Realizing Direct Hot-Electron Transfer from Metal Nanoparticles to Per- and Polyfluoroalkyl Substances

Per- and polyfluoroalkyl substances (PFAS) are a group of forever synthetic chemicals. They are widely utilized in industries and household appliances because of their remarkable stability and distinctive oil- and water-repellent properties. Despite their broad applications, unfortunately, PFAS are hazardous to all forms of life, including humans. In recent years, the environmental persistence of PFAS has raised significant interest in degrading these substances. However, the strong C-F bonds in these chemicals pose several challenges to their degradation. Plasmons of noble metal nanoparticles (NPs) offer many exciting applications, including photocatalytic reactions. However, an atomistic understanding of plasmon-driven processes remains elusive. In this work, using the real-time time-dependent density functional theory, we have studied the real-time formation of plasmons, hot-carrier generation, and subsequent direct hot-carrier transfer from metal NPs to the PFAS. Our simulations show that there is an apparent direct hot-electron transfer from NPs to PFAS. Moreover, using Ehrenfest dynamics simulations, we demonstrated that the transferred hot electrons can efficiently degrade PFAS without requiring any external thermal bath. Thus, our work provides an atomistic picture of plasmon-induced direct hot-carrier transfer from NPs to PFAS and the efficient degradation of PFAS. We strongly believe that this work generates the impetus to utilize plasmonic NPs to mitigate PFAS.