Preparation, characterization and photocatalytic degradation of methylene blue by Fe3+ doped TiO2 supported on natural zeolite using response surface methodology

Document Type: Research Paper


Department of Chemical Engineering, Faculty of Engineering, University of Isfahan, Isfahan, Iran


The photocatalytic degradation of methylene blue was investigated with TiO2 and Fe2O3 nanoparticles supported on natural zeolite. The synthesized photocatalyst was characterized by XRD, XRF, FT-IR, EDX, FE-SEM, and BET analyses. The results of XRD, FT-IR, and EDX confirmed the successful loading of Fe3+ doped TiO2 nanoparticles on natural zeolite. Further, the FE-SEM results confirmed the deposition of TiO2/Fe2O3 on the zeolite, with the approximate particle size being 52.3 nm. According to the XRF results, the synthesized nanoparticles had Fe3+/TiO2 molar ratios of 0.06 in the synthesized photocatalyst. Based on BET analysis, the surface area of TiO2/Fe3+/natural zeolite was about 112.69 m2/g.  The effects of operational factors such as pH (6-10), dye concentration (25-75 mg/L) and H2O2 concentration (10-40 mg/L) were considered and optimized via response surface methodology utilizing Box-Behnken design. The optimization results indicated that the maximum percentage of degradation was achieved at a dye concentration of 25 mg/L, initial pH of 10, and H2O2 concentration of 40 mg/L with a 90 min irradiation time and a 1 g/l photocatalyst concentration. The dye degradation efficiency reached 92% under this optimum condition.


Main Subjects

[1] Alimohammadi, Z., Younessi, H., Bahramifar, N. (2016). Desorption reactive red 198 from activated carbon prepared from walnut shells: Effects of temperature, sodium carbonate concentration and organic solvent dose. Environmental science and technology, 3, 137-141.

[2] Yang, Y., Xu, L., Wang, H., Wang, W., Zhang, L. (2016). TiO2/graphene porous composite and its photocatalytic degradation of methylene blue. Materials and design, 108, 632-639.

[3] Bhuyan, B., Paul, B., Dhar, S. S., Vadivel, S. (2017). Facile hydrothermal synthesis of ultrasmall W18O49 nanoparticles and studies of their photocatalytic activity towards degradation of methylene blue. Materials chemistry and physics, 188, 1-7.

[4] Asl, M. I., Ghazi, M. M., Jahangiri, M. (2016). Synthesis, characterization and degradation activity of Methyl orange Azo dye using synthesized CuO/α-Fe2O3 nanocomposite, Advances in Environmental Technology, 2(3), 143-151.

[5] Dariani, R. S., Esmaeili, A., Mortezaali, A., Dehghanpour, S. (2016). Photocatalytic reaction and degradation of methylene blue on TiO2 nano-sized particles. Optik-international journal for light and electron optics, 127(18), 7143-7154.

[6] Bian, X., Hong, K., Liu, L., Xu, M. (2013). Magnetically separable hybrid CdS-TiO2-Fe3O4 nanomaterial: Enhanced photocatalystic activity under UV and visible irradiation. Applied sSurface science, 280, 349-353

[7] Asvadi, F., Fallah, N., Elyasi, S., Mohseni, F. (2017). Investigation of affecting operational parameters in photocatalytic degradation of reactive red 198 with TiO2: optimization through response surface methodology, Advances in Environmental Technology, 2(4) 169-177.

[8] Arimi, A., Farhadian, M., Solaimany Nazar, A.R., Homayoonfal, M. (2016). Assessment of operating parameters for photocatalytic degradation of a textile dye by Fe2O3/TiO2/clinoptilolite nanocatalyst using Taguchi experimental design. Research on Chemical Intermediates, 42, 4021-4040.

[9] Liu, H., Shon, H. K., Sun, X., Vigneswaran, S., Nan, H. (2011). Preparation and characterization of visible light responsive Fe2O3–TiO2 composites. Applied surface science, 257(13), 5813-5819.

[10] Yao, K., Basnet, P., Sessions, H., Larsen, G. K., Murph, S. E. H., Zhao, Y. (2016). Fe2O3–TiO2 core–shell nanorod arrays for visible light photocatalytic applications. Catalysis today, 270, 51-58.

[11] Niu, P., Hao, J. (2013). Photocatalytic degradation of methyl orange by titanium dioxide-decatungstate nanocomposite films supported on glass slides. Colloids and Surfaces A: Physicochemical and engineering aspects, 431, 127-132.

[12] Song, J., Xu, Z., Liu, W., Chang, C. T. (2016). KBrO3 and graphene as double and enhanced collaborative catalysts for the photocatalytic degradation of amoxicillin by UVA/TiO2 nanotube processes. Materials science in semiconductor processing, 52, 32-37.

[13] Zheng, R., Zhang, H., Liu, Y., Wang, X., Han, Z. (2017). Ag-ligand modified tungstovandates and their efficient catalysis degradation properties for methylene blue. Journal of solid state chemistry, 246, 258-263.

[14] Liu, F., Jamal, R., Wang, Y., Wang, M., Yang, L., Abdiryim, T. (2017). Photodegradation of methylene blue by photocatalyst of DAD type polymer/functionalized multi-walled carbon nanotubes composite under visible-light irradiation. Chemosphere, 168, 1669-1676.

[15] Park, J. H., Jang, I., Song, K., Oh, S. G. (2013). Surfactants-assisted preparation of TiO2–Mn oxide composites and their catalytic activities for degradation of organic pollutant. Journal of physics and chemistry of solids, 74(7), 1056-1062

[16] Amini, M., Pourbadiei, B., Ruberu, T. P. A., Woo, L. K. (2014). Catalytic activity of MnO x/WO3 nanoparticles: synthesis, structure characterization and oxidative degradation of methylene blue. New journal of chemistry, 38(3), 1250-1255.

[17] Zhang, L., Nie, Y., Hu, C., Hu, X. (2011). Decolorization of methylene blue in layered manganese oxide suspension with H2O2. Journal of hazardous materials, 190(1-3), 780-785.

[18] Mehrabian, M., Esteki, Z. (2017). Degradation of methylene blue by photocatalysis of copper assisted ZnS nanoparticle thin films. Optik-international journal for light and electron optics, 130, 1168-1172.

[19] Wang, C., Shi, H., Li, Y. (2011). Synthesis and characteristics of natural zeolite supported Fe3+-TiO2 photocatalysts. Applied surface science, 257(15), 6873-6877.

[20] Korkuna, O., Leboda, R., Skubiszewska-Zie, J., Vrublevs’ka, T., Gun’ko, V. M., Ryczkowski, J. (2006). Structural and physicochemical properties of natural zeolites: clinoptilolite and mordenite. Microporous and mesoporous materials, 87(3), 243-254.

[21] Battisha, I. K., Afify, H. H., Ibrahim, M. (2006). Synthesis of Fe2O3 concentrations and sintering temperature on FTIR and magnetic susceptibility measured from 4 to 300 K of monolith silica gel prepared by sol–gel technique. Journal of magnetism and magnetic materials, 306(2), 211-217.

[22] Kannaiyan, D., Kochuveedu, S. T., Jang, Y. H., Jang, Y. J., Lee, J. Y., Lee, J., Kim, D. H. (2010). Enhanced photophysical properties of nanopatterned titania nanodots/nanowires upon hybridization with silica via block copolymer templated sol-gel process. Polymers, 2(4), 490-504.

[23] Sohrabi, M. R., Khavaran, A., Shariati, S., Shariati, S. (2017). Removal of Carmoisine edible dye by Fenton and photo Fenton processes using Taguchi orthogonal array design. Arabian journal of chemistry, 10, S3523-S3531

[24] Nadarajan, R., Bakar, W. A. W. A., Ali, R., Ismail, R. (2016). Photocatalytic degradation of 1, 2-dichlorobenzene using immobilized TiO2/SnO2/WO3 photocatalyst under visible light: application of response surface methodology. Arabian journal of chemistry, 11(1), 34-47.

[25] Lambropoulou, D., Evgenidou, E., Saliverou, V., Kosma, C., & Konstantinou, I. (2017). Degradation of venlafaxine using TiO2/UV process: kinetic studies, RSM optimization, identification of transformation products and toxicity evaluation. Journal of hazardous materials, 323, 513-526.

[26] Devadi, M. A. H., Krishna, M., Murthy, H. N., & Sathyanarayana, B. S. (2014). Statistical optimization for photocatalytic degradation of methylene blue by Ag-TiO2 nanoparticles. Procedia materials science, 5, 612-621.