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.

Graphical abstract

Keywords

ZnFe₂O₄/BiVO₄ / Z-scheme heterojunction / photocatalytic degradation / ciprofloxacin

References

[1] Hu Y, Jin L, Zhao Y, Jiang L, Yao S, Zhou W, Lin K, Cui C. Annual trends and health risks of antibiotics and antibiotic resistance genes in a drinking water source in East China. Science of the Total Environment, 2021, 791: 148152

[2] Huang H, Zeng S, Dong X, Li D, Zhang Y, He M, Du P. Diverse and abundant antibiotics and antibiotic resistance genes in an urban water system. Journal of Environmental Management, 2019, 231: 494–503

[3] Batard E, Ollivier F, Boutoille D, Hardouin J B, Montassier E, Caillon J, Ballereau F. Relationship between hospital antibiotic use and quinolone resistance in Escherichia coli. International Journal of Infectious Diseases, 2013, 17(4): 254–258

[4] Wang J, Wang S. Removal of pharmaceuticals and personal care products (PPCPs) from wastewater: a review. Journal of Environmental Management, 2016, 182: 620–640

[5] Quan H, Qian K, Xuan Y, Lou L L, Yu K, Liu S. Superior performance in visible-light-driven hydrogen evolution reaction of three-dimensionally ordered macroporous SrTiO₃ decorated with Zn_xCd_1−xS. Frontiers of Chemical Science and Engineering, 2021, 15(6): 1561–1571

[6] Wang W, Song L, Zhang H, Zhang G, Cao J. Graphene-like h-BN supported polyhedral NiS₂/NiS nanocrystals with excellent photocatalytic performance for removing rhodamine B and Cr(VI). Frontiers of Chemical Science and Engineering, 2021, 15(6): 1537–1549

[7] WangMZhangZChiZLouL LLiHYuHMaTYuKWangH. Alkali metal cations as charge-transfer bridge for polarization promoted solar-to-H₂ conversion. Advanced Functional Materials, 2022, 2211565

[8] Li R, Zhang F, Wang D, Yang J, Li M, Zhu J, Zhou X, Han H, Li C. Spatial separation of photogenerated electrons and holes among {010} and {110} crystal facets of BiVO₄. Nature Communications, 2013, 4(1): 1432

[9] Zhao Y, Li R, Mu L, Li C. Significance of crystal morphology controlling in semiconductor-based photocatalysis: a case study on BiVO₄ photocatalyst. Crystal Growth & Design, 2017, 17(6): 2923–2928

[10] Unsworth C A, Coulson B, Chechik V, Douthwaite R E. Aerobic oxidation of benzyl alcohols to benzaldehydes using monoclinic bismuth vanadate nanoparticles under visible light irradiation: photocatalysis selectivity and inhibition. Journal of Catalysis, 2017, 354: 152–159

[11] Han Q, Li L, Gao W, Shen Y, Wang L, Zhang Y, Wang X, Shen Q, Xiong Y, Zhou Y, Zou Z. Elegant construction of ZnIn₂S₄/BiVO₄ hierarchical heterostructures as direct Z-scheme photocatalysts for efficient CO₂ photoreduction. ACS Applied Materials & Interfaces, 2021, 13(13): 15092–15100

[12] Cao X, Gu Y, Tian H, Fang Y, Johnson D, Ren Z, Chen C, Huang Y. Microemulsion synthesis of ms/tz-BiVO₄ composites: the effect of pH on crystal structure and photocatalytic performance. Ceramics International, 2020, 46(13): 20788–20797

[13] Zhang D, Hao J, Wan P, Zhang D, Sun Q, Liu Z, Li F, Fang H, Wang Y. Synergy of charge pre-separation and direct Z-scheme bridge in BiVO₄{040}/Ag₆Si₂O₇ photocatalyst boosting organic pollutant degradation. Applied Surface Science, 2020, 513: 145832

[14] Sun M, Wang X, Pan H, Pang Z, Zhang Y. Defect engineering modified bismuth vanadate toward efficient solar hydrogen peroxide production. Journal of Colloid and Interface Science, 2023, 629: 215–224

[15] Yu K, Lou L L, Liu S, Zhou W. Asymmetric oxygen vacancies: the intrinsic redox active sites in metal oxide catalysts. Advanced Science, 2020, 7(2): 1901970

[16] Su R, He M, Li N, Ma D, Zhou W, Gao B, Yue Q, Li Q. Visible-light photocatalytic chlorite activation mediated by oxygen vacancy abundant Nd-doped BiVO₄ for efficient chlorine dioxide generation and pollutant degradation. ACS Applied Materials & Interfaces, 2022, 14(28): 31920–31932

[17] Zhang W, Zhang Y, Yuan H, Li J, Ding L, Chu S, Wang L, Zhai W, Zhu R, Cao H, Jiao Z. Built-in electron transport channels and interfacial ions doping in BiVO₄ modified with isolated Ni atoms anchored on carbon hollow matrix for boosting charge separation and transport efficiency. Chemical Engineering Journal, 2022, 437: 135272

[18] Kong H J, Kim K H, Kim S, Lee H, Kang J K. Unveiling the role of tetragonal BiVO₄ as a mediator for dual phase BiVO₄/g-C₃N₄ composite photocatalysts enabling highly efficient water oxidation via Z-scheme charge transfer. Journal of Materials Chemistry A, 2019, 7(46): 26279–26284

[19] Han B, Liu S, Xu Y J, Tang Z R. 1D CdS nanowire-2D BiVO₄ nanosheet heterostructures toward photocatalytic selective fine-chemical synthesis. RSC Advances, 2015, 5(21): 16476–16483

[20] Wang R, Zhu P, Liu M, Xu J, Duan M, Luo D. Synthesis and characterization of magnetic ZnFe₂O₄/Bi₀-Bi₂MoO₆ with Z-scheme heterojunction for antibiotics degradation under visible light. Separation and Purification Technology, 2021, 277: 119339

[21] Song K, Zhang C, Zhang Y, Yu G, Zhang M, Zhang Y, Qiao L, Liu M, Yin N, Zhao Y, Tao Y. Efficient tetracycline degradation under visible light irradiation using CuBi₂O₄/ZnFe₂O₄ type II heterojunction photocatalyst based on two spinel oxides. Journal of Photochemistry and Photobiology A: Chemistry, 2022, 433: 114122

[22] Truong H B, Huy B T, Ray S K, Gyawali G, Lee Y I, Cho J, Hur J. Magnetic visible-light activated photocatalyst ZnFe₂O₄/BiVO₄/g-C₃N₄ for decomposition of antibiotic lomefloxacin: photocatalytic mechanism, degradation pathway, and toxicity assessment. Chemosphere, 2022, 299: 134320

[23] Majumder S, Quang N D, Hien T T, Chinh N D, Hung N M, Yang H, Kim C, Kim D. Effect of SILAR-anchored ZnFe₂O₄ on the BiVO₄ nanostructure: an attempt towards enhancing photoelectrochemical water splitting. Applied Surface Science, 2021, 546: 149033

[24] Li J, Huang Y, Su M, Xie Y, Chen D. Dual light-driven p-ZnFe₂O₄/n-TiO₂ catalyst: benzene-breaking reaction for malachite green. Environmental Research, 2022, 207: 112081

[25] Behera A, Kandi D, Mansingh S, Martha S, Parida K. Facile synthesis of ZnFe₂O₄@RGO nanocomposites towards photocatalytic ciprofloxacin degradation and H₂ energy production. Journal of Colloid and Interface Science, 2019, 556: 667–679

[26] Das K K, Patnaik S, Mansingh S, Behera A, Mohanty A, Acharya C, Parida K M. Enhanced photocatalytic activities of polypyrrole sensitized zinc ferrite/graphitic carbon nitride n-n heterojunction towards ciprofloxacin degradation, hydrogen evolution and antibacterial studies. Journal of Colloid and Interface Science, 2020, 561: 551–567

[27] Ni Q, Cheng H, Ma J, Kong Y, Komarneni S. Efficient degradation of orange II by ZnMn₂O₄ in a novel photo-chemical catalysis system. Frontiers of Chemical Science and Engineering, 2020, 14(6): 956–966

[28] Wang X, Zhou J, Zhao S, Chen X, Yu Y. Synergistic effect of adsorption and visible-light photocatalysis for organic pollutant removal over BiVO₄/carbon sphere nanocomposites. Applied Surface Science, 2018, 453: 394–404

[29] Li L, Niu C G, Guo H, Wang J, Ruan M, Zhang L, Liang C, Liu H Y, Yang Y Y. Efficient degradation of levofloxacin with magnetically separable ZnFe₂O₄/NCDs/Ag₂CO₃ Z-scheme heterojunction photocatalyst: vis-NIR light response ability and mechanism insight. Chemical Engineering Journal, 2020, 383: 123192

[30] Deng Y, Tang L, Feng C, Zeng G, Wang J, Zhou Y, Liu Y, Peng B, Feng H. Construction of plasmonic Ag modified phosphorous-doped ultrathin g-C₃N₄ nanosheets/BiVO₄ photocatalyst with enhanced visible-near-infrared response ability for ciprofloxacin degradation. Journal of Hazardous Materials, 2018, 344: 758–769

[31] Chen Z, Mi N, Huang L, Wang W, Li C, Teng Y, Gu C. Snow-like BiVO₄ with rich oxygen defects for efficient visible light photocatalytic degradation of ciprofloxacin. Science of the Total Environment, 2022, 808: 152083

[32] Lai C, Zhang M, Li B, Huang D, Zeng G, Qin L, Liu X, Yi H, Cheng M, Li L, Chen Z, Chen L. Fabrication of CuS/BiVO₄ (040) binary heterojunction photocatalysts with enhanced photocatalytic activity for ciprofloxacin degradation and mechanism insight. Chemical Engineering Journal, 2019, 358: 891–902

[33] Zhao G, Ding J, Zhou F, Zhao Q, Wang K, Chen X, Gao Q. Insight into a novel microwave-assisted W doped BiVO₄ self-assembled sphere with rich oxygen vacancies oriented on rGO (W-BiVO₄-x/rGO) photocatalyst for efficient contaminants removal. Separation and Purification Technology, 2021, 277: 119610

[34] Chen M, Dai Y, Guo J, Yang H, Liu D, Zhai Y. Solvothermal synthesis of biochar@ZnFe₂O₄/BiOBr Z-scheme heterojunction for efficient photocatalytic ciprofloxacin degradation under visible light. Applied Surface Science, 2019, 493: 1361–1367

[35] Su Q, Li J, Wang B, Li Y, Hou L. Direct Z-scheme Bi₂MoO₆/UiO-66-NH₂ heterojunctions for enhanced photocatalytic degradation of ofloxacin and ciprofloxacin under visible light. Applied Catalysis B: Environmental, 2022, 318: 121820

[36] Zhou Y, Jiao W, Xie Y, He F, Ling Y, Yang Q, Zhao J, Ye H, Hou Y. Enhanced photocatalytic CO₂-reduction activity to form CO and CH₄ on S-scheme heterostructured ZnFe₂O₄/Bi₂MoO₆ photocatalyst. Journal of Colloid and Interface Science, 2022, 608: 2213–2223

[37] Guo H, Niu H Y, Liang C, Niu C G, Huang D W, Zhang L, Tang N, Yang Y, Feng C Y, Zeng G M. Insight into the energy band alignment of magnetically separable Ag₂O/ZnFe₂O₄ p-n heterostructure with rapid charge transfer assisted visible light photocatalysis. Journal of Catalysis, 2019, 370: 289–303

[38] Huang H, He Y, Du X, Chu P K, Zhang Y. A general and facile approach to heterostructured Core/Shell BiVO₄/BiOI p–n junction: room-temperature in situ assembly and highly boosted visible-light photocatalysis. ACS Sustainable Chemistry & Engineering, 2015, 3(12): 3262–3273

[39] Chen F, Yang Q, Sun J, Yao F, Wang S, Wang Y, Wang X, Li X, Niu C, Wang D, Zeng G. Enhanced photocatalytic degradation of tetracycline by AgI/BiVO₄ heterojunction under visible-light irradiation: mineralization efficiency and mechanism. ACS Applied Materials & Interfaces, 2016, 8(48): 32887–32900

[40] Zhang X, Duan J, Tan Y, Deng Y, Li C, Sun Z. Insight into peroxymonosulfate assisted photocatalysis over Fe₂O₃ modified TiO₂/diatomite composite for highly efficient removal of ciprofloxacin. Separation and Purification Technology, 2022, 293: 121123

[41] PiaoHZhaoJZhangSQuanQHuJHuangQZhuRFanLXiaoC. Polypyrrole/cadmium sulfide/nickel hollow fiber as an enhanced and recyclable intrinsic photocatalyst for pollutant removal and high-effective hydrogen evolution. International Journal of Hydrogen Energy, 2022, in press

[42] Cui C, Zhao X, Su X, Xi N, Wang X, Yu X, Zhang X L, Liu H, Sang Y. Porphyrin-based donor−acceptor covalent organic polymer/ZnIn₂S₄ Z-scheme heterostructure for efficient photocatalytic hydrogen evolution. Advanced Functional Materials, 2022, 32(47): 2208962

[43] Hu X, Hu X, Peng Q, Zhou L, Tan X, Jiang L, Tang C, Wang H, Liu S, Wang Y, Ning Z. Mechanisms underlying the photocatalytic degradation pathway of ciprofloxacin with heterogeneous TiO₂. Chemical Engineering Journal, 2020, 380: 122366

[44] Deng J, Ge Y, Tan C, Wang H, Li Q, Zhou S, Zhang K. Degradation of ciprofloxacin using α-MnO₂ activated peroxymonosulfate process: effect of water constituents, degradation intermediates and toxicity evaluation. Chemical Engineering Journal, 2017, 330: 1390–1400

[45] Zhang X, Kamali M, Xue Y, Li S, Costa M E V, Cabooter D, Dewil R. Periodate activation with copper oxide nanomaterials for the degradation of ciprofloxacin—a new insight into the efficiency and mechanisms. Journal of Cleaner Production, 2023, 383: 135412

[46] Sturini M, Speltini A, Maraschi F, Profumo A, Pretali L, Irastorza E A, Fasani E, Albini A. Photolytic and photocatalytic degradation of fluoroquinolones in untreated river water under natural sunlight. Applied Catalysis B: Environmental, 2012, 119–120: 32–39

[47] Zheng X, Xu S, Wang Y, Sun X, Gao Y, Gao B. Enhanced degradation of ciprofloxacin by graphitized mesoporous carbon (GMC)-TiO₂ nanocomposite: strong synergy of adsorption-photocatalysis and antibiotics degradation mechanism. Journal of Colloid and Interface Science, 2018, 527: 202–213

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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