Photocatalytic Activation of C-H Bonds by Spatially Controlled Chlorine and Titanium on the Silicate Layer

Owing to the economic and environmental benefits, photocatalytic organic transformation via C-H activation is a crucially important, while still challenging area. We report photocatalytic process for partial cyclohexane oxidation with enhanced catalytic activity that exploits chlorine and titanium atoms spatially arranged on a silica substrate. Silica-based catalysts bearing grafted titanium that effectively interacts with photochemically adsorbed chlorine were prepared. The catalysts were synthesized by reacting a layered silicate with titanium(IV) acetylacetonate and subsequent chlorination treatment. Characterization by a variety of techniques revealed that the organic ligand of the titanium species that is grafted onto the silicate layer surface is converted into chlorine while maintaining its coordination state. However, upon subsequent hydration, the chlorine existed as HCl. We investigated the performance of the catalyst for the production of cyclohexanol and cyclohexanone from cyclohexane with mol...