Titanosilicate molecular sieve as a photocatalyst for size-screening conversion

ORGN 123

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 efficient and highly selective methods for photocatalytic organic synthesis is one of the biggest challenges in chemistry. Here we report that ultraviolet light activation of titanosilicate molecular sieves, a Ti-containing silicious zeolite, in water in the presence of molecular oxygen, catalyze a conversion of molecules having a size close to the pore of the catalysts but are inactive for molecules having much larger or smaller size. This unprecedented "size-screening" photocatalytic activity is triggered by a combination of water-induced shortened lifetime of active species (charge-transfer excited state of tetrahedrally coordinated titanium oxide) and restricted diffusion of a molecule inside the pore. We highlight here a successful application of this unusual photocatalytic activity to a selective transformation of molecules that is associated with a size reduction of molecules, so-labeled "molecular shave" transformation.