Abstract

Per- and polyfluoroalkyl substances (PFAS) such as perfluorooctanoic acid (PFOA) persist in aquatic environments due to their extremely strong C–F bonds and high environmental stability/poor biodegradability, creating an urgent demand for high-performance and scalable adsorption treatment technologies. This study reports the synthesis, characterization, and fixed-bed column adsorption performance of a dual-polymer-modified activated carbon adsorbent engineered for enhanced PFAS capture. Activated carbon (AC) was sequentially functionalized with polyethyleneimine (PEI) and poly(chlorotrifluoroethylene–co-vinylidene fluoride) (Kel–F) to form the fluorine-rich, amine-grafted composites AC–PEI–KelF and AC–PEI–KelF–PEI. Surface-area studies of the modified AC adsorbents showed a reduction in surface area of about a factor of two, possibly due to pore blockage by the polymers. Continuous-flow column breakthrough studies demonstrated dramatic improvements in perfluorooctanoic acid (PFOA) removal efficiency, with 50% maximum breakthrough time increasing from 80 min for AC to 540 min for AC–PEI–KelF and 1500 min for the AC–PEI–KelF–PEI formulation. Thomas model adsorption capacities for AC, AC–PEI–KelF and AC–PEI–KelF–PEI were, respectively, 65, 490, and 1130 mg/g. The adsorption mechanism, using selective mobile phases, was shown to be due to a combination of electrostatic and hydrophobic/fluorophilic interactions. Kinetic analysis showed that adsorption exhibited pseudo-second-order behavior, with multi-stage intraparticle diffusion. The optimized composite also exhibited strong regeneration stability, retaining 79% performance after six adsorption–desorption cycles, and displayed high selectivity for PFOA, even in the presence of structurally related competitors such as octanoic acid. The adsorption of perfluoropentanoic acid and undecafluoro-2-methyl-3-oxahexanoic acid (GenX) was also significant, and some interaction with trifluoroacetic acid was noted.

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