Defect Engineering on a Ti₄O₇ Electrode by Ce³⁺ Doping for the Efficient Electrooxidation of Perfluorooctanesulfonate

Defect engineering in an electrocatalyst, such as doping, has the potential to significantly enhance its catalytic activity and stability. Herein, we report the use of a defect engineering strategy to enhance the electrochemical reactivity of Ti₄O₇ through Ce³⁺ doping (1-3 at. %), resulting in the significantly accelerated interfacial charge transfer and yielding a 37-129% increase in the anodic production of the hydroxyl radical (OH^•). The Ce³⁺-doped Ti₄O₇ electrodes, [(Ti_1-Ce)₄O₇], also exhibited a more stable electrocatalytic activity than the pristine Ti₄O₇ electrode so as to facilitate the long-term operation. Furthermore, (Ti_1-Ce)₄O₇ electrodes were also shown to effectively mineralize perfluorooctanesulfonate (PFOS) in electrooxidation processes in both a trace-concentration river water sample and a simulated preconcentration waste stream sample. A 3 at. % dopant amount of Ce³⁺ resulted in a PFOS oxidation rate 2.4× greater than that of the pristine Ti₄O₇ electrode. X-ray photoelectron spectroscopy results suggest that Ce³⁺ doping created surficial oxygen vacancies that may be responsible for the enhanced electrochemical reactivity and stability of the (Ti_1-Ce)₄O₇ electrodes. Results of this study provide insights into the defect engineering strategy for boosting the electrochemical performance of the Ti₄O₇ electrode with a robust reactivity and stability.