Efficient Electrochemical Oxidation of Perfluorooctanoate Using a Ti/SnO₂-Sb-Bi Anode

The electrochemical decomposition of persistent perfluorooctanoate (PFOA) with a Ti/SnO2-Sb-Bi electrode was demonstrated in this study. After 2 h electrolysis, over 99% of PFOA (25 mL of 50 mg·L(-1)) was degraded with a first-order kinetic constant of 1.93 h(-1). The intermediate products including short-chain perfluorocarboxyl anions (CF3COO-, C2F5COO-, C3F7COO-, C4F9COO-, C5F11COO-, and C6F13COO-) and F- were detected in the aqueous solution. The electrochemical oxidation mechanism was revealed, that PFOA decomposition first occurred through a direct one electron transfer from the carboxyl group in PFOA to the anode at the potential of 3.37 V (vs saturated calomel electrode, SCE). After that, the PFOA radical was decarboxylated to form perfluoroheptyl radical which allowed a defluorination reaction between perfluoroheptyl radical and hydroxyl radical/O2. Electrospray ionization (ESI) mass spectrum further confirmed that the oxidation of PFOA on the Ti/SnO2-Sb-Bi electrode proceeded from the carboxyl group in PFOA rather than C-C cleavage, and the decomposition processes followed the CF2 unzipping cycle. The electrochemical technique with the Ti/SnO2-Sb-Bi electrode provided a potential method for PFOA degradation in the aqueous solution.