Abstract
HIGHLIGHTS: What are the main findings? Grid-shaped Ti(4)O(7) enables efficient PFOA/PFOS electro-oxidation. EO-EF mainly accelerates kinetics, with a stronger benefit for PFOA. At 0.2 ppm (EO-EF), fluoride release indicates partial C-F bond cleavage. What are the implications of the main findings? EO-EF mitigates organic-matter inhibition compared with EO alone. Ti(4)O(7) anodes are promising for dilute PFAS treatment at moderate energy demand levels. ABSTRACT: The persistence of per- and polyfluoroalkyl substances (PFASs) in aquatic environments requires efficient and sustainable treatment technologies. In this study, the electrochemical degradation of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) was investigated using a grid-shaped Ti(4)O(7) Magnéli-phase anode under electro-oxidation (EO) and electro-oxidation coupled with electro-Fenton (EO-EF) conditions. Structural characterization confirmed the predominance of Ti(4)O(7) in the electrode material. At an initial concentration of 2 ppm, PFOS was rapidly and almost completely removed under both EO and EO-EF, whereas PFOA exhibited slower degradation kinetics, identifying it as the kinetically limiting compound. Coupling EO with electro-Fenton mainly enhanced the degradation kinetics, particularly for PFOA, while final removal efficiencies remained comparable. The influence of initial concentration was further examined, showing that lowering the PFOA concentration to 0.2 ppm, representative of environmentally relevant levels, enabled nearly complete removal within 300 min. Fluoride ion monitoring under optimized EO-EF conditions confirmed partial defluorination, demonstrating that PFOA removal is accompanied by C-F bond cleavage. These findings highlight the respective roles of EO and EO-EF processes and support the potential of Ti(4)O(7)-based anodes for energy-competitive PFAS remediation.