Elsevier

Microporous Materials

Volume 2, Issue 5, June 1994, Pages 297-411
Microporous Materials

Review
Organic catalysis over zeolites: A perspective on reaction paths within micropores

This paper is dedicated to my father, L.J. Venuto, a pioneer in the field of carbon black chemistry and its application in the paint and ink industry; to Dr. S.L. Meisel, an inspiring leader of Mobil's research effort, who initiated the organic catalysis effort at Mobil in the early 1960s; to Dr. C.D. Prater of Mobil, an outstanding scientist and research manager, for his guidance over the years; to Professor J. Wei of Princeton University for many stimulating discussions and penetrating insights into catalytic phenomena; and to Professor A.G. Oblad of the University of Utah, a pathbreaker in catalytic science, for his longstanding friendship and support.
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Abstract

Since the early 1960s, the field of organic catalysis over zeolites and related microporous materials has shown enormous international expansion. Not only has a multiplicity of new reactions been explored over a continually increasing assemblage of zeolite structures, but also the depth of understanding of the catalytic chemistry and structure—reactivity relationships has shown dramatic growth. Further, the utilization of ZSM-5 and related medium-pore zeolites has truly enabled a revolution in shape-selective control of reaction selectivity. In the present review, we first conduct a broad classification and survey of organic chemistry over zeolites. This reflects, for the most part, a mechanistic rather than a process or applications frame of reference. We then examine selected examples of underlying physicochemical phenomena and structure—reactivity patterns that are peculiar to heterogeneous catalytic reactions within zeolite micropores. These include diffusion/adsorption effects, shape-selective principles, mechanistic disguises, catalyst deactivation pathways and related considerations.

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