Visible-light-assisted peroxymonosulfate activation by metal-free bifunctional oxygen-doped graphitic carbon nitride for enhanced degradation of imidacloprid: Role of non-photochemical and photocatalytic activation pathway

Bifunctional oxygen-doped graphitic carbon nitride (OCN) was fabricated to activate peroxymonosulfate (PMS) for degrading imidacloprid (IMD). The modulated electronic structure of OCN promoted the adsorption, electron transfer, and formation of the redox site of PMS. The light absorption capacity, and the separation and migration speed of photogenerated carriers of OCN were increased. Consequently, 94.5% of IMD (3.0 mg/L) was removed by OCN-10/PMS process in 2.0 h. Compared with g-C3N4/PMS (0.048 h(-1)), the IMD degradation rate constant of OCN-10/Vis/PMS system (1.501 h(-1)) was increased by 30.3 times. The PMS oxidation on electron-deficient C atoms and holes, the PMS reduction around electron-rich O atoms and photogenerated electrons, and the multiple reactions of superoxide radical were the sources of the main active species singlet oxygen. Moreover, even under different pH conditions, coexisting anions, humic acid, and other neonicotinoid pesticides, the OCN-10/ Vis/PMS system still showed acceptable applicability. Finally, mass spectrometry identified that hydroxylation and N-dealkylation of amines were the primary degradation pathways of IMD. This paper demonstrates an environmental-friendly combined activation strategy of PMS that can be operated day and night with low energy consumption, aiming to pave the way for developing metal-free photocatalysts for high-efficient environmental purification based on advanced oxidation coupling technology.

Automated summary

Bifunctional oxygen-doped graphitic carbon nitride (OCN) was fabricated to activate peroxymonosulfate (PMS) for degrading imidacloprid (IMD). The modulated electronic structure of OCN promoted the adsorption, electron transfer, and formation of the redox site of PMS, leading to improved removal efficiency. Additionally, the PMS oxidation and reduction pathways on OCN, as well as the multiple reactions of superoxide radicals, contributed to the generation of singlet oxygen as the main active species.