Fabrication of zirconium-based metal-organic frameworks@tungsten trioxide (UiO-66-NH₂@WO₃) heterostructure on carbon cloth for efficient photocatalytic removal of tetracycline antibiotic under visible light

Designing recyclable photocatalysts with high activity and stability has drawn considerable attention in the fields of sewage treatment. Herein, a series of heterojunctions constructed by zirconium-based metal-organic frameworks (UiO-66-NH₂) and tungsten trioxide (WO₃) is immobilized on carbon cloth via a facile solvothermal method, resulting in highly recyclable photocatalysts. Multiple characterization techniques, such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy, verify the successful synthesis of UiO-66-NH₂ nanospheres on the surface of needlelike WO₃ modified carbon cloth. Results show that the optimal heterojunction photocatalyst exhibits excellent photocatalytic degradation efficiency for the removal of tetracycline (TC) from water, for which nearly 100% of TC is degraded within 60 min under visible light. Trapping experiments and electron spin resonance (ESR) spectra analyses demonstrate that the superoxide radicals O₂^- and photogenerated hole h⁺ play a dominant role in the degradation process. Excellent photocatalytic activity is dominantly attributed to the effective separation of photoinduced carriers in this type-Ⅱ heterostructure system. Moreover, the possible photocatalytic oxidation degradation pathway is confirmed by analyzing intermediates using liquid chromatography mass spectrometry (LC-MS). This study offers a highly efficient strategy to design recyclable heterojunction photocatalysts for the degradation of refractory antibiotics in sewage.