Metal-Organic Frameworks E-Book

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

Seitenzahl: 745

Veröffentlichungsjahr: 2011

Beschreibung

An international and interdisciplinary team of leading experts from both academia and industry report on the wide range of hot applications for MOFs, discussing both the advantages and limits of the material. The resulting overview covers everything from catalysis, H2 and CH4 storage and gas purification to drug delivery and sensors.

From the Contents:
- Design of Porous Coordination Polymers/Metal-Organic Frameworks: Past, Present and Future
- Design of Functional Metal-Organic Frameworks by Post-Synthetic Modification
- Thermodynamic Methods for Prediction of Gas Separation in Flexible Frameworks
- Separation and purification of gases by MOFs
- Opportunities for MOFs in CO2 capture from flue gases, natural gas and syngas by adsorption
- Manufacture of MOF thin films on structured supports for separation and catalysis
- Research status of Metal-Organic Frameworks for on-board cryo-adsorptive hydrogen storage applications
- Separation of xylene isomers
- Metal-Organic Frameworks as Catalysts for Organic Reactions
- Biomedical applications of Metal Organic Frameworks
- Metal Organic Frameworks for Biomedical Imaging
- Luminescent Metal-Organic Frameworks
- Deposition of thin films for sensor applications
- Industrial MOF Synthesis
- MOF shaping and immobilisation

A must-have for every scientist in the field.

Leseprobe

Contents

Cover

Related Titles

Title Page

Copyright

Preface

List of Contributors

Part One: Design of Multifunctional Porous MOFs

Chapter 1: Design of Porous Coordination Polymers/Metal–Organic Frameworks: Past, Present and Future

1.1 Introduction

1.2 Background and Ongoing Chemistry of Porous Coordination Polymers

1.3 Multifunctional Frameworks

1.4 Preparation of Multifunctional Frameworks

1.5 Perspectives

References

Chapter 2: Design of Functional Metal–Organic Frameworks by Post-Synthetic Modification

2.1 Building a MOFs Toolbox by Post-Synthetic Modification

2.2 Post-Functionalization of MOFs by Host–Guest Interactions

2.3 Post-Functionalization of MOFs Based on Coordination Chemistry

2.4 Post-Functionalization of MOFs by Covalent Bonds

2.5 Tandem Post-Modification for the Immobilization of Organometallic Catalysts

2.6 Critical Assessment

2.7 Conclusion

References

Part Two: Gas Storage and Separation Applications

Chapter 3: Thermodynamic Methods for Prediction of Gas Separation in Flexible Frameworks

3.1 Introduction

3.2 Theoretical Background

3.3 Molecular Simulation Methods

3.4 Analytical Methods Based on Experimental Data

3.5 Outlook

Acknowledgments

References

Chapter 4: Separation and Purification of Gases by MOFs

4.1 Introduction

4.2 General Principles of Gas Separation and Purification

4.3 MOFs for Separation and Purification Processes

4.4 Conclusions and Perspectives

References

Chapter 5: Opportunities for MOFs in CO2 Capture from Flue Gases, Natural Gas, and Syngas by Adsorption

5.1 Introduction

5.2 General Introduction to Pressure Swing Adsorption

5.3 Production of H2 from Syngas

5.4 CO2 Removal from Natural Gas

5.5 Post-combustion CO2 Capture

5.6 MOFs

5.7 Conclusions

References

Chapter 6: Manufacture of MOF Thin Films on Structured Supports for Separation and Catalysis

6.1 Advantages and Limitations of Membrane Technologies for Gas and Liquid Separation

6.2 Mechanism of Mass Transport and Separation

6.3 Synthesis of Molecular Sieve Membranes

6.4 Application of MOF Membranes

6.5 Limitations

6.6 Conclusions and Outlook

References

Chapter 7: Research Status of Metal–Organic Frameworks for On-Board Cryo-Adsorptive Hydrogen Storage Applications

7.1 Introduction – Research Problem and Significance

7.2 MOFs as Adsorptive Hydrogen Storage Options

7.3 Experimental Techniques and Methods for Performance and Thermodynamics Assessment of Porous MOFs for Hydrogen Storage

7.4 Material Research Results

7.5 From Laboratory-Scale Materials to Engineering

7.6 Conclusion

References

Part Three: Bulk Chemistry Applications

Chapter 8: Separation of Xylene Isomers

8.1 Xylene Separation: Industrial Processes, Adsorbents, and Separation Principles

8.2 Properties of MOFs Versus Zeolites in Xylene Separations

8.3 Separation of Xylenes Using MIL-47 and MIL-53

8.4 Conclusions

Acknowledgments

References

Chapter 9: Metal–Organic Frameworks as Catalysts for Organic Reactions

9.1 Introduction

9.2 MOFs with Catalytically Active Metal Nodes in the Framework

9.3 Catalytic Functionalization of Organic Framework Linkers

9.4 Homochiral MOFs

9.5 MOF-Encapsulated Catalytically Active Guests

9.6 Mesoporous MOFs

9.7 Conclusions

List of Abbreviations

Acknowledgments

References

Part Four: Medical Applications

Chapter 10: Biomedical Applications of Metal–Organic Frameworks

10.1 Introduction

10.2 MOFs for Bioapplications

10.3 Therapeutics

10.4 Diagnostics

10.5 From Synthesis of Nanoparticles to Surface Modification and Shaping

10.6 Discussion and Conclusion

Acknowledgments

References

Chapter 11: Metal–Organic Frameworks for Biomedical Imaging

11.1 Introduction

11.2 Gadolinium Carboxylate NMOFs

11.3 Manganese Carboxylate NMOFs

11.4 Iron Carboxylate NMOFs: the MIL Family

11.5 Iodinated NMOFs: CT Contrast Agents

11.6 Lanthanide Nucleotide NMOFs

11.7 Guest Encapsulation within NMOFs

11.8 Conclusion

References

Part Five: Physical Applications

Chapter 12: Luminescent Metal–Organic Frameworks

12.1 Introduction

12.2 Luminescence Theory

12.3 Ligand-Based Luminescence

12.4 Metal-Based Luminescence

12.5 Guest-Induced Luminescence

12.6 Applications of Luminescent MOFs

12.7 Conclusion

Acknowledgments

References

Chapter 13: Deposition of Thin Films for Sensor Applications

13.1 Introduction

13.2 Literature Survey

13.3 Signal Transduction Modes

13.4 Considerations in Selecting MOFs for Sensing Applications

13.5 MOF Thin Film Growth: Methods, Mechanisms, and Limitations

13.6 Conclusions and Perspectives

References

Part Six: Large-Scale Synthesis and Shaping of MOFs

Chapter 14: Industrial MOF Synthesis

14.1 Introduction

14.2 Raw Materials

14.3 Synthesis

14.4 Shaping

14.5 Applications

14.6 Conclusion and Outlook

References

Chapter 15: MOF Shaping and Immobilization

15.1 Introduction

15.2 MOF@Fiber Composite Materials

15.3 Requirements of Adsorbents for Individual Protection

15.4 MOFs in Monolithic Structures

References

Index

Related Titles

Tremel, W., zur Loye, H. (eds.)

Handbook of Solid State Chemistry

Hardcover

ISBN: 978-3-527-32587-0

Schubert, U., Hüsing, N.

Synthesis of Inorganic Materials

Softcover

ISBN: 978-3-527-32714-0

MacGillivray, L.

Metal-Organic Frameworks

Design and Application

Hardcover

ISBN: 978-0-470-19556-7

Stolten, D. (ed.)

Hydrogen and Fuel Cells

Fundamentals, Technologies and Applications

2010

Hardcover

ISBN: 978-3-527-32711-9

Hirscher, M. (ed.)

Handbook of Hydrogen Storage

New Materials for Future Energy Storage

2010

Hardcover

ISBN: 978-3-527-32273-2

Züttel, A., Borgschulte, A.,

Schlapbach, L. (eds.)

Hydrogen as a Future Energy Carrier

2008

Hardcover

ISBN: 978-3-527-30817-0

Öchsner, A., Murch, G. E., de Lemos,

M. J. S. (eds.)

Cellular and Porous Materials

Thermal Properties Simulation and Prediction

2008

Hardcover

ISBN: 978-3-527-31938-1

The Editor

Dr. David Farrusseng

University Lyon 1, CNRS

IRCELYON

2, Av. Albert Einstein

69626 Villeurbanne

France

Cover

The structures on the front covers are based on material supplied by the editor David Farrusseng and images from chapter 1 (authored by Satoshi Horike and Susumu Kitagawa).

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Library of Congress Card No.: applied for

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.d-nb.de.

© 2011 Wiley-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.

Print ISBN: 978-3-527-32870-3

ePDF ISBN: 978-3-527-63587-0

ePub ISBN: 978-3-527-63586-3

Mobi ISBN: 978-3-527-63588-7

oBook ISBN: 978-3-527-63585-6

Preface

This deliberately application-oriented book is divided into six parts. Each chapter refers to the original literature and can be read independently of the other chapters.

The first part of this book emphasizes the uniqueness of MOFs compared with other porous solids in terms of intrinsic material properties and engineering capabilities. In particular, MOFs are characterized by their softness and by their associated host–guest dynamic properties that make them “smart” materials. The first chapter establishes the mechanisms and provides an outlook on how to proceed in designing multifunctional MOFs, using techniques for addition or modification of physical or chemical features within the frameworks. The second chapter gives a critical review of post-modification methods with emphasis on catalytic applications.

The second part deals with gas storage and separation. The different types of flexibility and the thermodynamic description of breathing are given in Chapter 3, and the associated solids and applications are detailed in Chapter 4. Carbon dioxide capture is treated in detail for PSA/TSA processes in Chapter 5 and for membrane processes in Chapter 6. The topic of hydrogen storage is discussed in Chapter 7.

The third part deals with bulk chemistry. Chapter 8 deals with the separation of xylenes, and Chapter 9 provides a review of MOF applications in catalysis, with particular focus placed on structure–activity relationships.

The fourth part encompasses an overview of medical applications of MOFs (Chapter 10) and imaging (Chapter 11).

In the fifth part, the use of MOFs in the design of small-scale devices and sensors is discussed. Luminescence properties and possible applications are described in Chapter 12. Thin-film preparations for sensor applications are detailed in Chapter 13.

The sixth part discusses the mass production of MOFs, with attention devoted to economic criteria (Chapter 14), and also the shaping of MOFs as large bodies and their immobilization as composite materials with polymer fibers (Chapter 15).

I hope that the information in this book will be of interest both to researchers involved in the development of chemical and physical processes and to scientists focusing on porous solids. I also hope that it will help establish a common ground between different communities by providing a multidisciplinary point of view, including solid-state chemistry, materials science, and process engineering.

The European Community is acknowledged for supporting R&D in this field through the Integrated Projects NanoMOF and Macademia (FP7-NMP).

David Farrusseng

List of Contributors

Sonia Aguado

Université Lyon 1

IRCELYON

CNRS UMR 5256

2 avenue Albert Einstein

69626 Villeurbanne

France

Luc Alaerts

Katholieke Universiteit Leuven

Centre for Surface Chemistry

and Catalysis

Kasteelpark Arenberg 23

3001 Leuven

Belgium

Mark D. Allendorf

Sandia National Laboratories

Department of Energy Nanomaterials

7011 East Avenue

Livermore, CA 94550

USA

Elisa Barea

Universidad de Granada

Facultad de Ciencias

Departamento de Química Inorgánica

Av. Fuentenueva S/N

18071 Granada

Spain

Christina A. Bauer

University of California, Los Angeles

Department of Chemistry and Biochemistry

607 Charles E. Young Drive East

Los Angeles, CA 90095

USA

Angélique Bétard

Ruhr-Universität Bochum

Anorganische Chemie II –

Organometallics & Materials

Universitätsstrasse 150

44801 Bochum

Germany

Bertram Böhringer

Blücher GmbH

Mettmannerstrasse 25

40699 Erkrath

Germany

Jérôme Canivet

Université Lyon 1

IRCELYON

CNRS UMR 5256

2 avenue Albert Einstein

69626 Villeurbanne

France

François-Xavier Coudert

Chimie ParisTech

11 rue Pierre et Marie Curie

75005 Paris

France

Alexander Czaja

BASF SE

GCC/PZ – CNSI

570 Westwood Plaza

Los Angeles, CA 90095

USA

Anne Dailly

General Motors Company

R&D Technical Center

Hydrogen Fuel Chemistry and Systems

30500 Mount Road

Warren, MI 48090

USA

Joseph Della Rocca

University of North Carolina

at Chapel Hill

School of Pharmacy

Department of Chemistry

125 South Road

Chapel Hill, NC 27599

USA

Joeri F.M. Denayer

Vrije Universiteit Brussel

Department of Chemical Engineering

Pleinlaan 2

1050 Brussels

Belgium

Dirk De Vos

Katholieke Universiteit Leuven

Centre for Surface

Chemistry and Catalysis

Kasteelpark Arenberg 23

3001 Leuven

Belgium

David Farrusseng

Université Lyon 1

IRCELYON

CNRS UMR 5256

2 avenue Albert Einstein

69626 Villeurbanne

France

Roland Fischer

Norafin GmbH

Gewerbegebiet Nord 3

09456 Mildenau

Germany

Roland A. Fischer

Ruhr-Universität Bochum

Anorganische Chemie II –

Organometallics & Materials

Universitätsstrasse 150

44801 Bochum

Germany

Patricia Horcajada

Université de Versailles St.-Quentin

en Yvelines

Institut Lavoisier

UMR CNRS 8180

45 Avenue des Etats-Unis

78035 Versailles

France

Satoshi Horike

Kyoto University

Graduate School of Engineering

Department of Synthetic Chemistry

and Biological Chemistry

Kyoto Daigaku Katsura

Nishikyo-ku

615-8510 Kyoto

Japan

Stefan Kaskel

Technische Universität Dresden

Institut für Anorganische Chemie

Bergstrasse 66

01069 Dresden

Germany

Susumu Kitagawa

Kyoto University

Graduate School of Engineering

Department of Synthetic Chemistry

and Biological Chemistry

Kyoto Daigaku Katsura

Nishikyo-ku

615-8510 Kyoto

Japan

Pia Küsgens

Technische Universität Dresden

Institut für Anorganische Chemie

Bergstrasse 66

01069 Dresden

Germany

Philibert Leflaive

IFP-Lyon

Separation Department

Rond-point de l.échangeur de Solaize

69360 Solaize

France

Emi Leung

BASF SE

GCC/PZ – CNSI

570 Westwood Plaza

Los Angeles, CA 90095

USA

Wenbin Lin

University of North Carolina

at Chapel Hill

School of Pharmacy

Department of Chemistry

125 South Road

Chapel Hill, NC 27599

USA

Philip L. Llewellyn

Universités Aix-Marseille I, II,

et III – CNRS

Laboratoire Chimie Provence

(UMR 6264)

Centre de Saint Jérôme

Avenue Escadrille Normandie-Niemen

13397 Marseille

France

Martin R. Lohe

Technische Universität Dresden

Institut für Anorganische Chemie

Bergstrasse 66

01069 Dresden

Germany

Johan A. Martens

Katholieke Universiteit Leuven

Centre for Surface Chemistry

and Catalysis

Kasteelpark Arenberg 23

3001 Leuven

Belgium

Alistair C. McKinlay

University of St. Andrews

EaStChem School of Chemistry

Purdie Building

North Haugh

St. Andrews KY16 9ST

UK

Russell E. Morris

University of St. Andrews

EaStChem School of Chemistry

Purdie Building

North Haugh

St. Andrews KY16 9ST

UK

Ulrich Müller

BASF SE

GCC/PZ – CNSI

570 Westwood Plaza

Los Angeles, CA 90095

USA

John J. Perry IV

Sandia National Laboratories

Department of Energy Nanomaterials

7011 East Avenue

Livermore, CA 94550

USA

Gerhard D. Pirngruber

IFP Energies Nouvelles

Rond-point de l.échangeur de Solaize

69360 Solaize

France

Alessandra Quadrelli

Université de Lyon

ESCPE Lyon

CNRS UMR 9986

43 boulevard du 11 Novembre 1918

69616 Villeurbanne

France

Jorge A. Rodriguez Navarro

Universidad de Granada

Facultad de Ciencias

Departamento de Química Inorgánica

Av. Fuentenueva S/N

18071 Granada

Spain

Marcus Rose

Technische Universität Dresden

Institut für Anorganische Chemie

Bergstrasse 66

01069 Dresden

Germany

Christian Serre

Université de Versailles St.-Quentin

en Yvelines

Institut Lavoisier

UMR CNRS 8180

45 Avenue des Etats-Unis

78035 Versailles

France

Natalia Trukhan

BASF SE

GCC/PZ – CNSI

570 Westwood Plaza

Los Angeles, CA 90095

USA

Fabrizio Turra

SIAD SpA

Stabilimento di Osio Sopra (BG)

SS 525 del Brembo no 1

24040 Osio Sopra, BG

Italy

Lik Hong Wee

Katholieke Universiteit Leuven

Centre for Surface Chemistry and

Catalysis

Kasteelpark Arenberg 23

3001 Leuven

Belgium

Part One

Design of Multifunctional Porous MOFs

Chapter 2

Design of Functional Metal–Organic Frameworks by Post-Synthetic Modification

David Farrusseng, Jérôme Canivet, and Alessandra Quadrelli

During the past decade, metal–organic frameworks (MOFs) have become probably the most studied family of porous solids because of their almost infinite variations in structure and composition. However, the use of their full synthetic potential might be further improved, and post-synthetic modification, that is modification of the solid after synthesis, is a powerful tool to achieve that aim.

2.1 Building a MOFs Toolbox by Post-Synthetic Modification

2.1.1 Taking Advantage of Immobilization in a Porous Solid

Zeolites, which belong to the great family of crystalline porous materials, are widely used in gas separation, catalysis (petrochemical cracking) and ion-exchange beds (water purification). However, post-modification of microporous zeolites is limited to just cation exchange or silanation. In addition, zeolites also have a drastic limitation to their pore size. Among other porous materials, mesoporous silicate (MS) materials, such as MCM-41 and SBA-15 [1, 2] are widely used as adsorbents or catalysts. Unlike the highly ordered MOFs, they are amorphous and therefore exhibit relatively disordered hydroxyl groups at the wall surface [3]. In addition, the diversity of MS materials is limited in terms of composition and porous structure, thus narrowing the scope of applications.

Many research groups have already reported the use of post-modified porous solids for adsorption applications. The post-calcination silanation of mesoporous silica such as SBA-15 led to the development of interesting mercury-selective adsorbents, as reported by Jaroniec and co-workers, these functionalized solids being able to remove contaminant mercury from waste oils [4, 5]. These materials were obtained by silanol capping of thiourea derivatives on the silica pore surface. Similar materials have been prepared using amine-terminated organolisilanes, but coverage of the silica surface was complicated by the presence of the basic N atoms and their interactions with the surface silanols and/or the remaining hydroxyl groups [6]. Post-modification involving amine functionalization was also successfully applied to zeolites and mesoporous silicates for the adsorption of carbon dioxide [7].