Titanium containing molecular sieves have been widely studied as heterogeneous catalysts for selective oxidation using hydrogen peroxide or organic hydroperoxides. The superior epoxide selectivity of isolated framework Ti sites in olefin epoxidation has driven the effort to prepare different Ti molecular sieves. In particular, mesoporous Ti molecular sieves enable the oxidation of large organic substrates which cannot diffuse into the micropores of Ti-zeolites. We will report the synthesis of a series of Ti containing wrinkled mesoporous silicas (WMS) having a radial pore structure. Ti periodic mesoporous organosilicas (PMO) were also synthesized with the same radial pore structure. These catalysts were further modified by trimethylsilylation to improve the surface hydrophobicity. The unique radial wrinkled pore structure of these catalysts offers advantages over conventional Ti-MCM-41 having a one dimensional pore structure in the epoxidation of cyclohexene using t-butyl hydroperoxide. For oxidation of cyclohexene without solvent, silylated Ti wrinkled mesoporous silica shows a maximum turnover frequency of 1401 h<sup>-1</sup> with an epoxide selectivity of 95%.<br/>

Synthesis of wrinkled mesoporous titanosilicate for selective oxidation of cyclohexene

253rd National Meeting (2017)

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