Titania-Silica Materials from the Molecular Precursor Ti[OSi(OtBu)3]4: Selective Epoxidation Catalysts

Coles, Martyn P, Lugmair, Claus G, Terry, Karl W and Tilley, T Don (2000) Titania-Silica Materials from the Molecular Precursor Ti[OSi(OtBu)3]4: Selective Epoxidation Catalysts. Chemistry of Materials, 12 (1). 122 - 131. ISSN 0897-4756

Full text not available from this repository.

Abstract

The tris(tert-butoxy)siloxy complex Ti[OSi(OtBu)3]4 (1) was pyrolytically converted at low temperatures to the theoretical yield of homogeneous TiO4SiO2 materials. 1 also serves as a soluble model for isolated, tetrahedral titanium atoms in a silica matrix. The solid-state transformation of 1 to TiO4SiO2 affords a low-surface-area material (2a, 22 m2 g-1 for samples heated to 500 C) consisting of roughly spherical particles with an average diameter of ca. 25 nm (by transmission electron microscopy). The solution-phase thermolysis of 1 affords a xerogel (2b) consisting of smaller primary particles (ca. 5 nm) and possessing a much higher surface area (552 m2 g-1 for samples heated to 500 C). Acid catalysis of the pyrolytic conversion in solution affords a xerogel (2c) with a lower surface area (399 m2 g-1 for samples heated to 500 C). Supercritical drying of the "wet-gel" in CO2 affords an aerogel (2d) with a morphology similar to that of the xerogel and a slightly higher surface area (677 m2 g-1 for samples heated to 500 C). The TiO4SiO2 materials are amorphous as initially formed, and subsequent crystallizations of anatase (2a, 2b), rutile, and cristobalite (2a) occur at relatively high temperatures. 1 is a homogeneous catalyst for the selective epoxidation of cyclohexene to cyclohexene oxide (64% yield; 20 turnovers after 2 h) using cumene hydroperoxide (CHP) as the limiting reagent. 2a-d are heterogeneous catalysts that produce 6% (2a)-49% (2d) yields of cyclohexene oxide after 2 h (with 0.05 g of catalyst). Supporting 1 on silica affords a highly active epoxidation catalyst that provides yields of 94% cyclohexene oxide after 2 h (with a standard amount of 0.05 g of catalyst). The molecular route to homogeneous titania-silica materials described here represents an alternative to the sol-gel method, affording materials with surface areas comparable to those of related aerogels and moderate-to-excellent activities for the epoxidation of cyclohexene.

Item Type: Article
Additional Information: Post-doctoral work
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Martyn Coles
Date Deposited: 06 Feb 2012 18:49
Last Modified: 19 Mar 2013 13:55
URI: http://sro.sussex.ac.uk/id/eprint/18476
📧 Request an update