Unveiling the Contribution of Hydrogen Radicals to Per- and Polyfluoroalkyl Substances (PFASs) Defluorination: Applicability and Degradation Mechanisms

At present, the defluorination of per- and polyfluoroalkyl substances (PFASs), including perfluoroether compounds as substitutes of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate, is limited by the effective active species produced during the oxidation–reduction process. The contribution of the hydrogen radical (•H) as a companion active substance in the photoreduction and electrocatalytic degradation of PFASs has been neglected. Herein, we demonstrate that perfluorocarboxylic acids and perfluoroether compounds such as PFOA and hexafluoropropylene oxide dimer acid (GenX) underwent near-complete photodegradation and effective defluorination by continuously generating •H through perfluoroalkyl radical activation of water under UV irradiation without any reagents and catalysts. Importantly, the initial dissolved oxygen, H⁺, and impurities in surface water scarcely inhibited the defluorination of the PFASs. The difference in the defluorination mechanism between PFOA and GenX under the action of •H was elucidated by combining theoretical calculations with targeted and nontargeted analysis methods. The investigation of the photodegradation of different PFASs indicates that perfluoroether compounds were not easily photodegraded via reduction of •H compared with other compounds, whereas polyfluorinated compounds in which some F atoms were replaced with Cl were more prone to elimination. However, the UV/•H system was ineffective against perfluorosulfonic acids. This study provides an unprecedented perspective for further development of the removal technology of PFASs and the design of alternative PFASs that are easy to eliminate.