Engineering of graphitic carbon nitride with simultaneous potassium doping sites and nitrogen defects for notably enhanced photocatalytic oxidation performance

Abstract

Graphitic carbon nitride (g-C3N4) offers exciting opportunities for sustainable photocatalytic oxidation of organic pollutants but suffers from drawbacks of insufficient oxidation driving force and low quantum efficiency. To over the drawbacks, here a simple and effective strategy was developed to engineer g-C3N4 with simultaneous interstitially embedded potassium dopant and nitrogen defects, and the process included supramolecular preorganization followed by KOH-assisted thermal polycondensation. In the prepared DN-K-CN catalysts, potassium doping level and the amount of nitrogen defects were both controllable. With the increment of potassium doping level, the bandgap of the DN-K-CN became narrow, along with continuously downshifted valence band position. The DN-K-CN showed greatly enhanced visible-light photocatalytic oxidation performance with respect to g-C3N4 in the degradation of emerging phenolic pollutants, acetaminophen and methylparaben; meanwhile, the oxidation performance of DN-K-CN depended on potassium doping level and the amount of nitrogen defects. Combination of experimental findings and theory calculations it is confirmed that the enhanced photocatalytic oxidation performance of DN-K-CN was attributed to the synergistic effect of potassium dopant and nitrogen defects, which resulted in the generation of plentiful active oxygen species and the improvement of oxidation driving force of valence holes. The influence of potassium dopant and nitrogen defects on the electronic and band structures of g-C3N4 was revealed; simultaneously, mechanism of the enhanced photocatalytic oxidation performance of g-C3N4 after the introduction of potassium dopant and nitrogen defects was studied. The present work provided new insights into the electronic and band structure tuning for the improvement of the photocatalytic oxidation performance of g-C3N4.