Photo-Induced Holes Initiating Peroxymonosulfate Oxidation for Carbamazepine Degradation via Singlet Oxygen

Abstract

Peroxymonosulfate (PMS) has been intensively used to enhance the photocatalytic activity of catalysts, which is adopted as an electron acceptor to inhibit the recombination of electrons and holes. However, the effect of holes generated by visible light (VL) on PMS activation is always overlooked. Herein, the VL/Bi2WO6/PMS process was constructed for the efficient removal of organics, in which the degradation rate of carbamazepine (CBZ) increased by over 33.0 times by the introduction of PMS into Bi2WO6 under visible light. The radical quenching and determination experiments confirmed that the photogenerated holes could firstly oxidize PMS to form SO5•− and react with HSO5− to produce 1O2, then inducing the formation of other reactive species to greatly enhance the performance of pollutant removal by the VL/Bi2WO6/PMS process. Density functional theory (DFT) predicted that sites with high Fukui index (f0) on CBZ were more susceptible to being attacked, resulting in hydroxylation, ring closure, and C=C bond cleavage of CBZ. Toxicity estimation indicated that photocatalysis degradation products from CBZ were less toxic compared to the parent compound. This study provides a potential avenue for improving photocatalytic efficiency and widening the application of photocatalytic technology in wastewater purification.