Properties and Applications of Perovskite-Type Oxides

401 Pages·1992·40.579 MB·English

by  L.G. Tejuca (Editor), J.L.G. Fierro (Editor)

PROPERTIES
AND APPbiCATIONS
OF PEROUSHITE-TYPE
OXIDES
CHEMICAL INDUSTRIES
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PROPERTIES
AND APPbiCATIONS
OF PEROUSHITE-TYPE
OXIDES
edited by
L.G.Tejuca
J.L. G. Fierro
lnstituto de· Cata /isis y Petroleoqufmica
CS/C
Madrid, Spain
Marcel Dekker New York
Library of Congress Cataloging-in-Publication Data
Properties and applications of perovskite-type oxides I edited by L.G.
Tejuca, J.L.G. Fierro.
p. em. --(Chemical industries; v. 50)
Includes bibliographical references and index.
ISBN 0-8247-8786-2
1. Perovskite. 2. Catalysts. I. Tejuca, L. G. (Luis G.), 1939-1989.
II. Fierro, J. L. G. (Jose L. G.). III. Series.
QD181.01P83 1992
541.3'95--dc20 92-36741
CIP
This book is printed on acid-free paper.
Copyright @ 1993 by MARCEL DEKKER All Rights Reserved.
Neither this book nor any part may be reproduced or transmitted in any form or by any
means, electronic or mechanical, including photocopying, microfilming, and recording,
or by any information storage and retrieval system, without permission in writing from
the publisher.
MARCEL DEKKER ...
~.·
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Current printing (last digit):
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PRINTED IN THE UNITED STATES OF AMERICA
In Memoriam
With my deepest regret, I must report the unexpected death
of Dr. L.G. Tejuca, who first accepted the task of editing this
book almost three years ago. Born on September 25, 1939 in
Asturias, Dr. Tejuca received the master's degree in chemistry
from Oviedo University in 1965 and the doctoral degree, also in
chemistry, from the Complutense University in 1970. After serving
as Associate Scientist from 1971 to 1975, he assumed a position
as Staff Senior Scientist in 1976 at the Institute of Catalysis
and Petrochemistry of the National Council for Scientific
Research. He was also a postdoctoral research fellow at the
University of Nottingham (Great Britain), Princeton University,
and the University of Dundee (Great Britain).
Dr. Tejuca was best known for his pioneering research on the
perovskite-type oxides, including synthesis, structural
characterization, and application in several catalytic test
reactions. His most important contribution was the establishment
of the relationship between the local symmetry of the 3d
transition cations in perovskite surfaces· and the surfaces'
adsorption and catalytic properties. The close parallelism he
found between the extent of oxygen adsorption and the rate of
carbon monoxide and low-mole.cular-weight olefin oxidations
permitted him to discuss catalytic trends in terms of crystal
field effects. Another major area of Dr. Tejuca's work involved
the use of adsorption models to evaluate the number of surface
sites on unsupported and supported metal oxides. These efforts
of Dr. Tejuca resulted in over 130 original publications which
have stimulated research in this paticular area of heterogeneous
catalysis over the past decade.
As his friend and coworker, I decided to continue with the
task of editing this pivotal book. All friends at the Institute,
authors of the different chapters, the publisher, and readers of
the book mourn the passing of Dr. Tejuca.
J .L.G. Fierro
III

Preface
Many progress reports and a large body of publications in
specialized surface science and catalysis journals have provided
a convincing description of the processes taking place at the
surface of perovskite-type structures. Accordingly, it has been
our endeavor to offer the reader of this book an overview of the
bulk and surface properties of these marvelous materials and how
they can be related to the catalytic performance in many model
and practical reactions.
Chapter 1 surveys the methods of preparation of bulk
perovskites and offers the possibility of synthesizing these
compounds on moderate- or high-surface-area carriers. Special
emphasis is placed in Chapter 2 on the methods employed in the
processing of high temperature superconductive cuprates. Chapter
3 provides a comprehensive review of the oxidative
nonstoichiometric behavior of perovskites, including not only the
excess oxygen but also the cation vacancies. This analysis is
extended in Chapter 4 to several nigh-temperature superconductive
cuprates for which a careful crystallographic analysis is made.
Chapter 5 deals with the thermoelectric properties of various
cuprates and the comparative analysis of the critical behavior
of thermopower and electrical conductivity in the mean field
region. Chapter 6 is concerned with the optical properties of
perovskites and doped perovskites in which the ions may adopt a
large variety of configurations.
Chapters 7 and 8 focus on methods used to evaluate the
surface sites, including poisoning with sulfur dioxide, the study
of the vibrational modes of adsorbed molecules, and the analysis
of the desorption products of chemisorbed probe molecules. The
role of surface impurities and phase segregation and the
relevance of the surface structure on chemisorptiv e and catalytic
properties are discussed in Chapter 9. Chapters 10 to 17 survey
several practical and model catalytic reactions such as total
oxidation of hydrocarbons, hydrogenation and hydrogenolysis of
hydrocarbons, hydrogenation of carbon oxides, CO oxidation and
NO reduction, partial oxidation of hydrocarbons and oxygenates,
hydrogen evolution from water, reduction of sulfur dioxide, and
decomposition of nitrous oxide. Finally, the use of these
compounds as solid state chemical sensors is reviewed in Chapter
18.
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