Insight into the Photocatalytic Degradation Mechanism for “Forever Chemicals” PFNA by Reduced Graphene Oxide/WO₃ Nanoflower Heterostructures

Water contamination with "forever chemicals" like per- and polyfluoroalkyl substances (PFAS) poses significant toxicity to the environment. Since they are the most persistent synthetic chemicals that hardly degrade in the natural environment and are carcinogenic to humans, there is an urgent need to discover novel processes for destroying PFAS. Herein, we report on the design of a reduced graphene oxide (r-GO)/WO₃ nanoflower (WO₃-NF)-based heterostructure for harnessing 365 nm light-driven photocatalytic oxidation and reduction process toward the photocatalytic degradation of perfluorononanoic acid (PFNA). Moreover, reported data reveal that using an r-GO/WO₃-NF heterostructure photocatalyst, 100% PFNA degradation and 14% defluorination can be achieved in the presence of isopropyl alcohol as the hydroxy radical (^•OH) quencher or glucose as a hot hole (h⁺) quencher after exposure to 365 nm light for 22 h. A reported mechanistic study shows synergistic oxidation and reduction processes are vital for the complete degradation of PFNA, where the hydrated electron (e_aq ^-) plays a key role as a reducing agent and h⁺ and ^•OH act as oxidation agents. Furthermore, the photocatalytic destruction mechanism study indicates that chain shortening via C-C bond breaking and defluorination via C-F bond breaking are major pathways for PFNA degradation. A wavelength-dependent study shows that only 22% degradation can be achieved after exposure to 532 nm light for 22 h, which is due to the lack of the formation of hydrated electrons (e_aq ^-). The current study sheds light on the construction of the r-GO/WO₃ NF heterojunction for the highly efficient degradation of PFAS.