Visible-Light Photocatalytic Chlorite Activation Mediated by Oxygen Vacancy Abundant Nd-Doped BiVO₄ for Efficient Chlorine Dioxide Generation and Pollutant Degradation

Visible-light photocatalytic chlorite activation has emerged as an efficient oxidation process for micropollutant elimination. However, the in-depth mechanism of chlorite activation is not understood. In this study, using neodymium-doped bismuth vanadate (Nd_xBi_1-xVO_4-δ) as a model catalyst, we describe the oxygen vacancy (OV)-mediated chlorite activation process for efficient ClO₂ generation and cephalexin (CPX) degradation. DFT calculations and in situ DRIFTS suggest that the OV-introduced surface -OH serves as the Brønsted acidic center for chlorite adsorption. The OV-mediated chlorite activation involves multistep reactions that surface hydroxylation and proton transfer from the surface -OH to chlorite, forming metastable chlorous acid (HClO₂) and further disproportionating to ClO₂. As compared with vis-photocatalysis, the vis-photocatalysis coupled with chlorite activation (vis/chlorite) technique exhibits superior performance in antibiotic degradation and achieves efficient microorganism inactivation. This work uncovers the role of OVs on chlorite activation and provides a rational strategy for designing visible-light-driven oxidation techniques in water and wastewater treatment.