Abstract
We previously found that Ti-containing mesoporous silica (T-S) with isolated and tetrahedrally coordinated Ti-oxide species, when photoactivated in acetonitrile with molecular oxygen (O(2)), catalyzes highly selective epoxidation of olefins (Chem. Commun. 2005, 5977). The system showed the highest epoxide selectivity among the photocatalytic systems proposed so far, but showed insufficient olefin conversion. In the present work, we have employed Ti-containing mesoporous organosilicas (T-OS), synthesized by a surfactant-templating method with an organosilane precursor, as the photocatalyst and have studied the effects on the olefin conversion and the epoxide selectivity. The T-OS catalysts demonstrate the same high epoxide selectivity as does T-S, but scarcely improve the olefin conversion. Photoluminescence measurement reveals that the T-OS catalysts with high surface hydrophobicity enhance the access of hydrophobic olefins to the photoexcited Ti-oxide species as expected, but destabilize the excited species themselves. ESR analysis demonstrates that the T-OS catalysts also destabilize the active oxygen radical (O(3)(*-)), a crucial oxidant for olefin epoxidation, formed on the excited Ti-oxide species. These destabilizations counteract the enhanced olefin access to the excited species, resulting in almost no improvement in olefin conversion. Through detailed analyses, we have summarized the changes in photocatalytic properties of the Ti-oxide species, associated with the organic modification of the catalyst.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.