New insights into ferric iron-facilitated UV254 photolytic defluorination of perfluorooctanoic acid (PFOA): Combined experimental and theoretical study

Abstract

UV/Fe³⁺-facilitated PFOA defluorination was often reported and recognized to proceed through a "ligand-to-metal charge transfer (LMCT)" mechanism in the literatures. Sufficient Fe³⁺ supply is important for sustaining the LMCT reaction pathway. In this study, an interesting "excessive defluorination" was observed, even the continuous Fe³⁺ supply was cut off, implying a parallel mechanism strengthening PFOA defluorination. Based the results of intermediate products detection, ¹⁹F NMR analysis, and exploration of electron density alternation, transition energy evolution, and bonds characteristics, remarkable electron density perturbation in [PFOA-Fe]²⁺ was revealed. This effect was triggered by the complexation between PFOA anion and Fe³⁺, diminishing electron shielding on the perfluorinated carbon chain. Hence, the dissociation energy of C-C bonds was reduced by maximally 53% (C4-C5). Once attacked by high-flux UV₂₅₄ photons, the perfluorinated carbon chain underwent scission, and subsequent defluorination was achieved via hydrolysis reactions. This parallel mechanism cooperated with the LMCT mechanism, leading to the observed "excessive defluorination." The degree of UV/Fe³⁺-synergized PFOA defluorination depended on UV₂₅₄ photon flux and Fe³⁺ dosage. High UV₂₅₄ intensity guaranteed fast defluorination kinetics. A [Fe³⁺]/[PFOA] molar ratio near 1 showed the best UV/Fe³⁺ synergic effect on PFOA defluorination.

Keywords: Electron density; Fe(3+) complexing; PFOA; UV(254) photolytic defluorination.