Removing per- and polyfluoroalkyl substances (PFAS) in water resources at trace concentrations (ng/L) is scientifically challenging. Herein, a cation-π system was constructed comprising a Fe(II)/Fe(III) coordinated graphene-like structure encapsulating Fe° catalyst (Fe(II)/Fe(III)-GL@Fe), realizing rapid PFAS mineralization in municipal wastewater and raw drinking water under ambient atmospheric conditions without external energy input. The strong electric field was generated from DOC-PFAS-HO-O synergistic coordination at Fe species area and GL area on Fe(II)/Fe(III)-GL@Fe via surface charge rearrangement by Fe-π interaction, triggering surface electrochemical-like redox reactions: sequential adsorbed C-F bond oxidation, adjacent bond homolysis, and O reduction until complete PFAS mineralization.
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