Characterization of Solid Materials and Heterogeneous Catalysts E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 2346

Veröffentlichungsjahr: 2012

Beschreibung

This two-volume book provides an overview of physical techniques used to characterize the structure of solid materials, on the one hand,
and to investigate the reactivity of their surface, on the other. Therefore this book is a must-have for anyone working in fields related to surface
reactivity. Among the latter, and because of its most important industrial impact, catalysis has been used as the directing thread of the book.
After the preface and a general introduction to physical techniques by M. Che and J.C. Vedrine, two overviews on physical techniques are
presented by G. Ertl and Sir J.M. Thomas for investigating model catalysts and porous catalysts, respectively.
The book is organized into four parts: Molecular/Local Spectroscopies, Macroscopic Techniques, Characterization of the Fluid Phase (Gas and/
or Liquid), and Advanced Characterization. Each chapter focuses upon the following important themes: overview of the technique, most important parameters to interpret the experimental data, practical details, applications of the technique, particularly during chemical processes,
with its advantages and disadvantages, conclusions.

Leseprobe

Contents

Cover

Related Titles

Title Page

Copyright

Dedication

About the Editors

List of Contributors

Preface

General Introduction

1 Basic Phenomenon and Classification of Physical Techniques

2 Coupling of Physical Techniques

3 The Latest Challenge: Characterization of the Surface Reactivity of Solid Materials Under Working/Catalytic Reaction Conditions

4 Book Content and Chapter Order

5 SI Units and Conversions

Acknowledgments

References

Overview on Physical Techniques for Investigating Model Solid Catalysts

1 Why Model Systems?

2 Interactions of Molecules with Surfaces; Kinetics and Dynamics

3 The Structure of Surfaces

4 Electron Spectroscopies

5 Vibrational Spectroscopies

6 Conclusions

References

Overview on Physical Techniques for Investigating Porous Catalysts

1 Why Porous and Nanoporous Systems?

2 New Families of Nanoporous Catalysts

3 Which Physical Techniques are Preferred for the Characterization of Nanoporous and Powdered Catalysts?

4 The Special Merits of New Techniques and Recent Advances in Older Ones

5 The Potential and Promise of Neutron Scattering

References

Part One: Molecular/Local Spectroscopies

Chapter 1: Infrared Spectroscopy

1.1 Introduction

1.2 Principles of IR Spectroscopy and Basic Knowledge for Its Use

1.3 Experimental Considerations

1.4 Use of IR Spectroscopy to Characterize Solids

1.5 Application to Surface Reactivity: Operando Spectroscopy

1.6 Conclusion

References

Chapter 2: Raman and UV-Raman Spectroscopies

2.1 Introduction

2.2 Characterization of Active Sites and Phase Structure of Metal Oxides

2.3 Characterization of Surface Metal Oxide Species on Supported Metal Oxides

2.4 Electron–Phonon Coupling in Nanostructured Materials

2.5 Characterization of sp2 Carbon Materials

2.6 Characterization of Transition Metal-Containing Microporous and Mesoporous Materials

2.7 Synthesis Mechanisms of Molecular Sieves

2.8 Conclusions

References

Chapter 3: Electronic Spectroscopy: Ultra Violet-visible and Near IR Spectroscopies

3.1 Introduction and Overview

3.2 UV–vis–NIR Spectra

3.3 Experimental Considerations

3.4 Formation and Alteration of Solids

3.5 Surface Reactivity and Catalysis

3.6 Conclusions

References

Chapter 4: Photoluminescence Spectroscopy

4.1 Introduction

4.2 Basic Principles of Photoluminescence

4.3 General Aspects of Photoluminescence Measurements

4.4 Characterization of Catalysts by Photoluminescence and Time-Resolved Photoluminescence Spectroscopy

4.5 Investigations of the Dynamics of Photocatalysis by Time-Resolved Photoluminescence Spectroscopy

4.6 Conclusion

References

Chapter 5: Neutron Scattering

5.1 Introduction

5.2 Introduction to the Theory

5.3 Experimental

5.4 Structure

5.5 Dynamics

5.6 Conclusion

References

Chapter 6: Sum Frequency Generation and Infrared Reflection Absorption Spectroscopy

6.1 Introduction

6.2 Theoretical Background of SFG

6.3 Spectrometer Setup

6.4 Case Studies

6.5 Conclusion

Acknowledgements

References

Chapter 7: Infra Red Reflection Absorption Spectroscopy and Polarisation Modulation-IRRAS

7.1 Introduction

7.2 Principle of IRAS

7.3 Principle of PM-IRAS

7.4 Applications of IRAS and PM-IRAS

7.5 Conclusion

References

Chapter 8: Nuclear Magnetic Resonance Spectroscopy

8.1 Introduction and Historical Perspective

8.2 Theory

8.3 Popular NMR Techniques for Studying Solids

8.4 Characterization of Heterogeneous Catalysts

8.5 Porosity, Adsorption, and Transport Processes

8.6 “In Situ” NMR

8.7 Towards “Operando” Studies

8.8 Conclusion and Outlook

References

Chapter 9: Electron Paramagnetic Resonance Spectroscopy

9.1 Introduction

9.2 Principles of EPR

9.3 Electron–Nucleus Hyperfine Interaction

9.4 Experimental Background

9.5 Anisotropy of Magnetic Interactions in EPR: the g, A, and D Tensors

9.6 EPR Spectra and the Solid State: Single Crystal Versus Powders

9.7 Guidelines to Interpretation of EPR Spectra

9.8 Computer Simulation of Powder Spectra

9.9 Molecular Interpretation of Parameters

9.10 Quantum Chemical Calculations of Magnetic Parameters

9.11 Advanced EPR Techniques

9.12 Characteristics of EPR Techniques in Application to Catalysis and Surfaces

9.13 Interfacial and Surface Charge-Transfer Processes

9.14 In Situ and Operando EPR Techniques

9.15 Conclusions and Prospects

References

Chapter 10: Mössbauer Spectroscopy

10.1 Introduction

10.2 The Mössbauer Effect

10.3 Radiation Source

10.4 Mössbauer Absorbers

10.5 Hyperfine Interactions

10.6 Experimental Setups

10.7 Evaluation of Experimental Data

10.8 Theoretical Calculation of Mössbauer Parameters

10.9 Common Mössbauer-Active Transitions

10.10 Survey of Applications of the Mössbauer Effect in the Study of Catalytic Materials

10.11 Conclusion

References

Chapter 11: Low Energy Ion Scattering and Secondary Ion Mass Spectrometry

11.1 Introduction

11.2 Secondary Ion Mass Spectrometry

11.3 Low-Energy Ion Scattering (Ion Scattering Spectroscopy)

11.4 Single-Crystal and Polycrystalline Metal Surfaces

11.5 Amorphous Metallic Alloys

11.6 From Model to Real Catalysts

11.7 Conclusion

References

Chapter 12: X-ray Absorption Spectroscopy

12.1 Introduction

12.2 History of X-Ray Absorption Spectroscopy

12.3 Principle of X-Ray Absorption Spectroscopy: XANES, EXAFS

12.4 Experimentation and Data Processing

12.5 Application to Oxide Materials

12.6 Applications to the Study of Sulfide Catalysts

12.7 Application to Metal Catalysts

12.8 Conclusion and Perspectives

References

Chapter 13: Auger Electron, X ray and UV Photoelectron Spectroscopies

13.1 Introduction

13.2 Sources of Analytical Information

13.3 Instrumentation

13.4 Case Studies

13.5 Outlook

Acknowledgments

References

Chapter 14: Single Molecule Spectroscopy

14.1 Introduction

14.2 Description of the Method

14.3 Experimental Considerations and Constraints

14.4 Mesoporous Silica Materials

14.5 Selected Studies

14.6 Conclusion

References

Part Two: Macroscopic Techniques

Chapter 15: X-Ray Diffraction and Small Angle X-Ray Scattering

15.1 Introduction

15.2 Theoretical Background of X-Ray Diffraction

15.3 Experimental Aspects

15.4 Application to Phase Identification

15.5 Application to Phase Characterization: Ideal Structure

15.6 Application for Phase Characterization: Real Structure

15.7 X-Ray Diffraction of Catalysts in a Reactive Atmosphere

15.8 Small-Angle X-Ray Scattering (SAXS)

15.9 Conclusion

Acknowledgments

References

Chapter 16: Transmission Electron Microscopy

16.1 History and Overview

16.2 Introduction

16.3 Specimen Preparation and Experimental Considerations

16.4 Examples of General Characterization Studies

16.5 Examples of Reactivity and Catalysis Studies

16.6 Recent Developments and Future Prospects

References

Chapter 17: Scanning Probe Microscopy and Spectroscopy

17.1 Introduction

17.2 Scanning Tunneling Microscopy

17.3 Atomic Force Microscopy

17.4 Conclusion

References

Chapter 18: Thermal Methods

18.1 Main Thermal Methods

18.2 Acidity/Basicity

18.3 Redox Properties of Solids

18.4 Conclusion

References

Chapter 19: Surface Area/Porosity, Adsorption, Diffusion

19.1 Introduction

19.2 Gas Adsorption for the Characterization of Surface Area and Porosity

19.3 Diffusion in Porous Solids

19.4 Conclusion

References

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

Chapter 20: Mass Spectrometry

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

20.2 Basics of Mass Spectrometry

20.3 Direct Surface Analysis: Imaging Mass Spectrometry for Biologists

20.4 From Collision Activation to Ion–Surface Chemical Reactions for New Preparative Mass Spectrometry

20.5 Petroleomics: Role of Ultra-High Resolution and Data Treatment

20.6 Conclusion

References

Chapter 21: Chromatographic Methods

21.1 Introduction

21.2 Analysis at Different Scales

21.3 GC × GC: a Revolutionary Analytical Technique for Detailed Molecular Analysis

21.4 Towards Molecular Analysis Systems Highly Coupled Around GC × GC

21.5 Conclusion

References

Chapter 22: Transient Techniques: Temporal Analysis of Products and Steady State Isotopic Transient Kinetic Analysis

22.1 Scope

22.2 Temporal Analysis of Products (TAP)

22.3 Steady-State Isotopic Transient Kinetic Analysis (SSITKA)

22.4 Conclusion

References

Part Four: Advanced Characterization

Chapter 23: Techniques Coupling for Catalyst Characterisation

23.1 Introduction

23.2 Basic Tenets Behind Technique Combining

23.3 Illustrations of Setups Combining Multiple in Situ Techniques

23.4 Conclusion

References

Chapter 24: Quantum Chemistry Methods

24.1 Introduction and Historical Perspective

24.2 Building Models of Heterogeneous Catalysts

24.3 Electronic Structure Calculations

24.4 Application of Total Energy Calculations to the Structure of Catalytic Surfaces Under the Conditions of Catalysis

24.5 Conclusions and Outlook

Acknowledgments

References

Conclusions

Index

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For our mentor Dr. Boris Imelik, and our Families

About the Editors

Michel Che

After a chemical engineering degree from Ecole Supérieure de Chimie Industrielle (Lyon, F), M. Che joined the Institut de Recherches sur la Catalyse (Lyon) as member of CNRS (National Center of Scientific Research). After a Doctorat ès Sciences in 1968 (Université de Lyon), he was postdoctoral fellow (1969-1971) at Princeton University. Between 1972 and 1982, he frequently worked as visiting scientist at the Atomic Energy Research Establishment at Harwell (UK). He became Professor at Université Pierre & Marie Curie-Paris 6 in 1975, and Senior Member of Institut Universitaire de France in 1995.

His research concerns the reactivity of solid surfaces investigated from a molecular standpoint based on the combined use of transition metal complexes, specific isotopes and physical techniques. His work, which led to 450 publications and 5 patents, has contributed to 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 International Association of Catalysis Societies. He received awards in France (A. Joannides and P. Sue), Netherlands (J. H. Van't Hoff), Poland (M. Sklodowska-Curie & P. Curie lectureship), Germany (Von Humboldt - Gay-Lussac Award, and GDCh Grignard-Wittig lectureship), UK (RSC Centenary lectureship), USA (Frontiers in Chemical Research lectureship, Texas), Japan (Japanese Society for the Promotion of Science lectureship), China (Gold Medal of Chinese Academy of Sciences, Friendship Award and International Science and Technology Cooperation Award) and Europe (François Gault EFCATS lectureship). His work earned him several honorary doctorates and fellowships (German Academy of Sciences-Leopoldina, Academia Europaea, Hungarian Academy of Sciences, Polish Academy of Arts and Sciences).

Jacques C. Védrine

After a chemical engineering degree from Ecole Supérieure de Chimie Industrielle (Lyon, F), J.C. Védrine joined the Institut de Recherches sur la Catalyse (IRC) in Lyon as member of CNRS. After a Docteur ès Sciences degree in 1968 (Université de Lyon), he was post-doc in USA at Varian Ass., Palo Alto (1969-1970) and Princeton University (1970-1971). He then returned to IRC and became deputy director in 1988. In 1998, he moved to the University of Liverpool, UK as Chair Professor and Deputy Director of the Leverhulme Centre for Innovative Catalysis. In 2003, he returned to France and was chargé de mission at the Ministry of National Education and Research. In 2006, he joined the Laboratory of Surface Reactivity at Université 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 nature determination. He worked on combinatorial catalysis (high throughput technique) and contributed in the 1990s to the EUROCAT group activities in standardizing heterogeneous catalyst 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 characterization of solid catalysts, including under working conditions. This led to two books on Physical Characterization of Solid Catalysts (Technip, Paris, 1988 and Plenum Press, New York, 1994).

He was awarded the Grand Prix Pierre Sue of the French Chemical 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 holds honorary doctorate from the University of Lisbon.

List of Contributors

Sandra AlvesUniversité Pierre et Marie Curie, CNRSInstitut Parisien de ChimieMoléculaireLaboratoire de Chimie BiologiqueOrganique et Structurale4 place Jussieu75252 ParisFrance

Masakazu AnpoOsaka Prefecture UniversityGraduate School of EngineeringDepartment of Applied Chemistry1-1 Gakuen-cho, Naka-KuSakai-CityOsaka 599-8531Japan

Aline AurouxUniversité Lyon 1, CNRSInstitut de Recherches sur la Catalyse etl'Environnement de Lyon2 avenue Albert Einstein69626 VilleurbanneFrance

Andrew M. BealeUtrecht UniversityDebye Institute forNanoMaterials ScienceInorganic Chemistry andCatalysis GroupSorbonnelaan 163584 CA UtrechtThe Netherlands

Malte BehrensFritz-Haber-Institut derMax-Planck-GesellschaftFaradayweg 4–614195 BerlinGermany

Thomas BeinLudwig-Maximilians University of MunichDepartment of ChemistryCenter for Nanoscience and Center forIntegrated Protein ScienceButenandtstraße 1181377 MunichGermany

Fabrice BertonciniIFP Energies Nouvellesétablissement de LYONCatalysis and Separation DivisionRond-Point de l'échangeur de Solaize69360 SolaizeFrance

Emily BlochUniversité Aix-Marseille, CNRSCentre de St. JérômeLaboratoire Chimie Provenceavenue Normandie-Niemen13397 MarseilleFrance

Sandrine BourrellyUniversité Aix-Marseille, CNRSCentre de St. JérômeLaboratoire Chimie Provenceavenue Normandie-Niemen13397 MarseilleFrance

Christoph BräuchleLudwig-Maximilians University ofMunichDepartment of ChemistryCenter for Nanoscience and Centerfor Integrated Protein ScienceButenandtstraße 1181377 MunichGermany

Michel CheInstitut Universitaire de FranceUniversité Pierre et Marie Curie, CNRSLaboratoire de Réactivité de Surface4 place Jussieu75252 ParisFrance

Sergey ChenakinUniversité Libre de Bruxelles (ULB)Chimie-Physique des MatériauxCP 243 Campus Plaine1050 BrusselsBelgium

Marion CourtiadeIFP Energies Nouvellesétablissement de LYONPhysics and Analysis DivisionRond-Point de l'échangeur de Solaize69360 SolaizeFrance

Caterina DucatiUniversity of CambridgeDepartment of Materials Science andMetallurgyPembroke StreetCambridge CB2 3QZUK

Thomas DutriezIFP Energies Nouvellesétablissement de LYONPhysics and Analysis DivisionRond-Point de l'échangeur de Solaize69360 SolaizeFrance

Angelos M. EfstathiouUniversity of CyprusChemistry DepartmentHeterogeneous Catalysis LaboratoryUniversity Campus1678 NicosiaCyprus

Gerhard ErtlFritz-Haber-Institut derMax-Planck-GesellschaftFaradayweg 4–614195 BerlinGermany

Fengtao FanChinese Academy of SciencesDalian Institute of Chemical PhysicsState Key Laboratory of Catalysis457 Zhongshan RoadDalian 116023China

Zhaochi FengChinese Academy of SciencesDalian Institute of Chemical PhysicsState Key Laboratory of Catalysis457 Zhongshan RoadDalian 116023China

Karin FöttingerVienna University of TechnologyInstitute of Materials ChemistryGetreidemarkt 9 BC1060 ViennaAustria

Christophe GeantetUniversité Lyon 1, CNRSInstitut de Recherches sur la Catalyse et l'Environnement de Lyon2 avenue Albert Einstein69626 VilleurbanneFrance

Elio GiamelloUniversità di TorinoDipartimento di Chimica IFM and NISCentre of Excellencevia P. Giuria 710125 TurinItaly

Lynn F. GladdenUniversity of CambridgeDepartment of Chemical Engineeringand BiotechnologyPembroke StreetCambridge CB2 3RAUK

John T. GleavesWashington University in St. LouisDepartment of Energy, Environmentaland Chemical Engineering1 Brookings DriveSt. Louis, MO 63130USA

Wolfgang GrünertRuhr-Universität BochumLehrstuhl Technische ChemieUniversitätsstraße 15044801 BochumGermany

Friederike C. JentoftUniversity of OklahomaSchool of Chemical, Biological andMaterials EngineeringSarkeys Energy Center T-335100 East Boyd StreetNorman, OK 73019USA

Hervé JobicUniversité Lyon 1, CNRSInstitut de Recherches sur la Catalyse etl'Environnement de Lyon2 avenue Albert Einstein69626 VilleurbanneFrance

Norbert KruseUniversité Libre de Bruxelles (ULB)Chimie-Physique des MatériauxCP 243 Campus Plaine1050 BrusselsBelgium

Timo LeboldLudwig-Maximilians University ofMunichDepartment of ChemistryCenter for Nanoscience and Center forIntegrated Protein ScienceButenandtstraße 1181377 MunichGermany

Can LiChinese Academy of SciencesDalian Institute of Chemical PhysicsState Key Laboratory of Catalysis457 Zhongshan RoadDalian 116023China

Philip L. LlewellynUniversité Aix-Marseille, CNRSCentre de St. JérômeLaboratoire Chimie Provenceavenue Normandie-Niemen13397 MarseilleFrance

Michal LuteckiUniversity of CambridgeDepartment of Chemical Engineeringand BiotechnologyPembroke StreetCambridge CB2 3RAUK

Masaya MatsuokaOsaka Prefecture UniversityGraduate School of EngineeringDepartment of Applied Chemistry1-1 Gakuen-cho, Naka-KuSakai-CityOsaka 599-8531Japan

Françoise MaugéENSICAEN–Université de Caen, CNRSLaboratoire Catalyse et Spectrochimie6 boulevard Maréchal Juin14050 CaenFrance

James McGregorUniversity of CambridgeDepartment of Chemical Engineeringand BiotechnologyPembroke StreetCambridge CB2 3RAUK

Adrien Mekki-BerradaUniversité Lyon 1, CNRSInstitut de Recherches sur la Catalyse etl'Environnement de Lyon2 avenue Albert Einstein69626 VilleurbanneFrance

Christophe MéthivierUniversité Pierre et Marie Curie, CNRSLaboratoire de Réactivité de Surface4 place Jussieu75252 ParisFrance

Jens MichaelisLudwig-Maximilians University ofMunichDepartment of ChemistryCenter for Nanoscience and Center forIntegrated Protein ScienceButenandtstraße 1181377 MunichGermany

Tomoaki NishinoOsaka Prefecture UniversityResearch Organization for the21st centuryNanoscience and NanotechnologyResearch CenterSakaiOsaka 599-8570Japan

Matthew G. O'BrienUtrecht UniversityDebye Institute forNanoMaterials ScienceInorganic Chemistry andCatalysis GroupSorbonnelaan 163584 CA UtrechtThe Netherlands

Christophe PichonIFP Energies Nouvellesétablissement de LYONPhysics and Analysis DivisionRond-Point de l'échangeur de Solaize69360 SolaizeFrance

Piotr PietrzykJagiellonian UniversityFaculty of Chemistryul. Ingardena 330-060 KrakowPoland

Claire-Marie PradierUniversité Pierre et Marie Curie, CNRSLaboratoire de Réactivité de Surface4 place Jussieu75252 ParisFrance

Günther RupprechterVienna University of TechnologyInstitute of Materials ChemistryGetreidemarkt 9 BC1060 ViennaAustria

Masakazu SaitoOsaka Prefecture UniversityGraduate School of EngineeringDepartment of Applied Chemistry1-1 Gakuen-cho, Naka-KuSakai-CityOsaka 599-8531Japan

Philippe SautetUniversité Lyon 1, CNRSEcole Normale Supérieure de LyonInstitut de Chimie15 parvis Descartes69342 LyonFrance

Robert SchlöglFritz-Haber-Institut derMax-Planck-GesellschaftFaradayweg 4–614195 BerlinGermany

Zbigniew SojkaJagiellonian UniversityFaculty of Chemistryul. Ingardena 330-060 KrakowPoland

Lorenzo StievanoUniversité Montpellier 2Institut Charles Gerhardt, CNRSplace Eugène Bataillon34095 MontpellierFrance

Jean-Claude TabetUniversité Pierre et Marie Curie, CNRSInstitut Parisien de ChimieMoléculaireLaboratoire de Chimie BiologiqueOrganique et Structurale4 place Jussieu75252 ParisFrance

Frédéric Thibault-StarzykENSICAEN–Université de Caen, CNRSLaboratoire Catalyse et Spectrochimie6 boulevard Maréchal Juin14050 CaenFrance

Didier ThiebautCNRSLaboratoire Physicochimie desElectrolytes Colloïdes et SciencesAnalytiquesESPCI ParisTech10 rue Vauquelin75231 ParisFrance

John Meurig ThomasUniversity of CambridgeDepartment of Materials Science andMetallurgyPembroke StreetCambridge CB2 3QZUK

Jacques C. VédrineUniversité Pierre et Marie Curie, CNRSLaboratoire de Réactivité de Surface4 place Jussieu75252 ParisFrance

Friedrich E. WagnerTechnische Universität MünchenPhysik-Department E15James-Franck-Strasse 185748 GarchingGermany

Bert M. WeckhuysenUtrecht UniversityDebye Institute forNanoMaterials ScienceInorganic Chemistry andCatalysis GroupSorbonnelaan 163584 CA UtrechtThe Netherlands

Christian WeilachVienna University of TechnologyInstitute of Materials ChemistryGetreidemarkt 9 BC1060 ViennaAustria

Gregory S. YablonskySaint Louis UniversityParks College of EngineeringDepartment of Chemistry3450 Lindell BoulevardSt. Louis, MO 63130USA

Preface

Michel Che and Jacques C. Védrine

The spectacular progress achieved in chemistry is largely due to the use of physical techniques implemented at the level of the element, molecule, or phase with reliability and accuracy unattainable a few decades ago. Moreover, microscopic (molecular) and macroscopic (molar) information can be obtained by small-scale and often non-destructive experiments. Many of these techniques are now in routine use, essentially because of the progress of technology and availability of always more powerful and user-friendly computers.

We therefore thought that it was timely to provide a survey of the major techniques used to characterize solid materials and investigate their surface reactivity, a domain of chemistry, relevant to a variety of fields including adsorption, geochemistry, coatings, electrochemistry, corrosion, formation of biofilms, toxicity and catalysis. Those fields however do not require the same surface reactivity: for corrosion, the latter has to be inhibited, or even suppressed, because of its dramatic consequences on metals, while for catalysis not only it has to be enhanced but also selectively oriented to obtain the desired product.

From all the fields related to surface reactivity, catalysis appears to be unique because i) it has a large industrial impact, ii) it lies at the core of chemistry, i.e., starting with chemistry to prepare the catalytic system and ending with chemistry to promote a specific reaction, and iii) it involves physical and chemical processes developing mostly at liquid-solid, solid-solid, and/or gas-solid interfaces present at the successive steps of catalyst life, from its preparation to its use in the catalytic reaction. For those reasons, catalysis will be used as the directing thread of this book.

Investigations on solid materials have shown that their surfaces may change with the chemical environment to which they are exposed and that the more divided the solid, the more reactive it becomes. This book title illustrates this paradigm, with its dual aspects, the structure of the material on one hand and its surface reactivity on the other. For instance, for metals, it is known that metal-metal bond distances at the surface often contract under vacuum with respect to the bulk, while they relax in the presence of gaseous molecules reaching values close to those characteristic of the bulk. For alloys or mixed oxides, surface enrichment in one component is often observed under reaction conditions. For some reactions, e.g. selective oxidation of olefins on metal oxide catalysts, the surface atoms of the solid catalyst may react, and even be incorporated into reactant molecules. For such redox-type reactions, surface atoms have to be mobile enough to allow the redox process to occur.

This book is intended to consider all those aspects with the objective to offer a general survey on the “Characterization of Solid Materials: From Structure to Surface Reactivity”, useful to junior and senior research scientists, engineers and industrialists. We deemed it essential to present a portofolio of the techniques most frequently used and to dwell on those which appear to be most promising. For this reason, the space allocated to each chapter is different. Although still used, some techniques are not discussed in this book, because little improvement has been achieved since the publication of earlier books in 1988 [1] and 1994 [2].

Because of the large number of chapters/authors, consistency and homogeneity were felt to be essential. Therefore, the following format was suggested to authors:

1. Introduction covering the discovery and development of the technique,

2. Description of the basic phenomenon with a theoretical background including, where appropriate, its dimension/time/energy scales, energy states, terminology, units (those conventionally used in the field but also SI units), the strategy used and the essential parameters necessary to interpret experimental data,

3. Experimental considerations/constraints, relative to the characterization technique and to the surface reactivity,

4. Uses of the technique for the characterization of both model and real solid materials at different stages of their life (i.e., during preparation, functionalization, chemical or thermal activation, surface reactivity) with emphasis on the coupling with other techniques with its advantages and disadvantages,

5. Key examples of application of the technique to surface reactivity. For the field of catalysis, the reaction, deactivation, ageing, and regeneration steps had to be considered with emphasis on the identification and implication of intermediates in reaction mechanisms,

6. Conclusions including information gained with the technique, its advantages, limitations, and latest developments,

7. References.

We have tried to offer a book presenting a unique set of features:

it deals with an ensemble of physical techniques commonly used at present to i) characterize solid materials and ii) investigate their surface reactivity,it provides overviews written by two outstanding scholars who have largely contributed to the development of physical techniques to investigate solid materials (single crystals and porous catalysts),each chapter aims at being both general and concise enough for the readers to understand the technique, and the meaning of the essential key parameters,it gives general data for each technique, with its historical background, domains of energy involved, spatial and time resolution, experimental constraints (vacuum or presence of gaseous phase, temperature,...), atomic/molecular or macroscopic aspects,it emphasises the characterization of the solid material throughout its life: from its preparation to its application in surface reactivity-related domains,it includes the use of both experimental and theoretical approaches as a guide in designing experiments and interpreting results,it deals with both model and real solid materials,it aims at being a toolbox from which any researcher should be able to find the appropriate technique(s) for solving a specific problem.

To conclude, this book aims at being pedagogical, illustrative and practical, hoping that after having read the book, the reader be in a position to identify the most appropriate technique(s) able to answer his questions.

References

1. Imelik, B. and Védrine, J.C. (Eds.)(1988) Les Techniques Physiques de Caractrisation des Catalyseurs, Technip, Paris.

2. Imelik, B. and Védrine, J.C. (Eds.)(1994) Catalyst Characterization: Physical Techniques for Solid Materials, Plenum Press, New York.

General Introduction

Michel Che and Jacques C. Védrine

The two main goals of the book are to show how physical techniques can be used to characterize solid materials and to investigate their surface reactivity. The first goal corresponds to establishing the “identity card” of the material, including its structure, morphology, porosity, and chemical composition, and the second to obtaining characteristics of the surface related to its reactivity (nature and number of surface sites, subsequent modification upon functionalization, nature and number of adsorbed species and possible intermediates in surface-promoted phenomenon/reaction).

1 Basic Phenomenon and Classification of Physical Techniques

All techniques are based on the same phenomenon, often referred to as the Propst diagram (Figure 1): an incident beam hits the sample, giving rise to an emitted beam which is detected and analyzed because of the information it contains, leading to the “fingerprint” of the solid and/or of species or reaction intermediates adsorbed on it. The incident beam can be composed of photons, electrons, ions, neutrals, or magnetic, electric, acoustic, or thermal fields, and also the emitted beam.

Figure 1 Basic phenomenon of physical techniques. The incident beams are defined by arrows oriented towards the sample while the emitted beams are defined by arrows oriented away from the sample. Adapted from [1].

Table 1 presents the main acronyms of the physical techniques presented or mentioned in this book and Table 2 gives the classification of typical techniques as a function of the nature of the incident and emitted beams. In Table 2, one distinguishes the diagonal techniques, for which incident and emitted beams are identical in nature and the information comes from the analysis of the modifications in intensity, energy, or frequency of the incident beam, from the off-diagonal techniques (shaded areas) for which those two beams are different in nature [2].

Table 1 Acronyms and names of the techniques presented or mentioned in this book.

AcronymTechniqueAAatomic absorptionAC-EMaberration-corrected-electron microscopyADFannular dark fieldAESAuger electron spectroscopyAFMatomic force microscopyAIUPangle-integrated ultraviolet spectroscopyAPSappearance potential spectroscopyATRattenuated total reflectionCEMSconversion electron Mössbauer spectroscopyCLcathodoluminescenceCTEMconventional transmission electron microscopy