Vol. 29 No. 3 (2026) Cover Image
Vol. 29 No. 3 (2026)

Published: September 20, 2026

Pages: 413-425

Articles

Photocatalytic Degradation of Organic Dyes Using Zif-67-Based Heterojunction Photocatalysts: A Review

Zahraa Riyadh Muslim 1 Saad H. Ammar 2
1 Department of Chemical Engineering, College of Engineering, Al-Nahrain University
2 Department of Chemical Engineering, College of Engineering, Al-Nahrain University.
History
  • Received: October 11, 2023
  • Revised: December 31, 2023
  • Accepted: May 8, 2025
  • Available Online: September 20, 2026
DOI

https://doi.org/10.29194/NJES.29030413

Abstract

Semiconductor photocatalytic technology has become an area of extensive research due to the extensive environmental contamination. Zeolitic imidazolate frameworks (ZIFs) are a distinct class of metal-organic frameworks that exhibit promise in the field of photocatalysis. This is attributed to their inherent porosity structure, versatile functionalities, rapid electron transfer rate, and excellent chemical-thermal stability are exhibited by this material. In addition, the photocatalytic performance of ZIFs and their derivatives can be greatly increased with the incorporation of active metals or semiconductor materials that act as light collecting centers or electronic mediators. Lately, there has been a growing focus on producing and utilizing materials under consideration are derived from the Co-zeolitic imidazolate framework (ZIF-67).), due to their remarkably great surface area, controllable pore diameter, and outstanding responsively to visible light. This article provides an exhaustive review of the use of ZIF-67-based heterojunctions in visible light-promoted photo-catalytic breakdown of organic dye contaminants. The review discusses and summarizes representative works, with particular emphasis given to the synergistic impacts and proposed mechanisms of the ZIF-67 composite photocatalysts in boosting photocatalysis process. Finally, the recent achievements and challenges in this discipline are discussed, and potential avenues for future investigation are suggested.

Keywords

References

  1. S. E. Jabbar, Z. H. Ebrahim, "Recent advances in nano‑semiconductors photocatalysis for degrading organic contaminants and microbial disinfection in wastewater: A comprehensive review," Environ. Nanotechnol. Monit. Manag., vol. 17, no. Nov. 2021, p. 100666, 2022. https://doi.org/10.1016/j.enmm.2022.100666
  2. M. Hasanpour, M. Hatami, "Photocatalytic performance of aerogels for organic dyes removal from wastewaters: Review study," J. Mol. Liq., vol. 309, p. 113094, 2020. https://doi.org/10.1016/j.molliq.2020.113094
  3. A. K. D. Ammar, S. H. Attia, H. G. Affat, "Extraction of metal ions mixture cadmium, iron, zinc and copper from aqueous solutions using emulsion liquid membrane technique," in Proc. 1st Nat. Conf. Eng. Sci. (FNCES 2012), 2012, pp. 1-10. https://doi.org/10.1109/NCES.2012.6740483
  4. A. Benkhaya, S. M'rabet, S. El Harfi, "A review on classifications, recent synthesis and applications of textile dyes," Inorg. Chem. Commun., vol. 115, p. 107891, 2020. https://doi.org/10.1016/j.inoche.2020.107891
  5. S. H. A. Sajjad, M. Flihh, "Fabrication and photocatalytic degradation activity of core/shell ZIF‑67@CoWO4@CoS heterostructure photocatalysts under visible light," Envir. Nanotech., Monit. & Manag., 16, p.100595 2021. https://doi.org/10.1016/j.enmm.2021.100595
  6. D. Zhu, Q. Zhou, "Action and mechanism of semiconductor photocatalysis on degradation of organic pollutants in water treatment: A review," Environ. Nanotechnol. Monit. Manag., vol. 12, 2019. https://doi.org/10.1016/j.enmm.2019.100255
  7. G. S. Ananth, R. Kumar, P. Singh, "Recent trends in the application of metal‑organic frameworks (MOFs) for the removal of toxic dyes and their removal mechanism - a review," J. Environ. Chem. Eng., 31, p.e00378 2020. https://doi.org/10.1016/j.susmat.2021.e00378
  8. S. Rojas, P. Horcajada, "Metal‑Organic Frameworks for the removal of emerging organic pollutants," Chem. Rev., 2019. https://doi.org/10.1021/acs.chemrev.9b00797
  9. M. T. Yagub, T. K. Sen, S. Afroze, H. M. Ang, "Dye and its removal from aqueous solution by adsorption: A review," Adv. Colloid Interface Sci., pp. 172-184, 2014. https://doi.org/10.1016/j.cis.2014.04.002
  10. M. A. Lafta, B. Saad, H. Ammar, H. J. Kareem, Z. H. Jabbar, "Improved photocatalytic degradation of methyl violet dye and pathogenic bacteria using g‑C3N4 supported phosphotungstic acid heterojunction," J. of Photoch. and Photobio. A: Chem. Vol. 437, p.114506. 2017. https://doi.org/10.1016/j.jphotochem.2022.114506
  11. K. S. Arora, S. A. Ali, "Removal of synthetic textile dyes from wastewaters: A critical review on present treatment technologies," Crit. Rev. Environ. Sci. Technol., vol. 41, no. 9, pp. 807-878, 2011. https://doi.org/10.1080/10643380903218376
  12. V. C. Padmanaban, S. Jose, C. Rapheal, "Reactor systems for the degradation of textile dyes," Int. J. Environ. Sci., vol. 3, no. 6, pp. 1868-1873, 2013. https://doi:10.6088/ijes.2013030600008
  13. A. Mills, R. H. Davies, D. Worsley, "Water purification by semiconductor photocatalysis," Chem. Soc. Rev., vol. 22, no. 6, pp. 417-425, 1993. https://doi.org/10.1039/cs9932200417
  14. M. Pirilä, J. Lahtinen, T. Kallio, J. Keiski, "Photocatalytic degradation of organic pollutants in wastewater," Top. Catal., vol. 58, no. 14-17, pp. 1085-1099, 2015. https://doi.org/10.1007/s11244-015-0477-7
  15. Z. H. Jabbar, S. E. Ebrahim, "Recent advances in nano‑semiconductors photocatalysis for degrading organic contaminants and microbial disinfection in wastewater: A comprehensive review," Environ. Nanotechnol. Monit. Manag., vol. 17, 2022. https://doi.org/10.1016/j.enmm.2022.100666
  16. A. H. Al‑Obaidy, R. H. Al‑Anbari, E. A. Mohammed, "Solar photocatalytic of reactive blue dye in aqueous suspension of V2O5," Eng. Technol. J., vol. 35, no. 1, pp. 1-8, 2017. https://doi.org/10.30684/etj.35.1A.1
  17. A. Malathi, J. Madhavan, M. Ashokkumar, P. Arunachalam, "A review on BiVO4 photocatalyst: Activity enhancement methods for solar photocatalytic applications," Appl. Catal. A Gen., vol. 555, pp. 47-74, 2018. https://doi.org/10.1016/j.apcata.2018.02.010
  18. K. A. Isai, V. S. Shrivastava, "Photocatalytic degradation of methylene blue using ZnO and 2% Fe-ZnO semiconductor nanomaterials synthesized by sol-gel method: A comparative study," SN Appl. Sci., vol. 1, no. 10, 2019. https://doi.org/10.1007/s42452-019-1279-5
  19. Y. Zhong, C. Peng, Z. He, D. Chen, H. Jia, H. Ding, X. Wu, J. Zhang, "Interface engineering of heterojunction photocatalysts based on 1D nanomaterials," Adv. Mater., 11(1), pp.27-42 2019. https://doi.org/10.1039/d0cy01847c
  20. R. Marschall, "Semiconductor composites: Strategies for enhancing charge carrier separation to improve photocatalytic activity," Adv. Funct. Mater., vol. 24, no. 17, pp. 2421-2440, 2014. https://doi.org/10.1002/adfm.201303214
  21. M. A. Fox, M. T. Dulay, "Heterogeneous photocatalysis," Chem. Rev., vol. 93, no. 1, pp. 341-357, 1993. https://doi.org/10.1021/cr00017a016
  22. Y. Ren, D. Zeng, W.‑J. Ong, "Interfacial engineering of graphitic carbon nitride (g‑C3N4)‑based metal sulfide heterojunction photocatalysts for energy conversion: A review," Chin. J. Catal., vol. 40, no. 3, pp. 289-319, 2019. https://doi.org/10.1016/S1872-2067(19)63293-6
  23. V. Dutta, S. Sharma, P. Raizada, A. Hosseini‑Bandegharaei, V. K. Gupta, P. Singh, "Review on augmentation in photocatalytic activity of CoFe2O4 via heterojunction formation for photocatalysis of organic pollutants in water," J. Saudi Chem. Soc., vol. 23, no. 8, pp. 1119-1136, 2019. https://doi.org/10.1016/j.jscs.2019.07.003
  24. Q. Xu, L. Zhang, J. Yu, M. Wageh, A. Al‑Ghamdi, "Direct Z‑scheme photocatalysts: Principles, synthesis, and applications," Small Methods, vol. 1, no. 5, 2017. https://doi.org/10.1002/smtd.201700080
  25. J. Low, C. Jiang, B. Cheng, S. Wageh, A. Al‑Ghamdi, J. Yu, "A review of direct Z‑scheme photocatalysts," Small Methods, vol. 1, no. 5, 2017. https://doi.org/10.1002/smtd.201700080
  26. Q. Xu, L. Zhang, B. Cheng, J. Fan, J. Yu, "S‑scheme heterojunction photocatalyst," Adv. Mater., 2020. https://doi.org/10.1016/j.chempr.2020.06.010
  27. I. Y. Chistyakov, A. G. Zavyalova, D. V. Kladko, V. V. Vinogradov, "Large MOFs: Synthesis strategies and applications where size matters," J. of Mat. Chem. A, 9(45), pp.25258-25271, 2020. https://doi.org/10.1039/d1ta05283g
  28. S. Yuan, L. Feng, K. Wang, J. Pang, M. Bosch, Y. Sun, J. Qin, X. Yang, P. Zhang, Q. Wang, Y. Zhang, L. Zhang, Y. Fang, J. Li, "Stable metal-organic frameworks: Design, synthesis, and applications," Adv. Mat., 30(37), p.1704303, 2020. https://doi.org/10.1002/adma.201704303
  29. A. J. Howarth, M. J. Katz, T. D. Chapman, O. K. Farha, J. T. Hupp, "Chemical, thermal and mechanical stabilities of metal‑organic frameworks," Nat. Rev. Mater., vol. 1, 2016. https://doi.org/10.1038/natrevmats.2015.18
  30. G. Bellussi, A. Carati, C. Rizzo, R. Millini, "New trends in the synthesis of crystalline microporous materials," Catal. Sci. Technol., vol. 3, no. 4, pp. 833-857, 2013. https://doi.org/10.1039/C2CY20510F
  31. Z. L. Zhang, X. Qi, D.‑Y. Wang, "Recent progress on metal-organic framework and its derivatives as novel fire retardants to polymeric materials," Polym. Degrad. Stab., 2019. https://doi.org/10.1007/s40820-020-00497-z
  32. B. Chen, Z. Yang, Y. Xu, C. Zhong, "Zeolitic imidazolate framework materials: Recent progress in synthesis and applications," J. Mater. Chem., 2(40), pp.16811-16831 2012. https://doi.org/10.1039/c4ta02984d
  33. A. Zanon, F. Verpoort, "Metals@ZIFs: Catalytic applications and size selective catalysis," Coord. Chem. Rev., vol. 353, pp. 201-222, 2017. https://doi.org/10.1016/j.ccr.2017.09.030
  34. O. M. Yaghi, Z. Ni, A. P. Côté, J. Y. Choi, R. Huang, F. J. Uribe‑Romo, H. K. Chae, M. O'Keeffe, "Exceptional chemical and thermal stability of zeolitic imidazolate frameworks," Proceed. of the Nat. Acad. of Scie., 103(27), pp.10186-10191, 2005. https://doi.org/10.1073/pnas.0602439103
  35. K. Noh, J. Lee, J. Kim, "Compositions and structures of zeolitic imidazolate frameworks," Isr. J. Chem., vol. 58, no. 9-10, pp. 1075-1088, 2018. https://doi.org/10.1002/ijch.201800107
  36. O. M. Yaghi, R. Banerjee, A. Phan, B. Wang, C. Knobler, H. Furukawa, M. O'Keeffe, " High-throughput synthesis of zeolitic imidazolate frameworks and application to CO2 capture," Sci., 319(5865), pp.939-943, 2008. https://doi.org/10.1126/science.1152516
  37. J. Zakzeski, A. Dębczak, P. C. A. Bruijnincx, B. M. Weckhuysen, "Catalytic oxidation of aromatic oxygenates by the heterogeneous catalyst Co‑ZIF‑9," Appl. Catal. A Gen., vol. 394, no. 1-2, pp. 79-85, 2011. https://doi.org/10.1016/j.apcata.2010.12.026
  38. R. M. Abdelhameed, M. Abu‑Elghait, M. El‑Shahat, "Hybrid three MOFs composites (ZIF‑67@ZIF‑8@MIL‑125‑NH2): Enhancement of biological and visible‑light photocatalytic activity," J. Environ. Chem. Eng., vol. 8, no. 5, p. 104107, 2020. https://doi.org/10.1016/j.jece.2020.104107
  39. Z. Yu, Y. Zhang, L. Wang, H. Li, "Enhanced visible light photocatalytic activity of CdS through controllable self‑assembly compositing with ZIF‑67," Mater. Chem. Phys., 2020. https://doi.org/10.1016/j.mcat.2020.110797
  40. K. Shen, X. Chen, J. Chen, Y. Li, "Development of MOF‑derived carbon‑based nanomaterials for efficient catalysis," ACS Catal., vol. 6, no. 9, pp. 5887-5903, 2016. https://doi.org/10.1021/acscatal.6b01222
  41. Y. Liu, A. A. S. Goncalves, Y. Zhou, "Importance of surface modification of γ‑alumina in creating its nanostructured composites with ZIF‑67," Microporous Mesoporous Mater., 2019. https://doi.org/10.1016/j.jcis.2018.05.008
  42. K.‑Y. Lin, "Ultra‑high adsorption capacity of ZIF‑67 for removal of malachite green from water," Chemosph., 139, pp.624-631, 2015. https://doi.org/10.1016/j.chemosphere.2015.01.041
  43. Q. Chen, Z. Pan, N. Liu, S. Shang, D. Shi, "Construction of hollow ZnO/Mn‑ZIF‑67 heterojunction photocatalysts: Enhanced photocatalytic performance and mechanistic insight," New J. of Chem., 45(4), pp.2285-2294, 2021. https://doi.org/10.1039/d0nj05616b
  44. C. Duan, Y. Yu, A. Li, "Recent progress on synthesis of ZIF‑67‑based materials and their application to heterogeneous catalysis," Green Ene. & Env., 7(1), pp.3-15, 2020. https://doi.org/10.1016/j.gee.2020.12.023
  45. J. Ethiraj, S. Palla, "Insights into high pressure gas adsorption properties of ZIF‑67: Experimental and theoretical studies," Microporous Mesoporous Mater., 2020. https://doi.org/10.1016/j.micromeso.2019.109867
  46. Z. Pouramini, S. M. Mousavi, A. Babapoor, Y. Mazaheri, W.‑H. Chiang, C. W. Lai, "Effect of metal atom in ZIF‑8 and ZIF‑67 for removal of dyes and antibiotics from wastewater: A review," Catalysts, 13(1), p.155, 2023. https://doi.org/10.3390/catal13010155
  47. K. Sumida, K. Liang, J. Reboul, I. A. Ibarra, S. Furukawa, "Sol‑gel processing of metal‑organic frameworks," Chem. Soc. Rev., 2012.
  48. L. Xu, Y. Xiong, B. Dang, Z. Ye, C. Jin, Q. Sun, "In‑situ anchoring of Fe3O4/ZIF‑67 dodecahedrons in highly compressible wood aerogel with excellent microwave absorption properties," J. Mater. Chem. C, 2020. https://doi.org/10.1016/j.matdes.2019.108006
  49. P. Sarawade, H. Tan, "Shape‑ and morphology‑controlled sustainable synthesis of Cu, Co, and In MOFs with high CO2 capture capacity," ACS Sust. Chem. & Eng., 1(1), pp.66-74, 2013. https://doi.org/10.1021/sc300036p
  50. S.‑H. Hsu, Y. Yang, C.‑T. Li, H.‑T. Chien, R. R. Salunkhe, N. Suzuki, K.‑C. Ho, K. C.‑W. Wu, " Platinum-free counter electrode comprised of metal-organic-framework (MOF)-derived cobalt sulfide nanoparticles for efficient dye-sensitized solar cells (DSSCs)," Scie. reports, 4(1), p.6983, 2014. https://DOI:10.1038/srep06983
  51. W. Li, K. Wang, X. Yang, F. Zhan, Y. Wang, M. Liu, X. Qiu, J. Li, J. Zhan, Q. Li, "Surfactant‑assisted controlled synthesis of MOF on Fe2O3 nanorod for boosted photoelectrochemical water oxidation," Chem. Eng. J., 379, p.122256, 2020. https://doi.org/10.1016/j.cej.2019.122256
  52. P. Chalati, P. Horcajada, R. Gref, "Optimisation of the synthesis of MOF nanoparticles made of flexible porous iron fumarate MIL‑88A," J. Mater. Chem., 2012. https://doi.org/10.1039/C0JM03563G
  53. R. Babu, R. Roshan, A. C. Kathalikkattil, D. W. Kim, D.‑W. Park, "Microwave‑assisted synthesis of cubic, porous MOF‑205 for CO2 fixation via cyclic carbonate synthesis," ACS Appl. Mater. Interfaces, vol. 8, no. 49, pp. 33723-33731, 2016. https://doi.org/10.1021/acsami.6b12458
  54. N. M. Ali, A. T. Ahmed, J. A. Abbas, B. H. Bakir, A. A. Shekarchi, "Bio‑based magnetic MOF nanocomposite: Ultrasound‑assisted synthesis and pollutant removal from aqueous media," App. Surf. Sci., 480, pp.288-299, 2019. https://doi.org/10.1016/j.apsusc.2019.02.211
  55. K. Choudhury, S. V. Patel, T. V. M. Singh, K. S. Yadav, P. C. Nair, J. Shim, "Hydrogen production and photocatalytic activity of g‑C3N4/Co‑MOF (ZIF‑67) nanocomposite under visible light irradiation," App.Organomet. Chem., 34(3), p.e5376, 2020. https://doi.org/10.1002/aoc.5376
  56. R. Zhong, H. Liao, Q. Deng, X. Zou, "Preparation of BiOBr/ZIF‑67 composite photocatalyst for enhanced visible‑light degradation of RhB," J. of Molec. Struc., 1259, p.132768, 2022. https://doi.org/10.1016/j.molstruc.2022.132768
  57. Y. Li, W. Zhang, K. Wang, X. Yang, F. Zhan, Y. Wang, M. Liu, X. Qiu, J. Li, J. Zhan, Q. Li, " Covalent organic frameworks@ ZIF-67 derived novel nanocomposite catalyst effectively activated peroxymonosulfate to degrade organic pollutants," Chemosphere, 311, p.137038, 2023. https://doi.org/10.1016/j.chemosphere.2022.137038
  58. M. A. Lafta, S. H. Ammar, "Synthesis and photocatalytic activity of polyoxometalates immobilized onto g‑C3N4/ZIF‑67 heterostructures," Mater. Sci. Semicond. Process., 2022. https://doi.org/10.1016/j.mssp.2022.107131
  59. W. Fan, C. Zhou, G. Tai, Y. Ma, X. Yang, Y. Pan, J. Han, G. Wu, "ZIF‑67/BiOCl Z‑scheme heterojunction photocatalyst for photodegradation of organic dyes and antibiotics," ACS App. Nano Mat., 6(19), pp.17814-17825, 2023. https://doi.org/10.1021/acsanm.3c03094
  60. M. A. Lafta, S. H. Ammar, "Synthesis and photocatalytic activity of polyoxometalates immobilized onto g‑C3N4/ZIF‑67 heterostructure," J. Mater. Sci., 2022. https://doi.org/10.1016/j.mssp.2022.107131
  61. X. Li, S. Raza, "Enhanced photocatalytic efficiency through dual‑functional ZIF‑based materials: Fabrication and application for degradation of organic dyes," J. Environ. Chem. Eng., 2021. https://doi.org/10.1016/j.jtice.2021.03.022
  62. W. Guan, X. Gao, G. Ji, Y. Xing, C. Du, "Fabrication of magnetic nanocomposite photocatalysts Fe3O4@ZIF‑67 for degradation of dyes in water under visible light irradiation," J. Photochem. Photobiol. A Chem., 2017. https://doi.org/10.1016/j.jssc.2017.08.012
  63. H. Yang, X. He, F. Wang, "Doping copper into ZIF‑67 for enhancing gas uptake capacity and visible‑light‑driven photocatalytic degradation of organic dye," J. Mater. Chem., vol. 22, pp. 21849-21851, 2012. https://doi.org/10.1039/c2jm35602c
  64. Z. Wang, B. Wen, J. Zhou, X. Zhao, X. Zhang, "Heterostructured ZnCdS@ZIF‑67 as a photocatalyst for fluorescent dye degradation and selective nonenzymatic sensing of dopamine," Sens. Actuators B Chem., 15(21), p.7683 2020. https://doi.org/10.3390/ma15217683
  65. O. Khan, M. Ahmad, M. Nadeem, A. Ali, M. Javed, S. Shah, A. Rehman, "Strategic combination of MOFs and g‑C3N4 for expeditious photocatalytic degradation of dye pollutants," Env. Sci. and poll. Res., 29(23), pp.35300-35313, 2022. https://doi.org/10.1007/s11356-021-17366-w
  66. E. Khudhair, W. Khudhair, S. H. Ammar, "Assembling ZIF‑67@Cd0.5Zn0.5S nanocomposites with enhanced photocatalytic activity," Inorg. Chem. Comm., 142, p.109639, 2022. https://doi.org/10.1016/j.inoche.2022.109639
  67. M. Zabihi, A. Motavalizadehkakhky, "PbS/ZIF‑67 nanocomposite: Novel material for photocatalytic degradation of basic yellow 28 and direct blue 199 dyes," J. of the Taiwan Inst. of Chem. Eng., 140, p.104572, 2022. https://doi.org/10.1016/j.jtice.2022.104572
  68. Z. Huang, J. Zhou, Y. Zhao, H. Cheng, G. Lu, A. Morawski, Y. Yu, "Stable core-shell ZIF‑8@ZIF‑67 MOFs photocatalyst for highly efficient degradation of organic pollutants and hydrogen evolution," Chem. Eng. J., 2021. https://doi.org/10.1557/s43578-021-00117-5