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Mechanistic Studies of TiO 2 Photocatalysis and Fenton Degradation of Hydrophobic Aromatic Pollutants in Water.
Chemistry, An Asian Journal 2016 December 20
HO-adduct radicals have been investigated and confirmed as the common initial intermediates in TiO2 photocatalysis and Fenton degradations of water-insoluble aromatics. However, the evolution of HO-adduct radicals to phenols has not been completely clarified. When 4-d-toluene and p-xylene were degraded by TiO2 photocatalysis and Fenton reactions, respectively, a portion of the 4-deuterium or 4-CH3 group (18-100 %) at the attacked ipso position shifted to the adjacent position of the ring in the formed phenols (NIH shift; NIH is short for the National Institutes of Health, to honor the place where this phenomenon was first discovered). The results, combined with the observation of a key dienyl cationic intermediate by in situ attenuated total reflectance FTIR spectroscopy, indicate that, for the evolution of HO-adduct radicals, a mixed mechanism of both the carbocation intermediate pathway and O2 -capturing pathway occurs in both aqueous TiO2 photocatalysis and aqueous Fenton reactions.
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