Porous P, Fe-doped g-C3N4 nanostructure with enhanced photo-Fenton activity for removal of tetracycline hydrochloride: Mechanism insight, DFT calculation and degradation pathways

This study fabricated an efficient P and Fe co-doping graphitic carbon nitride catalyst (Fe- CN/P) by thermal polymerization of melamine, FeCl3, and 2-hydroxyphosphonoacetic acid (HPAA) mixture. The Fe-CN/P catalyst exhibited much better tetracycline hydrochloride (TCH) degradation performance than that of single doping and neat CN. Various characterizations indicated that the introduction of HPAA significantly increased the specific surface area of CN and improved charge separation as well as transfer efficiency. Based on Fe 2p XPS analysis and indirect determination of hydroxyl radical (·OH) content, the separated photogenerated electrons accelerated the reduction of Fe(III) and activated photo-Fenton reaction, resulting in more ·OH species generation. The effect of pH value, catalyst dosages, H2O2 concentration, the type of cations and anions as well as water matrices on the degradation of TCH by Fe-CN/P was systematically investigated. The main degradation pathways of TCH were proposed according to the LC-MS intermediates detection and DFT calculation. The results indicated that reactive oxide species (ROS) were more likely to attack the atoms with high Fukui index (f0). This work provides new ideas for adjusting the morphology and electronic structure of CN to enhance its photo-Fenton catalytic activity.