Cobalt doped nitrogen-vacancies-rich C₃N₅ with optimizing local electron distribution boosts peroxymonsulfate...

Heterogeneous photocatalysis coupled with peroxymonosulfate (PMS) activation is considered as an advanced water purification technology for emerging contaminates degradation. In this study, Cobalt (Co) doped nitrogen-vacancies-rich C₃N₅ photocatalysts (Co/Nv-C₃N₅) were designed to activate PMS for tetracycline removal. The photo-chemical oxidation system displayed superior advantage, in which the observed rate constant of tetracycline degradation (0.1488 min^-1) was 10.86 and 1.82 times higher than that of photo-oxidation and chemical-oxidation systems. Density functional theory calculation results verified the reconstruction of local charge distribution during PMS activation, indicating Co doping and nitrogen-vacancy engineering not only promoted photoelectrons capture, but also boosted electron transfer from the C-N framework to PMS and the generation of active species. Furthermore, several unique multiple electron transfer mechanisms were found in nonradicals (h⁺, ¹O₂ and Co(IV)) pathways. Additionally, three possible tetracycline degradation pathways were proposed and the toxicity of the intermediates was evaluated. Overall, the findings from this study provided a novel strategy for developing high-efficient photocatalyst for the rapid degradation of organic pollutants.