Synergistic enhancement of PFOA and 6:2-FTAB photodegradation using Au/Y-doped TiO2 nanocatalysts

• Facile synthesis of Au2/Y5/P25 with improved charge separation • 99 % PFOA stepwise degradation within 100 min to PFBA • 96 % Capstone B directly oxidized degradation within 20 min to 6:2 PFOS • High activity maintained at industrial relevant conditions (UV: 150 W, 366 nm) Efficient degradation of perfluoroalkyl substances (PFAS) requires photocatalysts capable of promoting strong C-F bond cleavage and selective interfacial charge transfer. In this proof-of-concept-study, a dual-doped TiO 2 nanophotocatalyst (Au2/Y5/P25) was synthesized by combining gold (Au) nanoparticles and yttrium (Y) dopants to enhance charge separation and reactive oxygen species (ROS) generation. Structural characterization supported Au deposition on the TiO 2 surface and Y incorporation into the lattice, accompanied by a slight band-gap narrowing. Under UV irradiation in aqueous solution (unbuffered pH 5.8, room temperature) the nanophotocatalyst exhibited distinct degradation pathways for 1000 µg L −1 of two representative PFAS, perfluorooctanoic acid (PFOA) and Capstone B (6:2 FTAB), reflecting environmentally prevalent groups. PFOA underwent 99 % degradation within 100 min via a stepwise CF 2 -cleavage mechanism, generating a sequence of perfluorocarboxylic acids down to perfluorobutanoic acid (PFBA), consistent with enhanced electron-hole separation. In contrast, Capstone B showed rapid, single-step S-N bond cleavage to 6:2 perfluorooctanesulfonic acid (6:2 PFOS), primarily driven by hole- and •OH-mediated oxidation under oxygen-rich conditions. This process achieved 96 % degradation within 20 min but did not proceed to further defluorination, indicating oxidative limitations. Dissolved oxygen analysis revealed efficient electron utilization and sustained oxidative turnover without excessive oxygen depletion. The findings demonstrate that Au/Y co-doping promotes selective PFAS activation, enabling rapid precursor oxidation while exposing the kinetic limits of secondary C-F bond cleavage. These discoveries offer new insights into the design of plasmonic-rare-earth-modified TiO 2 photocatalysts for efficient PFAS degradation through interface-driven oxidation pathways.