Real-Time raman monitoring during photocatalytic epoxidation of cyclohexene over V-Ti/MCM-41 Catalysts

Abstract

A series of V- and/or Ti-loading MCM-41 catalysts are successfully synthesized with a hydrothermal method. The photocatalytic and thermal epoxidations of cyclohexene in the presence of tert-butyl hydroperoxide (t-BuOOH) were investigated with real-time monitored by NIR-Raman spectroscopy. It suggests that both V- and Ti-loading can be responsible for the cyclohexene epoxidation. Moreover, the complementary behavior of V- and Ti-loading may be related to a similar role of activation. Interestingly, the progress of the photo-epoxidation on V0.25Ti2/MCM-41 photocatalyst was monitored by changes in intensity of the characteristic Raman bands without interference from the UV-light irradiation. The result, for the first time, reveals that cyclohexene was directly photo-epoxidized to 1,2-epoxycyclohexane by t-BuOOH during the reaction. A possible mechanism of cyclohexene photo-epoxidation is also proposed for this study.We gratefully acknowledge the National Science Council of Taiwan for financial support of this research under contract number NSC 99-2923-E-002-002-MY2 (Taiwan), CTQ2011-13343-E (Spain) and bilateral NSC-CSIC project 2009TW0021. We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI).Peer reviewe