Electron Catalysis for Enhanced Per‐ and Polyfluoroalkyl Substances Degradation in Nonthermal Plasma

Per‐ and polyfluoroalkyl substances (PFAS) are persistent environmental pollutants resistant to degradation due to strong C─F bonds. Efficient, energy‐saving methods for PFAS remediation remain a critical challenge. Here, we develop a computational framework revealing that radical anions of perfluorosulfonic acids serve as key intermediates where electron attachment weakens C─F and C─S bonds by up to 80 kcal/mol, enabling degradation pathways inaccessible to neutral or deprotonated species. Electrons and hydrogen atoms emerge as the dominant agents of defluorination, while hydroxyl radicals play a secondary role. Coupled with experimental validation in a nonthermal plasma reactor, we demonstrate that electron upconversion facilitates catalytic defluorination cycles through radical–anion cross‐reactions, enhancing fluoride release up to four‐fold. These findings unify plasma, photoredox, and electrochemical approaches under an electron‐catalytic mechanism, suggesting broadly applicable, greener strategies for destroying persistent fluorinated pollutants.