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

doi:10.1007/s11705-023-2322-z

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (11) : 1728-1740 https://doi.org/10.1007/s11705-023-2322-z

RESEARCH ARTICLE

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

Beibei Wang¹, Kejiang Qian², Weiping Yang¹, Wenjing An¹, Lan-Lan Lou²(

), Shuangxi Liu², Kai Yu¹(

)

¹. MOE Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Technology for Complex Transmedia Pollution, College of Environmental Science and Engineering, Nankai University, Tianjin 300350, China
². Institute of New Catalytic Materials Science, School of Materials Science and Engineering, National Institute of Advanced Materials, Nankai University, Tianjin 300350, China

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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.

Keywords ZnFe₂O₄/BiVO₄ Z-scheme heterojunction photocatalytic degradation ciprofloxacin

Corresponding Author(s): Lan-Lan Lou,Kai Yu

About author:

Peng Lei and Charity Ngina Mwangi contributed equally to this work.

Just Accepted Date: 15 May 2023 Online First Date: 28 June 2023 Issue Date: 25 October 2023

Cite this article:

Beibei Wang,Kejiang Qian,Weiping Yang, et al. ZnFe₂O₄/BiVO₄ Z-scheme heterojunction for efficient visible-light photocatalytic degradation of ciprofloxacin[J]. Front. Chem. Sci. Eng., 2023, 17(11): 1728-1740.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-023-2322-z
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I11/1728

Fig.1 XRD patterns of BiVO₄, ZnFe₂O₄ and ZFO/BVO composites.

Fig.2 (a) TEM and HRTEM images of BiVO₄; (b–c) TEM images of 30% ZFO/BVO with the inserted particle size distribution diagram of ZnFe₂O₄; and (d) HRTEM image and (e) EDS elemental mapping of 30% ZFO/BVO.

Fig.3 (a) DR UV–vis spectra with the inserted plots of (αhν)² vs. hν of the samples; and (b) N₂ adsorption–desorption isotherms and BET specific surface areas of the samples.

Fig.4 (a) The survey XPS spectra of the samples; and high-resolution XPS spectra in (b) Fe 2p, (c) Zn 2p, (d) Bi 4f, (e) V 2p and (f) O 1s regions of the samples.

Fig.5 (a) The degradation efficiencies, (b) pseudo-first order kinetic fitting results, and (c) the removal rates of TOC in photodegradation of CIP solution under visible light irradiation (λ > 420 nm); and (d) the cycling test for the photocatalytic degradation of CIP over 30% ZFO/BVO.

Fig.6 (a) Photocurrent responses and (b) EIS Nyquist plots of samples; (c) EIS spectra tested in the dark and under light illumination and (d) PL spectra of ZnFe₂O₄, BiVO₄ and 30% ZFO/BVO; and Mott–Schottky curves of (e) ZnFe₂O₄ and (f) BiVO₄ at different frequencies.

Fig.7 (a) Trapping experiments of active species during the CIP degradation over 30% ZFO/BVO under visible light irradiation; and (b) schematic diagram of possible photocatalytic mechanism in the photodegradation of CIP by 30% ZFO/BVO.

Fig.8 (a) Photocatalytic degradation pathways of CIP over 30% ZFO/BVO; and (b) Daphnia magna LC₅₀, (c) mutagenicity situation, and (d) bioaccumulation factor of CIP and its degradation intermediates based on QSAR analysis.

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