Table Of ContentStudies in Surface Science and Catalysis 67
STRUCTURE-ACTIVITY AND SELECTIVITY RELATIONSHIPSI N
HETEROGENEOUSC ATALYSIS
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Studies in Surface Science and Catalysis
Advisow Editors: 6.D elrnon and J.T. Yates
Vol. 68
STRUCTURE-ACTIVITY
AND SELECTIVITY
RELATIONSHIPS IN
HETEROGENEOUS
CATA LY S IS
Proceedings of the ACS Symposium on Structure-Activity Relationships
in Heterogeneous Catalysis, Boston, MA, April 22-2 7, 1990
Editors
R. K. Grasselli
Mobil Central Research Laboratory, P. 0. Box 1025, Princeton, N. 08543, ISA
and
A.W. Sleight
Department of Chemistry, Oregon State University, Corvallis, OR 9733 I , USA
ELSEVlE R Amsterdam - Oxford - New York - Tokyo 1991
ELSEVIER SCIENCE PUBLISHERS B.V.
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Library of Congress Cataloging-in-Publication Data
ACS Symposium on Structure-Activity Relationshlps in Heterogeneous
Catalysis (1990 Boston. Mass.)
Structure-activity and selectivity relationships i n heterogeneous
catalysis proceedings of the ACS Symposium on Structure-Activity
Relationships in Heterogeneous Catalysis. Boston. MA, April 22-27.
1990 / editors. R.K. Grasselli and A.W. Sleight.
p. cm. -- (Studies in surface science and catalysis ; vol.
67)
Includes bibllographlcal references and index.
ISBN 0-444-88942-6 (U.S.)
1. C a t a l y s t s - - S t r u c t u r e - a c t i v l t y relatlonshlps--Congresses.
2. Heterogeneous catalysis--Congresses. I. Grasselli. Robert K..
1930- . 11. Sleight. A W . 111. T i t l e . IV. Serfas Studias in
surface science and catalysis ; 67.
OD505.A27 1990
541.3’95--dc20 91- 16425
CI P
ISBN 0-444-88942-6
0 Elsevier Science Publishers B.V.. 1991
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V
CONTENTS
Preface.................................. ...................I X
Acknowledgment ............................................... X
OX1D ATION
Redox dynamics and structure/activity relationships of
vanadium-oxide on TiO, catalyst
G. Centi, M. Lopez Granados, D. Pinelli and F. Trifiro.......l
Molecular structure-reactivity relationships of supported
vanadium oxide catalysts
G. Deo and I.E. Wachs.......................................l3
Relative influence of structure and reactivity of V- and
Mo-containing catalysts in mild oxidation of hydrocarbons
E. Bordes...................................................2~
Key structure-activity relationships in the vanadium
phosphorus oxide catalyst system
J.R. Ebner and M.R. Thompson. ............................... 31
Structure-activity relationships in the oxidation of
alkylaromatics over metal oxides
A. Andersson, S . Hansen and M. Sanati ....................... 43
Catalyst oxide support oxide interaction to prepare
multifunctional oxidation catalysts
Y. Moro-oka, D.-H. He and W. Ueda...... ..................... 57
Structural-sensitivity in propylene mild oxidation on new
[loo] oriented MOO, catalysts
M. Abon, B. Mingot, J. Massardier and J.C. Volta............67
A comparison between low and high temperature Bi,O,.MoO,
phases for 1-butene reactions
M.F. Portela, C. Pinheiro, C. Dias and M.J. Pires...........77
Surface- and bulk-type catalysis of heteropolymolybdates.
Importance of the concept in the structure-activity
relationships for catalyst design
M. Misono, N. Mizuno, H. Mori, K . Y . Lee, J. Jiao and
T. Okuhara..................................................87
Active iron 0x0 centers for the selective catalytic
oxidation of alkanes
J.E. Lyons, P.E. Ellis, Jr. and V.A. Durante.............. ..99
The oxidative coupling of methane over Sm,O, and La203
S . J . Korf, J.G. van Ommen and J.R.H. Ross..................~~~
VI
Effects of metal particle size and carbon fouling on the
rate of heptane oxidation over platinum
R.F. Hicks, R.G. Lee, W.J. Han and A.B. Kooh.. .............1 27
Structure/function relations in transition metal sulfide
catalysts
R.R. Chainelli and M. Daage ................................ 137
HYDROGENATION
Enantioselective hydrogenation of ethyl pyruvate: effect
of catalyst and modifier structure
H.U. Blaser, H.P. Jalett, D.M. Monti, A. Baiker and
J.T. Wehrli... ............................................. 147
Non-stoichiometry, a key to modify the activity and
selectivity of spinel-type catalysts for hydrogenation
reactions
F. Trifiro and A. Vaccari........ .......................... 157
Supported metal catalysts prepared from amorphous metal
alloys
A. Baiker, J. De Pietro, M. Maciejewski and B. Walz........169
ZEO L I T E CATALYSIS
Structure sensitivity in zeolite catalysts
F.G. Dwyer ................................................. 179
Conformational effects in heterogeneous catalysis
D. F~rcaSiu.. .............................................. 193
Effects of morphology and electronic structure on the
catalysis of zeolite encaged palladium particles
Z . Karpidski, S.T. Homeyer and W.M.H. Sachtler .............2 03
Fundamental characteristics of the catalyst system
platinum-loaded zeolite L
J.M. Newsam, B.G. Silbernagel, A.R. Garcia, M.T. Melchior
and S.C. Fung .............................................. 211
Cation induced changes in chemical reactivity of small
metal particles
A.P.J. Jansen and R.A. van Santen..........................221
Structure-reactivity relationships in methanol to olefin
conversion on various microporous crystalline catalysts
T. Inui............ ........................................ 233
Titanium silicalite: a new selective oxidation catalyst
B. Notari..................................... .............2 43
Potential of zeolites as catalysts in organic synthesis
W.F. Hoelderich. ........................................... 257
VII
SURFACE SCIENCE AND MODELING
The influence of surface defect sites on chemisorption
and catalysis
J.T. Yates, Jr., A. Szabo and M.A. Henderson...............273
Correlations between structure and reactivity of metal
surfa ces
X. Jiang and D.W. Goodman....... ........................... 291
Alkyl iodides on copper surfaces: C-H activation and
coupling reactions of hydrocarbon fragments to produce
ethylene
C.J. Jenks, J.-L. Lin, C.-M. Chiang, L. Kang, P.S. Leang,
T.H. Wentzlaff and B.E. Bent..... .......................... 301
Effects of halogens on oxidation reactions over single
crystals of palladium
K. Klier, G.W. Simmons, Y.-N. Wang and J.A. Marcos.........309
Small molecule reactions on clean and modified iron
surfa ces
S.L. Bernasek, J.-P. Lu, M.R. Albert and W.-S. Hung ........3 15
Structure-activity and structure-selectivity relations
for reactions of carboxylic acids on TiO, (001) surfaces
H . Idriss, K.S. Kim and M.A. Barteau.......................327
Surface chemistry modelling of Ziegler-Natta catalysis
P.R. Watson, J. Mischenko I11 and S.M. Mokler .............. 337
Mathematical description of heterogeneous materials
-effect of the branching direction
J.W. Beeckman .............................................. 347
Author Index................ ............................... 359
Studies in Surface Science and Catalysis (other volumes
in the series) ............................................. 361
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IX
PREFACE
Structure plays an important role in heterogeneous catalysis. It provides a framework for
the arrangement and strategic placement of key catalytic elements, hosting them in a
prescribed manner so that their respective electronic properties can exhibit their desired
catalytic functions and mutual interactions. Under reaction conditions these framework
structures and their key catalytic guests undergo dynamic processes becoming active
participants of the overall catalytic process. They are not mere static geometric forms. The
framework provides the necessary crystal structure stabilization and hence acts as a
template. Non-stoichiometry and vacancy rearrangements of the solids are important
factors contributing to these dynamic processes of catalytic reactions. The dynamics of
catalytic structures are particularly vivid in selective oxidation catalysis where the lattice of
a given catalytic solid partakes as a whole, not only its surface, in the redox processes of the
reaction. The catalyst becomes actually a participating reagent. By proper choice of key
catalytic elements and their host structures preferred catalytic pathways can be selected
over less desired ones. However, not only in selective redox catalysis does structure play
an important role, its importance is also well documented, among others, in shape selective
zeolite catalysis, enantioselective hydrogenation and hydrodesulfurization.
The contributions presented in this book address the dynamic character of the solid state
under catalytic reaction conditions. By relating structure to activity and selectivity in
heterogeneous catalysis our understanding of such correlations has been significantly
enhanced through the use of sophisticated spectroscopic means, surface science and
modeling. Nonetheless, the ultimate test of the correlations remains the actual catalytic
reaction.
The individual contributors who made this update of structure activity and selectivity
correlations in heterogeneous catalysis possible are herewith sincerely thanked.
R. K. Grasselli A. W. Sleight
Mobil Central Research Laboratory Department of Chemistry
P. 0. Box 1025 Oregon State University
Princeton, NJ 08543 Corvallis, OR 97331
Princeton: February 28,1991
