Numerous approaches have been used to modify graphitic carbon nitride (g-C 3 N 4 ) for improving its photocatalytic activity. In this study, we demonstrated a facial post-calcination method for modified graphitic carbon nitride (g-C 3 N 4 -Ar/Air) to direct tuning band structure, i.e. , bandgap and positions of conduction band (CB)/valence band (VB), through the control of atmospheric condition without involving any additional elements or metals or semiconductors. The synthesized g-C 3 N 4 -Ar/Air could efficiently degrade sulfamethazine (SMT) under simulated solar light, i.e. , 99.0% removal of SMT with rate constant k 1 = 2.696 h −1 within 1.5 h (4.9 times than pristine g-C 3 N 4 ). Material characterizations indicated that the damaged/partial-collapsed structure and decreased nanosheet-interlayer distance for g-C 3 N 4 -Ar/Air resulted in the shift of band structure due to the denser stacking of pristine g-C 3 N 4 through oxidative exfoliation and planarization by air calcination. In addition, the bandgap of g-C 3 N 4 -Ar/Air was slightly shrunk from 2.82 eV (pristine g-C 3 N 4 ) to 2.79 eV, and the CB was significantly upshifted from −0.44 eV (pristine g-C 3 N 4 ) to −0.81 eV, suggesting the powerful ability for donating the electrons for O 2 to form • O 2 − . Fukui index ( f – ) based on theoretical calculation indicated that the sites of SMT molecule with high values, i.e. , N9, C4 and C6, preferred to be attacked by • O 2 − and • OH, which is confirmed by the intermediates’ analysis. The tuning method for graphitic carbon nitride provides a simple approach to regulate the charge carrier lifetime then facilitate the utilization efficiency of solar light, which exhibits great potential in efficient removal of emerging organic contaminants from wastewater. Modified graphitic carbon nitride (g-C3N4-Ar/Air) was synthesized via a facial post-calcination method and exhibited efficiently photocatalytic activity for SMT removal due to the tune of band structure.
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