Photoelectrochemical degradation of perfluorooctanoic acid (PFOA) with GOP25/FTO anodes: Intermediates and reaction pathways

Perfluorooctanoic acid (PFOA) have been widely studied due to their persistence, bioaccumulation and possible toxic effects. In this work, we investigated a photoelectrochemical (PEC) system consisting of a graphene oxide-titanium dioxide (GOP25) anode coated on fluorine-doped tin oxide (FTO) glass for removal of PFOA in an aquatic environment. The GOP25/FTO anode was fabricated and well characterized. Nearly complete decomposition of 0.5 mg/L PFOA was achieved after 4 h of PEC treatment with an initial pH of 5.3 and a current density of 16.7 mA cm-2. The presence of graphene oxide (GO) on the TiO2 anode could enhance its electrochemical performance, thereby leading to increased decomposition efficiency. A total of 18 PFOA transformation products, including short-chain perfluoroalkyl acids, are reported in this work, and 13 products were observed for the first time. Four possible routes of PFOA decomposition, namely, decarboxylation followed by oxidation, defluorination, hydroxylation and Cl atom substitution, were determined. The presence of chlorinated byproducts in the system indicated that reactive chlorine species contributed to PFOA degradation.