Environmentally friendly synthesis of Fe2O3@SiO2 nanocomposite: characterization and application as an adsorbent to aniline removal from aqueous solution

  • Abbas Rahdar
  • Somayeh RahdarEmail author
  • Georgia LabutoEmail author
Research Article


Silica-based nanocomposite syntheses employ many harmful substances, which, in turn, demand the development of new synthetic environmental-friendly routes that meet the principles of green chemistry. In this work, we present a novel magnetic adsorbent, Fe2O3@SiO2 nanocomposite (Fe@SiNp), successfully obtained without surfactant, employing an electrochemical method. We characterized the nanocomposite and then applied it to remove aniline from the water medium. Characterization was carried out by vibrating-sample magnetometry (VSM), X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR). The parameters to the adsorptive removal of aniline were successfully optimized, which made possible to remove 71.04 ± 0.06% (126.6 ± 2.0 mg/g) from a 100 mg/L aniline solution at pH 6 and 323 K, by employing around 50 mg of Fe@SiNp, at a contact time of 40 min. The adsorption of aniline by Fe@SiNp is a spontaneous and exothermic process according to the pseudo-second-order kinetic model (r2 = 1 at 20 mg/L aniline concentration) and the Freundlich isotherm model (r2 = 0.9986).


Magnetic nanoparticle synthesis Green chemistry Electrochemical synthesis Adsorption 


Supplementary material

11356_2019_7491_MOESM1_ESM.docx (15 kb)
ESM 1 (DOCX 15 kb)


  1. Adivi FG, Hashemi P, Tehrani AD (2018) Agarose-coated Fe3O4@SiO2 magnetic nanoparticles modifed with sodium dodecyl sulfate, a new promising sorbent for fast adsorption/desorption of cationic drugs. Polym Bull 76:1239–1256Google Scholar
  2. Afzali D, Biniaz Z, Mostafavi A (2011) Application of modified nanoclay sorbent for separation and preconcentration trace amount of cobalt. Int J Nanosci Nanotechnol 7(1):21–27Google Scholar
  3. Ahangaran F, Hassanzadeh A, Nouri S (2013) Surface modification of Fe3O4@SiO2 microsphere by silane coupling agent. Int Nano Lett 3:23Google Scholar
  4. Ahmadi S, Rahdar A, Rahdar S, Igwegbe CA (2019a) Removal of Remazol Black B from aqueous solution using P-γ-Fe2O3 nanoparticles: synthesis, physical characterization, isotherm, kinetic and thermodynamic studies. Desal Water Treat 152:401–410Google Scholar
  5. Ahmadi S, Rahdar S, Igwegbe CA, Rahdar A, Shafighi N, Sadeghfar F (2019b) Data on the removal of fluoride from aqueous solutions using synthesized P/γ-Fe2O3 nanoparticles: a novel adsorbent. Methods X 6:98–106Google Scholar
  6. Al-Johani H, Salam MA (2011) Kinetics and thermodynamic study of aniline adsorption by multi-walled carbon nanotubes from aqueous solution. J Collid Interf Sci 360:760–767Google Scholar
  7. Anastas P, Eghbali N (2010) Green chemistry: principles and practice. Chem Soc Rev 39:301–312Google Scholar
  8. Andrade AL, Souza DM, Pereira MC, Fabris JD, Domingues RZ (2009) Synthesis and characterization of magnetic nanoparticles coated with silica through a sol-gel approach. Cerâmica 55:420–424Google Scholar
  9. Arshad M, Mazhar A, Ehtisham-ul-Haque S, Akhyar Farrukh M, Abid A, Rizvi H, Soomro GA, Ayar N, Bilgin B, Atun G (2008) Kinetics and equilibrium studies of the herbicide 2,4-ichlorophenoxyacetic acid adsorption on bituminous shale. Chem Eng J 138:239–242Google Scholar
  10. Bazrafshan E, Kord Mostafapour F, Rahdar S, Mahvi AH (2015) Equilibrium and thermodynamics studies for decolorization of Reactive Black 5 (RB5) by adsorption onto MWCNTs. Desalin Water Treat 54:2241–2251Google Scholar
  11. Bose RS, Dey S, Saha S, Ghosh CK, Chaudhuri GM (2016) Enhanced removal of dissolved aniline from water under combined system of nano zero-valent iron and Pseudomonas putida. Sustain Water Resour Manag 2:143–159Google Scholar
  12. Caparrós C, Benelmekki M, Martins PM, Xuriguera E, Silva CGR, Martinez LM (2012) Hydrothermal assisted synthesis of iron oxide-based magnetic silica spheres and their performance in magnetophoretic water purification. Mater Chem Phys 135:510–517Google Scholar
  13. Cardona DS, Debs KB, Lemos SG, Vitale G, Nassar NN, Carrilho ENVM, Semensatto D, Labuto G (2019) A comparison study of cleanup techniques for oil spill treatment using magnetic nanomaterials. J Environ Manag 242:362–371Google Scholar
  14. Chang YP, Ren CL, Qu JC, Chen XG (2012) Preparation and characterization of Fe3O4/graphene nanocomposite and investigation of its adsorption performance for aniline and p-chloroaniline. Appl Surf Sci 261:504–509Google Scholar
  15. Chen N, Chen L, Cheng Y, Zhao K, Wu X, Xian Y (2015) Molecularly imprinted polymer grafted graphene for simultaneous electrochemical sensing of 4,4-methylene diphenylamine and aniline by differential pulse voltammetry. Talanta 132:155–161Google Scholar
  16. Chen C, Geng X, Huang W (2017) Adsorption of 4-chlorophenol and aniline by nanosized activated carbons. Chem Eng J 327:941–952Google Scholar
  17. Dada AO, Olalekan AP, Olatunya AM, Dada O (2010) Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms studies of equilibrium sorption of Zn2+ unto phosphoric acid modified rice husk. J Appl Chem 3:38–45Google Scholar
  18. Debs KB, Cardona DS, Silva HDT, Nassar NN, Carrilho ENVM, Ferreira PSH, Labuto G (2019) Oil spill cleanup employing magnetite nanoparticles and yeast-based magnetic bionanocomposite. J Environ Manag 230:405–412Google Scholar
  19. Dong W, Chen Q, Hou Y, Li S, Zhuang K, Huang F, Zhou J, Li Z, Wang J, Fu L (2015) Metabolic pathway involved in 2-methyl-6-ethylaniline degradation by Sphingobium sp. strain MEA3-1 and the cloning of a novel flavin-dependent monooxygenase system meaBA. Appl Environ Microbiol 81:8254–8264Google Scholar
  20. Fakhri A (2017) Adsorption characteristics of graphene oxide as a solid adsorbent for aniline removal from aqueous solutions: kinetics, thermodynamics and mechanism studies. Journal of Saudi Chemical Society 21:52–57Google Scholar
  21. Fatemeh Ahangaran F, Hassanzadeh A, Nouri S (2013) Surface modification of Fe3O4@SiO2 microsphere by silane coupling agent. Intl Nano Lett 3:23Google Scholar
  22. Foo KY, Hameed BH (2010) Insights into the modeling of adsorption isotherm systems. Chem Eng J 156:2–10Google Scholar
  23. Fu H-Y, Zhang Z-B, Chai T, Huang G-H, Yu S-J, Liu Z, Gao P-F (2017) Study of the removal of aniline from wastewater via meuf using mixed surfactants. Water 9:365Google Scholar
  24. Gheewala SH, Annachhatre AP (1997) Biodegradation of aniline. Wat Sci Technol 36:53–63Google Scholar
  25. Giraldo L, Erto A, Moreno-Piraján JC (2013) Magnetite nanoparticles for removal of heavy metals from aqueous solutions: synthesis and characterization. Adsorption 19:465–474Google Scholar
  26. Gómez JL, León G, Hidalgo AM, Gómez M, Murcia MD, Griñán G (2009) Application of reverse osmosis to remove aniline from wastewater. Desalination 245:687–693Google Scholar
  27. Gu Z, Gao M, Luo Z, Lu L, Ye Y, Liu Y (2014) Bis-pyridinium dibromides modified organo-bentonite for the removal of aniline from wastewater: a positive role of π–π polar interaction. Appl Surf Sci 290:107–115Google Scholar
  28. Guan Y, Qian H, Guo J, Yang S, Wang X, Wang S, Fu Y (2015) Synthesis of acidified palygorskite/BiOI with exceptional performances of adsorption and visible-light photoactivity for efficient treatment of aniline wastewater. Appl Clay Sci 114:124–132Google Scholar
  29. Hasan SH, Ranjan D, Talat M (2010) Water hyacinth biomass (WHB) for the biosorption of hexavalent chromium: optimization of process parameters. BioResources 5:563–575Google Scholar
  30. Hu Q, Gao DW, Pan H, Hao L, Wang P (2014) Equilibrium and kinetics of aniline adsorption onto crosslinked sawdust-cyclodextrin polymers. RSC Adv 75:40071–40077Google Scholar
  31. Hwang W, Umar A, Dar GN, Kim SH, Badran RI (2014) Synthesis and characterization of iron oxide nanoparticles for phenyl hydrazine sensor applications. Sens Lett 12:1–5Google Scholar
  32. Jianguo C, Aimin L, Hongyan S, Zhenghao F, Chao L, Quanxing Z (2005) Adsorption characteristics of aniline and 4-methylaniline onto bifunctional polymeric adsorbent modified by sulfonic groups. J Hazard Mat 124:173–180Google Scholar
  33. Jing Z, Cao S, Yu T, Hu J (2015) Degradation characteristics of aniline with ozonation and subsequent treatment analysis. J Chem Sci 2015:1–6Google Scholar
  34. Kakavandi B, Jafari JA, Kalantary RR, Nasseri S, Ameri A, Esrafily A (2013) Synthesis and properties of Fe3O4-activated carbon magnetic nanoparticles for removal of aniline from aqueous solution: equilibrium, kinetic and thermodynamic studies. Iranian J Environ Health Sci Eng 10:19Google Scholar
  35. Kermani M, Pourmoghaddas H, Bina B, Khazaei Z (2006) Removal of phenol from aqueous solutions by rice husk ash and activated carbon. Pak J Biol Sci 9:1905–1910Google Scholar
  36. Kilianová M, Prucek R, Filip J, Kolařík J, Kvítek L, Panáček A, Tuček J, Zbořil R (2013) Remarkable efficiency of ultrafine superparamagnetic iron(III) oxide nanoparticles toward arsenate removal from aqueous environment. Chemosphere 93:2690–2697Google Scholar
  37. Kuang W, Liu YN, Huang J (2017) Phenol-modified hyper-cross-linked resins with almost all micro/mesopores and their adsorption to aniline. J Colloid Interface Sci 487:31–37Google Scholar
  38. Labuto G, Cardona DS, Debs KB, Imamura AR, Bezerra KCH, Carrilho ENVM, Ferreira PSH (2018) Low cost agroindustrial biomasses and ferromagnetic bionanocomposites to cleanup textile effluents. Desalin Water Treat 12:80–89Google Scholar
  39. Liao MH, Chen DH (2002) Preparation and characterization of a novel magnetic nano-adsorbent. J Mat Chem 12:3654–3659Google Scholar
  40. Limousin G, Gaudet JP, Charlet L, Szenknect S, Barthe’s V, Krimissa M (2007) Sorption isotherms: a review on physical bases, modeling and measuremen. App Geo Chem 22:249–275Google Scholar
  41. Lin X, Zhang J, Luo X, Zhang C, Zhou Y (2011) Removal of aniline using lignin grafted acrylic acid from aqueous solution. Chem Eng J 172:856–863Google Scholar
  42. Liu L, Li C, Bao C, Jia Q, Xiao P, Liu X (2012) Preparation and characterization of chitosan/graphene oxide composites for the adsorption of Au(III) and Pd(II). Talanta 93:350–357Google Scholar
  43. Liu G, Wang Z, Zheng W, Yang S, Sun C (2014) Visible-light driven photocatalytic degradation of aniline over NaBiO3. Adv Cond Matter PhysGoogle Scholar
  44. Liu Q, Zhang L, Hu P, Huang R (2015) Removal of aniline from aqueous solutions by activated carbon coated by chitosan. J Water Reuse Desal 5:610–618Google Scholar
  45. Malekian R, Abedi-Koupai J, Eslamian SS, Afyuni M (2013) Ion-exchange process for nitrate removal and release using surfactant modified zeolite. JWSS - Isfahan Univ Technol 63:191–201Google Scholar
  46. Moghaddam MS, Rahdar S, Taghavi M (2015) Cadmium removal from aqueous solutions using saxaul tree ash. Iran J Chem Chem Eng 35:45–52Google Scholar
  47. Mohamadiyan J, Shams-Khoramabadi G, Mussavi SA, Kamarehie B, Shahamat YD, Godini H (2017) Aniline degradation using advanced oxidation process by UV/peroxy disulfate from aqueous solution. IJE Transactions B: Applications 30:684–690Google Scholar
  48. Mokadem Z, Mekki S, Saїdi-Besbes S, Agusti G, Elaissari A, Derdour A (2017) Triazole containing magnetic core-silica shell nanoparticles for Pb2+, Cu2+ and Zn2+ removal. Arab J Chem 10:1039–1051Google Scholar
  49. Park JO, Rhee KY, Park SJ (2010) Silane treatment of Fe3O4 and its effect on the magnetic and wear properties of Fe3O4/epoxy nanocomposites. Appl Surf Sci 256:6945–6950Google Scholar
  50. Peng ZG, Hidajat K, Uddin MS (2004) Adsorption of bovine serum albumin on nanosized magnetic particles. J Colloid Interf Sci 271:277–283Google Scholar
  51. Rahdar A, Ahmadi S, Fu J, Rahdar S (2019a) Iron oxide nanoparticle preparation and its use for the removal of fluoride from aqueous solution: application of isotherm, kinetic, and thermodynamics. Desalin Water Treat 137:174–182Google Scholar
  52. Rahdar S, Igwegbe CA, Ghasemi M, Ahmadi S (2019b) Degradation of aniline by the combined process of ultrasound and hydrogen peroxide (US/H2O2). MethodsX 6:492–499Google Scholar
  53. Rahdar S, Rahdar A, Ahmadi S, Trant J (2019c) Adsorption of bovine serum albumin (BSA) by bare magnetite nanoparticles with surface oxidative impurities that prevent aggregation. Can J Chem in press. Google Scholar
  54. Rahdar S, Rahdar A, Igwegbec CA, Moghaddama F, Ahmadia S (2019d) Synthesis and physical characterization of nickel oxide nanoparticles and its application study in the removal of ciprofloxacin from contaminated water by adsorption: equilibrium and kinetic studies. Desalin Water Treat 141:386–393Google Scholar
  55. Roshan B, Kadirvelu K, Kumar NS (2013) Investigation of aniline adsorption onto spherical carbon: optimization using response surface methodology. Int J Eng Res Appl 3(5):943–952Google Scholar
  56. Salam MA, Gabal MA, Obaid AY (2012) Preparation and characterization of magnetic multi-walled carbon nanotubes/ferrite nanocomposite and its application for the removal of aniline from aqueous solution. Synth Met 161:2651–2658Google Scholar
  57. Shahmohammadi SH, Babazadeh H (2014) Isotherms for the sorption of zinc and copper onto kaolinite: comparison of various error functions. Environ Sci Technol Journal 11:111–118Google Scholar
  58. Shao D, Hu J, Chen C, Sheng G, Ren X, Wan X (2010) Polyaniline multiwalled carbon nanotube magnetic composite prepared by plasma-induced graft technique and its application for removal of aniline and phenol. J Phys Chem 114:21524–21530Google Scholar
  59. Sheet I, Kabbani A, Holail H (2014) Removal of heavy metals using nanostructured graphite oxide, silica nanoparticles and silica/graphite oxide composite. Energy Procedia 50:130–138Google Scholar
  60. Shen H-Y, Zhu Y, Wen X-E, Zhuang Y-M (2007) Preparation of Fe3O4–C18 nano-magnetic composite materials and their cleanup properties for organophosphorous pesticides. Anal Bioanal Chem 387:2227–2237Google Scholar
  61. Suresh S, Srivastava V, Mishra I (2012) Adsorptive removal of aniline by granular activated carbon from aqueous solutions with catechol and resorcinol. Environ Technol 33:773–781Google Scholar
  62. Taimoory SM, Rahdar A, Aliahmad M, Sadeghfar F, Hajinezhad MR, Jahantigh M, Shahbazi P, Trant JF (2018) The synthesis and characterization of a magnetite nanoparticle with potent antibacterial activity and low mammalian toxicity. J Mol Liq 265:96–104Google Scholar
  63. Tang B, Lin Y, Yu P, Luo Y (2012) Study of aniline/ɛ-caprolactam mixture adsorption from aqueous solution onto granular activated carbon: kinetics and equilibrium. Chem Eng J 187:69–78Google Scholar
  64. Tzvetkova P, Vassileva P, Nickolov R (2009) Modified silica gel with 5-amino-1,3,4-thiadiazole-2-thiol for heavy metal ions removal. J Porous Mater 17:459–456Google Scholar
  65. Wade LG, Simek JW  (2017) Organic chemistry, 9th edition, Pearson, New York.Google Scholar
  66. Wang L, Barrington S, Kim J (2007) Biodegradation of pentyl amine and aniline from petrochemical wastewater. J Environ Manag 83:191–197Google Scholar
  67. Wang J, Zheng S, Shao Y, Liu J, Xu Z, Zhu D (2010) Amino functionalized Fe3O4@SiO2 core-shell magnetic nanomaterial as a novel adsorbent for aqueous heavy metals removal. J Colloid Interface Sci 349:293–299Google Scholar
  68. Wang F, Dong C, Wang Z, Cui Y, Wang C, Zhao Y, Li G (2014) Fluorescence detection of anilines and photocatalytic degradation of Rhodamine B by a multifunctional metal–organic framework. Eur J Inorg Chem 36:6239–6245Google Scholar
  69. Wu GO, Zhang X, Hui H, Yan J, Zhang QS, Wan JL (2012) Adsorptive removal of aniline from aqueous solution by oxygen plasma irradiated bamboo based activated carbon. Chem Eng J 185:201–210Google Scholar
  70. Xie J, Meng W, Wu D, Zhang Z, Kong H (2012a) Removal of organic pollutants by surfactant modified zeolite: comparison between ionizable phenolic compounds and non-ionizable organic compounds. J Hazard Mater 231:57–63Google Scholar
  71. Xie X, Zhang Y, Huang W, Huang S (2012b) Degradation kinetics and mechanism of aniline by heat-assisted persulfate oxidation. J Environ Sci 24:821–826Google Scholar
  72. Yang J, Hou B, Wang J, Tian B, Bi J, Wang N, Li X, Huang X (2019) Nanomaterials for the removal of heavy metals from wastewater. Nanomaterials 9:424Google Scholar
  73. Yan-Yang C, Ling-Ling L, Mao-Juan B (2011) Dual-electrode oxidation used for aniline degradation in aqueous electrolyte. Water Sci Technol 63:2583–2589Google Scholar
  74. Zhang A, Li D, Cui J, Yang FM (2011) Performance of enhanced biological SBR process for aniline treatment by mycelial pellet as biomass carrier. Bioresour Technol 102:4360–4365Google Scholar
  75. Zhang L, Lian J, Wang L, Jiang J, Duan Z, Zhao L (2014) Markedly enhanced coercive field and Congo red adsorption capability of cobalt ferrite induced by the doping of non-magnetic metal ions. Chem Eng J 241:384–392Google Scholar
  76. Zhang J, Wu Y, Qin C, Liu L, Lan Y (2015) Rapid degradation of aniline in aqueous solution by ozone in the presence of zero-valent zinc. Chemosphere 141:258–264Google Scholar
  77. Zhang M, Shi H, Meng D, Chen K, Lin RL, Sun WQ, Liu JX (2019) Encapsulation and removal of aniline by di-cyclohexanocucurbit[6]uril. New J Chem 43:1487–1493Google Scholar
  78. Zhu L, Lv M, Dai X, Xu X, Qi H, Yu Y (2012) Reaction kinetics of the degradation of chloroanilines and aniline by aerobic granule. Biochem Eng J 68:215–220Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2020

Authors and Affiliations

  1. 1.Department of PhysicsUniversity of ZabolZabolIran
  2. 2.Department of Environmental HealthZabol University of Medical SciencesZabolIran
  3. 3.Department of ChemistryUniversidade Federal de São PauloSão PauloBrazil

Personalised recommendations