Regulation of carboxyl groups and structural defects of graphitic carbon nitride via environmental-friendly glucose oxidase ring-opening modulation

Abstract Structural defects and surface functional groups defects engineering in the graphitic carbon nitride (g-C3N4) polymer semiconductor usually has great benefit in optimizing its electron structure and photocatalytic performance. In this study, one type of carboxyl group defects-grafting g-C3N4 was prepared through glucose oxidase treatment on the initial O sites in the g-C3N4, which played multi-functional roles in the generation of carboxyl groups and melon structure defect. FT-IR, XPS and 13C NMR analysis verified the presence of highly favorable carboxyl groups, which was beneficial to the fast separation and migration of photogenerated carriers. The singularity of enzyme mediated defects control of carbon nitride materials was greatly boosted on O-enriched g-C3N4 (OCN) further supporting the overall O sites ring-opening hypothesis. The glucose oxidase (GOD) treated reconstructed g-C3N4 photocatalysts showed narrowed band gaps and fast charge separation ability as verified by UV–vis DRS and electrochemical tests. As a result, the optimized photocatalyst (GOD-OCN-3d) showed a high Cr(VI) photocatalytic detoxification rate of 99 %, which was 6.6 times higher than that of raw g-C3N4 (15 %) in 120 min. These findings open the understanding on precise molecular defects modulation of g-C3N4 via an environmental-friendly enzyme treatment approach, as well as providing a new avenue for understanding the function of structural defects of photocatalysts on prompting charge separation.