The Study of Photocatalytic Performance of ZIF-67 and Zn/Co-ZIF for the Removal of Organic Pollutants from Wastewater

Document Type : Research Paper


1 Former Graduate Student in Chemical Engineering, Dept. of Chemical Engineering, Amirkabir University of Technology, Tehran, Iran

2 Assoc. Prof., Dept. of Chemical Engineering, Amirkabir University of Technology, Tehran, Iran

3 Prof., Dept. of Chemical Engineering, Amirkabir University of Technology, Tehran, Iran


Due to environmental issues caused by pollution of water resources with organic pollutants, research to provide effective methods for removing these pollutants has received considerable attention. In the present work, the application of Metal Organic Frameworks for the photocatalytic treatment of wastewater containing organic pollutants was studied. Due to the high porosity, suitable band gap, good thermal and chemical stability, ZIF-67 was selected for photocatalytic removal of organic pollutants from wastewater. The ZIF-67 photocatalyst was synthesized and characterized by XRD, FTIR, BET, ICP and UV-DRS techniques. To study the photocatalytic activity of ZIF-67, degradation of methylene blue as an organic model compound has been performed and the effects of catalyst loading, dye concentration and pH on MB removal were studied. Also, the effect of zinc addition to ZIF-67 strucure on the performance of photocatalytic activity was studied. According to the BET results, the specific surface area of catalyst was measured about 1750 m2/g which indicates the high porous structure of ZIF-67. A catalyst loading of 0.5 g/L resulted in 68% removal of MB with initial concentration of 15 ppm after 2 hours of exposure. By addition of zinc to the structure, Zn/Co-ZIF was synthesized and not only showed better crystallization, but also photocatalytic activity increased to 79%. Also, increasing pH and catalyst loading resulted in higher removal efficiency. Both ZIF-67 and Zn/Co-ZIF structures exhibited higher activity in the basic environment (pH 8-12). Although increasing catalyst loading increases removal efficiency, it entails the increase of turbidity which could affect the removal efficiency inversely for higher values. Band gap measurements by UV-DRS analysis indicated that both ZIF-67 and Zn/ZIF-67 can be active under visible light irradiation, and hence may be applicable for degradation of organic pollutant in wastewater.


Ameta, A., Ameta, R. & Ahuja, M. 2013. Photocatalytic degradation of methylene blue over ferric tungstate. Scientific Reviews and Chemical Communications, 3, 172-180.
Chakrabarti, S. & Dutta, B. K. 2004. Photocatalytic degradation of model textile dyes in wastewater using ZnO as semiconductor catalyst. Journal of Hazardous Materials, 112, 269-278.
Daneshvar, N., Salari, D. & Khataee, A. 2004. Photocatalytic degradation of azo dye acid red 14 in water on ZnO as an alternative catalyst to TiO2. Journal of Photochemistry and Photobiology A: Chemistry, 162, 317-322.
Doğan, M., Özdemir, Y. & Alkan, M. 2007. Adsorption kinetics and mechanism of cationic methyl violet and methylene blue dyes onto sepiolite. Dyes and Pigments, 75, 701-713.
Forgacs, E., Cserhati, T. & Oros, G. 2004. Removal of synthetic dyes from wastewaters: a review. Environment International, 30, 953-971.
Ginimuge, P. R. & Jyothi, S. 2010. Methylene blue: revisited. Journal of Anaesthesiology, Clinical Pharmacology, 26, 517.
Gürses, A., Doğar, Ç., Yalçın, M., Açıkyıldız, M., Bayrak, R. & Karaca, S. 2006. The adsorption kinetics of the cationic dye, methylene blue, onto clay. Journal of Hazardous Materials, 131, 217-228.
Hu, Y., Kazemian, H., Rohani, S., Huang, Y. & Song, Y. 2011. In situ high pressure study of ZIF-8 by FTIR spectroscopy. Chemical Communications, 47, 12694-12696.
Jing, H. P., Wang, C. C., Zhang, Y. W., Wang, P. & Li, R. 2014. Photocatalytic degradation of methylene blue in ZIF-8. RSC Advances, 4, 54454-54462.
Lee, J., Farha, O. K., Roberts, J., Scheidt, K. A., Nguyen, S. T. & Hupp, J. T. 2009. Metal-organic framework materials as catalysts. Chemical Society Reviews, 38, 1450-1459.
Li, X., Gao, X., Ai, L. & Jiang, J. 2015. Mechanistic insight into the interaction and adsorption of Cr(VI) with zeolitic imidazolate framework-67 microcrystals from aqueous solution. Chemical Engineering Journal, 274, 238-246.
Lin, K. Y. A. & Chang, H. A. 2015a. Ultra-high adsorption capacity of zeolitic imidazole framework-67 (ZIF-67) for removal of malachite green from water. Chemosphere, 139, 624-631.
Lin, K. Y. A. & Chang, H. A. 2015b. Zeolitic Imidazole Framework-67 (ZIF-67) as a heterogeneous catalyst to activate peroxymonosulfate for degradation of Rhodamine B in water. Journal of the Taiwan Institute of Chemical Engineers, 53, 40-45.
Murray, L. J., Dincă, M. & Long, J. R. 2009. Hydrogen storage in metal-organic frameworks. Chemical Society Reviews, 38, 1294-1314.
Park, H., Reddy, D. A., Kim, Y., Ma, R., Choi, J., Kim, T. K., et al. 2016. Zeolitic imidazolate framework-67-(ZIF-67) rhombic dodecahedrons as full-spectrum light harvesting photocatalyst for environmental remediation. Solid State Sciences, 62, 82-89.
Ravelli, D., Dondi, D., Fagnoni, M. & Albini, A. 2009. Photocatalysis. A multi-faceted concept for green chemistry. Chemical Society Reviews, 38, 1999-2011.
Schejn, A., Aboulaich, A., Balan, L., Falk, V., Lalevee, J., Medjahdi, G., et al. 2015. Cu2+-doped zeolitic imidazolate frameworks (ZIF-8): efficient and stable catalysts for cycloadditions and condensation reactions. Catalysis Science and Technology, 5, 1829-1839.
Sobana, N., Krishnakumar, B. & Swaminathan, M. 2013. Synergism and effect of operational parameters on solar photocatalytic degradation of an azo dye (Direct Yellow 4) using activated carbon-loaded zinc oxide. Materials Science in Semiconductor Processing, 16, 1046-1051.
Toor, A. P., Verma, A., Jotshi, C., Bajpai, P. & Singh, V. 2006. Photocatalytic degradation of Direct Yellow 12 dye using UV/TiO2 in a shallow pond slurry reactor. Dyes and Pigments, 68, 53-60.
Umar, M. & Aziz, H. A. 2013. Photocatalytic degradation of organic pollutants in water. Organic Pollutions-Monitoring, Risk and Treatemnt, 8, 196-197.
Vučurović, V. M., Razmovski, R. N. & Tekić, M. N. 2012. Methylene blue (cationic dye) adsorption onto sugar beet pulp: equilibrium isotherm and kinetic studies. Journal of the Taiwan Institute of Chemical Engineers, 43, 108-111.
Yaghi, O. M., O'keeffe, M., Ockwig, N. W., Chae, H. K., Eddaoudi, M. & Kim, J. 2003. Reticular synthesis and the design of new materials. Nature, 42(3), 705-714.
Yang, H., He, X. W. Wang, F., Kang, Y. & Zhang, J. 2012. Doping copper into ZIF-67 for enhancing gas uptake capacity and visible-light-driven photocatalytic degradation of organic dye. Journal of Materials Chemistry, 22, 21849-21851.
Yang, H., Kruger, P. E. & Telfer, S. G. 2015. Metal–organic framework nanocrystals as sacrificial templates for hollow and exceptionally porous titania and composite materials. Inorganic Chemistry, 54, 9483-9490.
Yao, J., He, M., Wang, K., Chen, R., Zhong, Z. & Wang, H. 2013. High-yield synthesis of zeolitic imidazolate frameworks from stoichiometric metal and ligand precursor aqueous solutions at room temperature. Cryst Eng Comm, 15, 3601-3606.
Zaghbani, N., Hafiane, A. & Dhahbi, M. 2007. Separation of methylene blue from aqueous solution by micellar enhanced ultrafiltration. Separation and Purification Technology, 55, 117-124.
Zhang, M. H., Dong, H., Zhao, L., Wang, D. X. & Meng, D. 2019. A review on Fenton process for organic wastewater treatment based on optimization perspective. Science of the Total Environment, 670, 110-121.
Zhou, K., Mousavi, B., Luo, Z., Phatanasri, S., Chaemchuen, S. & Verpoort, F. 2017. Characterization and properties of Zn/Co zeolitic imidazolate frameworks vs. ZIF-8 and ZIF-67. Journal of Materials Chemistry A, 5, 952-957.