Surface fluorination mediated electro-oxidative degradation of HFPO-DA on boron-doped diamond electrode

Heptafluoropropylene oxide dimer acid (HFPO-DA), as an alternative to perfluorooctanoic acid (PFOA), has been shown to pose similar environmental and health risks as other perfluorinated compounds. The electrochemical-based advanced oxidation processes are promising techniques for the treatment of perfluorinated compounds, and the boron-doped diamond (BDD) anode could degrade HFPO-DA under mild conditions. However, the roles of radicals in the degradation and how to overcome the steric hindrance of the -CF₃ branch on the carboxyl group were not yet clear. In this study, we investigated the degradation mechanism of HFPO-DA on the BDD anode. Instead of other non-active anodes (PbO₂ and SnO₂ electrodes), HFPO-DA can be degradable on the BDD electrode with a rate constant logarithmic correlation to the applied current density. The hydroxyl radical (•OH) was one of the key factors in the degradation of HFPO-DA, accounting for almost 89% of the significant effect, and the direct electron transfer was the rate-limiting step in the degradation reaction. Physicochemical characterization including field emission scanning electron microscope (FE-SEM), X-ray photo-electron spectroscopy (XPS), water contact angle, and electrochemical property indicated that the BDD electrode was fluorinated after electrolysis, the electrode surface became more hydrophobic due to the bonding of -C_xF_y, leading to a decrease in the electrochemically active area. Moreover, degradation products (pentafluoropropionic acid, trifluoroacetic acid, and fluorine ion) were detected and the mass balance of carbon and fluorine was calculated during the degradation. Therefore, a degradation mechanism for HFPO-DA was proposed, which involved direct electron transfer, decarboxylation, radical reaction, decarboxylation, and decarboxylation. The de-CF₃ step initiated the fluorination of the BDD electrode, which was initiated by the defluorination process. This study contributes to the understanding of the electro-oxidative degradation of perfluoroalkyl ether carboxylic acids and provides guidance for the application of electrochemical advanced oxidation processes.