Robust titanium suboxide anodes doped by sintering enhance PFOS degradation in water

Per- and Polyfluoroalkyl Substances (PFAS) are a class of persistent organic pollutants that are ubiquitous in the environment, while PFOS is one most representative PFAS of extraordinary persistence. Electrochemical oxidation (EO) is promising for destructive treatment of PFAS in water, and Magnéli phase titanium suboxide (TSO) is regarded as one of only few suitable anode materials for this application. We herein conducted an in-silico survey with Density Functional Theory (DFT) simulations to identify possible beneficial dopant elements, and then prepared TSO anodes doped with Niobium (Nb-TSO) or Cerium (Ce-TSO) by sintering. The doped TSO thus prepared exhibited great robustness, having service lifetimes longer than the pristine Ti₄O₇ anode, making them useful for EO applications in PFAS treatment. PFOS degradation by EO using Nb-TSO anode was faster than that on the pristine Ti₄O₇ anode, with energy consumption approximately 1.8 times lower. Further characterizations and DFT simulations reveal that the enhanced efficiency of Nb-TSO anode is attributed to its reduced charge transfer resistance and increased effective electroactive surface area (EESA). The EESA of the Ce-TSO anode was reduced in comparison to the pristine Ti₄O_7, but PFOS degradation rates normalized by EESA were increased significantly for EO with Ce-TSO anode, due to its increased oxygen evolution potential (OEP) and hydroxyl radical production. The doped TSO anodes prepared in this study by sintering will be useful in EO treatment of PFAS-contaminated waters, with improved service life and performance, and the study provides understandings to guide further improvements of the TSO anodes via doping.