O and S co-doping induced N-vacancy in graphitic carbon nitride towards photocatalytic peroxymonosulfate activation for sulfamethoxazole degradation

Abstract

Doping-induced vacancy engineering of graphitic carbon nitride (GCN) is beneficial for bandgap modulation, efficient electronic excitation, and facilitated charge carrier migration. In this study, synthesis of oxygen and sulphur co-doped induced N vacancies (OSGCN) by the hydrothermal method was performed to activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) antibiotic degradation and H₂ production. The results from experimental and DFT simulation studies validate the synergistic effects of co-dopants and N-vacancies, i.e., bandgap lowering, electron-hole pairs separation, and high solar energy utilization. The substitution of sp² N atom by O and S co-dopants causes strong delocalization of HOMO-LUMO distribution, enhancing carrier mobility, increasing reactive sites, and facilitating charge-carrier separation. Remarkably, OSGCN/PMS photocatalytic system achieved 99.4% SMX degradation efficiency and a high H₂ generation rate of 548.23 μ mol g^-1 h^-1 within 60 min and 36 h, respectively under visible light irradiations. The SMX degradation kinetics was pseudo-first-order with retained recycling efficiency up to 4 catalytic cycles. The results of EPR and chemical scavenging experiments revealed the redox action of reactive oxidative species, wherein ¹O₂ was the dominant reactive species in SMX degradation. The identification of formed intermediates and the SMX stepwise degradation pathway was investigated via LC-MS analysis and DFT studies, respectively. The results from this work anticipated deepening the understanding of PMS activation by substitutional co-doping favoring N-vacancy formation in GCN lattice for improved photocatalytic activity.

Keywords: Degradation pathway; N-vacancies; Non-metal co-doping; Peroxymonosulfate activation; Photocatalysis; Sulfamethoxazole antibiotic degradation.