4.4 Article Proceedings Paper

Nanoparticles in catalysis

Journal

TOPICS IN CATALYSIS
Volume 24, Issue 1-4, Pages 147-159

Publisher

KLUWER ACADEMIC/PLENUM PUBL
DOI: 10.1023/B:TOCA.0000003086.83434.b6

Keywords

nanocatalysts; bimetallic catalysts; mesoporous support; heterogenised-homogenous catalysts; hydrogenation

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In this article, we report studies of two new forms of highly active supported catalysts. First, those derived from supported carbonylate clusters-nanocatalysts and second, those produced from the heterogenization of known chiral homogeneous systems. The utilization of established cluster compounds of precisely known composition and structure have proved invaluable in the preparation of mixed metal nanoparticles of well-defined composition. The attachment of these nanoparticles to the inner walls of mesoporous silica has led to the development of highly active and effective catalysts for a series of hydrogenation reactions, emphasizing the enhanced reactivity of these metal systems as a consequence of their size and of the low coordination numbers of the metal atoms involved. These attributes combined with the relative ease of characterization of both the active sites and their location has led to a detailed examination of the role of these nanosystems in a new approach to clean technology. In an alternative strategy, the use of heterogenized homogeneous chiral catalysts based on the ferrocenyl moiety and diamino ligands and linked to the inner surface of mesoporous materials either by a direct chemical bond or by an ionic interaction has also been explored. These catalysts have been shown to be highly effective in the enantioselective synthesis of organic compounds. Significantly, we have found that the mesopore (usually MCM-41) imposes spatial restrictions arising from the concavity of the inner surface and leads to greatly enhanced enantioselective (ee) performance.

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