Insight into mechanochemical destruction of PFOA by BaTiO₃: An electron-dominated reduction process

Perfluorooctanoic acid (PFOA) is a representative persistent organic pollutant and its disposal by mechanochemical (MC) technology emerges in recent years. However, degradation mechanism of PFOA especially rupture of C-F bonds during MC process is still unclear. Therefore, we innovatively employed barium titanate as co-milling reagent in MC system to disclose an electron-dominated reduction process. By stimulating piezoelectric effect of BaTiO₃ under MC impact, free electrons were generated. The results implied more than 95.00% degradation and 60.00% defluorination efficiency were obtained after 6 h' ball milling. DPPH• was used as probe to confirm the existence of piezo-excited electrons, which were further verified to be major reactive species by atmosphere experiments. Thus, PFOA destruction was dominated by reduction process, characterizing by breakage of C-F bonds induced by electrons. Accordingly, the fate of organic fluorides was explored and BaF₂ was identified as final product. The cleavage of carboxyl group initiated PFOA decomposition, following by successive removal of CF₂ groups and elimination of F^-. Moreover, the practical experiments and reusable trials implied promising application of this method. Overall, this paper provides a novel perspective for reductive decomposition of PFOA by MC technology and reveals the major role of electrons during reaction process.