Synthesis of a Co/Ni-MOF-74@PDI Z-scheme photocatalyst as a highly efficient photo-assisted Fenton-like catalyst for the removal of chlortetracycline hydrochloride

Abstract

In this paper, ultra-thin nanofiber PDI was obtained by self-assembly dispersion of commercial PDINH. A novel Co/Ni-MOF-74@PDI Z-scheme heterojunction photocatalyst material was constructed by a simple solvothermal method. XRD, SEM, TEM, FT-IR and other characterization techniques proved the successful preparation of the Co/Ni-MOF-74@PDI Z-scheme heterojunction photocatalyst material. By degrading chlortetracycline hydrochloride, it was found that the photocatalytic activity of Co/Ni-MOF-74@PDI was much higher than that of pure Co/Ni-MOF-74 and PDI. Subsequently, Co/Ni-MOF-74@PDI was used to activate H₂O₂ to further improve the degradation efficiency of chlortetracycline hydrochloride. It was found that the photocatalytic performance was greatly improved after the addition of 19.6 mM H₂O₂ to the system, and the degradation rate of chlortetracycline hydrochloride was 87% within 90 min. The electron transfer pathway and H₂O₂ activation mechanism of the Co/Ni-MOF-74@PDI composite photocatalyst were proved by free radical quenching experiments, electron paramagnetic resonance analysis and X-ray electron spectroscopy. Finally, the easy exfoliation point and degradation pathway of chlortetracycline hydrochloride were studied using density functional theory, UPLC-MS and toxicity evaluation software. It was found that the main active substances were h⁺, ˙O₂, ¹O₂ and ˙OH, and the toxicity of chlortetracycline hydrochloride and its intermediates was evaluated.