Contribution of electrolyte in parametric optimization of perfluorooctanoic acid during electro-oxidation: Active...

The present study investigated the roles of peroxydisulfate (PDS) radicals and sulfate radicals (SO₄^•-) that formed from sulfate (SO₄^2-) during electrochemical oxidation of perfluorooctanoic acid (PFOA). The effect of operating parameters such as different types of electrolytes (NaCl, NaClO₄, and Na₂SO₄), initial pH, current density, dose of electrolyte, and initial concentration of PFOA using electrochemical oxidation for perfluorooctanoic acid (PFOA) decomposition study was investigated. A difference in the removal efficiency with different electrolytes (i.e., Cl^-, ClO₄^-, and SO₄^2-) illustrated an increasing effect of electrooxidation of PFOA in the order of ClO₄^- < Cl^- < SO₄^2-, which suggested that ^•OH induced oxidation and direct e^- transfer reaction continued to play a crucial role in oxidation of PFOA. At the optimum treatment condition of j = 225.2 Am^-2, Na₂SO₄ concentration = 1.5 gL^-1, [PFOA]_o = 50 mgL^-1 and initial pH = 3.8 maximum PFOA removal of 92% and TOC removal of 80% was investigated at 240 min. The formation of three shorter-chain perfluorocarboxylates (i.e., perfluoroheptanoic acid (PFHpA), perfluorohexanoic acid (PFHxA), and perfluoropentanoic acid (PFPeA) and formate (HCOO^-) ions were detected as by-products of PFOA electro-oxidation, showing that the C-C bond first broken in C₇F₁₅ and then mineralized into CO₂, and fluoride ion (F^-). The fluorine recovery as F^- ions and the organic fluorine as the shorter-chain by-products were also obtained. The degradation kinetic has also been studied using the nth-order kinetic model.