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

Abstract

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, [(Ti1–xCex)4O7], also exhibited a more stable electrocatalytic activity than the pristine Ti4O7 electrode so as to facilitate the long-term operation. Furthermore, (Ti1–xCex)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 (Ti1–xCex)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.