Adsorption-controlled selective photocatalytic transformation on mesoporous titanium dioxide

ORGN 124

Yasuhiro Shiraishi, shiraish@cheng.es.osaka-u.ac.jp, Naoya Saito, and Takayuki Hirai. Research Center for Solar Energy Chemistry, Osaka University, 1-3 Machikaneyama-cho, Toyonaka, 560-8531, Japan
Development of highly selective methods for photochemical organic synthesis, driven by a heterogeneous catalyst, is one of the biggest challenges in chemistry. Much investigation has been made based on systems using a semiconductor, titanium dioxide; however, oxidation of substrates by hydroxyl radical is nonselective, resulting in insufficient product selectivity. Herein, we report that titanium dioxide with a mesoporous structure, when photoactivated in water, demonstrates an unprecedented photocatalytic activity, driven strongly by an adsorption degree of molecules onto the catalyst surface. This promotes a preferential conversion of well-adsorbed molecule. We highlight a successful application of this unusual catalytic property to selective transformation of a well-adsorbed molecule into a less-adsorbed molecule, labeled as "stick-and-leave" transformation, which enables a transformation of benzene into phenol, one of the most difficult synthetic reactions, with very high selectivity (>80%).