Metal Oxide Nanostructures Chemistry:

Synthesis from Aqueous Solutions 2nd

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i

Metal Oxide Nanostructures Chemistry

ii
iii

Metal Oxide Nanostructures

Chemistry
SYNTHESIS FROM AQUEOUS SOLUTIONS
SECOND EDITION

Jean-​Pierre Jolivet

1
iv

1
Oxford University Press is a department of the University of Oxford. It furthers
the University’s objective of excellence in research, scholarship, and education
by publishing worldwide. Oxford is a registered trade mark of Oxford University
Press in the UK and certain other countries.

Published in the United States of America by Oxford University Press

198 Madison Avenue, New York, NY 10016, United States of America.

Translation of the French language edition of:

De la solution à l’oxyde—2e edition
De Jean-Pierre Jolivet
© 2015 Editions EDP Sciences

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, without the
prior permission in writing of Oxford University Press, or as expressly permitted
by law, by license, or under terms agreed with the appropriate reproduction
rights organization. Inquiries concerning reproduction outside the scope of the
above should be sent to the Rights Department, Oxford University Press, at the
address above.

You must not circulate this work in any other form

and you must impose this same condition on any acquirer.

Library of Congress Cataloging-​in-​Publication Data

Names: Jolivet, Jean-Pierre, author.
Title: Metal oxide nanostructures chemistry : synthesis from aqueous solutions /
Jean-Pierre Jolivet.
Other titles: De la solution a l’oxyde. Chimie aqueuse des cations metalliques,
synthese de nanostructures. English
Description: 2nd edition. | New York, NY : Oxford University Press, 2019. |
Translation of the French language edition of: De la solution a l’oxyde, 2e edition :
chimie aqueuse des cations metalliques, synthese de nanostructures (2015). |
Includes bibliographical references and index. Identifiers:
LCCN 2018045235 | ISBN 9780190928117
Subjects: LCSH: Oxides—Surfaces. | Precipitation (Chemistry) |
Metallic oxides. | Nanostructured materials.
Classification: LCC QD181.O1 J6513 2019 | DDC 546/.72159—dc23
LC record available at https://lccn.loc.gov/2018045235

1 3 5 7 9 8 6 4 2

Printed by Sheridan Books, Inc., United States of America

v

CONTENTS

Preface ix
List of Abbreviations xi
1. Nanomaterials: Specificities of Properties and Synthesis 1
1.1 Specific Properties of Nanoparticles 2
1.1.1 Volume Effects 2
1.1.2 Surface Effects 6
1.1.3 The Influence of Size Effect on Thermodynamic, Structure, and
Reactivity of Oxide Nanoparticles 7
1.2 Specificity and Requirements in the Fabrication Methods of
Nanoparticles 13

2. Water and Metal Cations in Solution 19

2.1 Water as Solvent, Physicochemistry of the Liquid 20
2.1.1 Electronic Structure of the Water Molecule 20
2.1.2 Structure of Liquid Water 22
2.1.3 Hydration of Ions and Structure of Solutions 24
2.1.4 Water under Hydrothermal Conditions 28
2.2 Acidity and Cation Speciation 30
2.3 Mechanisms of Hydroxylation and Redox Reactions in Solution 36
2.4 Evaluation of Partial Charges on Atoms in Combination 38
2.4.1 Ionocovalency and Partial Charges 39
2.4.2 Electronegativity 39
2.4.3 Partial Charges Model 41

3. Condensation in Solution: Polycations and Polyanions 49

3.1 Hydroxylation and Condensation of Cations 49
3.1.1 Mechanisms and Structural Considerations 50
3.1.2 The Different Behaviors of Cations Against Condensation 55
3.2 Olation: Formation of Polycations 57
3.2.1 Mechanisms and Structural Considerations 57
3.2.2 Chromium III Polycations 61
3.3 Oxolation: Formation of Polyanions 64
3.3.1 Elements of the p-​Block 66
3.3.2 Transition Elements under High Oxidation
States: Polyoxometalates 72
vi

vi { Contents

4. Precipitation: Structures and Mechanisms 107

4.1 The Formation of Solids: Thermodynamics and Crystal Structure 108
4.1.1 Divalent Elements 108
4.1.2 Layered Double Hydroxides 116
4.1.3 Trivalent Elements 119
4.1.4 Tetra-​and Pentavalent Elements 124
4.1.5 Transition Elements under High Oxidation States 131
4.1.6 Summary 143
4.1.7 Polymetallic Oxides 143
4.2 Kinetics of Precipitation and Mechanisms of Crystallization 149
4.2.1 The Steps in the Formation of a Solid 150
4.2.2 Nucleation and Growth: Energetics and Dynamics 152
4.2.3 Mechanisms of Crystallization: Structural and Morphological
Evolution of Oxide Nanoparticles in Suspension 161
4.2.4 Effect of Microwave Heating on Crystallization in Solution 172

5. Surface Chemistry and Physicochemistry of Oxides 181

5.1 The Oxide–​Solution Interface 182
5.1.1 Origin of the Electrostatic Surface Charge 182
5.1.2 Surface Acidity: Multisite Complexation Modeling 184
5.2 Solvation and Structure of the Solid–​Solution Interface 191
5.2.1 Solvation of Particles 191
5.2.2 Surface–​Electrolyte Interactions 193
5.3 Stability of Nanoparticle Dispersions Against Aggregation 197
5.3.1 Van der Waals Forces 198
5.3.2 Electrostatic Forces 199
5.3.3 Total Potential Energy of the Interaction 199
5.4 Surface Reactivity: Adsorption 202
5.4.1 Electrostatic Interactions, Outer-​Sphere Surface Complexes 202
5.4.2 Specific Interactions: Inner-​Sphere Surface Complexes 203
5.4.3 Adsorption and Transfers Through the Oxide–​Solution
Interface 211
5.4.4 Adsorption and Surface Energy: Role of Acidity in Particle Size and
Morphology 216

6. Aluminum Oxides: Alumina and Aluminosilicates 227

6.1 Introduction 227
6.2 Hydroxylation and Condensation in Solution: Polycations 228
6.3 Formation of Solid Phases 237
6.3.1 Aluminum Hydroxides, Oxyhydroxides, and Oxides 237
6.3.2 Aluminosilicates 249

7. Iron Oxides: An Example of Structural Versatility 263

7.1 Speciation of Iron and Condensation in Aqueous Solution 265
7.2 Formation of Solid Phases 269
vi

Contents } vii

7.2.1 Ferrous Hydroxide and Oxidized Derivatives: Feroxyhyte and

Lepidocrocite 269
7.2.2 Ferric Compounds: Ferrihydrite, Goethite, Hematite,
Akaganeite 271
7.2.3 Mixed Ferric-​Ferrous Phases: Green Rusts and Magnetite 290
7.2.4 Polymetallic Ferrites: Spinels, Hexaferrites, Garnets 308

8. Titanium, Manganese, and Zirconium Dioxides 325

8.1 Speciation of TiIV, MnIV, and ZrIV in Solution 326
8.2 Titanium Oxide 327
8.2.1 Precipitation of Ti4+ Ions in Acidic to Neutral Media 329
8.2.2 Transformation of Layered Titanates 338
8.2.3 Oxidation of TiIII and Ti0 in Acidic to Neutral Medium 343
8.2.4 Synthesis of Barium Titanate BaTiO3 347
8.3 Manganese Oxides 351
8.3.1 The Main Crystal Phases of MnO2 Dioxide 351
8.3.2 Precipitation of Manganese Oxides 353
8.4 Zirconium Oxides 364
8.4.1 The Crystal Varieties of Zirconia 365
8.4.2 Precipitation of Zirconia 365
8.4.3 Synthesis of Stabilized Zirconia 369

Conclusion 383

Index 385
vi
ix

PREFACE

The aim of this book is to present an overview of metal oxide nanoparticle fabri-
cation in aqueous solution. Indeed, nanomaterials generate considerable interest
because of their specific behaviors and properties, which have made their use in-
creasingly diversified. Among these nanomaterials, metal oxides hold a special
place because of the diversity of their properties.
The synthesis of oxide nanoparticles in allowing the control of their crystal
structure, shape, size, and size distribution to optimize their physical properties
has long been one of the ultimate goals of colloidal chemistry. This goal is still part
of an intense effort, as shown by the huge number of articles published on this
subject even to the present day. Of the large variety of synthesis pathways, pre-
cipitation in aqueous solution from metal salts is the most common and versatile
method for obtaining oxide nanoparticles by sustainable green chemistry corre-
sponding to an ecodesign of materials. Indeed, the technique does not require
the use of solvents or ligands that present unwanted effects, even toxic ones. The
environmental interest in the technique may consequently be added to the tech-
nological interest it has inspired.
This book is intended for students, researchers, and engineers interested in the
precipitation of nano-​oxides and their surface physical chemistry, not only in the
field of materials but also in geochemistry and mineralogy—​two fields that are di-
rectly and deeply associated with the aqueous chemistry of metal cations.
This book is in fact the second completely revised and extended edition of
Metal Oxide Chemistry and Synthesis published in 2000 by John Wiley and Sons.
The basic concepts of the chemistry of cations in solution are still valid, but after
almost 20 years, immense progress has been achieved: the precipitation of most
of the elements has been widely studied; the growth of particles by ordered aggre-
gation (oriented attachment) today represents experimental evidence; theoretical
modeling of oxide surface energy and the dynamics of nucleation and growth have
been developed; and so on. It therefore became necessary to update the presen-
tation of knowledge in this field, and it is for this reason that I rewrote this book,
based on the course I was teaching at the University Pierre and Marie Curie, Paris,
France. In the new edition of the book, the first five chapters include the major
concepts: specificity of nanostructures, mechanisms of hydroxylation and con-
densation of cations in solution, structural and kinetic aspects of precipitation,
and surface reactivity of oxides. The last three chapters are devoted to the chem-
istry of some technologically and environmentally important elements, such as
aluminum, iron, titanium, manganese, and zirconium.

ix
x

x { Preface

I warmly thank Philippe Belleville, Corinne Chanéac, David Chiche, Anne

Duchateau, Cédric Froidefond, Julien Hernandez, Hanno Kamp, Magali Koelsh,
Stéphane Lemonnier, Micaela Nazaraly, Thierry Pagès, Céline Pérégo, Agnès
Pottier, David Portehault, Tamar Saison, and Lionel Vayssières, who completed
their PhDs under my (co)direction. Their work added considerably to this book.
I am greatly indebted to Elisabeth Tronc, Marc Henry, Corinne Chanéac,
Sophie Cassaignon, Olivier Durupthy, and all post–​PhD students for the work we
achieved together. I hope that in this book they find my expression of gratitude
and friendship.
I would also like to thank all my colleagues from the French and foreign aca-
demic communities as well as from industry, who, through diverse collaborations
or during simple exchanges, contributed closely and even furthered this work.
I particularly want to thank Benjamin Gilbert (Lawrence Berkeley National
Laboratory, USA), Alain Manceau (University of Grenoble, France), and Claudine
Noguera (University P. & M. Curie, Paris, France) for their advice, suggestions,
and exciting discussions.
Finally, I wish to express my gratitude and extend my friendship to Jacques
Livage and Clément Sanchez for the high quality of their scientific work and for the
happy years we spent together in the laboratory Chimie de la Matière Condensée
de Paris.
xi

ABBREVIATIONS

AO atomic orbital
EPR electron paramagnetic resonance
EXAFS extended X-​ray absorption fine structure
FESEM field effect scanning electron microscopy
HRTEM high-​resolution transmission electron microscopy
IEP isoelectric point
MO molecular orbital
NMR nuclear magnetic resonance
PZC point of zero charge
SAXS small angle X-​ray scattering
SEM scanning electron microscopy
TEM transmission electron microscopy

xi
xi
xi

Metal Oxide Nanostructures Chemistry

xvi
1

FIGURE 1.1 (c) Light emission under UV irradiation of CdSe nanoparticles dispersed in hexane. The
particle size varies from 1.5 nm (blue) to 7 nm (red) (courtesy of B. Dubertret, ESPCI, Paris, France).

(a) (b)

FIGURE 1.2 TEM images of aqueous dispersions of gold nanospheres (a) and nanorods (b) and colors
of these dispersions (reproduced from Liz-​Marzan L.M., Nanometals: formation and color, Materials
Today 2004, 26–​31 with permission of Elsevier).
2

FeTdvacancies
As(III)

(a) (b) (c) (d)

FIGURE 1.7 Scheme of adsorption sites for As on nanoparticles 6 nm in diameter based on
III

structural information deduced from X-​ray diffraction and As K-​edge XAS analyses. (a) Idealized
structure of {111} faces of maghemite, γ-​Fe2O3 (octahedra and tetrahedra are FeO6 and FeO4,
respectively). (b) Nanoparticle exhibiting FeIII vacancies. (c) Filling of the most reactive sites by arsenic
at low coverage rate. (d) Adsorption on lattice positions at higher surface coverage allowing a decrease
of surface energy.

FIGURE 3.37 Scheme of the structure of [Mo132O372(CH3COO)30(H2O)72]42–​, including 12 (Mo6) units

(dark gray) linked by (Mo2) bridges (light gray).
3

C7

FIGURE 3.38 Scheme of the structure of the (Mo154) wheel. Left, view perpendicular to the C7 axis.
Polyhedral representation of a (Mo6) unit with the linkage MoO6 octahedra. Right, polyhedral
representation along the C7 axis (reproduced from [Müller A., Kögerler P., Kuhlmann C., A variety of
combinatorially linkable units as disposition: from a giant icosahedral keplerate to multi-​functional
metal–​oxide based network structures, Chem. Commun. 1999, 1347–​1358] with permission of The
Royal Society of Chemistry).

(Mo176) (Mo248) (Mo36) (Mo176) (Mo36)

~8.5Å

FIGURE 3.39 Schematic view of (Mo176) and (Mo248) (the MoO7 polyhedra are in Turkish blue).
View of the cavity in (Mo248) and sketch of the association of the two (Mo36) fragments with (Mo172)
(reproduced from [107] with permission of the Nature Publishing Group).
4

C4

b
b
c a
FIGURE 3.40 Scheme of the structure of (Mo368) along th C4 axis. The MoO7 polyhedra are in Turkish
blue (reproduced from [101] with permission of Elsevier).

(a) (b) (c)

(d)

(e)
(f)

(g)

FIGURE 6.5 Structures of (a) Na[Al13O4(OH)24(H2O)12]8+ (δ-​Al13) and (b) [Al30O8(OH)56(H2O)24]18+

(Al30); (c) 27Al-​NMR spectra of ε-​Al13 and Al30 species in solution (reproduced with permission from
[22] Copyright 2000 American Chemical Society); (d) 27Al-​NMR MAS spectrum of the sulfate salt
Al30(SO4)9·xH2O (130.3 MHz, rot 5 kHz) (*rotation peaks) (reproduced with permission from [23]
Copyright 2000 American Chemical Society); (e) structure of [Al32O8(OH)60(H2O)28(SO4)2]16+ (Al32);
( f) structure of [Al26O8(OH)50(H2O)20]12+ (Al26); (g) structure of [Ga2Al18O8(OH)36(H2O)12]8+ (Ga2Al18).
5

∆Ec + ∆Ee < 0

Elasticity

∆Ec > 0

∆Ec + ∆Ee > 0

∆Ee < 0
Electrostatic
attraction

FIGURE 6.29 Schematic sketch for the proto-​imogolite transformation into single-​or double-​wall
imogolite nanotubes, depending on the energetic balance between electrostatic interaction and
curvature change in the sheet (reproduced with permission from [102] Copyright 2012 American
Chemical Society).

FIGURE 7.1 (a) Landscape of Luberon (southwestern France) showing a deposit of ochre (goethite and
hematite).
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