The extraordinary stability of the C-F bond imparts many commercially useful properties to poly- and per-fluoroalkyl substances (PFASs). Among the properties imparted by the stability of the C-F bond is a high resistance to degradation via traditional oxidative/reductive processes. As a consequence PFAS is a persistent contaminant upon environmental exposure; especially in water. In this work, we examine the impact of nanodiamond photochemistry on the degradation of one of the more resilient in the class of PFASs, perfluorooctane sulfonate (PFOS). Using nanosecond transient absorption we find that hydrated electrons result by photodetachment from hydrogen-terminated (negative electron affinity) detonation nanodiamond (HDND) suspensions in water upon sub-bandgap (266nm) irradiation. Hydrated electron photogeneration from oxygen-terminated (positive electron affinity) detonation nanodiamond (ODND), on the other hand, is not observed. The transient absorption data suggest the presence of an interaction between PFOS and HDND and, more so, an interaction between PFOS and the hydrated electrons. Finally, we show that prolonged sub-bandgap (254nm) irradiation of aqueous HDND in the presence of PFOS leads to full decomposition of PFOS by reductive fragmentation, consistent with hydrated electron reductive chemistry.

Degradation of perfluorooctane sulfonate by sub-bandgap irradiation of hydrogen terminated detonation nanodiamond

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.