Multiphoton‐driven Photocatalytic Defluorination of Persistent Perfluoroalkyl Substances and Polymers by Visible Light

Perfluoroalkyl substances (PFASs) and fluorinated polymers (FPs) have been extensively utilized in various industries, whereas their extremely high stability poses environmental persistence and waste treatment. Current decomposition approaches of PFASs and FPs typically require harsh conditions such as heating over 400°C. Thus, there is a pressing need to develop a new technique capable of decomposing them under mild conditions. Here, we demonstrated that perfluorooctanesulfonate (PFOS), known as a "persistent chemical," and Nafion, a widely utilized sulfonated FP for ion‐exchange membranes, can be efficiently decomposed into fluorine ions under ambient conditions via the irradiation of visible LED light onto semiconductor nanocrystals (NCs). PFOS was completely defluorinated within 8‐h irradiation of 405‐nm LED light, and the turnover number of the C–F bond dissociation per NC was 17200. Furthermore, 81% defluorination of Nafion was achieved for 24‐h light irradiation, demonstrating the efficient photocatalytic properties under visible light. We revealed that this decomposition is driven by cooperative mechanisms involving light‐induced ligand displacements and Auger‐induced electron injections via hydrated electrons and higher excited states. This study not only demonstrates the feasibility of efficiently breaking down various PFASs and FPs under mild conditions but also paves the way for advancing toward a sustainable fluorine‐recycling society.