Evaluation of the efficiency of the photocatalytic one-electron oxidation reaction of aromatic compounds adsorbed on a TiO2 surface.

Abstract

The TiO2 photocatalytic one-electron oxidation mechanism of aromatic sulfides with a methylene bridging group (-(CH2)n-, n=0-4) between the 4-(methylthio)phenyl chromophore and the carboxylate binding group on the surface of a TiO2 powder slurried in acetonitrile (MeCN) has been investigated by time-resolved diffuse reflectance (TDR) spectroscopy. The electronic coupling element (H(DA)) between the hole donor and acceptor, which was estimated from the spectroscopic characteristics of the charge transfer (CT) complexes of the substrates (S) and the TiO2 surface, exhibited an exponential decline with the increasing of the methylene number of S. The determined decay factor (beta) of 9 nm(-1) also supports the fact that the 4-(methylthio)phenyl chromophore is separated from the TiO2 surface. The efficiency of the one-electron oxidation of S adsorbed on the TiO2 surface, which was determined from the relationship between the amount of adsorbates and the concentration of the generated radical cations, significantly depended on the H(DA) value, but not on the oxidation potential of S determined in homogeneous solution.