K.M. Christopher, I.V. Alabugin, B.R. Locke, R. Bulusu
Florida State University,
United States
Keywords: Electron Upconversion, Electron Catalysis, Nonthermal Plasma, Energy Efficient PFAS Degradation
Summary:
Electrons are often regarded as reagents in PFAS remediation, yet they possess the capacity to act catalytically when coupled to electron upconversion, i.e., the generation of stronger reductants in situ. Here, we develop a comprehensive computational framework showing how electron upconversion can be harnessed to drive the degradation of perfluorosulfonic acids (PFSAs), among the most recalcitrant PFAS. We identify radical anions of sulfonic acids as viable intermediates where the C–S and C–F bonds are weakened by up to 100 kcal/mol, enabling pathways inaccessible to neutral or deprotonated PFSAs. Electrons and hydrogen atoms emerge as the dominant agents for bond activation, while hydroxyl radicals play only a minor supporting role. We further show that radical and anion cross-reactions can regenerate upconverted electrons, establishing the basis for catalytic defluorination cycles. These findings unify plasma, photoredox and redox catalysis through a shared mechanistic principle and point toward more energy-efficient PFAS destruction.