Low-Dimensional Solids E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Fachliteratur
• Serie: Inorganic Materials Series
• Sprache: Englisch

Seitenzahl: 546

Veröffentlichungsjahr: 2011

Beschreibung

With physical properties that often may not be described by the transposition of physical laws from 3D space across to 2D or even 1D space, low-dimensional solids exhibit a high degree of anisotropy in the spatial distribution of their chemical bonds. This means that they can demonstrate new phenomena such as charge-density waves and can display nanoparticulate (0D), fibrous (1D) and lamellar (2D) morphologies.

This text presents some of the most recent research into the synthesis and properties of these solids and covers:

• Metal Oxide Nanoparticles
• Inorganic Nanotubes and Nanowires
• Biomedical Applications of Layered Double Hydroxides
• Carbon Nanotubes and Related Structures
• Superconducting Borides

Introducing topics such as novel layered superconductors, inorganic-DNA delivery systems and the chemistry and physics of inorganic nanotubes and nanosheets, this book discusses some of the most exciting concepts in this developing field.

Additional volumes in the Inorganic Materials Book Series:

Molecular Materials
Functional Oxides
Porous Materials
Energy Materials

All volumes are sold individually or as comprehensive 5 Volume Set.

Leseprobe

Contents

Cover

Half Title page

Title page

Copyright page

Inorganic Materials Series Preface

Preface

List of Contributors

Chapter 1: Metal Oxide Nanoparticles

1.1 Introduction

1.2 Oxide types; point defects and electrical conductivity

1.3 Preparation of nanoionic materials

1.4 Characterisation

1.5 Review of the current experimental data and their agreement with theory

1.6 Applications

1.7 Overview and prospects

References

Chapter 2: Inorganic Nanotubes and Nanowires

2.1 Introduction

2.2 Inorganic Nanotubes

2.3 Nanowires

2.4 Outlook

References

Chapter 3: Biomedical Applications of Layered Double Hydroxides

3.1 Introduction

3.2 Nanomaterials for Biological Applications

3.3 Nanomaterials for Dna Molecular Code System

3.4 Conclusion

References

Chapter 4: Carbon Nanotubes and Related Structures

4.1 Introduction

4.2 Endohedral fullerenes

4.3 Carbon nanotubes

4.4 Other carbon nanotube forms

4.5 Carbon Nano-onions

4.6 Graphenes

4.7 Summary and Outlook

Acknowledgements

References

Chapter 5: Carbon Nanotubes and Related Structures

5.1 Introduction

5.2 Preparation of Pure and Alloyed MgB2

5.3 Physical Properties of MB2

5.4 Flux Line Properties in Single Crystals of MgB2, Mg1−xAlxB2 AND MgB2−xCx

5.5 Conclusions

References

Index

Low-Dimensional Solids

Inorganic Materials Series

Editors:

Professor Duncan W. BruceDepartment of Chemistry, University of York, UK

Professor Dermot O’HareChemistry Research Laboratory, University of Oxford, UK

Professor Richard I. WaltonDepartment of Chemistry, University of Warwick, UK

Series Titles

Functional Oxides

Molecular Materials

Porous Materials

Low-Dimensional Solids

Energy Materials

This edition first published 2010

© 2010 John Wiley & Sons, Ltd

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Library of Congress Cataloging-in-Publication Data

Low-dimensional solids / edited by Duncan W. Bruce, Dermot O'Hare, Richard I. Walton.

p. cm. — (Inorganic materials series)

Includes bibliographical references and index.

ISBN 978-0-470-99751-2 (cloth)

1. Nanotubes. 2. Nanowires. 3. Metallic oxides. 4. Inorganic compounds.

5. Superconducting composites. I. Bruce, Duncan W. II. O’Hare, Dermot.

III. Walton, Richard I.

TA418.9.N35L69 2010

620′.5—dc22

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

Print ISBN: 978-0-470-99751-2 (Cloth)

ePDF ISBN: 978-0-470-66139-0

oBook ISBN: 978-0-470-66140-6

Inorganic Materials Series Preface

Back in 1992, two of us (DWB and DO’H) edited the first edition of Inorganic Materials in response to the growing emphasis and interest in materials chemistry. The second edition, which contained updated chapters, appeared in 1996 and was reprinted in paperback. The aim had always been to provide the reader with chapters that while not necessarily comprehensive, nonetheless gave a first-rate and well-referenced introduction to the subject for the first-time reader. As such, the target audience was from first-year postgraduate student upwards. Authors were carefully selected who were experts in their field and actively researching their topic, so were able to provide an up-to-date review of key aspects of a particular subject, whilst providing some historical perspective. In these two editions, we believe our authors achieved this admirably.

In the intervening years, materials chemistry has grown hugely and now finds itself central to many of the major challenges that face global society. We felt, therefore, that there was a need for more extensive coverage of the area and so Richard Walton joined the team and, with Wiley, we set about a new and larger project. The Inorganic Materials Series is the result and our aim is to provide chapters with a similar pedagogical flavour but now with much wider subject coverage. As such, the work will be contained in several themed volumes. Many of the early volumes concentrate on materials derived from continuous inorganic solids, but later volumes will also emphasise molecular and soft matter systems as we aim for a much more comprehensive coverage of the area than was possible with Inorganic Materials.

We approached a completely new set of authors for the new project with the same philosophy in choosing actively researching experts, but also with the aim of providing an international perspective, so to reflect the diversity and interdisciplinarity of the now very broad area of inorganic materials chemistry. We are delighted with the calibre of authors who have agreed to write for us and we thank them all for their efforts and cooperation. We believe they have done a splendid job and that their work will make these volumes a valuable reference and teaching resource.

DWB, YorkDO’H, OxfordRIW, WarwickJuly 2010

Preface

The late Professor Jean Rouxel once wrote that ‘solids bring to mind the idea of volume, and it may therefore seem paradoxical to discuss solids of low dimensionality’. Nonetheless, the concept has remained useful and is still widely used by both chemists and physicists but perhaps not to describe the same thing!

To a chemist a low-dimensional solid may refer to a structure or compound in which there is a high degree of anisotropy in the spatial distribution of the chemical bonds, which may lead to nanoparticulate (0D), fibrous (1D), or lamellar (2D) morphologies. On the other hand a physicist may take advantage of the anisotropy of a certain physical property such as electrical conductivity, optical response or magnetisation. In fact the physical properties of low-dimensional solids cannot be fully described by simply transposing in 2 or 1 dimension the physical laws that hold for 3D space. Low-dimensional solids can exhibit new phenomena, for example the well-known case of charge density waves that were observed in the layered, transition-metal dichalogenides.

In this book we would like to introduce you to new, relevant, contemporary topics, which deal with the synthesis and properties of low-dimensional solids. The five chapters describe structures, applications or phenomena not known when Inorganic Materials was produced. Our line-up of distinguished international authors have written on topics ranging from the chemistry and physics of inorganic nanotubes and sheets, quantum effects in nanoparticles, novel layered superconductors to inorganic-DNA delivery systems.

We are delighted by their efforts and trust you find what they have written both fascinating and exciting.

DWB, YorkDO’H, OxfordRIW, WarwickJuly 2010

List of Contributors

Alan V. Chadwick School of Physical Sciences, University of Kent, Canterbury, UK

Jin-Ho Choy Center for Intelligent Nano-Bio Materials, Department of Bioinspired Science and Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea

Juan Luis Delgado IMDEA-Nanociencia, Facultad de Ciencias, Univer-sidad Autónoma de Madrid, Madrid, Spain

A. Govindaraj CSIR Centre of Excellence in Chemistry, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore, India

M. Ángeles Herranz Departamento de Química Orgánica, Universidad Complutense, Madrid, Spain

Nazario Martín Departamento de Química Orgánica, Universidad Com-plutense, Madrid, Spain

Jae-Min Oh Center for Intelligent Nano-Bio Materials, Department of Bioinspired Science and Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea

Dae-Hwan Park Center for Intelligent Nano-Bio Materials, Department of Bioinspired Science and Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea

Michael Pissas Institute of Materials Science, NCSR Demokritos, Athens, Greece

C. N. R. Rao CSIR Centre of Excellence in Chemistry, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore, India

Shelley L. P. Savin School of Physical Sciences, University of Kent, Canterbury, UK

S. R. C. Vivekchand CSIR Centre of Excellence in Chemistry, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore, India

Chapter 1

Metal Oxide Nanoparticles

Alan V. Chadwick Shelley L.P. Savin

Functional Materials Group, School of Physical Sciences, University of Kent, Canterbury, Kent, UK

1.1 INTRODUCTION

Systems that contain particles with one dimension in the nanometre regime are now referred to as nanomaterials. Over the last decade there has been a growing interest from biologists, chemists, physicists and engineers in the applications of these materials, so-called nanotechnology, which is often referred to as ‘the next industrial revolution’.[1,2] The reasons for this interest are the unusual properties, with potential technological applications, that are exhibited by these materials when compared with their bulk counterparts.[3–11] Amongst the vast array of chemical compounds that have been prepared as nanomaterials there has been a particular attention on polar oxides, where the bonding is ionic or semi-ionic, and these systems will be the focus of this chapter. There are several reasons for the interest in these materials. First, these materials were amongst the earliest nano-materials subjected to detailed investigation and there is now a sound background in their preparation and characterisation. For over twenty years there has been continuous research in this area following the pion-eering work of Gleiter.[3,4,8]Secondly, the interatomic interactions are often predominantly Coulomb forces, or if not can be modelled quite well with an empirical ionic potential,[12–15]and therefore are an ideal test-bed for models of nanocrystalline properties. Finally, these oxides are used in a vast array of important commercial applications. These applications are wide ranging; from electronics and optoelectronics (e.g. sensors), to energy storage and production (fuel cells and batteries), and to usage in the chemical industry (catalysts and supports).

The origins of the unusual properties of nanomaterials can be considered as twofold; (i) the fact that the dimensions of the particles approach, or become smaller than, the critical length for certain phenomena (e.g. the de Broglie wavelength for the electron, the mean free path of excitons, the distance required to form a Frank–Reed dislocation loop, thickness of the space-charge layer, etc.) and (ii) surface effects dominate the thermodynamics and energetics of the particles (e.g. crystal structure, surface morphology, reactivity, etc.). In nanostructured semiconductors it is the first of these which leads to special electrical, magnetic and optical properties and the possibility of quantum dot devices. It is also an explanation of unusual hardness, sometimes referred to as super-hardness, of nanocrystals.[16]The second factor can lead to nanocrystals adopting different morphologies to bulk crystals with different exposed lattice planes leading to an extraordinary surface chemistry and catalytic activity.[17]The importance of surfaces and boundaries in nanocrystalline systems is demonstrated in Figure 1.1, which shows the fraction of atoms in these regions as a function of grain size.

Figure 1.1 Percentage of atoms in grain boundaries as a function of grain size assuming boundary widths of 0.5 and 1 nm (after[9]

Many of the unusual features of nanocrystalline oxides, such as superplasticity – the observation of higher strain rates of nanocrystalline ceramics than for their microcrystalline counterparts[16] – are due to unusually high atomic transport, which has been assigned to the special nature of the interfaces between the crystallites. The earliest experimental studies of self-diffusion in nanocrystalline metals yielded diffusion coefficients many orders of magnitude higher than the values found for bulk diffusion in single crystals[4,18,19]and even higher than the values found for grain boundary diffusion, which is usually regarded as the fastest diffusion process in a solid. The phenomenon has been regarded as generic to nanocrystals independent of the interatomic bonding. An early explanation of the origin of this unusually fast atomic transport was that the interfaces between the grains in a nanocrystalline compact were highly disordered in comparison with the normal grain boundaries found in normal solids. The two types of interface are illustrated in Figure 1.2. The model assumed for a nanocrystalline sample is drawn schematically in Figure 1.2a, with extensive disorder in the interface that is several atoms in width. In this figure the black circles represent atoms in the grains and the open circles are the atoms in the interfaces. In some of the early work on nanocrystals this was intuitively assumed to be the case and the interfaces were referred to as ‘gas-like’ or ‘liquid-like’. This structure would clearly account for rapid diffusion in nanocrystalline samples. More recently an alternative view has emerged in which the nanocrystalline interface is similar to a grain boundary in normal bulk materials, as shown in b. In this case the interfaces would exhibit usual behaviour, although they would be present in unusually large number, and therefore the compacted nanocrystalline sample would show higher diffusivity than a coarse-grained counterpart. Since many of the applications of ionic materials are due to their transport of charge by the ions the use of nanocrystalline samples offers an obvious means of improved performance.