ZnFe₂O₄/BiVO₄ Z-scheme heterojunction for efficient visible-light photocatalytic degradation of ciprofloxacin

Abstract

A novel Z-scheme ZnFe₂O₄/BiVO₄ heterojunction photocatalyst was successfully synthesized using a convenient solvothermal method and applied in the visible light photocatalytic degradation of ciprofloxacin, which is a typical antibiotic contaminant in wastewater. The heterostructure of as-synthesized catalysts was confirmed using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy characterizations. Compared with the single-phase counterparts, ZnFe₂O₄/BiVO₄ demonstrated considerably enhanced photogenerated charge separation efficiencies because of the Z-scheme transfer mechanism of electrons between the composite photocatalysts. Consequently, the 30% ZnFe₂O₄/BiVO₄ catalyst afforded a degradation rate of up to 97% of 20 mg/L ciprofloxacin under 30 min of visible light irradiation with a total organic carbon removal rate of 50%, which is an excellent activity compared with ever reported BiVO₄-based catalysts. In addition, the liquid chromatography-mass spectrometry and quantitative structure-activity relationships model analyses demonstrated that the toxicity of the intermediates was lower than that of the parent ciprofloxacin. Moreover, the as-synthesized ZnFe₂O₄/BiVO₄ heterojunctions were quite stable and could be reused at least four times. This study thus provides a promising Z-scheme heterojunction photocatalyst for the efficient removal and detoxication of antibiotic pollutants from wastewater.

Key words： ZnFe₂O₄/BiVO₄; Z-scheme heterojunction; photocatalytic degradation; ciprofloxacin

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 22172081), the National Key Research and Development Program of China (Grant No. 2022YFC3901401), Special Funds for Science and Technology Innovation in Tianjin (Grant No. 21ZXCCSN00010), and the Fundamental Research Funds for the Central Universities.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-023-2322-z and is accessible for authorized users.

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