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
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.
Y Hu, L Jin, Y Zhao, L Jiang, S Yao, W Zhou, K Lin, C Cui. 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 https://doi.org/10.1016/j.scitotenv.2021.148152
2
H Huang, S Zeng, X Dong, D Li, Y Zhang, M He, P Du. Diverse and abundant antibiotics and antibiotic resistance genes in an urban water system. Journal of Environmental Management, 2019, 231: 494–503 https://doi.org/10.1016/j.jenvman.2018.10.051
3
E Batard, F Ollivier, D Boutoille, J B Hardouin, E Montassier, J Caillon, F Ballereau. Relationship between hospital antibiotic use and quinolone resistance in Escherichia coli. International Journal of Infectious Diseases, 2013, 17(4): 254–258 https://doi.org/10.1016/j.ijid.2012.10.005
4
J Wang, S Wang. Removal of pharmaceuticals and personal care products (PPCPs) from wastewater: a review. Journal of Environmental Management, 2016, 182: 620–640 https://doi.org/10.1016/j.jenvman.2016.07.049
5
H Quan, K Qian, Y Xuan, L L Lou, K Yu, S Liu. Superior performance in visible-light-driven hydrogen evolution reaction of three-dimensionally ordered macroporous SrTiO3 decorated with ZnxCd1−xS. Frontiers of Chemical Science and Engineering, 2021, 15(6): 1561–1571 https://doi.org/10.1007/s11705-021-2089-z
6
W Wang, L Song, H Zhang, G Zhang, J Cao. 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 https://doi.org/10.1007/s11705-021-2094-2
7
M WangZ ZhangZ ChiL L LouH LiH YuT MaK YuH Wang. Alkali metal cations as charge-transfer bridge for polarization promoted solar-to-H2 conversion. Advanced Functional Materials, 2022, 2211565
8
R Li, F Zhang, D Wang, J Yang, M Li, J Zhu, X Zhou, H Han, C Li. Spatial separation of photogenerated electrons and holes among {010} and {110} crystal facets of BiVO4. Nature Communications, 2013, 4(1): 1432 https://doi.org/10.1038/ncomms2401
9
Y Zhao, R Li, L Mu, C Li. Significance of crystal morphology controlling in semiconductor-based photocatalysis: a case study on BiVO4 photocatalyst. Crystal Growth & Design, 2017, 17(6): 2923–2928 https://doi.org/10.1021/acs.cgd.7b00291
10
C A Unsworth, B Coulson, V Chechik, R E Douthwaite. 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 https://doi.org/10.1016/j.jcat.2017.08.023
11
Q Han, L Li, W Gao, Y Shen, L Wang, Y Zhang, X Wang, Q Shen, Y Xiong, Y Zhou, Z Zou. 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 https://doi.org/10.1021/acsami.0c21266
12
X Cao, Y Gu, H Tian, Y Fang, D Johnson, Z Ren, C Chen, Y Huang. Microemulsion synthesis of ms/tz-BiVO4 composites: the effect of pH on crystal structure and photocatalytic performance. Ceramics International, 2020, 46(13): 20788–20797 https://doi.org/10.1016/j.ceramint.2020.05.048
13
D Zhang, J Hao, P Wan, D Zhang, Q Sun, Z Liu, F Li, H Fang, Y Wang. 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 https://doi.org/10.1016/j.apsusc.2020.145832
14
M Sun, X Wang, H Pan, Z Pang, Y Zhang. Defect engineering modified bismuth vanadate toward efficient solar hydrogen peroxide production. Journal of Colloid and Interface Science, 2023, 629: 215–224 https://doi.org/10.1016/j.jcis.2022.08.142
15
K Yu, L L Lou, S Liu, W Zhou. Asymmetric oxygen vacancies: the intrinsic redox active sites in metal oxide catalysts. Advanced Science, 2020, 7(2): 1901970 https://doi.org/10.1002/advs.201901970
16
R Su, M He, N Li, D Ma, W Zhou, B Gao, Q Yue, Q Li. 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 https://doi.org/10.1021/acsami.2c06011
17
W Zhang, Y Zhang, H Yuan, J Li, L Ding, S Chu, L Wang, W Zhai, R Zhu, H Cao, Z Jiao. 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 https://doi.org/10.1016/j.cej.2022.135272
18
H J Kong, K H Kim, S Kim, H Lee, J K Kang. 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 https://doi.org/10.1039/C9TA10704E
19
B Han, S Liu, Y J Xu, Z R Tang. 1D CdS nanowire-2D BiVO4 nanosheet heterostructures toward photocatalytic selective fine-chemical synthesis. RSC Advances, 2015, 5(21): 16476–16483 https://doi.org/10.1039/C4RA16397D
20
R Wang, P Zhu, M Liu, J Xu, M Duan, D Luo. 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 https://doi.org/10.1016/j.seppur.2021.119339
21
K Song, C Zhang, Y Zhang, G Yu, M Zhang, Y Zhang, L Qiao, M Liu, N Yin, Y Zhao, Y Tao. 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 https://doi.org/10.1016/j.jphotochem.2022.114122
22
H B Truong, B T Huy, S K Ray, G Gyawali, Y I Lee, J Cho, J Hur. 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 https://doi.org/10.1016/j.chemosphere.2022.134320
23
S Majumder, N D Quang, T T Hien, N D Chinh, N M Hung, H Yang, C Kim, D Kim. Effect of SILAR-anchored ZnFe2O4 on the BiVO4 nanostructure: an attempt towards enhancing photoelectrochemical water splitting. Applied Surface Science, 2021, 546: 149033 https://doi.org/10.1016/j.apsusc.2021.149033
24
J Li, Y Huang, M Su, Y Xie, D Chen. Dual light-driven p-ZnFe2O4/n-TiO2 catalyst: benzene-breaking reaction for malachite green. Environmental Research, 2022, 207: 112081 https://doi.org/10.1016/j.envres.2021.112081
25
A Behera, D Kandi, S Mansingh, S Martha, K Parida. Facile synthesis of ZnFe2O4@RGO nanocomposites towards photocatalytic ciprofloxacin degradation and H2 energy production. Journal of Colloid and Interface Science, 2019, 556: 667–679 https://doi.org/10.1016/j.jcis.2019.08.109
26
K K Das, S Patnaik, S Mansingh, A Behera, A Mohanty, C Acharya, K M Parida. 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 https://doi.org/10.1016/j.jcis.2019.11.030
27
Q Ni, H Cheng, J Ma, Y Kong, S Komarneni. 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 https://doi.org/10.1007/s11705-019-1907-z
28
X Wang, J Zhou, S Zhao, X Chen, Y Yu. Synergistic effect of adsorption and visible-light photocatalysis for organic pollutant removal over BiVO4/carbon sphere nanocomposites. Applied Surface Science, 2018, 453: 394–404 https://doi.org/10.1016/j.apsusc.2018.05.073
29
L Li, C G Niu, H Guo, J Wang, M Ruan, L Zhang, C Liang, H Y Liu, Y Y Yang. 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 https://doi.org/10.1016/j.cej.2019.123192
30
Y Deng, L Tang, C Feng, G Zeng, J Wang, Y Zhou, Y Liu, B Peng, H Feng. 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 https://doi.org/10.1016/j.jhazmat.2017.11.027
31
Z Chen, N Mi, L Huang, W Wang, C Li, Y Teng, C Gu. Snow-like BiVO4 with rich oxygen defects for efficient visible light photocatalytic degradation of ciprofloxacin. Science of the Total Environment, 2022, 808: 152083 https://doi.org/10.1016/j.scitotenv.2021.152083
32
C Lai, M Zhang, B Li, D Huang, G Zeng, L Qin, X Liu, H Yi, M Cheng, L Li, Z Chen, L Chen. 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 https://doi.org/10.1016/j.cej.2018.10.072
33
G Zhao, J Ding, F Zhou, Q Zhao, K Wang, X Chen, Q Gao. 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 https://doi.org/10.1016/j.seppur.2021.119610
34
M Chen, Y Dai, J Guo, H Yang, D Liu, Y Zhai. Solvothermal synthesis of biochar@ZnFe2O4/BiOBr Z-scheme heterojunction for efficient photocatalytic ciprofloxacin degradation under visible light. Applied Surface Science, 2019, 493: 1361–1367 https://doi.org/10.1016/j.apsusc.2019.04.160
35
Q Su, J Li, B Wang, Y Li, L Hou. 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 https://doi.org/10.1016/j.apcatb.2022.121820
36
Y Zhou, W Jiao, Y Xie, F He, Y Ling, Q Yang, J Zhao, H Ye, Y Hou. 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 https://doi.org/10.1016/j.jcis.2021.10.053
37
H Guo, H Y Niu, C Liang, C G Niu, D W Huang, L Zhang, N Tang, Y Yang, C Y Feng, G M Zeng. 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 https://doi.org/10.1016/j.jcat.2019.01.009
38
H Huang, Y He, X Du, P K Chu, Y Zhang. 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 https://doi.org/10.1021/acssuschemeng.5b01038
39
F Chen, Q Yang, J Sun, F Yao, S Wang, Y Wang, X Wang, X Li, C Niu, D Wang, G Zeng. 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 https://doi.org/10.1021/acsami.6b12278
40
X Zhang, J Duan, Y Tan, Y Deng, C Li, Z Sun. Insight into peroxymonosulfate assisted photocatalysis over Fe2O3 modified TiO2/diatomite composite for highly efficient removal of ciprofloxacin. Separation and Purification Technology, 2022, 293: 121123 https://doi.org/10.1016/j.seppur.2022.121123
41
H PiaoJ ZhaoS ZhangQ QuanJ HuQ HuangR ZhuL FanC Xiao. 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
C Cui, X Zhao, X Su, N Xi, X Wang, X Yu, X L Zhang, H Liu, Y Sang. Porphyrin-based donor−acceptor covalent organic polymer/ZnIn2S4 Z-scheme heterostructure for efficient photocatalytic hydrogen evolution. Advanced Functional Materials, 2022, 32(47): 2208962 https://doi.org/10.1002/adfm.202208962
43
X Hu, X Hu, Q Peng, L Zhou, X Tan, L Jiang, C Tang, H Wang, S Liu, Y Wang, Z Ning. Mechanisms underlying the photocatalytic degradation pathway of ciprofloxacin with heterogeneous TiO2. Chemical Engineering Journal, 2020, 380: 122366 https://doi.org/10.1016/j.cej.2019.122366
44
J Deng, Y Ge, C Tan, H Wang, Q Li, S Zhou, K Zhang. 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 https://doi.org/10.1016/j.cej.2017.07.137
45
X Zhang, M Kamali, Y Xue, S Li, M E V Costa, D Cabooter, R Dewil. 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 https://doi.org/10.1016/j.jclepro.2022.135412
46
M Sturini, A Speltini, F Maraschi, A Profumo, L Pretali, E A Irastorza, E Fasani, A Albini. Photolytic and photocatalytic degradation of fluoroquinolones in untreated river water under natural sunlight. Applied Catalysis B: Environmental, 2012, 119–120: 32–39 https://doi.org/10.1016/j.apcatb.2012.02.008
47
X Zheng, S Xu, Y Wang, X Sun, Y Gao, B Gao. 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 https://doi.org/10.1016/j.jcis.2018.05.054
