Magnetic Fe3O4 nanoparticles coated with Thiol functionalized mesoporous Silica as a novel adsorbent for Pb2+ and Ag+ removal

Document Type : Reasearch Paper


1 Department of Chemistry, Yadegar -e- Imam Khomeini (RAH) Shahre Rey Branch, Islamic Azad University, Tehran, Iran.

2 School of Chemistry, College of Science, University of Tehran, Tehran, Iran.

3 Center of Excellence in Electrochemistry, School of Chemistry, College of Science, University of Tehran, Tehran, Iran.

4 Biosensor Research Center, Endocrinology & Metabolism Molecular-Cellular Sciences Institute, Tehran University of Medical Sciences, Tehran, Iran.

5 Department of Chemistry, Alzahra University, Tehran, Iran.


Magnetic Fe3O4 nanoparticles coated with thiol functionalized mesoporous silica (TFMS) were prepared and usedas a novel adsorbent for Pb2+ and Ag+ removal. FTIR spectra confirmed the Fe3O4 nanoparticle cores coated with mesoporous silica and indicated the presence of thiol groups on the surface. XRD analyses showed that synthesized adsorbent has a face-centered cubic magnetite phase structure. The best removal results were obtained at pH=5-7 and a stirring time of 15 minutes. The lowest amount of 3M nitric acid for stripping the target species from adsorbent was 40 mL. The data was found to fit the Langmuir model, and the respective maximum capacities of the adsorbent for Pb2+ and Ag+ ionswas 1000.0 (±1.5) µg and 1111.0 (±1.2) µg of the target species per mg of the adsorbent. The developed adsorbent was successfully applied in wastewater samples.


[1]     National Library of medicine, (1996), Hazardous Substances Data Bank (HSDB).
[2]     Amini Z., Hajiaghababaei L., Shahvelayati A. S., (2018), Removal of Pb+2, Cu+2 and Ag+ cations from wastewater by modified ZnO nanoparticles with S, N-substituted thiouracil derivative. J. Elem. 23: 1179-1196.
[3]     Mahmoud M. E., Osman M. M., Hafez O. F., Hegazi A. H., Elmelegy E., (2010), Removal and preconcentration of lead (II) and other heavy metals from water by alumina adsorbents developed by surface-adsorbed-dithizone. Desalination. 251: 123-130.
[4]      Mahmoud M. E., Kenawy I. M. M., Hafez M. A. H., Lashein R. R., (2010), Removal, preconcentration and determination of trace heavy metal ions in water samples by AAS via chemically modified silica gel N-(1-carboxy-6-hydroxy) benzylidenepropylamine ion exchanger. Desalination. 250: 62-70.
[5]     Ciftci H., Yalcin H., Eren E., Olcucu A., Sekerci M., (2010), Enrichment and determination of Ni2+ ions in water samples with a diamino-4-(4-nitro-phenylazo)-1H-pyrazole (PDANP) by using FAAS. Desalination. 256: 48-53.
[6]     Chakravarty P., Sen Sarma N., Sarma H. P., (2010), Removal of lead (II) from aqueous solution using heartwood of Areca catechu powder. Desalination. 256: 16-21.
[7]     Shamsipur M., Yousefi M., Ghasemi Z., Hajiaghababaei L., Ganjali M. R., (2002), Separation and preconcentration of trace amounts of cerium (III) on octadecyl silica membrane disk modified with 1,3,5-trithiacyclohexane and its spectrophotometric determination by Arsenazo (III). Sep. sci. Technol. 15: 3525-3534.
[8]     Dubey S., Banerjee S., Upadhyay S. N., Sharma Y. C., (2017), Application of common nano-materials for removal of selected metallic species from water and wastewaters: A critical.  J. Molec. Liq. 240: 656–677.
[9]     Vojoudi H., Badiei A., Banaei A., Bahar S., Karimi S., Ziarani G. M., Ganjali M. R., (2017), Extraction of gold, palladium and silver ions using organically modified silica-coated magnetic nanoparticles and silica gel as a sorbent. Microchim. Acta. 184: 3859-3866.
[10] Vojoudi H., Badiei A., Amiri A., Banaei A., Mohammadi Ziarani G., Schenk-Joß K., (2018), Efficient device for the benign removal of organic pollutants from aqueous solutions using modified mesoporous magnetite nanostructures. J. Phys. Chem. Solids. 113: 210-219.
[11] Vojoudi H., Badiei A., Amiri A., Banaei A., Mohammadi Ziarani G., Schenk-Joß K., (2018), Pre-concentration of Zn(II) ions from aqueous solutions using meso-porous pyridine-enrobed magnetite nanostructures. Food Chem. 257: 189-195.
[12] Vojoudi H., Badiei A., Bahar S., Mohammadi Ziarani G., Faridbod F., Ganjali M. R., (2017), A new nano-sorbent for fast and efficient removal of heavy metals from aqueous solutions based on modification of magnetic mesoporous silica nanospheres. J. Magn. Magn. Mater. 441: 193-203.
[13]  Saad A. H. A., Azzam A. M., El-Wakeel S. T., Mostafa B. B., Abd El-latif M. B., (2018), Removal of toxic metal ions from wastewater using ZnO@Chitosan core-shell nanocomposite. Environ. Nanotech. Monitor. Manage. 9: 67-75.
[14] Wang X., Guo Y., Yang L., Han M., Zhao J., Cheng X., (2012), Nanomaterials as sorbents to remove heavy metal Ions in wastewater treatment. J. Environ. Anal. Toxicol. 2: 2-7.
[15] Kanani N., Bayat M., Shemirani F., Ghasemi J. B., Bahrami Z., Badiei A., (2018), Synthesis of magnetically modified mesoporous nanoparticles and their application in simultaneous determination of Pb(II), Cd(II) and Cu(II). Res. Chem. Intermed. 44: 1689–1709.
[16] Poursaberi T., Ghanbarnejad H., Akbar V., (2013), Selective magnetic removal of Pb(II) from aqueous solution by porphyrin linked-magnetic nanoparticles. JNS.2: 417- 426.
[17] Kakaei A., Kazemeini M., (2016), Removal of Cd (II) in water samples using modified magnetic Iron Oxide nanoparticle. Iran. J. Toxicol. 10: 9-14.
[18] Nikpassand M., Zare L., Shafaati T., (2012), Regioselective synthesis of fused azo-linked pyrazolo [4, 3-e] pyridines using nano-Fe3O4. Chin. J. Chem. 30: 604-608.
[19] Zare Fekri L., Nikpassand M., Nazari Khakshoor S., (2019), Green, effective and chromatography free synthesis of benzoimidazo [1, 2-a]pyrimidine and tetrahydrobenzo [4, 5]imidazo [1, 2-d]quinazolin-1(2H)-one and their pyrazolyl moiety using Fe3O4@SiO2@l-proline reusable catalyst in aqueous media. J. Organomet. Chem. 894: 18-27.
[20] Lam K. F., Yeung K. L., Mckay J., (2007), Selective mesoporous adsorbents for Cr2O72- and Cu2+ separation. Micropor. Mesopor. Mater. 100: 191-201.
[21] Li X. D., Zhai Q. Z., (2020), Use of nanometer mesoporous MCM-41 for the removal of Pb(II) from aqueous solution. Appl. Water. Sci. 10:122-127.
[22] Hajiaghababaei L., Ghasemi B., Badiei A., Goldooz H., Ganjali M. R., Mohammadi Ziarani G., (2012), Highly efficient removal and preconcentration of lead and cadmium cations from water and wastewater samples using ethylenediamine functionalized SBA-15. J. Environ. Sci. 24: 1347-1354.
[23] Jang E. H., Pack S. P., Kim I., chung S., (2020), A systematic study of hexavalent chromium adsorption and removal from aqueous environments using chemically functionalized amorphous and mesoporous silica nanoparticles. Sci. Rep. 10:5558-5563.
[24] Hajiaghababaei L., Tajmiri T., Badiei A., Ganjali M. R., Khaniani Y., Mohammadi Ziarani G., (2013), Heavy metals determination in water and food samples after preconcentration by a new nanoporous adsorbent. Food Chem. 141: 1916-1922.
[25] Du L., Gao P., Liu Y., Minami T., Yu C., (2020), Removal of Cr(VI) from aqueous solution by Polypyrrole/Hollow mesoporous silica particles. Nanomaterials. 10: 686-694.
[26] Rabiul Awual M. d., (2019), Mesoporous composite material for efficient lead(II) detection and removal from aqueous media. J. Environ. Chem. Eng. 7: 103124-103129.
[27] Jadhav S. A., Patil V. S., Shinde P. S., Thoravat S. S., Patil P. S., (2020), A short review on recent progress in mesoporous silicas for the removal of metal ions from water. Chem. Pap. 74:4143–4157.
[28] Lim M. H., Stein A., (1999), Comparative studies of grafting and direct syntheses of inorganic−organic hybrid mesoporous materials. Chem. Mater. 11: 3285-3295.
[29] Ho K. Y., Mckay G., Yeung K. L., (2003), Selective adsorbents from ordered mesoporous silica. Langmuir. 19: 3019-3024.
[30] Hajiaghababaei L., Abozari S., Badiei A., Zarabadi Poor P., Dehghan Abkenar S., Ganjali M. R., Mohammadi Ziarani G., (2017), Amino ethyl-functionalized SBA-15: A promising adsorbent for anionic and cationic dyes removal. Iran. J. Chem. Chem. Eng. 36: 97-108.
[31] Habibi S., Hajiaghababaei L., Badiei A., Yadavi M., Dehghan Abkenar S., Ganjali M. R., Mohammadi Ziarani G., (2017), Removal of reactive black 5 from water using carboxylic acid-grafted SBA-15 nanorods. Desalin. Water Treat. 95: 333-341.
[32] Ju Y. H., Webb O. F., Dai S., Lin J. S., Barnes C. E., (2000), Synthesis and characterization of ordered mesoporous anion-exchange inorganic/organic hybrid resins for radionuclide separation. Ind. Eng. Chem. Res. 39: 550-553.
[33] Lee B., Bao L. L., Im H. J., Dai S., Hagaman E. W., Lin J. S., (2003), Synthesis and characterization of organic−inorganic hybrid mesoporous anion-exchange resins for perrhenate (ReO4-) anion adsorption. Langmuir. 19: 4246-4252.
[34] Fryxell G. E., Liu J., Hauser T. A., Nie Z., Ferris K. F., Mattigod S., Gong M., Hallen R. T., (1999), Design and synthesis of selective mesoporous anion traps. Chem. Mater. 11: 2148-2154.
[35] Saadat A., Hajiaghababaei L., Badiei A., Ganjali M. R., Mohammadi Ziarani G., (2019), Amino functionalized silica coated Fe3O4 magnetic nanoparticles as a novel adsorbent for removal of Pb2+ and Cd2+. Pollution. 4: 847-857.
[36] Vojoudi H., Badiei A., Bahar S., Ziarani G. M., Faridbod F., Ganjali M. R., (2017), Post-modification of nanoporous silica type SBA-15 by bis (3-triethoxysilylpropyl) tetrasulfide as an efficient adsorbent for arsenic removal. Powder Technol. 319: 271-278.
[37] Hajiaghababaei L., Ashrafi L., Dehghan Abkenar S., Badiei A., Ganjali M. R., Mohammadi Ziarani G., (2020), Fast removal of reactive blue-19 from textile wastewater by adsorption on methyl imidazolium modified LUS-1 and MCM-48 nanoporous. Int. J. Nano Dimens. 11: 237-247.
[38] Langmuir I., (1918), Adsorption of gases on plain surface of mica platinum. J. Am. Chem. Soc. 40: 136-403.
[39] Freundlich H. M. F., (1906), Over the adsorption in solution. J. Phys. Chem. 57: 385-470.
[40] Nikpassand M., Zare Fekri L., Nabatzadeh M., (2017), Fe3O4@SiO2@KIT-6 as an efficient and reusable catalyst for the synthesis of novel derivatives of 3, 3¢-((Aryl-1-phenyl-1H-pyrazol-4- yl)methylene) bis (1H-indole). Comb. Chem. High Throughput Screen.  20: 533-538.
[41] Zare Fekri L., Nikpassand M., Pourmirzajani S., Aghazadeh B., (2018), Synthesis and characterization of amino glucose-functionalized silica-coated NiFe2O4 nanoparticles: a heterogeneous, new and magnetically separable catalyst for the solvent-free synthesis of pyrano [3,2-c]chromen-5(4H)-ones. RSC Adv. 8: 22313-22320.
[42] Nikpassand M., (2020), NiFe2O4@SiO2@glucose amine nanoparticle catalyzed reaction of azo-linked thiosalicylic acid with CO2: Access to azo-linked benzo[d]oxathiine-2, 4-diones. Dyes Pigm. 173: 107936-107941.
[43] Hosseinzadeh M., Seyyed Ebrahimi S. A., Raygan S., Masoudpanah S. M., (2016), Removal of cadmium and lead Ions from aqueous solution by nanocrystalline magnetite through mechanochemical activation. J. Ultrafine Grain. Nanostruct. Mater. 49: 72-79.
[44] Chen K., He J., Li Y., Cai X., Zhang K., Liu T., Hu Y., Lin D., Kong L., Liu J., (2017), Removal of cadmium and lead ions from water by sulfonated magnetic nanoparticle adsorbents. J. Colloid Interf. Sci. 494: 307-316.
[45] Tan Y., Chen M., Hao Y., (2012), High efficient removal of Pb (II) by amino-functionalized Fe3O4 magnetic nano-particles. Chem. Eng. J. 191: 104-111.
[46] JEON C., (2017), Adsorption of silver ions from industrial wastewater using waste coffee grounds. Korean J. Chem. Engin. 34: 384-391.
[47] Jintakosol T., Nitayaphat W., (2016), Adsorption of silver (I) from aqueous solution using Chitosan/Montmorillonite composite beads. Mat. Res. 19: 1114-1121.
[48] Jalilian N., Ebrahimzadeh H., Akbar Asgharinezhad A., Molaei K., (2017), Extraction and determination of trace amounts of gold(III), palladium(II), platinum(II) and silver(I) with the aid of a magnetic nanosorbent made from Fe3O4-decorated and silica-coated graphene oxide modified with a polypyrrole-polythiophene copolymer. Microchim. Acta. 184: 2191-2200.
[49] Wu F., Zhang Y. X., Chen Y. L., Qian H., (2014), Recycle of Ag+ and Zn2+ with magnetic adsorbent in process of its purification from wastewater. Clean Soil Air Water. 42: 71–80.
[50] Sedghi R., Shojaee M., Behbahani M., Nabid M. R., (2015), Application of magnetic nanoparticles modified with poly(2-amino thiophenol) as a sorbent for solid phase extraction and trace detection of lead, copper and silver ions in food matrices. R. Soc. Chem. Adv. 5: 67418–67426.
[51] Gong t., Tang Y., (2020), Preparation of multifunctional nanocomposites Fe3O4@SiO2–EDTA and its adsorption of heavy metal ions in water solution. Water Sci. Technol. 81: 170-177.
[52] Nawaz T., Zulfiqar S., Ilyas Sarwar M., Iqbal M., (2020), Synthesis of diglycolic acid functionalized core-shell silica coated Fe3O4 nanomaterials for magnetic extraction of Pb(II) and Cr(VI) ions. Sci. Rep. 10: 10076-10080.