Ti-containing MCM-41 catalysts for liquid phase oxidation of cyclohexene with aqueous H2O2 and tert-butyl hydroperoxide

Abstract

Framework Ti-substituted and Ti-grafted MCM-41 mesoporous material has been prepared by direct hydrothermal synthesis and a post-synthesis grafting method. The materials have been tested as catalysts for cyclohexene oxidation with aqueous H2O2 and tert-butyl hydroperoxide (TBHP). With aqueous H2O2 in methanol, the major products were cyclohexene diol and its methyl ethers. No cyclohexene oxide was produced. Titanium leaching was a serious problem, and the catalyst lost its activity irreversibly after only one cycle of reaction. With TBHP, the selectivity for cyclohexene oxide was near 100%, titanium leaching was negligible, and the catalyst could be repeatedly used after regeneration without suffering significant activity loss. However, the reaction rate was lower than when H2O2 was used. Framework substituted material and catalysts prepared by Ti-grafting onto a MCM-41 support behaved similar, but the Ti-grafted MCM-41 is somewhat more active. The turnover frequency (TOF) per mole of Ti decreases with an increase of Ti content in the catalyst. This is caused by a reduced Ti dispersion within the silica matrix.