Redox-active rGO-nZVI nanohybrid-catalyzed chain shortening of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS)

Abstract Per- and polyfluoroalkyl substances (PFASs) are exceptionally stable chemicals due to their strong C-F bonds. Nanoscale zero-valent iron (nZVI) particles have the potential to remove and degrade PFASs through redox activity. In this study, we deposited nZVI onto two-dimensional reduced graphene oxide (rGO) nanosheets and tested these synthesized rGO-nZVI nanohybrid (NH) for the treatment of a mixture of short- and long-chain PFASs in water with and without H2O2. All PFASs were removed at a higher efficiency by the rGO-nZVI NH than by the parent materials rGO and nZVI. Notably, the long-chain PFASs were removed at a faster rate than the short-chain PFASs. After a 10 min exposure to the rGO-nZVI NH without H2O2, the long-chain PFASs (perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA)) were removed by 85% and 39%, respectively, while short-chain PFASs (perfluoropentane sulfonic acid and perfluoropentanoic acid) were removed by 19% and 18%, respectively. The addition of H2O2 enhanced the PFAS treatment performance by 10-18%, which can be attributed to the generation of reactive oxygen species by the rGO-nZVI NH. Liquid chromatography high-resolution mass spectrometry analysis confirmed the formation of unique shorter chain and partially defluorinated PFAS-Fe complexes from both PFOS and PFOA.