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 Ti 4 O 7 through Ce 3+ 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 Ce 3+ -doped Ti 4 O 7 electrodes, [(Ti 1−x Ce x ) 4 O 7 ], also exhibited a more stable electrocatalytic activity than the pristine Ti 4 O 7 electrode so as to facilitate the long-term operation. Furthermore, (Ti 1−x Ce x ) 4 O 7 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 Ce 3+ resulted in a PFOS oxidation rate 2.4× greater than that of the pristine Ti 4 O 7 electrode. X-ray photoelectron spectroscopy results suggest that Ce 3+ doping created surficial oxygen vacancies that may be responsible for the enhanced electrochemical reactivity and stability of the (Ti 1−x Ce x ) 4 O 7 electrodes. Results of this study provide insights into the defect engineering strategy for boosting the electrochemical performance of the Ti 4 O 7 electrode with a robust reactivity and stability.
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