Multi-shelled ZnO decorated with nitrogen and phosphorus co-doped carbon quantum dots: synthesis and enhanced photodegradation activity of methylene blue in aqueous solutions

Abstract

The presence of organic dyes in wastewater has posed a huge threat to aquatic life and human health. In this study, nitrogen and phosphorus co-doped carbon quantum dot (CQD)-decorated multi-shelled ZnO microsphere photocatalysts (NPCQD/ZnO) were obtained via a simple absorption process; ZnO was prepared by calcining carbon microspheres as the sacrificial template. The as-prepared NPCQD/ZnO showed an obvious multi-shelled structure with the nitrogen and phosphorus co-doped CQDs homogeneously attached onto the inner and outer shells of ZnO. According to the UV-Vis DRS results, all the co-doped, single-doped and undoped carbon quantum dots could enhance the efficiency of absorption of visible light and reduce the optical band gap. Furthermore, the PL characterization results showed that the NPCQD/ZnO composites had lowest fluorescence intensity because the decoration of ZnO with NPCQDs could effectively reduce the recombination rate of photogenerated electron–hole pairs in the ZnO semiconductor photocatalyst. Importantly, 2 g-NPCQD/ZnO composites exhibited higher photodegradation performance towards methylene blue (MB) than pure ZnO and even the newly reported series of ZnO catalysts under the same conditions. Moreover, the degradation obeyed the pseudo-first-order and Langmuir–Hinshelwood kinetics models with a reaction constant of 0.0725 min⁻¹, which was 1.05 times that of pure ZnO (0.0353 min⁻¹). The NPCQD/ZnO composites not only showed good photocatalytic performance, but also had excellent stability since the photocatalytic activity did not significantly decrease after five cycling tests. In addition, compared with single-doped and undoped carbon quantum dots, N and P co-doped carbon quantum dots have more significant efficiency for the modification of semiconductor photocatalysts. The present study shows that the CQD-decorated multi-shelled ZnO can be regarded as an excellent photocatalyst candidate in the field of water treatment. Moreover, this new concept is helpful in the controllable construction of other multi-shelled metal oxides decorated with co-doped carbon quantum dots with enhanced photocatalytic properties.