Pathways of the photocatalytic reaction of acetate in H2O and D2O: A combined EPR and ATR-FTIR study

The adsorption and photocatalytic degradation of acetate on TiO2 surfaces were investigated in H2O and D2O by ATR-FTIR and EPR Spectroscopy respectively. These studies were carried out in the dark and under UV(A) illumination to gain additional insights into the adsorption behaviour with the identification of paramagnetic species formed during the oxidation of acetate. Isotopic exchange during the adsorption of D2O on the TiO2 surface led to different interactions between the adsorbate and OD groups. At different pH levels, several surface complexes of acetate can be formed such as monodentates or bidentates. Under UV(A) irradiation of TiO2 aqueous suspensions, the formation of hydroxyl and methoxy radicals evidenced as the corresponding spin-adducts, was found to dominate in alkaline and acidic suspensions respectively. Two possible pathways for the oxidation of acetate have been suggested at different pH levels in solution in terms of the source of the spin adduct formed. These proposed pathways were found to be in good agreement with ATR-FTIR and EPR results. (C) 2016 Elsevier Inc. All rights reserved.