Iron Doping of hBNEnhances the Photocatalytic OxidativeDefluorination of Perfluorooctanoic Acid

There is a growing need to effectively eliminate perfluorooctanoic acid (PFOA) from contaminated water, which requires extensive defluorination. Photocatalysis offers potential for PFOA degradation under ambient conditions without the need for treatment chemicals. However, photocatalytic treatment generally results in limited defluorination and, thus, incomplete elimination of potential toxicity and liability. This underscores the need to advance mechanistic understanding of the factors limiting PFOA oxidative defluorination. Here, we tested the hypothesis that direct electron transfer from PFOA to transition metals enhances photocatalytic defluorination. We developed a novel, facile approach to simultaneously functionalize and dope hexagonal boron nitride (hBN) (which is known to effectively catalyze photocatalytic PFOA oxidation) with Fe(III), using deep-eutectic solvents (DES). Addition of Fe(III) to synthesize Fe-hBN created new active sites for PFOA oxidation and doubled the defluorination extent (>40% fluoride release from initial 50 mg L^–1 PFOA) compared to undoped hBN in 4 h reactions under 254 nm irradiation (64.4 W m^–2). The mechanism of defluorination was elucidated through scavenger experiments that show the importance of photocatalytically generated electron holes for initiating PFOA degradation. Experiments also suggest that Fe(III) played a key role in PFOA removal, contributing to the improved extent of defluorination over undoped hBN. Density functional theory indicates that Fe(III) sites enable electrostatic adsorption of PFOA to the catalyst surface, enhance charge transfer, and promote hole localization to improve charge carrier separation, which is essential for oxidative defluorination of PFOA. This mechanistic insight informs catalytic material design to enhance oxidative defluorination processes.