Photoelectrochemistry on TiO 2 /Ti anodes as a tool to increase the knowledge about some photo‐oxidation mechanisms in CH 3 CN

Through current efficiency measurements, obtained from the photoelectrochemical oxidation at TiO 2 (rutile)/Ti anodes, further mechanistic information has been obtained regarding the TiO 2 photosensitized oxidation of benzylic alcohols, ethers and 1,2‐diols in CH 3 CN. In deaerated medium, two electrons are captured by the semiconductor from all the considered substrates (one from the substrate, the second from the intermediate benzylic radical). In contrast, in aerated CH 3 CN, the number of TiO 2 ‐captured electrons can be reduced to one because, depending on its oxidizability, the benzylic radical can be competitively captured by oxygen. Copyright © 2008 John Wiley & Sons, Ltd.