Surfactant-encapsulated polyoxometalates as immobilized supramolecular catalysts for highly efficient and selective oxidation reactions

Abstract

A type of interesting immobilized supramolecular catalysts based on surfactant-encapsulated polyoxometalates has been developed for oxidation reactions. Through a sol-gel process with tetraethyl orthosilicate, hydroxyl-terminated surfactant-encapsulated polyoxometalate complexes have been covalently and uniformly bound to a silica matrix with unchanged complex structure. The formed hybrid catalysts possess a defined hydrophobic nano-environment surrounding the inorganic clusters, which is conducive to compatibility between the polyoxo metalate catalytic centres and organic substrates. The supramolecular synergy between substrate adsorption, reaction, and product desorption during the oxidation process has been found to have an obvious influence on the reaction kinetics, with the activity of the catalyst being greatly improved. The supra molecular catalysts performed effectively in the selective oxidation of several different kinds of organic compounds, such as alkenes, alcohols, and sulfides, and the main products were the corresponding epoxides, ketones, sulfoxides, and sulfones. More significantly, the catalyst could be easily recovered by simple filtration, and the catalytic activity was well retained for at least five cycles. Finally, the present strategy has proved to be a general route for the fabrication of supra- molecular hybrid catalysts containing common polyoxometalates suitable for various purposes.© 2010 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim.