Optimization of the Advanced Photocatalytic Oxidation Process in the Presence of NH2-MIL125(Ti) Catalysts in Wastewater Treatment of Pharmaceutical Industry

Document Type : Research Paper


1 MSc., Dept. of Environmental Science and Engineering, College of Arts and Architecture, West Tehran Branch, Islamic Azad University, Tehran, Iran

2 PhD., Dept. of Environmental Science and Engineering, College of Arts and Architecture, West Tehran Branch, Islamic Azad University, Tehran, Iran


Discharge of pharmaceutical industry wastewater by organic compounds containing pharmaceutical compounds, especially antibiotics into aquatic environments is one of the environmental issues. Advanced oxidation processes such as photocatalytic process is one of the processes which has attracted attention. The aim of this study was to optimize the efficiency of the advanced photocatalytic oxidation process in the presence of NH2-MIL125(Ti) catalyst in the treatment of pharmaceutical industry effluents. In this study, NH2-MIL125(Ti) catalyst was synthesized by solvothermal method and its characteristics were investigated by SEM, EDAX, FTIR and XRD analyzes. For optimization, use of the central composite design, and the effect of pH, nanocomposite dose and reaction time variables, on the COD removal in pharmaceutical wastewater was investigated. The results of the catalyst analysis illustrated that the synthesis of catalyst was successful. Also, the proposed optimization of the model based on the correlation coefficient (R2=0.99), is quadratic. Optimal conditions of process were pH 6.9, reaction time 79 min, and nanocomposite dose equal to 0.5 g/L. At optimal conditions, 68% of the initial COD was removed. Adsorption and photolysis mechanisms are much less efficient than the photocatalytic process. In this study, the soluble COD decreased from 3100 mg/L to 992 mg/L. The effluent from this system can be discharged to the municipal wastewater collection system.


Chen, Z., Hanna, S. L., Redfern, L. R., Alezi, D., Islamoglu, T. & Farha, O. K. 2019. Reticular chemistry in the rational synthesis of functional zirconium cluster-based MOFs. Coordination Chemistry Reviews, 386, 32-49.
Dey, C., Kundu, T., Biswal, B. P., Mallick, A. & Banerjee, R. 2014. Crystalline metal-organic frameworks (MOFs): synthesis, structure and function. Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 70, 3-10.
Du, J., Zhang, J., Yang, T., Liu, R., Li, Z., Wang, D., et al. 2020. The research on the construction and the photocatalytic performance of BiOI/NH2-MIL-125(Ti) composite. Catalysts, 11, 24.
Feng, Y., Wang, H., Zhang, S., Zhao, Y., Gao, J., Zheng, Y., et al. 2019. Antibodies@ MOFs: an in vitro protective coating for preparation and storage of biopharmaceuticals. Advanced Materials, 31, 1805148.
Fent, K., Weston, A. A. & Caminada, D. 2006. Ecotoxicology of human pharmaceuticals. Aquatic Toxicology, 76, 122-159.
Hao, R., Wang, G., Tang, H., Sun, L., Xu, C. & Han, D. 2016. Template-free preparation of macro/mesoporous g-C3N4/TiO2 heterojunction photocatalysts with enhanced visible light photocatalytic activity. Applied Catalysis B: Environmental, 187, 47-58.
Hu, L., Yan, J., Liao, M., Xiang, H., Gong, X., Zhang, L., et al. 2012. An optimized ultraviolet‐a light photodetector with wide‐range photoresponse based on ZnS/ZnO biaxial nanobelt. Advanced Materials, 24, 2305-2309.
Ji, H., Chang, F., Hu, X., Qin, W. & Shen, J. 2013. Photocatalytic degradation of 2, 4, 6-trichlorophenol over
g-C3N4 under visible light irradiation. Chemical Engineering Journal, 218, 183-190.
Jo, W. K., Kumar, S., Isaacs, M. A., Lee, A. F. & Karthikeyan, S. 2017. Cobalt promoted TiO2/GO for the photocatalytic degradation of oxytetracycline and Congo Red. Applied Catalysis B: Environmental, 201, 159-168.
Kashi, G. & Hydarian, N. 2015. Optimization electrophotocatalytic removal of sulfanilamide from aqueous water by taguchi model. Journal of Mathematics, 2015, 86-98.
Kim, S. N., Kim, J., Kim, H. Y., Cho, H. Y. & Ahn, W. S. 2013. Adsorption/catalytic properties of MIL-125 and NH2-MIL-125. Catalysis Today, 204, 85-93.
Krishnakumar, B., Subash, B. & Swaminathan, M. 2012. AgBr–ZnO–An efficient nano-photocatalyst for the mineralization of Acid Black 1 with UV light. Separation and Purification Technology, 85, 35-44.
Kumar, A., Kumar, A., Sharma, G., Ala'a, H., Naushad, M., Ghfar, A. A., et al. 2018. Quaternary magnetic BiOCl/g-C3N4/Cu2O/Fe3O4 nano-junction for visible light and solar powered degradation of sulfamethoxazole from aqueous environment. Chemical Engineering Journal, 334, 462-478.
Kumar, A., Kumar, A., Sharma, G., Naushad, M., Stadler, F. J., Ghfar, A. A., et al. 2017. Sustainable nano-hybrids of magnetic biochar supported g-C3N4/FeVO4 for solar powered degradation of noxious pollutants-synergism of adsorption, photocatalysis & photo-ozonation. Journal of Cleaner Production, 165, 431-451.
Kousha, M., Tavakoli, S., Daneshvar, E., Vazirzadeh, A., Bhatnagar, A. 2015. Central composite design optimization of Acid Blue 25 dye biosorption using shrimp shell biomass. Journal of Molecular Liquids, 207, 266-273.
Ma, Q., Zhang, H., Guo, R., Li, B., Zhang, X., Cheng, X., et al. 2018. Construction of CuS/TiO2 nano-tube arrays photoelectrode and its enhanced visible light photoelectrocatalytic decomposition and mechanism of penicillin G. Electrochimica Acta, 283, 1154-1162.
Mateen, Q. S., Khan, S. U., Islam, D. T., Khan, N. A. & Farooqi, I. H. 2020. Copper (II) removal in a column reactor using electrocoagulation: parametric optimization by response surface methodology using central composite design. Water Environment Research, 92, 1350-1362.
Mehralipour, J. & Kermani, M. 2021. Ultrasonic coupling with electrical current to effective activation of Persulfate for 2, 4 Dichlorophenoxyacetic acid herbicide degradation: modeling, synergistic effect and a by-product study. Journal of Environmental Health Science and Engineering, 19, 625-639.
Oh, W. D., Lok, L. W., Veksha, A., Giannis, A. & Lim, T. T. 2018. Enhanced photocatalytic degradation of bisphenol A with Ag-decorated S-doped g-C3N4 under solar irradiation: performance and mechanistic studies. Chemical Engineering Journal, 333, 739-749.
Olgun, Ö. B., Palas, B., Atalay, S. & Ersöz, G. 2021. Photocatalytic oxidation and catalytic wet air oxidation of real pharmaceutical wastewater in the presence of Fe and LaFeO3 doped activated carbon catalysts. Chemical Engineering Research and Design, 171, 421-432.
Oschatz, M., Pre, P., Dörfler, S., Nickel, W., Beaunier, P., Rouzaud, J. N., et al. 2016. Nanostructure characterization of carbide-derived carbons by morphological analysis of transmission electron microscopy images combined with physisorption and Raman spectroscopy. Carbon, 105, 314-322.
Oveisi, M., Asli, M. A. & Mahmoodi, N. M. 2018. MIL-Ti metal-organic frameworks (MOFs) nanomaterials as superior adsorbents: synthesis and ultrasound-aided dye adsorption from multicomponent wastewater systems. Journal of Hazardous Materials, 347, 123-140.
Pudukudy, M., Hetieqa, A. & Yaakob, Z. 2014. Synthesis, characterization and photocatalytic activity of annealing dependent quasi spherical and capsule like ZnO nanostructures. Applied Surface Science, 319, 221-229.
Saeedi, S., Godini, H., Almasian, M., Shams-Khorramabadi, G., Kamarehie, B., Mostafaie, P., et al. 2015. Photocatalytic degradation of phenol in water solutions using ZnO nanoparticles immobilized on glass. Journal of Advances in Environmental Health Research, 3, 204-213.
Senthilraja, A., Subash, B., Krishnakumar, B., Swaminathan, M. & Shanthi, M. 2014. Novel Sr–Au–ZnO: synthesis, characterization and photocatalytic activity. Superlattices and Microstructures, 75, 701-715.
Shahbeig, H., Mehrnia, M. R., Mohammadi, A. R., Moghaddam, P. E. & Rouini, M. R. 2017. Pharmaceutical wastewater treatment using membrane bioreactor‐ozonation system. Water and Environment Journal, 31, 57-63.
Shi, S., Gondal, M., Al-Saadi, A., Fajgar, R., Kupcik, J., Chang, X., et al. 2014. Facile preparation of g-C3N4 modified BiOCl hybrid photocatalyst and vital role of frontier orbital energy levels of model compounds in photoactivity enhancement. Journal of Colloid and Interface Science, 416, 212-219.
Su, Z., Zhang, B., Shi, J., Tan, D., Zhang, F., Liu, L., et al. 2019. An NH2-MIL-125(Ti)/Pt/gC3N4 catalyst promoting visible-light photocatalytic H2 production. Sustainable Energy and Fuels, 3, 1233-1238.
Talwar, S., Chaudhary, P., Sangal, V. K. & Verma, A. 2019. Study of degradation of pharmaceutical drug cetirizine using TiO2 photocatalysis. Sustainable Engineering, 30, 303-310.
Vayssieres, L. 2003. Growth of arrayed nanorods and nanowires of ZnO from aqueous solutions. Advanced Materials, 15, 464-466.
Wang, J. & Wang, S. 2016. Removal of pharmaceuticals and personal care products (PPCPs) from wastewater: a review. Journal of Environmental Management, 182, 620-640.
Wen, J., Xie, J., Chen, X. & Li, X. 2017. A review on g-C3N4-based photocatalysts. Applied Surface Science, 391, 72-123.
Wu, C. 2014. Synthesis of Ag2CO3/ZnO nanocomposite with visible light-driven photocatalytic activity. Materials Letters, 136, 262-264.
Wood, A., Giersig, M., Mulvaney, P. 2001. Fermi level equilibration in quantum dot− metal nanojunctions. The Journal of Physical Chemistry B, 105(37), 8810-8815.
Yang, Z., Xu, X., Liang, X., Lei, C., Cui, Y., Wu, W., et al. 2017. Construction of heterostructured MIL-125/Ag/g-C3N4 nanocomposite as an efficient bifunctional visible light photocatalyst for the organic oxidation and reduction reactions. Applied Catalysis B: Environmental, 205, 42-54.
Yue, K., Zhang, X., Jiang, S., Chen, J., Yang, Y., Bi, F., et al. 2021. Recent advances in strategies to modify MIL-125 (Ti) and its environmental applications. Journal of Molecular Liquids, 335, 116108.
Zhang, W., Zhou, L. & Deng, H. 2016. Ag modified g-C3N4 composites with enhanced visible-light photocatalytic activity for diclofenac degradation. Journal of Molecular Catalysis A: Chemical, 423, 270-276.
Zhang, Y., Wu, J., Deng, Y., Xin, Y., Liu, H., Ma, D., et al. 2017. Synthesis and visible-light photocatalytic property of Ag/GO/g-C3N4 ternary composite. Materials Science and Engineering: B, 221, 1-9.