Broad-bandgap porous graphitic carbon nitride with nitrogen vacancies and oxygen doping for efficient visible-light photocatalytic degradation of antibiotics

Abstract

Effective degradation methods are required to address the issue of antibiotics as organic pollutants in water resources. Herein, a two-stage thermal treatment method was used to prepare porous graphitic carbon nitride (g-C3N4) modified with nitrogen vacancies and oxygen doping at the N–(C)3 position and deep in the g-C3N4 framework. Compared with bulk g-C3N4 (BCN) (7 ± 1 m2/g), the modified sample (RCN-2h) possesses a larger specific surface area (224 ± 1 m2/g), a larger bandgap (by 0.19 eV), and a mid-gap state. In addition, RCN-2h shows 15.4, 11.2, and 9.5 times higher photodegradation rates than BCN for the degradation of 100% ofloxacin (OFX) (within 15 min), tetracycline (within 15 min), and sulfadiazine (within 35 min), respectively. The RCN-2h catalyst also exhibits superior stability and reusability. Systematic characterization and density functional theory calculations demonstrate that the synergistic effect of the porous structure, nitrogen vacancies, and oxygen doping in RCN-2h provides additional reaction sites, improved charge separation efficiency, and shorter diffusion paths for reactants and photogenerated charge carriers. Trapping experiments reveal that •O2− is the main active species in OFX photodegradation, and a possible photodegradation pathway is identified using liquid chromatography–mass spectrometry. Benefiting from the simplicity of synthesis methods and the superiority of elemental doping, carbon nitride materials with functional synergy have great potential for environmental applications.