Cobalt doped nitrogen-vacancies-rich C3N5 with optimizing local electron distribution boosts peroxymonsulfate activation for tetracycline degradation: Multiple electron transfer mechanisms

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.