An efficient metal-free phosphorus and oxygen co-doped g-C3N4 photocatalyst with enhanced visible light photocatalytic activity for the degradation of fluoroquinolone antibiotics

Non-metal doping has been frequently used in g-C3N4 (CN) as a feasible and economical technique for maintaining its metal-free properties, while improving its photocatalytic performance. In this study, a novel phosphorus and oxygen co-doped graphitic carbon nitride (POCN) was successfully synthesized through a one-step thermal polymerization method and exhibited remarkable photocatalytic activity for the photocatalytic degradation of fluoroquinolones (FQs). The degradation rate of enrofloxacin (ENFX) was 6.2 times higher than that of CN. Based on the results of X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance spectroscopy (NMR), P atoms replaced the corner and bay carbon sites, whereas O atoms replaced the nitrogen sites in the g-C3N4 framework. The improvement of the photocatalytic effect of POCN0.01 was attributed to its narrow bandgap, effective charge separation and enhanced specific surface area. This is the first report to describe the use of phosphorus doping to promote the generation of reactive oxygen species (ROS). ROS scavenging tests revealed that O2− was the primary active species during the degradation of ENFX. Furthermore, pathways for the degradation of ENFX were proposed via the detection of intermediate products via HRAM LC–MS/MS and the prediction of active sites using the Fukui function.