Skip to main content
SpringerLink
Log in

Insight into the Novel Z-Scheme ZIF67/WO3 Heterostructure for Improved Photocatalytic Degradation of Methylene Blue Under Visible Light

  • Published:
Journal of Inorganic and Organometallic Polymers and Materials Aims and scope Submit manuscript

Abstract

In this work, a novel Z-scheme heterojunction of ZIF67/WO3 nanocomposite is successfully prepared via immobilizing WO3 on the MOFs ZIF67 and confirmed by measuring XRD, FT-IR spectroscopy, XPS, SEM, TEM, and EDS. UV–vis and Mott-Schottky measurements. The photocatalytic activity of the as-prepared ZIF67/WO3 is evaluated by degrading methylene blue (MB) solution under simulated visible light irradiation. Obviously, the optimal ZIF67/WO3-0.3 (designated as 0.3 g addition of WO3) delivers significant photocatalytic degradation exceeding 90% toward MB within 120 min, which is about 3.0 and 4.2 times higher than those of pure ZIF67 (30.0%) and WO3 (21.2%). With the addition of 0.02 g ZIF67/WO3-0.3 composite, a total volume of 50 mL of MB at 10 mg/L was thoroughly degraded in 120 min with an apparent rate constant of 0.0184 min−1. Reactive species scavenging experiments indicated that the holes (h+) and hydroxyl radical (·OH) are mainly responsible for MB degradation. Moreover, the probable reaction mechanism is elucidated by detecting the intermediates by performing LC–MS measurements. The excellent photocatalytic performance of the ZIF67/WO3 is predominantly determined by the structural properties of the composite and the Z-scheme charge transfer pathway, which promote the efficient separation of photogenerated carriers and facilitate the transfer of photogenerated electrons to active sites. Therefore, it is a promising strategy for immobilizing the WO3 on MOFs for constructing Z-scheme heterojunction to degrade the refractory organic dyes.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. J. Zhou, C. Wang, C. Jia, Y. Zhou, F. Duo, Z. Wei, Intrinsic photocatalysis of morphology and oxygen vacancy-tunable ultrathin WO3 nanosheets. Chem. Select 5, 4008–4016 (2020)

    Article  CAS  Google Scholar 

  2. S.J. Peighambardoust, B. Pourabbas, Preparation and characterization of nylon-6/PPy/MMT composite of nanocomposite. J. Appl. Polym. Sci. 106, 697–705 (2007)

    Article  CAS  Google Scholar 

  3. R. Foroutan, R. Mohammadi, S.J. Peighambardoust, S. Jalali, B. Ramavandi, Application of nano-silica particles generated from offshore white sandstone for cadmium ions elimination from aqueous media. Environ. Technol. Innov. 19, 101031 (2020)

    Article  Google Scholar 

  4. R. Foroutan, S.J. Peighambardoust, S. Hemmati, H. Khatooni, B. Ramavandi, Preparation of clinoptilolite/starch/CoFe2O4 magnetic nanocomposite powder and its elimination properties for cationic dyes from water and wastewater. Int. J. Biol. Macromol. 189, 432–442 (2021)

    Article  CAS  Google Scholar 

  5. R. Foroutan, S.J. Peighambardoust, A. Ahmadi, A. Akbari, S. Farjadfard, B. Ramavandi, Adsorption mercury, cobalt, and nickel with a reclaimable and magnetic composite of hydroxyapatite/Fe3O4/polydopamine. J. Environ. Chem. Eng. 9, 105709 (2021)

    Article  CAS  Google Scholar 

  6. R. Foroutan, S.J. Peighambardoust, S.H. Peighambardoust, M. Pateiro, J.M. Lorenzo, Adsorption of crystal violet dye using activated carbon of lemon wood and activated carbon/Fe3O4 magnetic nanocomposite from aqueous solutions: a kinetic, equilibrium and thermodynamic study. Molecules 26, 2241 (2021)

    Article  CAS  Google Scholar 

  7. S. Peiris, H.B. de Silva, K.N. Ranasinghe, S.V. Bandara, I.R. Perera, Recent development and future prospects of TiO2 photocatalysis. J. Chin. Chem. Soc.-Taip 68, 738–769 (2021)

    Article  CAS  Google Scholar 

  8. C. Sotelo-Vazquez, R. Quesada-Cabrera, M. Ling, D.O. Scanlon, A. Kafizas, P.K. Thakur, T.L. Lee, A. Taylor, G.W. Watson, R.G. Palgrave, Evidence and effect of photogenerated charge transfer for enhanced photocatalysis in WO3/TiO2 heterojunction films: a computational and experimental study. Adv. Funct. Mater. 27, 1605413 (2017)

    Article  Google Scholar 

  9. L. Liang, Q. Chang, T. Cai, N. Li, C. Xue, J. Yang, S. Hu, Combining carbon dots with WO3-x nanodots for utilizing the full spectrum of solar radiation in photocatalysis. Chem. Eng. J. 428, 131139 (2022)

    Article  CAS  Google Scholar 

  10. X. Zeng, Z. Wang, G. Wang, T.R. Gengenbach, D.T. McCarthy, A. Deletic, J. Yu, X. Zhang, Highly dispersed TiO2 nanocrystals and WO3 nanorods on reduced graphene oxide: Z-scheme photocatalysis system for accelerated photocatalytic water disinfection. Appl. Catal. B 218, 163–173 (2017)

    Article  CAS  Google Scholar 

  11. B. Wang, X. Zhong, J. Zhu, Y. Wang, Y. Zhang, U. Cvelbar, K. Ostrikov, Single-step synthesis of TiO2/WO3−x hybrid nanomaterials in ethanoic acid: structure and photoluminescence properties. Appl. Surf. Sci. 562, 150180 (2021)

    Article  CAS  Google Scholar 

  12. S. Bassaid, C. Benhaoua, M. Taleb, M. Sahli, A. Dehbi, Physical and chemical properties of composites based on polythiophene and titanium dioxide nanoparticles for photocatalysis. Polym. Sci. Ser. B 63, 291–303 (2021)

    Article  Google Scholar 

  13. L. Zhao, X. Xi, Y. Liu, L. Ma, Z. Nie, Facile synthesis of WO3 micro/nanostructures by paper-assisted calcination for visible-light-driven photocatalysis. Chem. Phys. 528, 110515 (2020)

    Article  CAS  Google Scholar 

  14. L. Aamir, Novel p-type Ag-WO3 nano-composite for low-cost electronics, photocatalysis, and sensing: synthesis, characterization, and application. J. Alloys Compd. 864, 158108 (2021)

    Article  CAS  Google Scholar 

  15. M.G. Peleyeju, E.L. Viljoen, WO3-based catalysts for photocatalytic and photoelectrocatalytic removal of organic pollutants from water—a review. J. Water. Process Eng. 40, 101930 (2021)

    Article  Google Scholar 

  16. N. Stock, S. Biswas, Synthesis of metal-organic frameworks (MOFs): routes to various MOF topologies, morphologies, and composites. Chem. Rev. 112, 933–969 (2012)

    Article  CAS  Google Scholar 

  17. C. Zhang, S. Zhang, Y. Yang, H. Yu, X. Dong, Highly sensitive H2S sensors based on metal-organic framework driven γ-Fe2O3 on reduced graphene oxide composites at room temperature. Sens. Actuators B 325, 128804 (2020)

    Article  CAS  Google Scholar 

  18. R. Sule, A.K. Mishra, MOFs-carbon hybrid nanocomposites in environmental protection applications. Environ. Sci. Pollut. R 27, 16004–16018 (2020)

    Article  CAS  Google Scholar 

  19. R. Foroutan, S.J. Peighambardoust, M. Amarzadeh, A.K. Korri, N.S. Peighambardoust, A. Ahmad, B. Ramavandi, Nickel ions abatement from aqueous solutions and shipbuilding industry wastewater using ZIF-8-chicken beak hydroxyapatite. J. Mol. Liq. 356, 119003 (2022)

    Article  CAS  Google Scholar 

  20. W. Shao, Y.-R. Chen, F. Xie, H. Zhang, H.-T. Wang, N. Chang, Facile construction of a ZIF-67/AgCl/Ag heterojunction via chemical etching and surface ion exchange strategy for enhanced visible light driven photocatalysis. RSC Adv. 10, 38174–38183 (2020)

    Article  CAS  Google Scholar 

  21. R. Foroutan, S.J. Peighambardoust, R. Mohammadi, S.H. Peighambardoust, B. Ramavandi, Cadmium ion removal from aqueous media using banana peel biochar/Fe3O4/ZIF-67. Environ. Res. 211, 113020 (2022)

    Article  CAS  Google Scholar 

  22. R. Foroutan, S.J. Peighambardoust, R. Mohammadi, S.H. Peighambardoust, B. Ramavandi, Generation of biodiesel from edible waste oil using ZIF-67-KOH modified Luffa cylindrica biomass catalyst. Fuel 322, 124181 (2022)

    Article  CAS  Google Scholar 

  23. M.B. Tahir, G. Nabi, N. Khalid, Enhanced photocatalytic performance of visible-light active graphene-WO3 nanostructures for hydrogen production. Mater. Sci. Semicond. Proc. 84, 36–41 (2018)

    Article  CAS  Google Scholar 

  24. P. Su, J. Zhang, K. Xiao, S. Zhao, R. Djellabi, X. Li, B. Yang, X. Zhao, C3N4 modified with single layer ZIF67 nanoparticles for efficient photocatalytic degradation of organic pollutants under visible light. Chin. J. Catal. 41, 1894–1905 (2020)

    Article  CAS  Google Scholar 

  25. J. Qian, F. Sun, L. Qin, Hydrothermal synthesis of zeolitic imidazolate framework-67 (ZIF-67) nanocrystals. Mater. Lett. 82, 220–223 (2012)

    Article  CAS  Google Scholar 

  26. T. Zhao, R. Qian, G. Zhou, Y. Wang, W.I. Lee, J.H. Pan, Mesoporous WO3/TiO2 spheres with tailored surface properties for concurrent solar photocatalysis and membrane filtration. Chemosphere 263, 128344 (2021)

    Article  CAS  Google Scholar 

  27. V. Manikandan, S. Harish, J. Archana, M. Navaneethan, Fabrication of novel hybrid Z-Scheme WO3@g-C3N4@MWCNT nanostructure for photocatalytic degradation of tetracycline and the evaluation of antimicrobial activity. Chemosphere 287, 132050 (2022)

    Article  CAS  Google Scholar 

  28. P. Haghighi, S. Alijani, A. Bazyari, L.T. Thompson, Visible light dye degradation over fluorinated mesoporous TiO2−WO3−Bi2O3/SiO2 nanocomposite photocatalyst-adsorbent using immersion well reactor. J. Photoch. Photobiol. A 113790 (2022)

  29. M. Sachs, J.-S. Park, E. Pastor, A. Kafizas, A.A. Wilson, L. Francas, S. Gul, M. Ling, C. Blackman, J. Yano, Effect of oxygen deficiency on the excited state kinetics of WO3 and implications for photocatalysis. Chem. Sci. 10, 5667–5677 (2019)

    Article  CAS  Google Scholar 

  30. Q. Yang, R. Lu, S. Ren, C. Chen, Z. Chen, X. Yang, Three dimensional reduced graphene oxide/ZIF-67 aerogel: effective removal cationic and anionic dyes from water. Chem. Eng. J. 348, 202–211 (2018)

    Article  CAS  Google Scholar 

  31. Y. Li, S. Zhu, X. Kong, Y. Liang, Z. Li, S. Wu, C. Chang, S. Luo, Z. Cui, ZIF-67 derived Co@NC/g-C3N4 as a photocatalyst for enhanced water splitting H2 evolution. Environ. Res. 197, 111002 (2021)

    Article  CAS  Google Scholar 

  32. Q. Zeng, J. Li, J. Bai, X. Li, L. Xia, B. Zhou, Preparation of vertically aligned WO3 nanoplate array films based on peroxotungstate reduction reaction and their excellent photoelectrocatalytic performance. Appl. Catal. B 202, 388–396 (2017)

    Article  CAS  Google Scholar 

  33. H. Zhang, J. Qiao, G. Li, M. Zhang, S. Li, J. Wang, Y. Song, Construction of coated Z-scheme Pd-BaZrO3@WO3 composite with enhanced sonocatalytic activity for diazinon degradation in aqueous solution. Sci. Total Environ. 663, 97–109 (2019)

    Article  CAS  Google Scholar 

  34. R. Wang, L. Zhao, L. Li, Q. Song, J. Huang, Rose spherical structure Ag2S/ZnIn2S4/ZnS composites with visible light response: enhanced photodegradation and hydrogen production performance. J. Phys. Chem. Solids 136, 109148 (2020)

    Article  CAS  Google Scholar 

  35. S. Sharma, S. Basu, Highly reusable visible light active hierarchical porous WO3/SiO2 monolith in centimeter length scale for enhanced photocatalytic degradation of toxic pollutants. Sep. Purif. Technol. 231, 115916 (2020)

    Article  CAS  Google Scholar 

  36. V. Ramar, K. Balasubramanian, Reduced graphene Oxide/WO3 nanorod composites for photocatalytic degradation of methylene blue under sunlight irradiation. ACS Appl. Nano Mater. 4, 5512–5521 (2021)

    Article  CAS  Google Scholar 

  37. R. Lei, H. Zhang, H. Ni, R. Chen, H. Gu, B. Zhang, Novel ZnO nanoparticles modified WO3 nanosheet arrays for enhanced photocatalytic properties under solar light illumination. Appl. Surf. Sci. 463, 363–373 (2019)

    Article  CAS  Google Scholar 

  38. S. Singla, S. Sharma, S. Basu, MoS2/WO3 heterojunction with the intensified photocatalytic performance for decomposition of organic pollutants under the broad array of solar light. J. Clean Prod. 324, 129290 (2021)

    Article  CAS  Google Scholar 

  39. E. Hernández-Moreno, A.M. de la Cruz, L. Hinojosa-Reyes, J. Guzmán-Mar, M. Gracia-Pinilla, A. Hernández-Ramírez, Synthesis, characterization, and visible light–induced photocatalytic evaluation of WO3/NaNbO3 composites for the degradation of 2, 4-D herbicide. Mater. Today Chem. 19, 100406 (2021)

    Article  Google Scholar 

  40. R. Foroutan, S.J. Peighambardoust, P. Latifi, A. Ahmadi, M. Alizadeh, B. Ramavandi, Carbon nanotubes/β-cyclodextrin/MnFe2O4 as a magnetic nanocomposite powder for tetracycline antibiotic decontamination from different aqueous environments. J. Environ. Chem. Eng. 9, 106344 (2021)

    Article  CAS  Google Scholar 

  41. R. Foroutan, S.J. Peighambardoust, R. Mohammadi, S.H. Peighambardoust, B. Ramavandi, Development of new magnetic adsorbent of walnut shell ash/starch/Fe3O4 for effective copper ions removal: treatment of groundwater samples. Chemosphere 296, 133978 (2022)

    Article  CAS  Google Scholar 

  42. N.T. Tran, M.K. Nguyen, The degradation of organic dye contaminants in wastewater and solution from highly visible light responsive ZIF-67 monodisperse photocatalyst. J. Solid State Chem. 300, 122287 (2021)

    Article  CAS  Google Scholar 

  43. D. Lin, M. Gao, L. You, Y. Li, Z. Li, L. Guo, T. Li, M. Liu, Fabrication of novel Ag/AgVO3/WO3 homojunction/heterojunction nanomaterials with highly enhanced photocatalytic activity-Investigation on type Ӏ plus Z-scheme mechanism. J. Alloys Compd. 846, 156274 (2020)

    Article  CAS  Google Scholar 

  44. X. Jia, D. Jiang, P.-I. Gouma, Facile synthesis of self-supported WO3/PANI hybrid photocatalyst for methylene blue degradation under visible light. Mater. Lett. 314, 131869 (2022)

    Article  CAS  Google Scholar 

  45. S. Zhou, Y. Wang, K. Zhou, D. Ba, Y. Ao, P. Wang, In-situ construction of Z-scheme g-C3N4/WO3 composite with enhanced visible-light responsive performance for nitenpyram degradation. Chin. Chem. Lett. 32, 2179–2182 (2021)

    Article  CAS  Google Scholar 

  46. M. Tang, Y. Ao, P. Wang, C. Wang, All-solid-state Z-scheme WO3 nanorod/ZnIn2S4 composite photocatalysts for the effective degradation of nitenpyram under visible light irradiation. J. Hazard Mater. 387, 121713 (2020)

    Article  CAS  Google Scholar 

  47. B. Basumatary, R. Basumatary, A. Ramchiary, D. Konwar, Evaluation of Ag@ TiO2/WO3 heterojunction photocatalyst for enhanced photocatalytic activity towards methylene blue degradation. Chemosphere 286, 131848 (2022)

    Article  CAS  Google Scholar 

  48. J. Li, C. Guo, L. Li, Y. Gu, K. BoK-Hee, J. Huang, Construction of Z-scheme WO3-Cu2O nanorods array heterojunction for efficient photocatalytic degradation of methylene blue. Inorg. Chem. Commun. 109248 (2022).

  49. Q. Zhou, Y. Song, N. Li, D. Chen, Q. Xu, H. Li, J. He, J. Lu, Direct dual Z-scheme Bi2WO6/GQDs/WO3 inverse opals for enhanced photocatalytic activities under visible light. ACS Sustain. Chem. Eng. 8, 7921–7927 (2020)

    Article  CAS  Google Scholar 

  50. S. Khoomortezaei, H. Abdizadeh, M.R. Golobostanfard, Ferro-photocatalytic enhancement of photoelectrochemical water splitting using the WO3/BiFeO3 heterojunction. Energy Fuel 35, 9623–9634 (2021)

    Article  CAS  Google Scholar 

  51. H.-F. Shi, G. Yan, Y. Zhang, H.-Q. Tan, W.-Z. Zhou, Y.-Y. Ma, Y.-G. Li, W. Chen, E.-B. Wang, Ag/Ag-xH3–xPMo12O40 nanowires with enhanced visible-light-driven photocatalytic performance. ACS Appl. Mater. Int. 9, 422–430 (2017)

    Article  CAS  Google Scholar 

  52. X. Yuan, L. Jiang, X. Chen, L. Leng, H. Wang, Z. Wu, T. Xiong, J. Liang, G. Zeng, Highly efficient visible-light-induced photoactivity of Z-scheme Ag2CO 3/Ag/WO3 photocatalysts for organic pollutant degradation. Environ. Sci. Nano 4, 2175–2185 (2017)

    Article  CAS  Google Scholar 

  53. X. Liu, J. Jiang, Y. Jia, J. Qiu, T. Xia, Y. Zhang, Y. Li, X. Chen, 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 (2017)

    Article  CAS  Google Scholar 

  54. B. Li, L. Sun, J. Bian, N. Sun, J. Sun, L. Chen, Z. Li, L. Jing, Controlled synthesis of novel Z-scheme iron phthalocyanine/porous WO3 nanocomposites as efficient photocatalysts for CO2 reduction. Appl. Catal. B 270, 118849 (2020)

    Article  CAS  Google Scholar 

  55. M. Moztahida, D.S. Lee, Photocatalytic degradation of methylene blue with P25/graphene/polyacrylamide hydrogels: optimization using response surface methodology. J. Hazard Mater. 400, 123314 (2020)

    Article  CAS  Google Scholar 

  56. C. Yogi, K. Kojima, N. Wada, H. Tokumoto, T. Takai, T. Mizoguchi, H. Tamiaki, Photocatalytic degradation of methylene blue by TiO2 film and Au particles-TiO2 composite film. Thin Solid Films 516, 5881–5884 (2008)

    Article  CAS  Google Scholar 

  57. C. Shi, X. Zhou, D. Liu, L. Li, M. Xu, H. Sakiyama, M. Muddassir, J. Wang, A new 3D high connection Cu-based MOF introducing a flexible tetracarboxylic acid linker: photocatalytic dye degradation. Polyhedron 208, 115441 (2021)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Natural Science Foundation of Heilongjiang Province of China, Special funds from the central finance to support the development of local universities (Grant No. LH2019B020), the Research Foundation of Education Bureau of Heilongjiang Province of China (Grant No. 135109207) and the Innovation Project of Graduate Education of Qiqihar University (Grant No. YJSCX2021001).

Funding

Funding was provided by National Natural Science Foundation of China (Grant No. 21776144).

Author information

Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar, 161006, People’s Republic of China

    Wenzhi Zhang, Dongni Liu, Zhonghua Mu, Xiaohong Zhang, Guohua Dong, Liming Bai, Ruibo Guo, Jinlong Li, Ming Zhao & Zhuanfang Zhang

  2. Heilongjiang Provincial Key Laboratory of Catalytic Synthesis for Fine Chemicals, Qiqihar University, Qiqihar, 161006, People’s Republic of China

    Jinlong Li

  3. Technology Innovation Center of Industrial Hemp for State Market Regulation, Qiqihar University, Qiqihar, 161006, People’s Republic of China

    Ming Zhao

Authors
  1. Wenzhi Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dongni Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhonghua Mu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xiaohong Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Guohua Dong
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Liming Bai
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Ruibo Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jinlong Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Ming Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Zhuanfang Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Guohua Dong or Zhuanfang Zhang.

Ethics declarations

Conflict of interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOC 134 kb)

Rights and permissions

Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, W., Liu, D., Mu, Z. et al. Insight into the Novel Z-Scheme ZIF67/WO3 Heterostructure for Improved Photocatalytic Degradation of Methylene Blue Under Visible Light. J Inorg Organomet Polym 33, 90–104 (2023). https://doi.org/10.1007/s10904-022-02488-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10904-022-02488-6

Keywords

Search

Navigation