Electrooxidation of per- and polyfluoroalkyl substances in chloride-containing water on surface-fluorinated Ti4O7 anodes: Mitigation and elimination of chlorate and perchlorate formation

Electrooxidation (EO) has been shown effective in degrading per- and polyfluoroalkyl substances (PFASs) in water, but concurrent formation of chlorate and perchlorate in the presence of chloride is of concern due to their toxicity. This study examined EO treatment of three representative PFASs, perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and 6:2 fluorotelomer sulfonate (6:2 FTS), in chloride-containing solutions on pristine and surface-fluorinated Ti4O7 anodes having different percentage of surface fluorination. The experiment results indicate that surface fluorination of Ti4O7 anodes slightly inhibited PFAS degradation, while significantly decreased the formation of chlorate and perchlorate. Further studies with spectroscopic and electrochemical characterizations and density functional theory (DFT) computation reveal the mechanisms of the impact on EO performance by anode fluorination. In particular, chlorate and perchlorate formation were fully inhibited when fluorinated Ti4O7 anode was used in reactive electrochemical membrane (REM) under a proper anodic potential range (<3.0 V vs Standard Hydrogen Electrode), resulting from slower intermediate reaction steps and short residence time of the REM system. The results of this study provide a basis for design and optimization of modified Ti4O7 anodes for efficient EO treatment of PFAS while limiting chlorate and perchlorate formation.