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Photocatalytic degradation performance of antibiotics by WO3/α-Fe2O3/zeolite type II heterojunction with core-shell structure

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Abstract

The accumulation of antibiotics in the environment can be harmful to human health, and research on their disposal technologies is of increasing interest. In this study, WO3/α-Fe2O3/zeolite (WFZ) type II heterojunction composites with core-shell structures were prepared by coupling WO3 semiconductors with visible-light photocatalytic activity with α-Fe2O3 via hydrothermal synthesis using zeolite as a carrier for the adsorption of synergistic photocatalytic degradation of antibiotics in wastewater. X-ray diffraction, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), specific surface, and porosity measurements were used to characterize the structure of WFZ type II heterojunction. The performance of WFZ heterojunction for the visible photocatalytic degradation of antibiotics (tetracycline hydrochloride (TCH), ciprofloxacin (CIP), and levofloxacin hydrochloride (LVF)) was investigated. Through four photocatalytic cycles, the catalyst exhibited excellent durability and stability. This was attributed to the core-shell structure and type II heterojunction promoting the effective separation of photogenerated carriers and the extended visible light response range, which resulted in the best photocatalytic activity of the catalyst under visible light irradiation. Radical trap** experiments showed that superoxide radicals (•O2-) and hydroxyl radical (•OH) were the main active species that played a major role in the photocatalytic degradation. These findings show that the synthesized WFZ type-II heterojunction can be used as a reliable visible-light-responsive photocatalyst for the treatment of antibiotics in wastewater.

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References

  • Baeck SH, Choi KS, Jaramillo TF, Stucky GD, McFarland EW (2003) Enhancement of photocatalytic and electrochromic properties of electrochemically fabricated mesoporous WO3 thin films. Adv Mater 15:1269–1273

    Article  CAS  Google Scholar 

  • Bai L, Jiang Y, **a D, Wei Z, Spinney R, Dionysiou DD, Minakata D, **ao R, **e H-B, Chai L (2022) Mechanistic understanding of superoxide radical-mediated degradation of perfluorocarboxylic acids. Environ Sci Technol 56:624–633

    Article  CAS  Google Scholar 

  • Beyhaqi A, Zeng Q, Chang S, Wang M, Taghi Azimi SM, Hu C (2020) Construction of g-C3N4/WO3/MoS2 ternary nanocomposite with enhanced charge separation and collection for efficient wastewater treatment under visible light. Chemosphere 247:125784

    Article  CAS  Google Scholar 

  • Chen X, Fu W, Yang Z, Yang Y, Li Y, Huang H, Zhang X, Pan B (2023) Enhanced H2O2 utilization efficiency in Fenton-like system for degradation of emerging contaminants: oxygen vacancy-mediated activation of O2. Water Res 230:119562

    Article  CAS  Google Scholar 

  • Cheng Q, Li Y, Wang Z, Wang X, Zhang G (2023) Boosting full-spectrum light driven surface lattice oxygen activation of ZnMn2O4 by facet engineering for highly efficient photothermal mineralization of toluene. Appl Catal B Environ 324:122274

    Article  CAS  Google Scholar 

  • Ding M, Chen W, Xu H, Shen Z, Lin T, Hu K, Lu C, **e Z (2020) Novel α-Fe2O3/MXene nanocomposite as heterogeneous activator of peroxymonosulfate for the degradation of salicylic acid. J Hazard Mater 382:121064

    Article  CAS  Google Scholar 

  • Du H, Liu Y-N, Shen C-C, Xu A-W (2017) Nanoheterostructured photocatalysts for improving photocatalytic hydrogen production. Chin J Catal 38:1295–1306

    Article  CAS  Google Scholar 

  • Fan X, Wang T, Xue H, Gao B, Zhang S, Gong H, Guo H, Song L, **a W, He J (2019) Synthesis of tungsten trioxide/hematite core-shell nanoarrays for efficient photoelectrochemical water splitting. ChemElectroChem 6:543–551

    Article  CAS  Google Scholar 

  • Fellah I, Djellabi R, Amor HB, Abderrahim N, Bianchi CL, Giordana A, Cerrato G, Di Michele A, Hamdi N (2022) Visible light responsive heterostructure HTDMA-BiPO4 modified clays for effective diclofenac sodium oxidation: role of interface interactions and basal spacing. J Water Process Eng 48:102788

    Article  Google Scholar 

  • Fouad DE, Zhang C, Mekuria TD, Bi C, Zaidi AA, Shah AH (2019) Effects of sono-assisted modified precipitation on the crystallinity, size, morphology, and catalytic applications of hematite (α-Fe2O3) nanoparticles: a comparative study. Ultrason Sonochem 59:104713

    Article  CAS  Google Scholar 

  • Gorito AM, Ribeiro ARL, Rodrigues P, Pereira MFR, Guimarães L, Almeida CMR, Silva AMT (2022) Antibiotics removal from aquaculture effluents by ozonation: chemical and toxicity descriptors. Water Res 218:118497

    Article  CAS  Google Scholar 

  • Guo F, Shi W, Wang H, Han M, Guan W, Huang H, Liu Y, Kang Z (2018) Study on highly enhanced photocatalytic tetracycline degradation of type II AgI/CuBi2O4 and Z-scheme AgBr/CuBi2O4 heterojunction photocatalysts. J Hazard Mater 349:111–118

    Article  CAS  Google Scholar 

  • Guo S, Wang H, Yang W, Fida H, You L, Zhou K (2020) Scalable synthesis of Ca-doped α-Fe2O3 with abundant oxygen vacancies for enhanced degradation of organic pollutants through peroxymonosulfate activation. Appl Catal B Environ 262:118250

    Article  CAS  Google Scholar 

  • Hu T, Li J, Wang L, Wang H, Zhang Z, Jiang W, Xue C (2023) ZnO/ZnFe2O4/zeolite composite catalyst for peroxymonosulfate oxidation and photocatalysis. Mater Lett 330:133310

    Article  CAS  Google Scholar 

  • Hu T, Li P, Zhang J, Liang C, Dai K (2018) Highly efficient direct Z-scheme WO3/CdS-diethylenetriamine photocatalyst and its enhanced photocatalytic H2 evolution under visible light irradiation. Appl Surf Sci 442:20–29

    Article  CAS  Google Scholar 

  • Hua X, Chen H, Rong C, Addison F, Dong D, Qu J, Liang D, Guo Z, Zheng N, Liu H (2023) Visible-light-driven photocatalytic degradation of tetracycline hydrochloride by Z-scheme Ag3PO4/1T@2H-MoS2 heterojunction: degradation mechanism, toxicity assessment, and potential applications. J Hazard Mater 448:130951

    Article  CAS  Google Scholar 

  • Huo Q, Qi X, Li J, Liu G, Ning Y, Zhang X, Zhang B, Fu Y, Liu S (2019) Preparation of a direct Z-scheme α-Fe2O3/MIL-101(Cr) hybrid for degradation of carbamazepine under visible light irradiation. Appl Catal B Environ 255:117751

    Article  CAS  Google Scholar 

  • Ismail AA, Faisal M, Al-Haddad A (2018) Mesoporous WO3-graphene photocatalyst for photocatalytic degradation of methylene blue dye under visible light illumination. J Environ Sci 66:328–337

    Article  CAS  Google Scholar 

  • Jamila GS, Sajjad S, Leghari SAK, Long M (2020) Nitrogen doped carbon quantum dots and GO modified WO3 nanosheets combination as an effective visible photo catalyst. J Hazard Mater 382:121087

    Article  CAS  Google Scholar 

  • Jeevitha G, Sivaselvam S, Keerthana S, Mangalaraj D, Ponpandian N (2022) Highly effective and stable MWCNT/WO3 nanocatalyst for ammonia gas sensing, photodegradation of ciprofloxacin and peroxidase mimic activity. Chemosphere 297:134023

    Article  CAS  Google Scholar 

  • Ji X, Kang Y, Fan T, **ong Q, Zhang S, Tao W, Zhang H (2020) An antimonene/Cp*Rh(phen)Cl/black phosphorus hybrid nanosheet-based Z-scheme artificial photosynthesis for enhanced photo/bio-catalytic CO2 reduction. J Mater Chem A 8:323–333

    Article  CAS  Google Scholar 

  • Li C, Chen G, Sun J, Rao J, Han Z, Hu Y, ** effect of phosphate in Bi2WO6 and universal improved photocatalytic activity for removing various pollutants in water. Appl Catal B Environ 188:39–47

    Article  CAS  Google Scholar 

  • Li G, Hou J, Zhang W, Li P, Liu G, Wang Y, Wang K (2020) Graphene-bridged WO3/MoS2 Z-scheme photocatalyst for enhanced photodegradation under visible light irradiation. Mater Chem Phys 246:122827

    Article  CAS  Google Scholar 

  • Li J, Li Y, Wang X, Yang Z, Zhang G (2023) Atomically dispersed Fe sites on TiO2 for boosting photocatalytic CO2 reduction: enhanced catalytic activity, DFT calculations and mechanistic insight. Chin J Catal 51:145–156

    Article  CAS  Google Scholar 

  • Lin B, Li S, Peng Y, Chen Z, Wang X (2021) MOF-derived core/shell C-TiO2/CoTiO3 type II heterojunction for efficient photocatalytic removal of antibiotics. J Hazard Mater 406:124675

    Article  CAS  Google Scholar 

  • Liu J, Lin H, He Y, Dong Y, Gueret Yadiberet Menzembere ER (2020) Novel CoS2/MoS2@Zeolite with excellent adsorption and photocatalytic performance for tetracycline removal in simulated wastewater. J Clean Prod 260:121047

    Article  CAS  Google Scholar 

  • Liu X, Jiang J, Jia Y, Qiu J, **a T, Zhang Y, Li Y, Chen X (2017) Insight into synergistically enhanced adsorption and visible light photocatalytic performance of Z-scheme heterojunction of SrTiO3 (La,Cr)-decorated WO3 nanosheets. Appl Surf Sci 412:279–289

    Article  CAS  Google Scholar 

  • Liu Z, Liu Y, Sun X, Ji H, Liu W, Cai Z (2022) Construction of Z-scheme Ag/AgVO3/carbon-rich g-C3N4 heterojunction for enhanced photocatalytic degradation of sulfamethiadiazole: DFT calculation and mechanism study. Chem Eng J 433:133604

    Article  CAS  Google Scholar 

  • Lu N, Wang P, Su Y, Yu H, Liu N, Quan X (2019) Construction of Z-Scheme g-C3N4/RGO/WO3 with in situ photoreduced graphene oxide as electron mediator for efficient photocatalytic degradation of ciprofloxacin. Chemosphere 215:444–453

    Article  CAS  Google Scholar 

  • Lu Y, Liu G, Zhang J, Feng Z, Li C, Li Z (2016) Fabrication of a monoclinic/hexagonal junction in WO3 and its enhanced photocatalytic degradation of rhodamine B. Chin J Catal 37:349–358

    Article  CAS  Google Scholar 

  • Ma J, Mao K, Low J, Wang Z, ** D, Zhang W, Ju H, Qi Z, Long R, Wu X, Song L, **ong Y (2021) Efficient photoelectrochemical conversion of methane into ethylene glycol by WO3 nanobar arrays. Angew Chem Int Ed Engl 60:9357–9361

    Article  CAS  Google Scholar 

  • Mao G, Wu H, Qiu T, Bao D, Lai L, Tu W, Liu Q (2022) WO3@Fe2O3 core-shell heterojunction photoanodes for efficient photoelectrochemical water splitting. Chin J Struct Chem 41:2208025–2208030

    CAS  Google Scholar 

  • Mergbi M, Aboagye D, Contreras S, Amor HB, Medina F, Djellabi R (2023a) Fast g-C3N4 sonocoated activated carbon for enhanced solar photocatalytic oxidation of organic pollutants through Adsorb & Shuttle process. Ultrason Sonochem 99:106550

  • Mergbi M, Galloni MG, Aboagye D, Elimian E, Su P, Ikram BM, Nabgan W, Bedia J, Amor HB, Contreras S, Medina F, Djellabi R (2023b) Valorization of lignocellulosic biomass into sustainable materials for adsorption and photocatalytic applications in water and air remediation. Environ Sci Pollut Res 30:74544–74574

    Article  CAS  Google Scholar 

  • Min X, Chu C, Luo Z, Ma J, Fu Y, Wei Z, Spinney R, Dionysiou DD, **ao R (2022) Transformation of phenol and nitrobenzene by superoxide radicals: kinetics and mechanisms. Chem Eng J 442:136134

    Article  CAS  Google Scholar 

  • Ni T, Li Q, Yan Y, Wang F, Cui X, Yang Z, Wang Y, Yang Z, Chang K, Liu G (2020) N, Fe-doped carbon dot decorated gear-shaped WO3 for highly efficient UV-Vis-NIR-driven photocatalytic performance. Catalysts 10(4):416

    Article  CAS  Google Scholar 

  • Ni Z, Wang Q, Guo Y, Liu H, Zhang Q (2023) Research Progress of Tungsten Oxide-Based Catalysts in Photocatalytic Reactions. Catalysts 13(3):579

    Article  CAS  Google Scholar 

  • Pan T, Chen D, Xu W, Fang J, Wu S, Liu Z, Wu K, Fang Z (2020) Anionic polyacrylamide-assisted construction of thin 2D-2D WO3/g-C3N4 step-scheme heterojunction for enhanced tetracycline degradation under visible light irradiation. J Hazard Mater 393:122366

    Article  CAS  Google Scholar 

  • Pan Y, Zhang Y, Huang Y, Jia Y, Chen L (2022) Enhanced photocatalytic oxidation degradability for real cyanide wastewater by designing photocatalyst GO/TiO2/ZSM-5: performance and mechanism research. Chem Eng J 428:131257

    Article  CAS  Google Scholar 

  • Pham VV, Truong TK, Hai LV, La HPP, Nguyen HT, Lam VQ, Tong HD, Nguyen TQ, Sabbah A, Chen K-H, You S-J, Cao TM (2022) S-scheme α-Fe2O3/g-C3N4 nanocomposites as heterojunction photocatalysts for antibiotic degradation. ACS Appl Nano Mater 5:4506–4514

    Article  CAS  Google Scholar 

  • Qi K, Ye Y, Wei B, Li M, Lun Y, **e X, **e H (2022) N-CQDs from reed straw enriching charge over BiO2−x/BiOCl p-n heterojunction for improved visible-light-driven photodegradation of organic pollutants. J Hazard Mater 432:128759

    Article  CAS  Google Scholar 

  • Rong J, Zhang T, Qiu F, Rong X, Zhu X, Zhang X (2016) Preparation of hierarchical micro/nanostructured Bi2S3-WO3 composites for enhanced photocatalytic performance. J Alloys Compd 685:812–819

    Article  CAS  Google Scholar 

  • Saber AN, Djellabi R, Fellah I, Abderrahim N, Bianchi CL (2021) Synergistic sorption/photo-Fenton removal of typical substituted and parent polycyclic aromatic hydrocarbons from coking wastewater over CuO-montmorillonite. J Water Process Eng 44:102377

  • Shi R, Long J, Zou X, Fu G, Yu L, Tian Y, Chen Y, Luo F (2022) Porphyrin functionalized laser-induced graphene and porous WO3 assembled effective Z-scheme photocatalyst for promoted visible-light-driven degradation of ciprofloxacin. Catal Lett 152:1969–1980

    Article  CAS  Google Scholar 

  • Sotelo-Vazquez C, Quesada-Cabrera R, Ling M, Scanlon DO, Kafizas A, Thakur PK, Lee T-L, Taylor A, Watson GW, Palgrave RG, Durrant JR, Blackman CS, Parkin IP (2017) Evidence and effect of photogenerated charge transfer for enhanced photocatalysis in WO3/TiO2 heterojunction films: a computational and experimental study. Adv Funct Mater 27(18):1605413

    Article  Google Scholar 

  • Sun J, Li L, Ge S, Zhao P, Zhu P, Wang M, Yu J (2021) Dual-Mode Aptasensor Assembled by a WO3/Fe2O3 heterojunction for paper-based colorimetric prediction/photoelectrochemical multicomponent analysis. ACS Appl Mater Interfaces 13:3645–3652

    Article  CAS  Google Scholar 

  • Tsai C-K, Lee Y-C, Nguyen TT, Horng J-J (2022) Levofloxacin degradation under visible-LED photo-catalyzing by a novel ternary Fe–ZnO/WO3 nanocomposite. Chemosphere 298:134285

    Article  CAS  Google Scholar 

  • Ullah S, Ferreira-Neto EP, Hazra C, Parveen R, Rojas-Mantilla HD, Calegaro ML, Serge-Correales YE, Rodrigues-Filho UP, Ribeiro SJL (2019) Broad spectrum photocatalytic system based on BiVO4 and NaYbF4:Tm3+ upconversion particles for environmental remediation under UV-vis-NIR illumination. Appl Catal B Environ 243:121–135

    Article  CAS  Google Scholar 

  • Velempini T, Prabakaran E, Pillay K (2021) Recent developments in the use of metal oxides for photocatalytic degradation of pharmaceutical pollutants in water—a review. Mater Today Chem 19:100380

    Article  CAS  Google Scholar 

  • Wang C-C, Yi X-H, Wang P (2019) Powerful combination of MOFs and C3N4 for enhanced photocatalytic performance. Appl Catal B Environ 247:24–48

    Article  CAS  Google Scholar 

  • Wang Y, Wang Y, Zhao J, Chen M, Huang X, Xu Y (2021a) Efficient production of H2O2 on Au/WO3 under visible light and the influencing factors. Appl Catal B Environ 284:119691

  • Wang Z, Cheng Q, Wang X, Li J, Li W, Li Y, Zhang G (2021b) Carbon dots modified bismuth antimonate for broad spectrum photocatalytic degradation of organic pollutants: boosted charge separation, DFT calculations and mechanism unveiling. Chem Eng J 418:129460

    Article  CAS  Google Scholar 

  • Wei Z, Liu J, Shangguan W (2020) A review on photocatalysis in antibiotic wastewater: pollutant degradation and hydrogen production. Chin J Catal 41:1440–1450

    Article  CAS  Google Scholar 

  • Xu J, Yao Q, Li P, Zhang X, Wang S, Pan C (2022) Construction of amorphous carbon-coated alpha-Fe2O3 core–shell nanostructure for efficient photocatalytic performance. J Mater Sci Mater Electron 33:22549–22559

    Article  CAS  Google Scholar 

  • Yi X-H, Ji H, Wang C-C, Li Y, Li Y-H, Zhao C, Wang A, Fu H, Wang P, Zhao X, Liu W (2021) Photocatalysis-activated SR-AOP over PDINH/MIL-88A(Fe) composites for boosted chloroquine phosphate degradation: performance, mechanism, pathway and DFT calculations. Appl Catal B Environ 293:120229

    Article  CAS  Google Scholar 

  • Yu X, Zhang J, Zhang J, Niu J, Zhao J, Wei Y, Yao B (2019) Photocatalytic degradation of ciprofloxacin using Zn-doped Cu2O particles: analysis of degradation pathways and intermediates. Chem Eng J 374:316–327

    Article  CAS  Google Scholar 

  • Yuan X, Jiang L, Chen X, Leng L, Wang H, Wu Z, **ong T, Liang J, Zeng G (2017) Highly efficient visible-light-induced photoactivity of Z-scheme Ag2CO3/Ag/WO3 photocatalysts for organic pollutant degradation. Environ Sci Nano 4:2175–2185

    Article  CAS  Google Scholar 

  • Zhang S, Zhang Z, Li B, Dai W, Si Y, Yang L, Luo S (2021) Hierarchical Ag3PO4@ZnIn2S4 nanoscoparium: an innovative Z-scheme photocatalyst for highly efficient and predictable tetracycline degradation. J Colloid Interface Sci 586:708–718

    Article  CAS  Google Scholar 

  • Zhao C, Pan X, Wang Z, Wang C-C (2021) 1 + 1 > 2: a critical review of MOF/bismuth-based semiconductor composites for boosted photocatalysis. Chem Eng J 417:128022

    Article  CAS  Google Scholar 

  • Zhao J (2022) Excellent photocatalytic degradation and antibiosis of WO3/Fe2O3 heterojunction. Mater Res Express 9:055010

    Article  Google Scholar 

  • Zhong Q, Liu J, Wang J, Li Y, Li J, Zhang G (2022) Efficient degradation of organic pollutants by activated peroxymonosulfate over TiO2@C decorated Mg–Fe layered double oxides: Degradation pathways and mechanism. Chemosphere 300:134564

    Article  CAS  Google Scholar 

  • Zhou Y, Zhang J, Wu D (2022) Enhanced photocatalytic degradation of ciprofloxacin over Bi2MoO6/g-C3N4/BiFeO3 heterojunction photocatalyst under visible light irradiation. Mater Sci Semicond Process 151:107011

    Article  CAS  Google Scholar 

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Funding

This work was financially supported by the Hangzhou Science and Technology Project (20162013A07) and the Zhejiang Provincial Natural Science Foundation (LY15D010007).

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  1. College of Life and Environmental Sciences, Hangzhou Normal University, Hangzhou, 311121, China

    Jiaqi Chen & **njie Li

  2. School of Engineering, Hangzhou Normal University, 2318 Yuhangtang Road, Hangzhou, 311121, China

    Fan Wang

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  1. Jiaqi Chen
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  2. **njie Li
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All authors contributed to the study conception and design. JC: methodology, experiment, and writing—original draft. XL: data analysis. FW: writing—review and editing, supervision, and funding acquisition.

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Correspondence to Fan Wang.

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Chen, J., Li, X. & Wang, F. Photocatalytic degradation performance of antibiotics by WO3/α-Fe2O3/zeolite type II heterojunction with core-shell structure. Environ Sci Pollut Res 30, 119372–119384 (2023). https://doi.org/10.1007/s11356-023-30744-w

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