Highly efficient and mild electrochemical mineralization of long-chain perfluorocarboxylic acids (C9-C10) by Ti/SnO₂-Sb-Ce, Ti/SnO ₂-Sb/Ce-PbO₂, and Ti/BDD electrodes

The electrochemical mineralization of environmentally persistent long-chain perfluorinated carboxylic acids (PFCAs), i.e., perfluorononanoic acid (C ₈F₁₇COOH, PFNA) and perfluorodecanoic acid (C ₉F₁₉COOH, PFDA) was investigated in aqueous solutions (0.25 mmol L^-1) over Ti/SnO₂-Sb-Ce (SnO₂), Ti/SnO₂-Sb/Ce-PbO₂ (PbO₂), and Ti/BDD (BDD) anodes under galvanostatic control at room temperature. Based on PFCA decay rate, total organic carbon (TOC) reduction, defluorination ratio, safety, and energy consumption, the performance of PbO₂ electrode was comparable with that of BDD electrode. After 180 min electrolysis, the PFNA removals on BDD and PbO₂ electrodes were 98.7 ± 0.4% and 97.1 ± 1.0%, respectively, while the corresponding PFDA removals were 96.0 ± 1.4% and 92.2 ± 1.9%. SnO₂ electrode yielded lower PFCA removals and led to notable secondary pollution by Sb ions. The primary mineralization product, F^-, as well as trace amounts of intermediate PFCAs with shortened chain lengths, were detected in aqueous solution after electrolysis. On the basis of these results, a degradation mechanism including three potential routes is proposed: via formation of short-chain PFCAs by stepwise removal of CF₂; direct mineralization to CO₂ and HF; conversion to volatile fluorinated organic compounds. The results presented here demonstrate that electrochemical technique exhibits high efficiency in mineralizing PFNA and PFDA under mild conditions, and is promising for the treatment of long-chain PFCAs in wastewater.