Electroreductive Defluorination of Unsaturated PFAS by a Quaternary Ammonium Surfactant-Modified Cathode via Direct Cathodic Reduction.

Remediation of per- and polyfluoroalkyl substances (PFAS) in groundwater remains a technological challenge due to the trace concentrations of PFAS and the strength of their C-F bonds. This study investigated an electroreductive system with a quaternary ammonium surfactant-modified cathode for degrading ()-perfluoro(4-methylpent-2-enoic acid) (PFMeUPA) at a low cathodic potential. A removal efficiency of 99.81% and defluorination efficiency of 78.67% were achieved under -1.6 V (vs Ag/AgCl) at the cathode modified by octadecyltrimethylammonium bromide (OTAB). The overall degradation procedure started with the adsorption of PFMeUPA onto the modified cathode. This adsorption process was promoted by hydrophobic and electrostatic interactions between the surfactants and PFMeUPA, of which the binding percentage, binding mode, and binding energy were determined via molecular dynamics (MD) simulations and density functional theory (DFT) calculations. The step-wise degradation pathway of PFMeUPA, including reductive defluorination and hydrogenation, was derived. Meanwhile, C-F bond breaking with direct electron transfer only was achieved for the first time in this study, which also showed that the C═C bond structure of PFAS facilitates the C-F cleavage. Overall, this study highlights the crucial role of quaternary ammonium surfactants in electron transfer and electrocatalytic activities in the electroreductive system and provides insights into novel remediation approaches on PFAS-contaminated groundwater.