Response surface method Optimization of the Dyes Degradation using Zero-Valent Iron based Bimetallic Nanoparticle on the Bentonite Clay Surface

Document Type : Original Research Paper


1 Department of Chemistry, Islamic Azad University, North Tehran Branch, P.O. Box 1913674711, Tehran, Iran

2 Department of Chemistry College of Sciences, University of Birjand, P.O. Box 97175-615, Birjand, Iran


Immobilizing of zero-valent iron in mono- and bi-metallic systems on the bentonite clay surface as new nanocatalyst were synthesized and used to degrade model acidic dyes from aqueous media. The Fourier-transform infrared spectroscopy, scanning electron microscopy-energy dispersive X-ray spectroscopy, transmission electron microscopy, X-ray diffraction, and Brunauer-Emmett-Teller analysis were used to characterize the synthesized nanocomposites, which demonstrated successful loading of nanoscale Fe-Cu bi-metallic onto bentonite support. Different variables controlling the congo red, methyl orange and methyl red dyes degradation using zero-valent iron based bimetallic nanoparticle on the bentonite clay surface as new nanocatalyst were concurrently optimized through an experimental design. Basic evaluations proved the nanocatalyst quantity, medium pH, initial dye concentration, and contact time as the most important variables influencing the degradation phenomenon and hence a response surface methodology based on the central composite design was conducted to determine the relations between the variables and the degradation efficiencies. The statistical factors (e.g. R2 and F-value) of the derived models were considered. Using response surface plots obtained through the models, the effects of the variables on the degradation efficiencies for each dye were assessed. Also, the Nelder-Mead non-linear optimizations were performed and the optimal degradation efficiencies at a 95% confidence level were determined which were found to comply with the respective experimental response values.


Allègre, C., Moulin, P., Maisseu, M. and Charbit, F. (2006). Treatment and reuse of reactive dyeing effluents. J. Memb. Sci., 269(1-2); 15-34.
Asfaram, A., Ghaedi, M., Azqhandi, M.H.A., Goudarzi, A. and Dastkhoon, M. (2016). Statistical experimental design, least squares-support vector machine (LS-SVM) and artificial neural network (ANN) methods for modeling the facilitated adsorption of methylene blue dye. RSC Adv., 6; 40502-40516.
Bao, B., Damtie, M.M., Hosseinzadeh, A., Wei, W., Jin, J., Vo, H.N.P., Ye, J.S., Liu, Y., Wang, X.F., Yu, Z.M., Chen, Z.J., Wu, K., Frost, R.L. and Ni, B.N. (2020). Bentonite-supported nano zero-valent iron composite as a green catalyst for bisphenol A degradation: Preparation, performance, and mechanism of action. J. Environ. Manage., 260; 110105-110113.
Behbahani, M., Barati, M., Bojdi, M.K., Pourali, A.R., Bagheri, A. and Tapeh, N.A.G. (2013). A nanosized cadmium(II)-imprinted polymer for use in selective trace determination of cadmium in complex matrices. Microchim. Acta., 180; 117-1125.
Behbahani, M., Esrafili, A., Bagheri, S., Radfar, S., Kalate Bojdi, M. and Bagheri, A. (2014). Modified nanoporous carbon as a novel sorbent before solvent-based de-emulsification dispersive liquid-liquid microextraction for ultra-trace detection of cadmium by flame atomic absorption spectrophotometry. Meas. J. Int. Meas. Confed., 51; 174-181.
Belessi, V., Romanos, G., Boukos, N., Lambropoulou, D. and Trapalis, C. (2009). Removal of Reactive Red 195 from aqueous solutions by adsorption on the surface of TiO2 nanoparticles. J. Hazard. Mater., 170(2-3); 836-844.
Bojdi, M.K., Mashhadizadeh, M.H., Behbahani, M., Farahani, A., Davarani, S.S.H. and Bagheri, A. (2014). Synthesis, characterization and application of novel lead imprinted polymer nanoparticles as a high selective electrochemical sensor for ultra-trace determination of lead ions in complex matrixes. Electrochim. Acta., 136; 59-65.
Chakraborty, A., Islam, D.A. and Acharya, H. (2019). One pot synthesis of ZnO-CuO nanocomposites for catalytic peroxidase like activity and dye degradation. Mater. Res. Bull., 120; 110592-110602.
Derringer, G. and Suich, R. (1980). Simultaneous Optimization of Several Response Variables. J. Qual. Technol., 12(4); 214-219.
Diao, Z.H., Xu, X.R., Jiang, D., Kong, L.J., Sun, Y.X., Hu, Y.X., Hao, Q.W. and Chen, H. (2016). Bentonite-supported nanoscale zero-valent iron/persulfate system for the simultaneous removal of Cr(VI) and phenol from aqueous solutions. Chem. Eng. J., 302; 213-222.
Hajjaji, W., Ganiyu, S.O., Tobaldi, D.M., Andrejkovičová, S., Pullar, R.C., Rocha, F. and Labrincha, J.A. (2013). Natural portuguese clayey
Pollution, 6(3): 581-595, Summer 2020
Pollution is licensed under a "Creative Commons Attribution 4.0 International (CC-BY 4.0)"
materials and derived TiO2-containing composites used for decolouring methylene blue (MB) and orange II (OII) solutions. Appl. Clay Sci., 83-84; 91-98.
Hao, O.J., Kim, H. and Chiang, P.C. (2000). Decolorization of wastewater. Crit. Rev. Environ. Sci. Technol., 30(4); 449-505.
Jouali, A., Salhi, A., Aguedach, A., Aarfane, A., Ghazzaf, H., Lhadi, E.K., El krati, M. and Tahiri, S. (2019). Photo-catalytic degradation of methylene blue and reactive blue 21 dyes in dynamic mode using TiO2 particles immobilized on cellulosic fibers. J. Photochem. Photobiol. A Chem., 383; 112013-112021.
Karthiga, R., Kavitha, B., Rajarajan, M. and Suganthi, A. (2015). Photocatalytic and antimicrobial activity of NiWO4 nanoparticles stabilized by the plant extract. Mater. Sci. Semicond. Process., 40; 123-129.
Kurniawan, A., Sutiono, H., Indraswati, N. and Ismadji, S. (2012). Removal of basic dyes in binary system by adsorption using rarasaponin-bentonite: Revisited of extended Langmuir model. Chem. Eng. J., 189-190; 264-274.
Marković, M., Marinović, S., Mudrinić, T., Ajduković, M., Jović-Jovičić, N., Mojović, Z., Orlić, J., Milutinović-Nikolić, A. and Banković, P. (2019). Co(II) impregnated Al(III)-pillared montmorillonite–Synthesis, characterization and catalytic properties in Oxone® activation for dye degradation. Appl. Clay Sci., 182; 105276-105285.
Mittal, H. Ray, S.S. (2016). A study on the adsorption of methylene blue onto gum ghatti/TiO2 nanoparticles-based hydrogel nanocomposite. Int. J. Biol. Macromol., 88; 66-80.
Moghaddam, A.Z., Bojdi, M.K., Nakhaei, A., Ganjali, M.R., Alizadeh, T. and Faridbod, F. (2018). Ytterbium tungstate nanoparticles as a novel sorbent for basic dyes from aqueous solutions. Res. Chem. Intermed., 44; 6945-6962.
Moghaddam, A.Z., Jazi, M.E., Allahrasani, A., Ganjali, M.R. and Badiei, A. (2020). Removal of acid dyes from aqueous solutions using a new eco-friendly nanocomposite of CoFe2O4 modified with Tragacanth gum. J. Appl. Polym., Sci. 137(17); 48605-48617.
Montgomery, D.C. (2012). Design and Analysis of Experiments Eighth Edition, John Wiley & Sons Inc, Westford,.
O’Carroll, D., Sleep, B., Krol, M., Boparai, H. and Kocur, C. (2013). Nanoscale zero valent iron and bimetallic particles for contaminated site remediation. Adv. Water Resour., 51; 104-122.
Sabouri, M.R., Sohrabi, M.R. and Moghaddam, A.Z. (2020). A Novel and Efficient Dyes Degradation Using Bentonite Supported Zero-Valent Iron-Based Nanocomposites. ChemistrySelect, 5(1); 369-378.
Sahoo, A. and Patra, S. (2018). A Combined Process for the Degradation of Azo-Dyes and Efficient Removal of Aromatic Amines Using Porous Silicon Supported Porous Ruthenium Nanocatalyst. ACS Appl. Nano Mater., 1(9); 5169-5178.
Sahoo, A., Tripathy, S.K., Dehury, N. and Patra, S. (2015). A porous trimetallic Au@Pd@Ru nanoparticle system: Synthesis, characterisation and efficient dye degradation and removal. J. Mater. Chem. A, 3; 19376-19383.
Salama, A., Mohamed, A., Aboamera, N.M., Osman, T.A. and Khattab, A. (2018). Photocatalytic degradation of organic dyes using composite nanofibers under UV irradiation. Appl. Nanosci., 8; 155-161.
Shubair, T., Eljamal, O., Khalil, A.M.E., Tahara, A. and Matsunaga, N. (2018). Novel application of nanoscale zero valent iron and bimetallic nano-Fe/Cu particles for the treatment of cesium contaminated water. J. Environ. Chem. Eng., 6(4); 4253-4264.
Vijai Anand, K., Aravind Kumar, J., Keerthana, K., Deb, P., Tamilselvan, S., Theerthagiri, J., Rajeswari, V., Sekaran, S.M.S. and Govindaraju, K. (2019). Photocatalytic Degradation of Rhodamine B Dye Using Biogenic Hybrid ZnO-MgO Nanocomposites under Visible Light. ChemistrySelect, 4(17); 5178-5184.
Walsh, G.E., Bahner, L.H. and Horning, W.B. (1980). Toxicity of textile mill effluents to freshwater and estuarine algae, crustaceans and fishes. Environ. Pollution. Ser. A, Ecol. Biol., 21(3); 169-179.
Zeraatkar Moghaddam, A., Ghiamati, E., Pakar, R., Sabouri, M.R. and Ganjali, M.R. (2019). A novel and an efficient 3-D high nitrogen doped graphene oxide adsorbent for the removal of congo red from aqueous solutions. Pollution, 5; 501-514.
Zeraatkar Moghaddam, A., Ghiamati, E., Pourashuri, A. and Allahresani, A. (2018). Modified nickel ferrite nanocomposite/functionalized chitosan as a novel adsorbent for the removal of acidic dyes. Int. J. Biol. Macromol., 120; 1714-1725.