45711.2.2 Potential of SIMS 45911.3 Low-Energy Ion Scattering (Ion Scattering Spectroscopy) 46111.3.1 Main Concepts 46111.3.2 Potentialities of LEIS 46311.4 Single-Crystal and Polycrystalline Metal Surfaces 46511.4.1 Surface Defects and Adsorption of Simple Molecules 46511.4.2 Adsorption of Organic Molecules 46911.4.3 Oxidation and Corrosion 47011.5 Amorphous Metallic Alloys 47211.6 From Model to Real Catalysts 47411.6.1 Structural Effects 47411.6.2 Dispersion Effects 47711.6.3 Preparation and Activation Effects 48011.6.4 Compositional Effects in Various Catalytic Reactions 48411.6.4.1 CO Hydrogenation 484

Contents XV

11.6.4.2 Hydrocarbon Oxidation 48611.6.4.3 Hydrogenation and Oxidative Dehydrogenation 48911.6.5 Promotion and Poisoning Effects 48911.6.5.1 CO Hydrogenation to Methanol 49011.6.5.2 CO Oxidation 49011.6.5.3 Hydrocarbon Partial and Total Oxidation 49211.6.5.4 Cracking 49411.6.5.5 Beckmann Rearrangement 49411.6.5.6 Aldose Oxidation 49511.6.5.7 Nitrite and Nitrate Reduction 49511.6.5.8 Cl-Related Effects in Various Reactions 49611.6.6 Active Sites 49711.7 Conclusion 501

References 502

12 X-ray Absorption Spectroscopy 511Christophe Geantet and Christophe Pichon

12.1 Introduction 51112.2 History of X-Ray Absorption Spectroscopy 51112.3 Principle of X-Ray Absorption Spectroscopy: XANES, EXAFS 51212.4 Experimentation and Data Processing 51512.5 Application to Oxide Materials 52112.6 Applications to the Study of Sulfide Catalysts 52412.6.1 Structure of the Active Phase 52412.6.2 Activation of Sulfide Catalysts 52512.7 Application to Metal Catalysts 52712.7.1 Structure and Size of (Bi-)Metallic Particles 52812.7.2 Evolution of the Bimetallic Structure Under Reaction or Poisoning

Conditions 53012.8 Conclusion and Perspectives 533

References 534

13 Auger Electron, X ray and UV Photoelectron Spectroscopies 537Wolfgang Grünert

13.1 Introduction 53713.1.1 The Relation Between XPS, UPS, and AES 53713.1.2 A Glimpse at History 53913.2 Sources of Analytical Information 54013.2.1 XPS Binding Energies 54013.2.1.1 Parameters Affecting XPS Binding Energies 54013.2.1.2 Theoretical Prediction of XPS Binding Energies 54513.2.1.3 Practical Aspects 54713.2.2 The Analytical Potential of XPS Lineshapes 54813.2.2.1 Spin–Orbit Splitting 548

XVI Contents

13.2.2.2 Charge Transfer Satellites 54913.2.2.3 Other Shake-Up Type Satellites 55013.2.2.4 Multiplet Splitting 55113.2.3 Surface Sensitivity: Working with XPS Intensities 55313.2.3.1 Homogeneous and Inhomogeneous Sampling Region 55313.2.3.2 Increasing the Surface Sensitivity of XPS 55713.2.3.3 Determining XPS Intensities – Lineshapes and Signal

Backgrounds 56013.2.4 XAES and XPS – Structural Sensitivity via the

Auger Parameter 56213.2.5 Ultraviolet Photoelectron Spectroscopy 56513.2.6 XPS and Other Methods 56613.3 Instrumentation 56713.3.1 Conventional XPS 56713.3.2 Lateral Resolution, Imaging 56913.3.3 Ambient-Pressure Photoelectron Spectroscopy (APPES) 57013.4 Case Studies 57113.4.1 Combination of Methods: Strong Metal–Support Interaction in a

Ag/TiO2 Catalyst 57113.4.2 Depth Resolution: the Surface Composition of Stoichiometric

Bulk Mixed Vanadates and Molybdates 57313.4.3 APPES: on the Doorstep of a New Age of XPS 57413.5 Outlook 578

References 579

14 Single Molecule Spectroscopy 585Timo Lebold, Jens Michaelis, Thomas Bein, and Christoph Bräuchle

14.1 Introduction 58514.2 Description of the Method 58614.3 Experimental Considerations and Constraints 59114.4 Mesoporous Silica Materials 59214.5 Selected Studies 59314.5.1 Correlating Dynamic and Structural Information by Combining

Single-Molecule Microscopy and High-Resolution TransmissionElectron Microscopy 593

14.5.2 Analyzing the Diffusion Dynamics Within a Silica Mesopore withOne-Channel Accuracy Using Single-Molecule Microscopy andSingle-Particle Tracking 595

14.5.3 Analyzing Orientational and Spectral Dynamics at AdsorptionSites Inside a CTAB Templated Thin Mesoporous Silica Film 598

14.5.4 Visualization of the Mechanisms Governing the StructureFormation of Mesoporous Silica Nanochannels 601

14.6 Conclusion 605References 605

Contents XVII

Part Two Macroscopic Techniques 609

15 X-Ray Diffraction and Small Angle X-Ray Scattering 611Malte Behrens and Robert Schlögl

15.1 Introduction 61115.2 Theoretical Background of X-Ray Diffraction 61215.2.1 Fundamentals of X-Ray Diffraction 61215.2.2 Crystallography 61415.2.3 Powder X-Ray Diffraction 61615.2.4 Information Content of a Powder X-Ray Diffraction Pattern 61815.3 Experimental Aspects 61915.3.1 Practical Aspects 62215.4 Application to Phase Identification 62315.4.1 Identification Using Reference Compounds and Structure Databases 62315.4.2 Quantification of Phase Mixtures 62615.4.3 Effects of Anisotropy and Preferred Orientation 62815.5 Application to Phase Characterization: Ideal Structure 62915.5.1 Structure Refinement 62915.6 Application for Phase Characterization: Real Structure 63515.6.1 Crystalline Domain Size and Shape 63515.6.2 Lattice Strain and Separation of Size and Strain Effects 63915.7 X-Ray Diffraction of Catalysts in a Reactive Atmosphere 64215.8 Small-Angle X-Ray Scattering (SAXS) 64415.8.1 Fundamentals 64415.8.2 Experimental Aspects 64615.8.3 Application in Catalysis 64715.9 Conclusion 648

References 650

16 Transmission Electron Microscopy 655John Meurig Thomas and Caterina Ducati

16.1 History and Overview 65516.2 Introduction 65816.2.1 Why Electrons? 65816.2.2 Electron Microscopy in Transmission 65916.2.3 Basic TEM Techniques 66016.2.4 High-Resolution Transmission Electron Microscopy (HRTEM) 66116.2.5 High-Resolution Scanning Transmission Electron

Microscopy (HRSTEM) 66416.2.6 High-Precision Composition Analysis in the Electron Microscope 66516.2.7 Electron Energy-Loss Spectroscopy (EELS) and Energy-Filtered

TEM (EFTEM) 66516.2.8 Electron Crystallography 66616.2.9 Electron Tomography 66816.3 Specimen Preparation and Experimental Considerations 669

XVIII Contents

16.4 Examples of General Characterization Studies 67016.5 Examples of Reactivity and Catalysis Studies 68116.5.1 Clarifying the Nature and Designing Superior Supported

Oxide-on-Oxide, Solid-Acid Catalysts. The Case of WOx on ZrO2 68416.5.2 Oxygen Storage and Automobile Exhaust Catalysts 68516.5.3 Pt–Al2O3 Hydrogenation Catalysts 68616.5.4 Time-Resolved In Situ Studies of Catalysts by Electron Microscopy 68716.6 Recent Developments and Future Prospects 69316.6.1 4D Electron Microscopy 694

References 697

17 Scanning Probe Microscopy and Spectroscopy 703Tomoaki Nishino

17.1 Introduction 70317.2 Scanning Tunneling Microscopy 70517.2.1 Principle 70517.2.2 Catalytic Model Systems 70817.2.2.1 Adsorption 70817.2.2.2 Diffusion 70917.2.2.3 Surface Reactions 71117.2.2.4 High-Pressure Environment 71617.2.3 Solid–Liquid Interfaces 71917.2.3.1 Surface Reconstruction 72117.2.3.2 Specifically Adsorbed Anions 72117.2.3.3 Molecular Adsorbates 72317.2.4 Chemical Selectivity 72717.2.4.1 Molecular Tip 72717.2.4.2 Inelastic Tunneling Spectroscopy 73117.3 Atomic Force Microscopy 73417.3.1 Principle and Operation Modes 73417.3.1.1 Imaging Solid Surfaces and Single Adsorbates 73517.3.2 High-Speed Imaging 73817.3.3 Kelvin Probe Force Microscopy 73917.4 Conclusion 740

References 741

18 Thermal Methods 747Adrien Mekki-Berrada and Aline Auroux

18.1 Main Thermal Methods 74718.1.1 Short History of Thermal Measurement 74718.1.2 Differential Thermal Analysis (DTA) 74918.1.2.1 Principle 75018.1.2.2 Data Processing 75018.1.2.3 Examples 75118.1.3 Differential Scanning Calorimetry (DSC) 752

Contents XIX

18.1.3.1 Principle 75318.1.3.2 Data Processing 75318.1.3.3 Example 75618.1.4 Thermogravimetry or Thermogravimetric Analysis (TGA) 75718.1.4.1 Principle 75818.1.4.2 Data Processing 75818.1.4.3 Examples 75918.1.5 Thermogravimetric Analysis Coupled with Calorimetry

(TGA–DTA, TGA–DSC) 76118.1.5.1 Principle 76318.1.5.2 Examples 76318.1.6 Calorimetry 76518.1.6.1 The Tian–Calvet microcalorimeter 76618.1.6.2 Calorimetry–Volumetry 76918.1.6.3 Isoperibolic Calorimeter, Liquid Flow Calorimeter, Titration

Calorimeter, and Solid–Liquid Calorimetry 77118.1.6.4 Power-Compensated Calorimeter 77718.1.7 Temperature-Programmed Desorption (TPD) 77718.1.8 Temperature-Programmed Reduction andOxidation (TPR and TPO) 78218.1.8.1 Principle 78218.1.8.2 Data Processing 78318.1.8.3 Example 78318.1.9 Temperature-Programmed Surface Reaction (TPSR) 78518.1.9.1 Principle 78518.1.9.2 Data Processing 78618.1.9.3 Example 78618.2 Acidity/Basicity 78718.2.1 Acid–Base Properties of Solids 78718.2.2 Adsorption Techniques 78918.2.2.1 Volumetry–Microcalorimetry 78918.2.2.2 Adsorption Thermogravimetry–Calorimetry (TG–DSC) 79118.2.2.3 Adsorption Calorimetry–Mass Spectrometry 79218.2.2.4 Other Coupled Methods for Adsorption Calorimetry 79418.2.3 Desorption Techniques 79418.2.3.1 Temperature-Programmed Desorption followed by Mass Spectrometry

(TPD–MS) 79518.2.3.2 Thermogravimetry–Mass Spectrometry (TG–MS) 79518.2.3.3 Thermogravimetry–Calorimetry–Mass Spectrometry (TG–DSC–MS,

TG–DTA–MS) 79618.2.3.4 Other Coupled Methods (TPD–TCD, TPD–IR–MS, etc.) 79818.2.4 Acid–Base Properties of Common Catalysts 79918.2.4.1 Zeolites and Molecular Sieves 79918.2.4.2 Metal Oxide Catalysts 80518.2.4.3 Heteropolyacids 81618.3 Redox Properties of Solids 818

XX Contents

18.3.1 Characterization Techniques 81918.3.1.1 Characterization by TPR/TPO 81918.3.1.2 TPD of Redox Probes 82218.3.1.3 Adsorption Calorimetry of Redox Probes 82318.3.1.4 ‘‘Surface’’ Techniques (RFC, s-TPR) in Redox Studies 82518.3.2 Case Study of DeNOx Investigations with Thermal Methods 82518.3.2.1 Selective Catalytic Reduction (SCR) of NOx by Various Reductants 82718.3.2.2 Tuning the Surface Properties with Thermal Methods for DeNOx 83118.4 Conclusion 841

References 842

19 Surface Area/Porosity, Adsorption, Diffusion 853Philip L. Llewellyn, Emily Bloch, and Sandrine Bourrelly

19.1 Introduction 85319.2 Gas Adsorption for the Characterization of Surface Area and

Porosity 85419.2.1 What is Adsorption, Why and How Do Gases Adsorb? 85419.2.2 How Do We Measure and Represent Adsorption Isotherms 85719.2.2.1 Different Adsorption Devices 85719.2.2.2 Experimental Protocol 85819.2.3 How Do We Interpret These Isotherms to Estimate Various Porous

Solid Characteristics 86419.2.3.1 Evaluation of the Isotherm Type and Shape 86419.2.3.2 Evaluation of Specific Surface Area Using the BET Model 86619.2.3.3 Evaluation of the External Surface Area and Pore Volume Using

the t and �S Methods 86819.2.3.4 Evaluation of the Micropore Size: Horwath–Kawazoe 87119.2.3.5 Evaluation of Both Micropore and Mesopore Size Using

DFT/GCMC Treatment and Isotherm Reconstruction 87219.3 Diffusion in Porous Solids 87319.3.1 Some Notions of Diffusion 87419.3.2 Experiments Allowing the Measurement of Diffusion Constants 87519.3.2.1 Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR) 87519.3.2.2 Quasi-Elastic Neutron Scattering 87619.3.2.3 Zero Length Column (ZLC) 87619.3.2.4 Optical Impedance Spectroscopy 87619.4 Conclusion 877

References 878

Part Three Characterization of the Fluid Phase (Gas and/or Liquid) 881

20 Mass Spectrometry 883Sandra Alves and Jean-Claude Tabet

20.1 Linked Atom Theory and the Mass Spectrometry Stories: thePremises of Modern Mass Spectrometry Technology 883

Contents XXI

20.2 Basics of Mass Spectrometry 88920.2.1 Experimental Parameters for a High-Quality Mass Spectrum 88920.2.2 Spectacular Developments of Sources for Nonvolatile Materials 89120.2.2.1 In-Vacuum Ionization Techniques 89120.2.2.2 Atmospheric Pressure Ionization Techniques 89820.2.2.3 Combined Ionization Techniques 90020.3 Direct Surface Analysis: ImagingMass Spectrometry for Biologists 90120.3.1 State-of-the-Art of ImagingMass Spectrometry Technology for Biological

Applications: In-Vacuum Desorption Techniques 90320.3.1.1 Highly Resolved SIMS Images 90420.3.1.2 MALDI for Highly Selective Peptide/Protein Profiles 90520.3.2 New Perspectives for Imaging Mass Spectrometry Technology 90720.3.2.1 Mass Spectrometry Technology Development 90720.3.2.2 Imaging Mass Spectrometry Under Ambient Conditions 90820.4 From Collision Activation to Ion–Surface Chemical Reactions for

New Preparative Mass Spectrometry 91020.4.1 Surface-Induced Dissociation 91020.4.1.1 Tandem Mass Spectrometry and Collisional Activation 91020.4.1.2 Mass Spectrometers for SID Experiments 91220.4.1.3 From Surface-Induced Dissociations to Competing Ion–Surface

Reactions 91320.4.2 Soft Landing and Preparative Mass Spectrometry 91520.4.2.1 Soft Landing Instrumental Devices 91520.4.2.2 Applications of Preparative Mass Spectrometry 91820.5 Petroleomics: Role of Ultra-High Resolution and Data Treatment 92220.5.1 Ultra-High Resolution Mass Spectrometry for Complex Petroleum

Samples 92320.5.1.1 Accurate Mass Measurement 92420.5.1.2 Data Graphical Representations 92520.5.2 Improvements to Mass Spectrometry Methodology 92820.5.3 HRMS Analysis of Oil 93320.5.3.1 Chemical Composition of Crude Oils and Fractions 93320.5.3.2 Consequences for Oil Refinery Processes 93420.6 Conclusion 936

References 938

21 Chromatographic Methods 953Fabrice Bertoncini, Didier Thiebaut, Marion Courtiade, and Thomas Dutriez

21.1 Introduction 95321.2 Analysis at Different Scales 95521.2.1 Brief History of Chromatography 95521.2.2 From Global Analysis to Detailed Analysis of Petroleum Products 95621.2.3 Global Characterization 95721.2.4 Elemental and Structural Analysis 95721.2.5 Hydrocarbon Family Analysis 958

XXII Contents

21.2.5.1 Mass Spectrometry 95821.2.5.2 Liquid-Phase Chromatography 95921.2.5.3 Supercritical Fluid Chromatography 96021.2.6 Molecular Analysis by Gas Chromatography 96121.2.6.1 Simulated Distillation 96121.2.6.2 Detailed Analysis of Hydrocarbons 96321.2.6.3 Heteroelement Analysis 96721.2.6.4 Mass Detection 97121.2.7 Conclusion 97121.3 GC � GC: a Revolutionary Analytical Technique for Detailed

Molecular Analysis 97221.3.1 Historical Trends for Improving the Separation Capacity 97221.3.2 Principle of GC � GC 97321.3.2.1 Peak Capacity of GC � GC 97521.3.3 Instrumentation for GC � GC 97621.3.3.1 Modulation 97621.3.3.2 Detection 97921.3.3.3 Data Processing 97921.3.3.4 Chromatographic Aspects 98021.3.3.5 Conclusion 98221.3.4 Applications of GC � GC to Various Challenges 98321.3.4.1 Group–Type Analysis of Middle Distillates 98321.3.4.2 Sulfur and Nitrogen Speciation 98621.3.4.3 Petrochemical Applications 99021.3.4.4 Other Applications for GC � GC 99421.3.5 Conclusion 99421.4 Towards Molecular Analysis Systems Highly Coupled

Around GC � GC 99521.4.1 Position of the Problem 99521.4.2 Couplings Between 1D-GC and GC � GC 99621.4.2.1 Simple GC–GC � GC Coupling 99621.4.2.2 GC � GC � GC Total Coupling 99721.4.3 Coupling Between 1D LC and GC � GC 99821.4.3.1 Simple LC–GC � GC Coupling 99821.4.3.2 LC � GC � GC Total Coupling 99921.4.4 Coupling Between 1D SFC and GC � GC 100021.5 Conclusion 1003

References 1004

22 Transient Techniques: Temporal Analysis of Products andSteady State Isotopic Transient Kinetic Analysis 1013Angelos M. Efstathiou, John T. Gleaves, and Gregory S. Yablonsky

22.1 Scope 101322.2 Temporal Analysis of Products (TAP) 101422.2.1 Introduction 1014

Contents XXIII

22.2.2 The Goal of TAP Experiments and Theoretical Background 101922.2.3 Comparison of TAP Experiments with Other Kinetic Methods 102222.2.3.1 Uniformity of the Active Zone 102322.2.3.2 Domain of Conditions 102322.2.3.3 Relevance of Kinetic Information 102322.2.3.4 Applicability to Developing Structure–Properties Relationships 102422.2.3.5 Theoretical Models 102622.2.3.6 Model-Free Interpretation of Kinetic Data 102722.2.4 Experimental Results 102822.2.4.1 Bridging the Pressure Gap 102822.2.4.2 Tracking the Evolution of Catalytic Properties 103222.3 Steady-State Isotopic Transient Kinetic Analysis (SSITKA) 103822.3.1 Introduction 103822.3.2 SSITKA Theory 104122.3.2.1 Kinetic Parameter Estimation 104122.3.2.2 Mechanistic Implications 104722.3.3 Case Studies 104922.3.3.1 The Water-Gas Shift Reaction (CO þ H2O $ CO2 þ H2) 104922.3.3.2 The H2-SCR of NO 105722.4 Conclusion 1065

References 1068

Part Four Advanced Characterization 1075

23 Techniques Coupling for Catalyst Characterisation 1077Andrew M. Beale, Matthew G. O�Brien, and Bert M. Weckhuysen

23.1 Introduction 107723.2 Basic Tenets Behind Technique Combining 108223.2.1 Complementary Chemical Information 108323.2.2 Probing the Same Part of the Catalyst 108623.2.3 Setup Design 108623.2.4 Sample Stability 108723.2.5 Data Analysis 108823.2.5.1 Acquisition 108823.2.5.2 Analysis 108923.3 Illustrations of Setups Combining Multiple In Situ Techniques 108923.3.1 Formation of Microporous Materials 109023.3.2 Online Catalyst Preparation 109323.3.3 Probing the Active Cu Species Under Methanol Synthesis

Conditions 109423.3.4 Three-Way Catalyst (TWC) Components 109523.3.4.1 Examining Local Structure Effects as a Function of the Gas

Atmosphere 109523.3.4.2 Rationalizing Short-Range Behavior with the Observations Made

at Long Range 1097

XXIV Contents

23.3.5 Propane Dehydrogenation 109723.3.5.1 Catalyst Activation, Deactivation, and Regeneration 109823.3.6 Understanding the Key Stages in Methanol to Olefin Conversion 110023.3.7 De-NOx Over Pd/Al2O3 110123.3.8 Killing Three Birds with One Stone 110223.3.9 Propane Dehydrogenation Studied Using Three Techniques

Simultaneously 110323.3.10 Profiling a Reactor Bed with Multiple Techniques 110423.3.11 Reactions at the Solid–Liquid Interface 110623.3.11.1 Alcohol Oxidation 110623.3.11.2 Three Techniques Simultaneously Employed in a Batch Reactor 110723.3.12 Dynamic Imaging Studies 110723.3.12.1 Imaging of Catalyst Bodies During Catalyst Preparation 110823.3.12.2 Time- and Space-Resolved NOx Storage/Release 110923.4 Conclusion 1111

References 1114

24 Quantum Chemistry Methods 1119Philippe Sautet

24.1 Introduction and Historical Perspective 111924.2 Building Models of Heterogeneous Catalysts 112124.3 Electronic Structure Calculations 112324.3.1 The Hartree Approximation 112424.3.2 Pauli Principle and Hartree–Fock Approximation 112524.3.3 Introduction to Post-Hartree–Fock Methods 112624.3.4 Density Functional Theory 112724.3.5 Exchange-Correlation Functionals 113024.4 Application of Total Energy Calculations to the Structure of

Catalytic Surfaces Under the Conditions of Catalysis 113224.4.1 Termination of the (110) Surface of RuO2 113324.4.2 Pd Catalysts Under the Conditions of Partial Hydrogenation

of Alkynes 113424.4.3 The (110) Surface of Gold Under a Pressure of CO 113624.4.4 Alumina Surface at Realistic Water Pressure 113824.4.5 High Coverage and Reconstruction of Supported Pt Cluster

Under a Pressure of Hydrogen 113924.5 Conclusions and Outlook 1141

References 1142

Conclusions 1147Michel Che and Jacques C. Védrine

Index 1153

Contents XXV

About the Editors

Michel Che

After a chemical engineering degree from Ecole Sup�erieure de Chimie Industrielle(Lyon, F), M. Che joined the Institut de Recherches sur la Catalyse (Lyon) as memberof CNRS (National Center of Scientific Research). After a Doctorat �es Sciences in 1968(Universit�e de Lyon), he was postdoctoral fellow (1969-1971) at Princeton University.Between 1972 and 1982, he frequently worked as visiting scientist at the Atomic EnergyResearch Establishment at Harwell (UK). He became Professor at Universit�e Pierre &Marie Curie-Paris 6 in 1975, and Senior Member of Institut Universitaire de Francein 1995.His research concerns the reactivity of solid surfaces investigated from a molecular

standpoint based on the combined use of transitionmetal complexes, specific isotopes andphysical techniques.His work, which led to 450 publications and 5 patents, has contributedto improve our understanding of the elementary processes developing at solid/liquid (gas)interfaces and to bridge the gap between homo- and heterogeneous catalysis.Michel Che was President-Founder of EFCATS, the European Federation of Catalysis

Societies (creating the biennial EuropaCat congresses), and later President of the Inter-national Association of Catalysis Societies. He received awards in France (A. Joannides andP. Sue), Netherlands (J. H. Van�t Hoff), Poland (M. Sklodowska-Curie & P. Curielectureship), Germany (Von Humboldt - Gay-Lussac Award, and GDCh Grignard-Wittiglectureship), UK (RSC Centenary lectureship), USA (Frontiers in Chemical Researchlectureship, Texas), Japan (Japanese Society for the Promotion of Science lectureship),China (Gold Medal of Chinese Academy of Sciences, Friendship Award and InternationalScience and Technology Cooperation Award) and Europe (Francois Gault EFCATS lec-tureship). His work earned him several honorary doctorates and fellowships (GermanAcademy of Sciences-Leopoldina, Academia Europaea, Hungarian Academy of Sciences,Polish Academy of Arts and Sciences).

XXVII

Jacques C. V�edrine

After a chemical engineering degree from Ecole Sup�erieure de Chimie Industrielle (Lyon,F), J.C. V�edrine joined the Institut de Recherches sur la Catalyse (IRC) in Lyon as memberof CNRS. After a Docteur �es Sciences degree in 1968 (Universit�e de Lyon), he was post-docinUSAatVarianAss., PaloAlto (1969-1970) andPrincetonUniversity (1970-1971).He thenreturned to IRCand became deputy director in 1988. In 1998, hemoved to theUniversity ofLiverpool, UK as Chair Professor and Deputy Director of the Leverhulme Centre forInnovative Catalysis. In 2003, he returned to France and was charg�e de mission at theMinistry of National Education and Research. In 2006, he joined the Laboratory of SurfaceReactivity at Universit�e Pierre & Marie Curie, Paris.His scientific interests cover heterogeneous catalysis, especially selective oxidation on

mixed metal oxides, acid catalysis on oxide-based systems and acidity strength and naturedetermination. He worked on combinatorial catalysis (high throughput technique) andcontributed in the 1990s to the EUROCATgroup activities in standardizing heterogeneouscatalyst characterization. He co-authored over 350 publications and a few patents, and co-edited 7 books. He is one of the Editors of Appl. Catal. A: General.One of his major contributions was to organize in the 1980s regular training sessions to

help researchers use complementary physical techniques to improve the characterizationof solid catalysts, including under working conditions. This led to two books on PhysicalCharacterization of Solid Catalysts (Technip, Paris, 1988 and Plenum Press, New York,1994).Hewas awarded theGrandPrix Pierre Sue of the FrenchChemical Society (SCF) in 2001.

He was elected President of Catalysis Division of SCF (1994-1997), President of EFCATS(1997-1999) and President of the Acid-Base World Organization (2005-2009). He holdshonorary doctorate from the University of Lisbon.

XXVIII About the Editors