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This continuing authoritative series deals with the chemistry,
materials science, physics and technology of the rare earth
elements in an integrated manner. Each chapter is a comprehensive,
up-to-date, critical review of a particular segment of the field.
The work offers the researcher and graduate student a complete and
thorough coverage of this fascinating field.
Authoritative
Comprehensive
Up-to-date
Critical
Among the numerous applications of the rare-earth elements, the
field of catalysis accounts for a large number. Catalysis
represents approximately 20% of the total market sales of rare
earths worldwide. As a matter of fact two main applications have
been prominent in the last decades: zeolite stabilization for fluid
cracking catalysts, and automotive post-combustion catalytic
treatment.
The oldest use of rare earths in catalysis deals with the
structural and chemical stabilization of the zeolites for petroleum
cracking applications. For a long time this has been an area of
application for non-separated rare earths. The addition of several
percent of rare earths in the pores of the zeolite results in a
strong surface acidity, which is essential for an efficient
conversion of high-weight molecules into lighter species, like
low-octane fuel, even in the very aggressive conditions of the
petroleum industry.
The popular demand for high-quality air in spite of the traffic
congestion in large cities resulted in larger and larger
constraints in the emission exhaust from cars. Thus highly
efficient catalysts have had to be designed, and due to the
combination of its redox properties and very good thermal
stability, cerium oxide has been since the beginning, early in the
1980s, a major component of the three-way catalysts (TWC) now used
in all modern gasoline cars.
The future of rare earths in catalysis is probably bright. The fact
that approximately 400 patents are applied for yearly in the area
since 1992 is an illustration of a very active area. Usage of rare
earths in catalysis is expected to grow due to their highly
specific properties. Instead of the physical properties used in
electronic applications, one deals now with redox properties, water
and thermal stability, coordination numbers and so forth. The rare
earths are so specific in these properties that their use can
hardly be avoided, not only for the beauty of academic studies but
also for the development of industrial applications with immediate
influence on everyday life.
Careful control of the synthesis conditions and the definition of
optimum composition in each case are the keys to the preparation of
highly performing compounds for catalytic applications. They must
actually be considered as high performance products with functional
properties, and not just chemical species.
Chapters devoted primarily to catalysis have been published in
earlier volumes of the Handbook. In this volume several more are
added. The first is an extension of the earlier chapter 43, on
interactions at surfaces of metals and alloys, to reactions such as
hydrogenation, methanation, ammonia synthesis, saturated
hydrocarbon reactions, dehydrogenation of hydrogenated materials,
hydrodesulfurization, and carbon monoxide oxidation. The second
chapter reports on the wide variety of catalyzed reactions
involving metals and alloys in the innovated form of metal
overlayers or bimetallic compounds with some transition metals
produced from ammonia solutions. This is followed by a chapter on
catalysis with mixed oxides usually having perovskite or
perovskite-related structures.
Then follows a comprehensive discussion on the background and
current role of cerium oxide and associated materials for
post-treatment of exhaust gases for pollution control. These
three-way catalysts (TWC) are designed to render harmless the CO,
NOx, and unburned hydrocarbons from internal combustion engines.
The next chapter considers the wide field of zeolite catalysts
containing rare earths from their historic use in petroleum
refining in the 1960s to other petrochemical and fine chemical
applications today. The final chapter documents the use of the
triflates (the trifluoro-methane-sulfonyl group which is a hard
Lewis acid in both aqueous and organic solutions) as versatile
catalysts in carbon-carbon bond-forming reactions. Their stability
in the presence of water, in spite of their being hard Lewis acids,
enhances their growing usefulness.
This volume of the Handbook is the first of a two-volume set of
reviews devoted to the rare-earth-based high-temperature oxide
superconductors (commonly known as hiTC superconductors). The
history of hiTC superconductors is a few months short of being 14
years old when Bednorz and Muller published their results which
showed that (La, BA)2CuO4 had a superconducting transition of ~30
K, which was about 7K higher than any other known superconducting
material. Within a year the upper temperature limit was raised to
nearly 100K with the discovery of an ~90K superconducting
transition in YBa2Cu3O7-&dgr;. The announcement of a
superconductor with a transition temperature higher than the
boiling point of liquid nitrogen set-off a frenzy of research on
trying to find other oxide hiTC superconductors. Within a few
months the maximum superconducting transition reached 110 K
(Bi2Sr2Ca2Cu3010, and then 122K (TlBa2Ca3Cu4O11. It took several
years to push TC up another 11 K to 133 K with the discovery of
superconductivity in HgBa2Ca2Cu3O8, which is still the record
holder today.
This volume of the Handbook illustrates the rich variety of topics
covered by rare earth science. Three chapters are devoted to the
description of solid state compounds: skutterudites (Chapter 211),
rare earth -antimony systems (Chapter 212), and rare
earth-manganese perovskites (Chapter 214). Two other reviews deal
with solid state properties: one contribution includes information
on existing thermodynamic data of lanthanide trihalides (Chapter
213) while the other one describes optical properties of rare earth
compounds under pressure (Chapter 217). Finally, two chapters focus
on solution chemistry. The state of the art in unraveling solution
structure of lanthanide-containing coordination compounds by
paramagnetic nuclear magnetic resonance is outlined in Chapter 215.
The potential of time-resolved, laser-induced emission spectroscopy
for the analysis of lanthanide and actinide solutions is presented
and critically discussed in Chapter 216.
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