Metal-Organic Frameworks E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 588

Veröffentlichungsjahr: 2010

Beschreibung

Metal-organic frameworks represent a new class of materials that may solve the hydrogen storage problem associated with hydrogen-fueled vehicles. In this first definitive guide to metal-organic framework chemistry, author L. MacGillivray addresses state-of-art developments in this promising technology for alternative fuels. Providing professors, graduate and undergraduate students, structural chemists, physical chemists, and chemical engineers with a historical perspective, as well as the most up-to-date developments by leading experts, Metal-Organic Frameworks examines structure, symmetry, supramolecular chemistry, surface engineering, metal-organometallic frameworks, properties, and reactions.

Leseprobe

Contents

Cover

Title Page

Copyright

Preface

Reference

Contributors

Chapter 1: From Hofmann Complexes to Organic Coordination Networks

1.1 Introduction

1.2 Discovery of a Coordination Network

1.3 Organic Coordination Network: Organic Modification of the Hofmann Complex

1.4 M-Bipyridine Square Grids: Two-Way Link. Toward New Functions and Applications of Organic Coordination Networks

1.5 Single-Crystal-to-Single-Crystal Phenomena in Porous Coordination Networks

1.6 Expansion From Two- to Three-Way Link: Construction of TPT Coordination Networks

1.7 Biporous Coordination Networks

1.8 Concluding Remarks

References

Chapter 2: Insight into the Development of Metal-Organic Materials (MOMs): At Zeolite-like Metal-Organic Frameworks (ZMOFs)

2.1 Introduction

2.2 Metal-Organic Materials (MOMs)

2.3 Conclusion

References

Chapter 3: Topology and Interpenetration

3.1 Introduction

3.2 Nomenclature

3.3 Common 2D Nets

3.4 Common 3D Nets

3.5 Interpenetration

References

Chapter 4: Highly Connected Metal-Organic Frameworks

4.1 Introduction

4.2 Metal Cations as Highly Connected Nodes

4.3 Metal Clusters as Highly Connected Nodes

4.4 Framework Topologies

4.5 Conclusions

Acknowledgments

References

Chapter 5: Surface Pore Engineering of Porous Coordination Polymers

5.1 Introduction

5.2 Pore Surface with OMSs

5.3 Pore Surface with Functional Organic Sites (FOS)

5.4 Post-synthetic Pore Surface Modifications

5.5 Summary and Perspectives

Acknowledgment

References

Chapter 6: Rational Design of Non-centrosymmetric Metal-Organic Frameworks for Second-Order Nonlinear Optics

6.1 Introduction

6.2 Design Strategies for Non-Centrosymmetric Metal-Organic Frameworks

6.3 Non-Centrosymmetric Metal-Organic Frameworks for Second-Order Nonlinear Optical Applications

6.4 Conclusions and Outlook

Acknowledgments

References

Chapter 7: Selective Sorption of Gases and Vapors in Metal-Organic Frameworks

7.1 Introduction

7.2 Selective Gas Sorption by MOFs

7.3 Selective Vapor Sorption by MOFs

7.4 Potential Applications in Practical Separation Processes

7.5 Conclusions

Acknowledgments

List of abbreviations

Note Added in Proof

References

Chapter 8: Hydrogen and Methane Storage in Metal-Organic Frameworks

8.1 Introduction 1, 2

8.2 Hydrogen Storage

8.3 Methane Storage

8.4 Outlook

References

Chapter 9: Towards Mechanochemical Synthesis of Metal-Organic Frameworks: From Coordination Polymers and Lattice Inclusion Compounds to Porous Materials

9.1 Introduction

9.2 Advantages and Limitations of Mechanosynthesis

9.3 Methods for Mechanosynthesis of Coordination Bonds

9.4 Mechanochemical Reactivity Leading to Coordination Polymers

9.5 Construction of Coordination Polymers by Grinding

9.6 Related NonConventional Techniques

9.7 Conclusion

Acknowledgments

List of abbreviations

References

Chapter 10: Metal-Organic Frameworks with Photochemical Building Units

10.1 Introduction

10.2 [2 + 2] Photodimerization in the Solid State

10.3 [2 + 2] Photodimerizations Integrated into MOFs

10.4 Cyclobutanes as Organic Bridges of MOFs

10.5 Conclusion

References

Chapter 11: Molecular Modeling of Adsorption and Diffusion in Metal-Organic Frameworks

11.1 Models and Methods

11.2 Molecular Modeling of Adsorption in MOFs

11.3 Molecular Modeling of Diffusion in MOFs

11.4 Molecular Modeling of Hydrogen Storage in MOFs

11.5 Summary and Future Directions

Acknowledgments

References

Index

Copyright © 2010 by John Wiley & Sons, Inc. All rights reserved.

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

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Library of Congress Cataloging-in-Publication Data:

Metal-organic frameworks: design and application / edited by Leonard R. MacGillivray.

p. cm.

Includes index.

ISBN 978-0-470-19556-7 (cloth)

1. Supramolecular organometallic chemistry. 2. Organometallic polymers. 3. Porous materials. I. MacGillivray, Leonard R.

QD882.M48 2010

5470'.0504426-dc22

2009049259

Preface

The field of metal-organic frameworks, or MOFs, is undergoing accelerated and sustained growth. I personally became acquainted with MOFs, or more generally coordination polymers, as an undergraduate research student while at Saint Mary's University, Halifax, Nova Scotia, Canada, from 1991 to 1994. The process of mixing readily available metal precursors with organic linkers—many of which fell under the heading of being commercially available—to produce a wide array of extended frameworks clearly then, and now, captured the imagination of chemists and materials scientists worldwide.

From a fundamental standpoint, there is an important link between MOF chemistry and the field of inorganic chemistry. In many ways, MOF chemistry enables chemists to connect previously existing coordination complexes so as to make a conceptual link into the field of materials chemistry. This link has now evolved to afford applications ranging from catalysis to energy storage. Organic chemists are also able to contribute to the mix by crafting ligands with properties that one ultimately plans to express within the walls of MOFs. Solid-state chemists and X-ray crystallographers provide insights into the structures of MOFs so that the process of designing and synthesizing MOFs can be refined so as to ultimately control a targeted property and give rise to function.

My personal draw to MOFs was, in retrospect, also inspired by the field of supramolecular chemistry, particularly as it relates to the rational design of solids, or crystal engineering. The early 1990s witnessed supramolecular chemistry envelop the process of self-assembly, with a crystal being regarded as a supermolecule par excellence. [1] Metal–ligand bonding is reversible and, thus, fits within the realm of supramolecular chemistry. Self-assembly involves subunits of a larger superstructure being repeated in zero-dimensional (0D), 1D, 2D, or 3D space, with the solid state being a perfect resting place for intermolecular forces to dominate. Today, many of the boundaries between these areas have become increasingly more difficult to distinguish, which can be expected as more is being uncovered and as more emphasis is placed on properties and function.

It is, thus, with great pleasure that I am able to assemble a multi-author monograph that includes authoritative contributions from leading research laboratories in the field of MOF chemistry. My goal is to provide insights into where the field of MOFs began to take root and provide an account of the fundamentals that define where the field has come and is able to go. Indeed, MOFs provide chemists a means to think about how to utilize coordination space to mimic the chemistry of zeolites with an added degree of organic function. These possibilities have become apparent in key developments and important advances that are outlined in the chapters that follow.

Fujita (Chapter 1) and Eddaoudi (Chapter 2), for example, document the first reports of MOFs, or coordination networks, particularly those that exhibit catalysis, the emergence of heteroaromatic ligands, and how carboxylates provided an important entry to increasingly robust solids. Batten (Chapter 3) demonstrates a role of symmetry in defining and understanding the simple and complex frameworks that result from the solid-state assembly process that affords a MOF. Next, Schroder (Chapter 4) addresses the design and synthesis of extended frameworks of increasingly structural complexity in the form of highly connected MOFs based on lanthanide ions. Kitagawa (Chapter 5) then shows how the internal structures of coordination networks can be rationally modified and tailored with organic groups while Lin (Chapter 6) documents some of the first systematic applications of MOFs as they relate to the generation of nonlinear optic materials. A great challenge facing mankind is making efficient use of energy. MOFs have emerged as potentially useful platforms for facing this challenge in the form of gas storage, separation, and conversion. Thus, Kim (Chapter 7) and Zhou (Chapter 8) address how MOFs interact with small gas molecules (e.g., H2) and how these materials may be integrated into schemes for energy utilization. In a related topic, Friscic (Chapter 9) tackles the emerging issue of mechanochemical, or solvent-free, “green” preparation of MOFs while work by our group demonstrates how the walls of extended frameworks can be designed to serve as platforms for light-induced chemical reactions (Chapter 10). Finally, Snurr (Chapter 11) addresses how the field of computational chemistry can be used to understand, and ultimately, aide the design of MOFs, with targeted applications in separations, gas uptake, and materials characterization. Carefully chosen references serve to guide the reader through the extensive literature, which makes the field accessible to a wide and varied audience.

My initial interests in the chemistry of MOFs, and supramolecular chemistry and solid-state chemistry in general, stemmed from an experience as an undergraduate researcher. It is for this reason that I dedicate this monograph to the undergraduate research experience and to all of those that support undergraduate research.

Leonard R. MacGillivray

Iowa City, IA

March 2010

Reference

1. Dunitz, J. D. Pure Appl. Chem. 1991, 63, 177.

Contributors

Stuart R. Batten, School of Chemistry, Clayton Campus, Bldg. 19, Monash University, 3800 Australia

Neil R.Champness, School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK

Hyungphil Chun, Department of Applied Chemistry, College of Science and Technology, Hanyang University, 1271 Sadong, Ansan 426-791, Republic of Korea

David J. Collins, Department of Chemistry and Biochemistry, Miami University, Oxford, OH 45056, USA; Department of Chemistry, Texas A&M University, College Station, TX 77843, USA

David Dubbeldam, Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road E136, Evanston, IL 60208, USA

Saikat Dutta, Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA

Mohamed Eddaoudi, Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, CHE204, Tampa, FL 33620, USA

Jarrod F. Eubank, Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, CHE204, Tampa, FL 33620, USA

Tomislav Friši, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK

Houston Frost, Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road E136, Evanston, IL 60208, USA

Makoto Fujita, Department of Applied Chemistry, School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan

Ivan G. Georgiev, Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA

Sujit K. Ghosh, Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan; Department of Chemistry, Indian Institute of Science Education and Research (IISER), Pune, India

Peter Hubberstey, School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK

Hyunuk Kim, National Creative Research Initiative Center for Smart Supramolecules, Department of Chemistry and Division of Advanced Materials Science, Pohang University of Science and Technology, Pohang, 790-784, Republic of Korea

Kimoon Kim, National Creative Research Initiative Center for Smart Supramolecules, Department of Chemistry and Division of Advanced Materials Science, Pohang University of Science and Technology, Pohang, 790-784, Republic of Korea

Susumu Kitagawa, Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615–851 Japan; Kitagawa Integrated Pore Project, Exploratory Research for Advanced Technology (ERATO), Japan Science and Technology Agency (JST), Shimogyoku, Kyoto 600-8815, Japan; Institute for Cell Materials Sciences (iCeMS), Kyoto University, Sokyo-ku, Kyoto, Japan

Wenbin Lin, Department of Chemistry, CB3290, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, USA

Xiang Lin, School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK

Shengqian Ma, Department of Chemistry and Biochemistry, Miami University, Oxford, OH 45056, USA; Department of Chemistry, Texas A&M University, College Station, TX 77843, USA

Leonard R. MacGillivray, Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA

Martin Schröder, School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK

Randall Q. Snurr, Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road E136, Evanston, IL 60208, USA

A. ˝zgr Yazaydin, Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road E136, Evanston, IL 60208, USA

Shuting Wu, Department of Chemistry, CB3290, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, USA

Hong-Cai Zhou, Department of Chemistry and Biochemistry, Miami University, Oxford, OH 45056, USA; Department of Chemistry, Texas A&M University, College Station, TX 77843, USA