Catalysis by Ceria and Related Materials

909 Pages·2013·29.708 MB·English

by  Alessandro Trovarelli, Paolo Fornasiero (eds.)

Catalysis by
Ceria and Related
Materials
2nd Edition
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CATALYTIC SCIENCE SERIES
Series Editor: Graham J. Hutchings (Cardiff University)
Published
Vol. 1 Environmental Catalysis
edited by F. J. J. G. Janssen and R. A. van Santen
Vol. 2 Catalysis by Ceria and Related Materials
edited by A. Trovarelli
Vol. 3 Zeolites for Cleaner Technologies
edited by M. Guisnet and J.-P. Gilson
Vol. 4 Isotopes in Heterogeneous Catalysis
edited by Justin S. J. Hargreaves, S. D. Jackson and G. Webb
Vol. 5 Supported Metals in Catalysis
edited by J. A. Anderson and M. F. García
Vol. 6 Catalysis by Gold
edited by G. C. Bond, C. Louis and D. T. Thompson
Vol. 7 Combinatorial Development of Solid Catalytic Materials:
Design of High-Throughput Experiments, Data Analysis,
Data Mining
edited by M. Baerns and M. HoleÁa
Vol. 8 Petrochemical Economics: Technology Selection in a Carbon Constrained World
by D. Seddon
Vol. 9 Deactivation and Regeneration of Zeolite Catalysts
edited by M. Guisnet and F. R. Ribeiro
Vol. 10 Concepts in Syngas Manufacture
by J. Rostrup-Nielsen and L. J. Christiansen
Vol. 11 Supported Metals in Catalysis (2nd Edition)
by J. A. Anderson
Vol. 12 Catalysis by Ceria and Related Materials (2nd Edition)
edited by A. Trovarelli and P. Fornasiero
Catherine - Catalysis by Ceria.pmd 1 4/4/2013, 3:26 PM
CATALYTIC SCIENCE SERIES — VOL. 12
Series Editor: Graham J. Hutchings
Catalysis by
Ceria and Related
Materials
2nd Edition
edited by
Alessandro Trovarelli
Università di Udine, Italy
Paolo Fornasiero
Università di Trieste, Italy
Imperial College Press
ICP
P870_9781848169630_tp.indd 2 8/4/13 2:17 PM
Published by
Imperial College Press
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Covent Garden
London WC2H 9HE
Distributed by
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UK office: 57 Shelton Street, Covent Garden, London WC2H 9HE
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library.
Catalytic Science Series — Vol. 12
CATALYSIS BY CERIA AND RELATED MATERIALS
Second Edition
Copyright © 2013 by Imperial College Press
All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means,
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ISBN 978-1-84816-963-0
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Printed in Singapore
Catherine - Catalysis by Ceria.pmd 2 4/4/2013, 3:26 PM
b1469 Catalysis by Ceria and Related Materials
PREFACE
Ceria-based oxides have gained a major position in the list of non-
innocent supports, active co-catalysts and advanced materials, mainly
for environmental applications and for energy conversion systems.
The tremendous scientific interest is demonstrated by the fact that
in every year since 2006 over a thousand publications on related top-
ics are printed, a doubling of the already remarkable average num-
ber of manuscripts published every year in the previous five years.
Using the keywords “ceria/CeO2/cerium dioxide” and “cataly*” a
literature search returned almost 6,000 papers published since 1990,
many of which are from the last decade. The new century has con-
firmed the unique and irreplaceable role of ceria and ceria–zirconia
in advanced car converters for exhaust gas pollution control. Parallel
to this worldwide application, these materials have a bright future
in many new sectors, including as catalysts in hydrogen production
and purification and in fuel cells (either as electrolytes or catalytic
materials) and even as photocatalysts. One remarkable drawback
of the increasing popularity of ceria and related materials is their
availability, which is often dictated more by strategic and geopolitical
issues than technical issues. Cerium is the most abundant of the so-
called rare-earth elements, and is more abundant than copper or
nickel. Mining strategies, advances in extraction and separation
processes of cerium and its recovery from spent materials in con-
junction with strategic and geopolitical aspects, determine its actual
availability and possibilities for future applications. And this is true
of the entire market for rare-earth elements.
In this context, it is not surprising that the success achieved by
the volume Catalysis by Ceria and Related Materials, published in 2002,
v
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b1469 Catalysis by Ceria and Related Materials
vi Preface
prompted the publisher to suggest a second edition to review the
current work in this area. Based on the vastness of the subject, more
appropriate for an encyclopaedia rather than a single volume, we
decided to prepare a book with a good balance between conven-
tional applications and the study of ceria-based materials, and a
fundamental overview of “traditional” systems and strong view of the
emerging trends. Particularly important in our view are the novel
properties that nanostructured ceria has with respect to the bulk
material.
The book starts with a detailed and fundamental structural char-
acterization of the main ceria-based materials (Chapter 1), followed
by a careful overview of recent achievements in HR-TEM characteri-
zation (Chapter 2). Chapter 3 gives an insight into the oxygen
storage and release capacity of both model and commercial ceria-
containing three-way catalysts, which is one of the key properties in
their successful application. A discussion of the role of ceria-based
materials in the activation and conversion of nitrogen oxides
(Chapter 4) closes the first part of the book.
The second section of the book considers the peculiar aspects of
CeO -based nanosystems, starting with an introduction to the analy-
2
sis of their structural complexity by means of atomistic modelling
(Chapter 5). An overview of synthetic strategies and characteriza-
tion techniques to obtain 2D and 3D nanoarchitectures is given in
Chapter 6, while the following chapter deals with recent advances in
the use of metal core/ceria shell systems to gain novel catalytic and
morphological properties.
The third part of the book (Chapters 8–14) is on the use of
ceria-based materials in emerging and commercial applications.
Chapter 8 discusses synthetic strategies for the preparation of ceria-
based catalysts for oxidation and combustion. Chapters 9 and 10
carefully investigate hydrogen purification reactions, namely the
water gas shift reaction (WGSR) and preferential oxidation (PrOx).
Chapter 11 discusses the challenges in the use of ceria-containing
catalysts for diesel soot combustion, while Chapter 12 investigates
the role of these materials in solid oxide fuel cells (SOFCs) and in
oxygen separation membranes. Finally, an overview of the potential
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b1469 Catalysis by Ceria and Related Materials
Preface vii
application of ceria-based catalysts in the transformation of oxygen-
ated compounds in biomass into added-value products is presented.
The book ends with a panorama of the application of ceria-based
catalysts for air pollution abatement.
We thank all the contributors to the volume and we hope that
the book can stimulate further step changes in the sector while con-
tinuing to be a basic textbook for those who approach these interest-
ing and surprising materials.
The Editors
Alessandro Trovarelli
Paolo Fornasiero
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b1469 Catalysis by Ceria and Related Materials
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b1469 Catalysis by Ceria and Related Materials
CONTENTS
Preface v
Chapter 1 Crystal and Electronic Structures, Structural
Disorder, Phase Transformation, and Phase
Diagram of Ceria–Zirconia and Ceria-Based
Materials 1
Masatomo Yashima
1.1 Phase Diagram of the Ce–O System and Structural
Properties of Fluorite-Type CeO 1
2
1.2 Phases and Structure of Zirconia and Ceria–Zirconia
Solid Solutions 4
1.2.1 Phase transition and crystal structure of zirconia 5
1.2.2 Crystal structure of monoclinic CeZr O
x 1−x 2
and tetragonal-monoclinic phase transformation
−
in the CeO ZrO system 7
2 2
1.2.3 Phase identification and crystal structure
of tetragonal phase in the compositionally
− ′ ″
homogeneous Ce Zr O t, t , and t forms 11
x 1−x 2
1.3 Phase Diagram and Partitionless Transformation
in the CeO –ZrO System 15
2 2
1.3.1 Experimental and calculated equilibrium
−
phase diagram of the CeO ZrO system 15
2 2
1.3.2 Temperature-induced structural change
of tetragonal Ce Zr O and partitionless
x 1−x 2
tetragonal–cubic phase transformation
in compositionally homogeneous Ce Zr O
x 1−x 2
materials 17
ix
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