Adsorption of Methylene Blue (MB) Dye Using NiO-SiO2NPs Synthesized from Aqueous Solutions: Optimization, Kinetic and Equilibrium Studies

Document Type : Research Article


Department of Chemistry Omidiyeh Branch, Islamic Azad University, Omidiyeh, I.R. IRAN


The applicability of the synthesized NiO-SiO2NPs as a novel adsorbent for eliminating Methylene Blue (MB) dye from aqueous media was investigated. Various techniques including BET, FT-IR, XRD, SEM, and EDS were used to characterize this novel adsorbent. The investigation showed the applicability of NiO-SiO2NPs as an available, suitable, and low-cost adsorbent for the proper removal of MB dye from aqueous media. The effect of pH, adsorbent dosage (dose), initial MB dye concentration (C0) contact time (tc), and temperature (T) on the removal percentage (Ad%) of MB dye onto NiO-SiO2NPs was studied and the optimum value of each factor was determined (pH=7, dose=0.1g, C0=30 mg/L, tc=15 min, and T=298.0 K). The experimental equilibrium data were fitted to the conventional isotherm models and accordingly, Langmuir isotherm has good applicability for the explanation of experimental data with maximum adsorption capacity of the MB dye for SiO2 and NiO-SiO2NPs were roughly 117.0 and 140.0 mg/g respectively. Kinetics experiments were performed to investigate the adsorption kinetics, the pseudo-second-order kinetics coincided quite with the kinetic results. The thermodynamic behavior of the adsorption process was studied by considering the effect of temperature on the adsorption capacity, where the results showed that the process is spontaneous (DG0ad < 0) at the used temperature range and exothermic (DHad0 < 0) with DS0ad < 0. Based on the magnitude of DH0ad < 0, it was concluded that the studied adsorption process is a physisorption one.


Main Subjects

[2] Senthilkumar R., Reddy Prasad D.M., Govindarajan L., Saravanakumar K., Naveen Prasad B.S., Improved Sorption of Reactive Black 5 by Date Seed-Derived Biochar: Isotherm, Kinetic, and Thermodynamic Studies, Separa. Sci. Technol., 54(15): 2351-2360 (2019).
[3] Jawad A.H., Abdulhameed A.S., Mastuli M.S., Acid-Factionalized Biomass Material for Methylene Blue Dye Removal: A Comprehensive Adsorption and Mechanism Study, J. Taibah, Univ. Sci., 14(1): 305–313 (2020).
[4] Jawad A.H., Abdulhameed A.S., Statistical Modeling of Methylene Blue Dye Adsorption by High Surface Area Mesoporous Activated Carbon from Bamboo Chip Using KOH-Assisted Thermal Activation, Energ. Ecol. Environ., 5(5): 1-17 (2020).
[5] Azari A., Nabizadeh R., Nasseri S., Mahvi A.H., Mesdaghinia A.R., Comprehensive Systematic Review and Meta-Analysis of Dyes Adsorption
by Carbon-Based Adsorbent Materials: Classification and Analysis of Last Decade Studies, Chemosphere., 250: 126238- 126246 (2020).
[6] Ramezani F., Zare-Dorabei R., J. Simultaneous Ultrasonic-Assisted Removal of Malachite Green and Methylene Blue from Aqueous Solution by Zr-SBA-15, Polyhedron., 166: 153-162 (2019).
[7] Daraei H., Mittal A., Investigation of Adsorption Performance of Activated Carbon Prepared from Waste Tire for the Removal of Methylene Blue Dye from Wastewater, J. Desal. Water. Treat., 90: 294–298 (2017).
[8] Jawad A.H., Firdaus Hum N.N.M., Abdulhameed A.S., Mohd Ishak M.Z., Mesoporous Activated Carbon from Grass Waste Via H3PO4-Activation for Methylene Blue Dye Removal: Modelling, Optimisation, and Mechanism Study, Int. J. Environ. Anal. Chem., 99: 1-20 (2020).
[9] Jawad A.H., Abdulhameed A.S., Surip S.V., Sabar S., Adsorptive Performance of Carbon Modified Chitosan Biopolymer for Cationic Dye Removal: Kinetic, Isotherm, Thermodynamic, and Mechanism Study, Int. J. Environ. Anal. Chem., 99: 1-18 (2020).
[10] Abdulhameed A.S., Firdaus Hum N.N.M., Rangabhashiyam S., Jawad A.H., Wilson L.D.,  Yaseen Z.M., Al-Kahtani A.A., ALOthman Z.A., Statistical Modeling and Mechanistic Pathway for Methylene Blue Dye Removal by High Surface Area and Mesoporous Grass-Based Activated Carbon Using K2CO3 Activator, J. Environ. Chem. Eng., 9: 105530(2021). 
[11] Saravanakumar K., Naveen Prasad B.S., Senthilkumar R., Manickam S., Reddy Prasad D.M., Gajendiran V., Batch and Column Arsenate Sorption Using Turbinaria ornata Seaweed Derived Biochar: Experimental Studies and Mathematical Modeling, Chemistry Select., 5: 3661-3668 (2020). 
[12] Venkata Ratnam M., Nagamalleswara Rao K., Meena V., Methylene Blue Adsorption by Magnesium Oxide Nanoparticles Immobilized with Chitosan (CS-MgONP): Response Surface Methodology, Isotherm, Kinetics and Thermodynamic Studies, Iran. J. Chem. Chem. Eng. (IJCCE), 39(6): 29-42 (2020).
[13] Venkata Ratnam M., Punugoti T., Sasi Kala N., Kanidarapu N.R., Meena V., Modelling and Optimization of Methylene Blue Adsorption onto Magnesium Oxide Nanoparticles loaded onto Activated Carbon (MgONP-AC): Response Surface Methodology and Artificial Neural Networks, Materials. Today. Proceedings., 18: 4932–4941 (2019).
[14] Venkata Ratnam M., Karthikeyan C., Nagamalleswara Rao K., Meena, V., Magnesium Oxide Nanoparticles for Effective Photocatalytic Degradation of Methyl Red Dye in Aqueous Solutions: Optimization Studies Using Response Surface Methodology, Materials. Today. Proceedings., 26(2): 2308-2313 (2020).
[15] Marahel F., Mombini Godajdar B., Niknam L., Faridnia M., Pournamdari E., Mohammad Doost, S., Ultrasonic Assisted Adsorption of Methylene Blue Dye and Neural Network Model for Adsorption of Methylene Blue Dye by Synthesized Mn-doped PbS Nanoparticles, Int. J. Environ. Anal. Chem., 101(5): 1-22 (2021).
[16] Reghioua A., Barkat D., Jawad A.H., Abdulhameed A.S., Al-Kahtani A.A., ALOthman Z.A., Parametric Optimization by Box–Behnken Design for Synthesis of Magnetic Chitosan-Benzil/ZnO/Fe3O4 Nanocomposite and Textile Dye Removal, J. Environ. Chem. Eng., 9: 105166 (2021). 
[17] Reghioua A., Barkat D., Jawad A.H., Abdulhameed A.S., Khan M.R., Synthesis of Schiff's Base Magnetic Crosslinked Chitosan-Glyoxal/ZnO/Fe3O4 Nanoparticles for Enhanced Adsorption of Organic Dye: Modeling and Mechanism Study, Sustaina. Chem. Pharmac., 20: 100379 (2021).  
[18] Nourozi S., Zare-Dorabei R., Highly Efficient Ultrasonic-Assisted Removal of Methylene Blue from Aqueous Media By Magnetic Mesoporous Silica: Experimental Design Methodology, Kinetic and Equilibrium Studies, J. Desal. Water. Treat., 85: 184-196 (2017).
[19] Senthilkumar R., Reddy Prasad D.M., Govindarajan L., Saravanakumar K., Naveen Prasad B.S., Synthesis of Green Marine Algal-Based Biochar for Remediation of Arsenic(V) From Contaminated Waters in Batch and Column Mode of Operation, Int. J. Phytoremedia., 22(3): 1-18 (2019).
[20] Zhao G., Zhao Q., Jin X., Wang H., Zhang K., Li M., Wang N., Zhao W., Meng S., Mu R., Preparation of a Novel Hafnium-Loaded Fe3O4@SiO2 Superparamagnetic Nanoparticles and its Adsorption Performance for Phosphate in Water, J. Desal. Water. Treat., 216: 188-198 (2021).
[21] Sogut E.G., Ergan E., Cilic N.C., Donmaz H., Methylene Blue Adsorption from Aqueous Solution by Functionalized Perlites: An Experimental and Computational Chemistry Study, J. Desal. Water. Treat., 217: 391-410 (2021).
[22] Naushad Mu., Sharma G., Alothman A., Photodegradation of Toxic Dye Using Gum Arabic-Crosslinkedpoly (acrylamide) / Ni(OH)2 / FeOOH Nanocomposites Hydrogel. J. Clean. Production., 241: 112863 (2019).
[23] Arora C., Soni S., Sahu S., Mittal J., Kumar P., Bajpai P.K., Iron Based Metal Organic Framework for Efficient Removal of Methylene Blue Dye from Industrial Waste, J. Molecular. Liquids., 284: 373-352 (2019).
[24] Abdul Mubarak N.S., Bahrudin N.N., Jawad A.H., Hameed B.H., Sabar S., Microwave Enhanced Synthesis of Sulfonated Chitosan-Montmorillonite for Effective Removal of Methylene Blue, J. Polymers. Environment, 29(12): 4027- 4039 (2021).
[25] Liu J., Peng Z.Y., Huang H.W., Li Y., Wu M., Ke X.X., Tendeloo G.V., Su B.L., 2D ZnO Mesoporous Single-Crystal Nanosheets With 0001 Polar Facets for the Depollution of Cationic Dye Molecules by Highly Selective Adsorption and Photocatalytic Decomposition, J. Appl. Catal. B: Environ., 181: 138-145 (2016). 
[27] Tang R., Dai C., Li C., Liu W., Gao S., Wang C., Removal of Methylene Blue from Aqueous Solution Using Agricultural Residue Walnut Shell: Equilibrium, Kinetic, and Thermodynamic Studies, J. Chemistry., 10: 1155-1165 (2017).
[28] Auta M., Hameed B.H., Chitosan-Clay Composite as Highly Effective and Low-Cost Adsorbent for batch and Fixed-Bed Adsorption of Methylene Blue, J. Chem. Engineering., 237: 350-361 (2014).
[29] Feng J., Wang Y., Zou L., Li B., He X., Ren Y., Lv Y., Fan Z., Synthesis of Magnetic Zno/ZnFe2O4 by a Microwave Combustion Method and its high Rate of Adsorption of Methylene Blue, J. Colloid. Interf. Sci., 438: 318-322 (2015).
[30] Malek N.N.A., Jawad A.H., Abdulhameed A.S., New Magnetic Schiff's Base-Chitosan-Glyoxal/Fly Ash/Fe3O4 Biocomposite for the Removal of Anionic Azo Dye: An Optimized Process, Int. J. Biolog. Macromole., 146: 530-539 (2020).
[31] You K.E., Park J.H., Kim Y.C., Oh S.G., Magnetic Properties and Dye Adsorption Capacities of Silica - Hematite Nanocomposites with Well - Defined Structures Prepared in Surfactant Solutions, J. Solid. State. Sci., 33: 38-44 (2014).
[32] Hajati S., Ghaedi M., Mazaheri H., Removal of Methylene Blue from Aqueous Solution by Walnut Carbon: Optimization Using Response Surface Methodology, J. Desal. Water. Treat., 57: 3179-3193 (2016).
[33] Zare Khafri H., Ghaedi M., Asfaram A., Safarpoor M., Synthesis and Characterization of ZnS:Ni-NPs Loaded on AC Derived from Apple Tree Wood and their Applicability for the Ultrasound Assisted Comparative Adsorption of Cationic Dyes Based on the Experimental Design, Ultrason Sonochem., 38: 371 (2017).
[34] Wei W., Yang L., Zhong W.H., Li S.Y., Cui J., Wei Z.G., Fast Removal of Methylene Blue from Aqueous Solution by Adsorption onto Poorly Crystalline Hydroxyapatite Nanoparticles, Nanomaterials and Biostructures., 10: 1343-1363 (2015).
[35] Xiao N., Adsorptive Removal and Kinetics of Methylene Blue from Aqueous Solution Using NiO/MCM-41 composite, Phys. E: Low-Dimens, Syst. Nanostruct., 65: 4-12 (2015).
[36] Ali L., Zhang C., Chen Z., Removal of Methylene Blue from Aqueous Solution by a Solvothermal-Synthesized Graphene/Magnetite Composite, J. Hazard. Mater., 192: 1515–1524 (2011).
[37] Pathania D., Sharma S., Singh P., Removal of Methylene Blue by Adsorption onto Activated Carbon Developed from Ficus Carica Bast, Arab. J. Chem., 10: 1445–1451 (2017).
[38] Yang Y., Xie Y., Pang L., Li M., Song X., Wen J., Zhao H., Preparation of Reduced Graphene Oxide/Poly(Acrylamide) Nanocomposite and Its Adsorption of Pb2+ And Methylene Blue, Langmuir., 29: 10727-10736 (2013).
[39] Dehghani M.H., Dehghan A., Alidadi H., Dolatabadi M., Mehrabpour M., Converti A., Removal of Methylene Blue Dye from Aqueous Solutions by a New Chitosan/Zeolite Composite from Shrimp Waste: Kinetic and Equilibrium Study, Korean. J. Chem. Eng., 34(6): 1699-1707 (2017).
[40] Mahini R., Esmaeili H., Foroutan R., Adsorption of Methyl Violet from Aqueous Solution Using Brown Algae Padina Sanctae-Crucis, Turk. J. Biochem., 24: 1-12 (2018). 
[41] Zubair M., Ihsanullah I., Jarrah N., Khalid A., Manzar M.S., Kazeem T.S., Al- Harthi M.A., Starch-NiFe-Layered Double Hydroxide Composites: Efficient Removal of Methyl Orange from Aqueous Phase, J. Molecular. Liquids., 249: 254–264 (2018).
[42] Fu J., Chen Z., Wang M., Liu S., Zhang J., Han R., Xu Q., Adsorption of Methylene Blue by a High-Efficiency Adsorbent (Polydopamine Microspheres): Kinetics, Isotherm, Thermodynamics and Mechanism Analysis, Chem. Eng. J., 259: 53-61 (2015).
[43] Ghaedi M., Heidarpour S., Nasiri S., Kokhdan S., Daneshfar A., Brazesh B., Comparison of Silver and Palladium Nanoparticles Loaded on Activated Carbon for Efficient Removal of Methylene Blue: Kinetic and Isotherm Study of Removal Process, J. Powder. Technol., 228: 18-25 (2012).
[45] Aarfane A., Salhi A., El Krati M., Tahiri S., Monkade M., Lhadi E.K., Bensitel M., Kinetic and Thermodynamic Study of the Adsorption of Red195 and Methylene Blue Dyes on Fly Ash and Bottom Ash in Aqueous Medium, J. Mater. Environ. Sci., 5: 1927-1939 (2014).
[47] Yagub M.T., Sen T.K., Ang H.M., Equilibrium, Kinetics, and Thermodynamics of Methylene Blue Adsorption by Pine Tree Leaves, J. Water. Air. Soil. Pollut., 223: 5267–5282 (2012).
[48] Sabri A.A., Albayati T.M., Alazawi R.A., Synthesis of Ordered Mesoporous SBA-15 and Its Adsorption of Methylene Blue, Korean. J. Chem. Eng., 32(9): 1835-1841 (2015).