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.