Table Of ContentTransition Metal Sulphides
Chemistry and Catalysis
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3. High Technology- Volume 60
Transition Metal Sulphides
Chemistry and Catalysis
edited by
Thomas Weber
Laboratory for Technical Chemistry,
Swiss Federal Institute of Technology (ETH),
Zurich, Switzerland
Roel Prins
Laboratory for Technical Chemistry,
Swiss Federal Institute of Technology (ETH),
Zurich, Switzerland
and
Rutger A. van Santen
Schuit Institute of Catalysis,
Eindhoven University of Technology,
Eindhoven, The Netherlands
....
'Spr'ing er-Science+Business Media, B.V.
Proceedings of the NATO Advanced Research Workshop on
Challenges for Sulphides in Maternal Sciences and Catalysis
Varna, Bulgaria
September 27-October 1, 1997
A C.I.P. Catalogue record for this book is available from the Library of Congress.
Additional material to this book can be downloaded ftom http://extras.springer.com.
ISBN 978-90-481-5100-4 ISBN 978-94-017-3577-3 (eBook)
DOI 10.1007/978-94-017-3577-3
Printed on acid-free paper
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© 1998 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 1998
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TABLE OF CONTENTS
Preface Vll
1. Solid State Transition Metal Sulphides - Some Aspects of 1
Structure and Physical Properties
HS. Genin and J.A. !hers
2. Charge Transfer Phenomena in Transition Metal Sulphur 37
Chemistry
W Kaim, F.M Hornung, R. Schafer, J. Fiedler, M Krejcik and
s. Zalis
3. The Chemistry of the Dihydrogen Ligand in Transition Metal 57
Compounds with Sulphur-Donor Ligands
R.H Morris
4. Binding and Reactivity of Thiophene-Type Ligands in 89
Transition Metal Complexes and Clusters
R.J. Angelici
5. Hydrogenation, Hydrogenolysis and Desulphurization of 129
Thiophenes by Soluble Metal Complexes
C. Bianchini and A. Meli
6. Sulphur Bonding in Transition Metal Sulphides and MoS2 155
Based Structures
L.S. Byskov, J.K. Nerskov, B.S. Clausen and H Topsee
7. Chemistry and Reactivity of Transition Metal Sulphides 169
in Relation to their Catalytic Performance
E.J.M Hensen, V.HJ. de Beer and R.A. van Santen
8. Characterization of Unsupported and Alumina-Supported 189
Molybdenum Sulphides
H Knozinger
v
vi
9. Preparation, Structure and Surface Chemical Properties of 207
Hydrotreating Model Catalysts: A Surface Science Approach
A.M de Jong, J.C. Muijsers, Th. Weber, L.J. van /Jzendoorn,
V.HJ. de Beer, J.A.R. van Veen and J. W. Niemantsverdriet
10. Reaction Dynamics during C-S Bond Breaking in Sulphur- 235
Containing Molecules: Isotope Studies
V.M Kogan
11. Effects of Catalyst Composition and Pretreatment on the 273
Product Distribution in Hydrodesulphurization,
Hydrodenitrogenation and Hydrodechlorination
M Zdraiil
12. Metal Sulphides and Refinery Processes 311
J. W. Gosse link
PREFACE
Transition metal sulphides show a variety of unusual structural and
electronic properties which lead to important technical applications, such as in
the field of hydrotreating catalysis. Hydrotreating is concerned with reactions
for the removal of sulphur (hydrodesulphurization), nitrogen
(hydrodenitrogenation), oxygen (hydrodeoxygenation) and heavy metals
(hydrodemetallation) from crude oil. Sulphides of molybdenum with cobalt or
nickel, supported on y-Al203, constitute the catalytically active material in
industrial hydrotreating catalysts. The development and optimization of these
catalysts have traditionally been accomplished by empirical means. Further
scientific improvements, however, require in-depth knowledge of the structure
of the catalysts and of their catalytic actions. Most of the properties of
hydrotreating catalysts can be understood in terms of the properties of transition
metal sulphur compounds. Combining the expertise of the chemical and
catalytic research communities, many problems of industrial relevance
involving sulphides can be answered with the knowledge available today.
The chapters in this book include reviews concerning different aspects of
transition metal sulphides, i.e. solid-state, coordination, and organometallic
chemistry, surface science and spectroscopic studies, quantum chemical
calculations, catalytic work on model and real catalysts as well as their usage in
refineries. The chapters are based on lectures presented at the NATO Advanced
Research Workshop on Challenges For Sulphides In Material Sciences And
Catalyis (Varna, Bulgaria, September 27 to October 1, 1997), organized by
Thomas Weber, Roel Prins, Rutger A. van Santen and Lachezar A. Petrov.
The Advanced Research Workshop was sponsered by the Scientific Affairs
Division of NATO. We are grateful for this support as well as for the help of
Christoph Stinner in the production of this book and the proof-reading by
Marcia Schonberg and Mark E. Bussell.
Thomas Weber
Roel Prins
Rutger A. van Santen
Zurich and Eindhoven, Apri11998
vii
SOLID STATE TRANSITION METAL SULPHIDES
Some Aspects ofS tructure and Physical Properties
H.S. GENIN AND J.A. IBERS
Department ofC hemistry, Northwestern University
2145 Sheridan Road, Evanston, IL 60208-3113, U.S.A.
1. Introduction
From mineralogy and geology to theoretical chemistry and catalysis, transition
metal sulphides occupy important positions in many fields. Pyrite, a naturally
occurring form of iron disulphide (Fe~) known also as Fool's Gold, is one of the
three largest commercial sources of elemental sulphur, which in turn is vital to the
world economy as a starting material for the single most important industrial
chemical, sulphuric acid [1]. Sphalerite (ZnS) and cinnabar (HgS), common
sulphide minerals, are the largest sources of zinc and mercury, respectively [1].
Molybdenite, MoS2, is the principal ore of molybdenum, although most
molybdenum is obtained as a byproduct in the production of copper via formation
ofMoS2 as an intermediate [1]. Sulphide minerals are, in fact, the source of most
of the world's non-ferrous metals [2]. Geologically, pyrite and other sulphide
minerals serve as indicators of how and when rock formations were created;
troilite, FeS, is a rare mineral on earth but a common one on meteorites and lunar
rocks; this highlights the differences in their origins [2, 3]. Binary transition metal
sulphides, with their intriguing electrical and magnetic properties, are being
explored for device applications, such as semiconductors and magnetic recording
materials [2]. Another fascinating phenomenon found in some binary sulphides,
including MoS2> is that of charge-density waves, which in the last twenty five years
has been the subject of much theoretical study and has led to a better
understanding of chemical bonding in general [4 -7].
While providing some contextual glimpses of the broad and compelling field
of transition metal sulphides, the main purpose of this article is to discuss
T. Weber et al. (eds.), Transition Metal Sulphides, 1-35.
© 1998 Kluwer Academic Publishers.
2
structures of those transition metal sulphides that are important to
hydrodesulphurization (HDS) reactions, with particular emphasis on coordination
geometries and preferences oft he metal centres involved. We first describe general
properties of sulphides, comparing them with oxides, selenides, and tellurides,
followed by an exposition of layer-type structures that are so prevalent among
sulphides. We then briefly examine the relationship of geometrical structure to
electronic structure in transition metal sulphides. The main part of our
presentation, a discussion of important binary (and some ternary) transition-metal
sulphide structures, comes next. Last we present possible geometries for
catalytically active sites in molybdenum disulphide and offer a caveat.
Several excellent reviews of transition metal sulphides exist [2, 8-1 0].
Additionally, because sulphide minerals have been known and studied for
centuries much relevant information has filtered into general inorganic chemistry
texts. Useful discussions can be found particularly in references [1], [11], and [12].
Most of this literature presents a mineralogical perspective; we endeavour here to
discuss transition metal sulphides in a somewhat different context.
2. Oxides, Selenides, Tellurides
Some of the important distinctions between metal oxides on the one hand and
metal chalcogenides on the other are tabulated in Table 1. (A metal chalcogenide
contains a metal and a chalcogen Q = S, Se, or Te.) We now proceed to discuss
these and other differences.
TABLE 1. Comparison of Metal Oxides and Metal Chalcogenides
Feature Oxides Chalcogenides
Close packing Usually Sometimes
Octahedra/tetrahedra Yes Usually
Trigonal prisms Very Rarely Groups 5, 6
Layered structures Rarely Usually
Q-Q bonds Peroxides Common
