Oxygen vacancies assist a facet effect to modulate the microstructure of TiO₂ for efficient photocatalytic O₂...

Defect engineering is recognized as an effective route to obtaining highly active photocatalytic materials. However, the current understanding of the role of defects in photocatalysts mainly comes from their independent functional analysis, ignoring the synergy between defects and the chemical environment, especially with crystal facets. Herein, oxygen vacancy (V_O)-rich TiO₂ nanostructures with different dominant exposed facets were prepared, and the microstructural changes induced by the synergy between the V_O and facet effect and the performance difference of photocatalytic O₂ activation were explored. The results showed that the combination of high concentration V_O and the {101} facet is more conducive to improving the photocatalytic performance of TiO₂, which is significantly superior to the combination of low concentration V_O and the {101} facet as well as the combination of high concentration V_O and the {001} facet. The experimental and theoretical results clarified the dependence of each stage of photocatalysis on two factors. Specifically, V_O plays a more significant role in energy band regulation, improving the dynamic behavior of photogenerated charges and enhancing the adsorption and activation of O₂, while the facet effect made more contributions to reducing the thermodynamic energy barrier of ROS formation and conversion. The excellent ability of O₂ activation enables T101-V_O to show potential application characteristics in the removal of RhB and bacterial disinfection. This work established a link between defect and facet effects, providing new insights into understanding defect function in photocatalysts.