Oxygen vacancy engineering of cerium oxide for the selective photocatalytic oxidation of aromatic pollutants

The engineering of oxygen vacancies in CeO₂ nanoparticles (NPs) allows the specific fine-tuning of their oxidation power, and this can be used to rationally control their activity and selectivity in the photocatalytic oxidation (PCO) of aromatic pollutants. In the current study, a facile strategy for generating exceptionally stable oxygen vacancies in CeO₂ NPs through simple acid (CeO₂-A) or base (CeO₂-B) treatment was developed. The selective (or mild) PCO activities of CeO₂-A and CeO₂-B in the degradation of a variety of aromatic substrates in water were successfully demonstrated. CeO₂-B has more oxygen vacancies and exhibits superior photocatalytic performance compared to CeO₂-A. Control of oxygen vacancies in CeO₂ facilitates the adsorption and reduction of dissolved O₂ due to their high oxygen-storage ability. The oxygen vacancies in CeO₂-B as active sites for oxygen-mediated reactions act as (i) adsorption and reduction reaction sites for dissolved O₂, and (ii) photogenerated electron scavenging sites that promote the formation of H₂O₂ by multi-electron transfer. The oxygen vacancies in CeO₂-B are particularly stable and can be used repeatedly over 30 h without losing activity. The selective PCOs of organic substrates were studied systematically, revealing that the operating mechanisms for UV-illuminated CeO₂-B are very different from those for conventional TiO₂ photocatalysts. Thus, the present study provides new insights into the design of defect-engineered metal oxides for the development of novel photocatalysts.