Photocatalytic degradation of aromatic pollutants: a pivotal role of conduction band electron in distribution of hydroxylated intermediates

The modulation of the yield distribution of intermediates formed in the photocatalytic degradation of organic pollutants is of extreme importance for the application of photocatalysis in environmental cleanup, as different intermediates usually exhibit distinct biological toxicity and secondary reactivity. In this paper, we report that the distribution of monohydroxylated intermediates (m-, p- and o-) formed during the photocatalytic oxidation of aromatic compounds changes with the variation of reaction conditions, such as O(2) partial pressure and substrate concentration. By detailed product analysis, theoretical calculation, and oxygen isotope labeling experiments, we show that these changes are due to the selective reduction of HO-adduct radicals (the precursors of hydroxylated intermediates) by conduction band electrons (e(cb)(-)) back to the original substrate, that is, p- and o-HO-adduct radicals are more susceptible to e(cb)(-) than the m- one. Our experiments give an example that, even under oxidative conditions, the yield distribution of isomeric intermediates can be modulated by e(cb)(-)-initiated reduction. This study also illustrates that the unique redox characteristics of photocatalysis, that is, both oxidation and reduction reactions take place on or near the surface of a single nanoparticle, can provide opportunities for the reaction control.