Adsorption and Reductive Defluorination of Perfluorooctanoic Acid over Palladium Nanoparticles

Per- and polyfluoroalkyl substances (PFASs) comprise a group of widespread and recalcitrant contaminants that are attracting increasing concern due to their persistence and adverse health effects. This study evaluated removal of one of the most prevalent PFAS, perfluorooctanoic acid (PFOA), in H₂-based membrane catalyst-film reactors (H₂-MCfRs) coated with palladium nanoparticles (Pd⁰NPs). Batch tests documented that Pd⁰NPs catalyzed hydrodefluorination of PFOA to partially fluorinated and nonfluorinated octanoic acids; the first-order rate constant for PFOA removal was 0.030 h^-1, and a maximum defluorination rate was 16 μM/h in our bench-scale MCfR. Continuous-flow tests achieved stable long-term depletion of PFOA to below the EPA health advisory level (70 ng/L) for up to 70 days without catalyst loss or deactivation. Two distinct mechanisms for Pd⁰-based PFOA removal were identified based on insights from experimental results and density functional theory (DFT) calculations: (1) nonreactive chemisorption of PFOA in a perpendicular orientation on empty metallic surface sites and (2) reactive defluorination promoted by physiosorption of PFOA in a parallel orientation above surface sites populated with activated hydrogen atoms (H_ads*). Pd⁰-based catalytic reduction chemistry and continuous-flow treatment may be broadly applicable to the ambient-temperature destruction of other PFAS compounds.