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NANOSCALE MATERIALS
IN CHEMISTRY
NANOSCALE MATERIALS
IN CHEMISTRY
Edited by
Kenneth J. Klabunde
Copyright # 2001 by John Wiley & Sons, Inc. All rights reserved.
No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form
or by any means, electronic or mechanical, including uploading, downloading, printing, decompiling,
recording or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States
Copyright Act, without the prior written permission of the Publisher. Requests to the Publisher for
permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third
Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-Mail:
[email protected].
This publication is designed to provide accurate and authoritative information in regard to the subject
matter covered. It is sold with the understanding that the publisher is not engaged in rendering professional
services. If professional advice or other expert assistance is required, the services of a competent
professional person should be sought.
ISBN 0-471-22062-0
For more information about Wiley products, visit our web site at www.Wiley.com.
To Linda
CONTENTS
Preface ix
Contributors xi
1 Introduction to the Nanoworld 1
Kenneth J. Klabunde
2 Metals 15
Gunter Schmid
3 Semiconductor Nanocrystals 61
M. P. Pileni
4 Ceramics 85
Abbas Khaleel and Ryan M. Richards
5 Metal Nanoparticles: Double Layers, Optical Properties, and
Electrochemistry 121
Paul Mulvaney
6 Magnetism 169
C. M. Sorensen
7 Chemical and Catalytic Aspects of Nanocrystals 223
Kenneth J. Klabunde and Ravichandra S. Mulukutla
8 Specific Heats and Melting Points of Nanocrystalline Materials 263
Olga Koper and Slawomir Winecki
9 Applications of Nanocrystals 279
John Parker
Index 287
vii
PREFACE
DR. ABBAS KHALEEL, Dept. of Chemistry, UAE University, Al-Ain, United Arab
Emirates
PROFESSOR KENNETH J. KLABUNDE, Dept. of Chemistry, Kansas State University,
Manhattan, KS 66506
DR. OLGA KOPER, Nanoscale Materials, Inc., 1500 Hayes Drive, Manhattan, KS
66502
DR. RAVICHANDRA S. MULUKUTLA, Department of Chemistry, Kansas State
University, Manhattan, Kansas 66506
DR. PAUL MULVANEY, Advanced Mineral Products, School of Chemistry,
University of Melbourne, Parkville, VIC 3052, Australia
DR. JOHN C. PARKER, 1588 Clemson Dr., Naperville, IL 60565
PROFESSOR MARIE PILENI, Department of Chemistry, Laboratorie SRSI, URA
CNRS 1662, Universite P. et M. Curie (Paris VI), BP52, 4 Place Jussieu, 75231
Paris Cedex 05, France
DR. RYAN RICHARDS, Dept. of Chemistry, Max Planck Institute, Kaiser Wilhelm
Platz 1, 45470 Mulheim an der Ruhr, Germany
PROFESSOR GUNTER SCHMID, Institute fur Anorganische Chemie, Universitat
Essen, Essen, Germany
PROFESSOR CHRIS SORENSEN, Dept. of Physics, Cardwell Hall, Kansas State
University, Manhattan, KS 66506
DR. SLAWOMIR WINECKI, Nanoscale Materials, Inc., 1500 Hayes Drive, Manhat-
tan, KS 66502
xi
Index
1D Bacteria, 7
Assemblies, 52 Bactericide, 253
Channels, 53 Ballmilling, 239
Defined Steps, 53 Band Structure, 18
Nanoclusters, 52 Band Theory, 187
Pores, 53 Bandgap, 62, 64
2D Assemblies, 50 Bandgap Bowing, 70
3D Microcrystals, 50 Barkhausen Effect, 199, 200
Acid Gases, 247 Batteries, 5, 240
Acid-Base, 111 Beryllium, 17
Active Metals, 244, 246 BET, 9
Adsorbate Damping, 164 Bethe-Slater Curve, 187, 216
Adsorbents, 223, 238 Bioassays, 165
Adsorption, 112, 239 Biological Warfare, 253
Aerogel, 98 Biomedical, 283
Aerosol Methods, 88 Bismuth-Manganese, 187
Aerosol Thermolysis, 92 Bloch’s Law, 216
AFM, 8 Constant, 184, 216, 218
Alkane Isomerization, 237 Exponent, 184, 216
Alkylation, 234 Block Copolymers, 255
Alloy Semiconductors, 69 Blocking Temperature, 207,
Alloys, 189 208
Aluminosilicates, 241 Bonding in Ceramics, 104
Aluminum Nitride, 101 Borohydride, 240
Aluminum Oxide, 85, 95, 98, 101, Brillouin Functions, 181, 184
104, 114 Cadmium Sulfide Melting, 274
Anatase, 110 Cadmium, 246
Anisotropy, 194 Selenide, 63, 66
Crystal, 193 Sulfide, 63, 66
Magnetocrystalline, 193 Telluride, 63, 64
Shape, 195, 203 Calcium Fluoride, 86
Surface, 216 Calcium Oxide, 85
Antiferromagnetic, 186, 190, 191 Capacitance, 32
AOT, 62 Nanoparticles, 153
Applications, 279 Carbon Dioxide, 247
Arrangement Nanoparticles, 46 Carbon Nanotubes, 243
Asymmetric Catalysis, 230 Catalysis, 37, 223
Atomic Vibrations, 273 Ceramics, 2, 85
287
288 INDEX
1 Introduction to Nanotechnology
KENNETH J. KLABUNDE
Department of Chemistry, Kansas State University, Manhattan, Kansas and Nanoscale
Materials, Inc., Manhattan, Kansas
It has been said that a nanometer is ``a magical point on the length scale, for this is
the point where the smallest man-made devices meet the atoms and molecules of the
natural world.''1
Indeed, ``nanotechnology mania'' is sweeping through essentially all ®elds of
science and engineering, and the public is becoming aware of the quote of the
chemist and Nobel Laureate, Richard Smalley: ``Just waitÐthe next century is going
to be incredible. We are about to be able to build things that work on the smallest
possible length scales, atom by atom. These little nanothings will revolutionize our
industries and our lives.''2
In a recent report of the National Science Foundation to the President's Of®ce of
Science and Technology Policy it was stated that ``Nanoscience and technology will
change the nature of almost every human-made object in the next century.''3
So what are these ``nanothings'' that are going to change our lives? Perhaps the
best way to begin to convey the possibilities is to list topical areas that nano-
technology promises to affect.
1
2 INTRODUCTION TO NANOTECHNOLOGY
particles or larger particles cannot.3 Since over 50% of new drug formulations are
never brought to market because of solubility problems, this simple transformation
into a nano-form opens up broad new possibilities for drug synthesis and utiliza-
tion.3
Tagging of DNA and DNA Chips Nanoparticle assay of DNA has been possible by
coating gold nanoparticles with DNA strands. When these are exposed to comple-
mentary DNA, binding (hybridization) occurs, and this causes the colloidal gold
particles to aggregate, and as a result a color change takes place.4,5
Microarrays to detect and help identify DNA samples have been built by creating
devices with up to 100,000 different known DNA sequences. When the unknown
target DNA sequences match with any of the DNA chip arrays, then binding
(hybridization) occurs and the unknown sequence is identi®ed by its position on the
array.3
Information Storage Ultra®ne dye particles often yield higher quality inks in terms
of color, coverage, and color-fastness.6 Also, ``nanopens'' (atomic force microscope
tips) can write letters with features as small as 5 nm.1
Actually, nanoparticles have already found their way into modern audio and
videotapes and disks, which are dependent on magnetic and optical properties of ®ne
particles. Further advances will be made with smaller and smaller sizes and with
control of magnetic coercivity and optical absorption, so that much denser storage
media should be possible.6
that highly densi®ed nonporous materials can be prepared, these new materials may
®nd uses as replacements for metals in many applications.
Harder Metals Nanoparticulate metals when compressed into solid objects exhibit
unusual surface hardness, sometimes as high as ®ve times that of the normal
microcrystalline metal.3,10
Film Precursors Similar to their use in inks, nanoqueous metallic colloidal solu-
tions have proven useful as precursors for thin metallic ®lm formation when used as
spray paint.11 In particular, gilding of silver artifacts with gold has been accom-
plished with gold±acetone colloids.12,13
Environmental=Green Chemistry
Catalysts Successful catalytic processes developed over the last six decades have
led to a vital industry that contributes to the economy at least 20% of the GDP.21
What is signi®cant in the context of nanostructural materials in chemistry is that
heterogeneous catalysis is dependent on nanoparticles of metals, and research on the
effect of particle size (percent dispersion as a measure of the fraction of metal atoms
on the surface and thus available to incoming reactants) and shape (crystal faces,
edges, corners, defects that lead to enhanced surface reactivity) has been and
continues to be a vigorous ®eld.
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