Magnetic-Graphene Oxide Based Nanocomposites For Inorganic Pollutants

Subjects: Applied Chemistry View times: 788

Magnetic graphene oxide based nanocomposites (MGO) possess unique physicochemical properties including excellent magnetic characteristics, high specific surface area, surface active sites, high chemical stability, tunable shape and size, and the ease with which they can be modified or functionalized. As results of their multi-functional properties, affordability, and magnetic separation capability, MGO's have been widely used in the removal of heavy metals, radionuclides and organic dyes from the aqueous environment, and are currently attracting much attention.

1. Introduction

The numerous merits of graphene oxide including high specific surface area, and thermal conductivity, high optical transmittance, and large Young’s modulus have led to researchers paying great attention to it [1]. However, due to its imperishable hydrophilicity, GO found to be an efficient adsorbent and hence found many applications, including water purification [2]. Sreeprasad et al. [3] and Maaz et al. [4] have reported that nickel ferrite-GO composite is a better reaction media than iron ferrites, because of having higher catalytic and electron transfer efficiency through the Ni2+ in the nickel ferrite. Moreover, previous reports have proved the amazing removal response of magnetic nanoparticles/graphene or GO composites for pollutants like chromium [5, 6], copper [7], arsenic [8], cadmium [9], lead [10], and cobalt and an organic dye. Recently, Ligamdinne et al. reported (Fig. 1) the removal of Co(II), Pb(II), Cr(III), As(III) and As(V), and radionuclides, U(VI) and Th(IV) from water, using the synthesis of “inverse spinel nickel ferrite incorporated-graphene oxide” based nanocomposites [11,12]. The reported results demonstrated that the magnetic GO-based nanocomposites are promising, economic, could be separated by the external magnetic field.

Fig. 1 Graphical representation of a nano-magnetic GONF composite preparation, b Pb(II) and Cr(III) adsorption onto GONF [13]

 2.      Synthesis techniques of MGO Nanocomposites

Often magnetic-graphene oxide-based (MGO) nanocomposites have been synthesized by the hydrothermal or solvothermal method. Generally, the ultra-sonochemical method is used to prevent re-aggregation, and improve the dispersion and reduction of the size of material [11-14]. It was used mostly before or after the synthesis of MGO's by the hydrothermal method. Szabo et al. [15] successfully prepared MGOs by sonication of a mixture of magnetic nanoparticles and GO solution. Later, microwave synthesis has become of great significance in the preparation of inorganic nanomaterials. In the synthesis of inorganic nanomaterials, compared to conventional heating technique, the microwave synthesis technique consumes less energy, environmentally friendly, and provides a homogeneous heating process for the speedy reaction [14, 16, 17].

3. Structural characterization and properties of MGO

The formation and structural functionalities of the prepared MGOs can be characterized using spectroscopic techniques that include XRD, XPS and FT-IR, and Raman Spectroscopy. Raman Spectra is an important technique to qualitatively identify the MGO's. As is known, the graphitic materials show two prominent Raman peaks around (1,350 and 1,600) cm-1 called the D and G bands. Here, the G band corresponds to the stretching vibrations of carbons at sp2 hybridization, whereas the D band represents the vibrations of carbons at sp3 hybridization, which can break the symmetry and selection rule [18, 19]. By the magnetization of GO, these D and G bonds alter their positions, based on their principal interactions. But, in the case of nickel ferrite-rGO (rGONF), both the sp2 domain (D) and sp3 domain (G) carbons are shifted to lower range at (~1303 and ~1591) cm-1, which indicates that both D and G band carbons are involved in the formation of reduced GO-based magnetic nanocomposite. The XPS is used to qualitative and quantitative identify the chemical composition of MGOs. The bonding energy peaks of (700–730) eV indicate the Fe peaks of magnetic materials [11, 12].

The microscopic techniques, including SEM, TEM, and AFM, are used to measure the size of nanocomposites, MGOs, and their surface morphology, which is an important factor to know for the adsorption process [11, 12]. Their porous structure and surface area can be further evaluated by using (N2) adsorption-desorption isotherms through BET analysis. The magnetic nature of MGO's is identified using the magnetic measurement system (MPMS). When the size of MGO's decreases to the nanoscale, it shows superparamagnetic nature. Lingamdinne et al. [19] confirmed the superparamagnetic property of magnetic nanocomposite by MT curves obtained at 1,000 Oe magnetic field. They also observed the increase of superparamagnetic property by the reduction of nanocomposite [20, 21].

4. Applications of MGO for inorganic pollutants removal from water purification

Due to the magnetic and chemical stability along with high surface porous structure and of them, magnetic inverse spinel ferrites and its derivatives are widely used for water purification [22, 23]. However, the nano metal ferrites show poor stability [4]. To overcome these difficulties, the hybrid materials synthesized through magnetic ferrites and GO by hydrothermal method. Recently, some of the researchers are used the functionalized magnetic-carbon composites [24] and magnetic organic composites [25, 26] for recovery and separation of precious metals. Due to the presence of hydroxyl, carboxylic and epoxy functions at GO, it can enhance the adsorption of heavy metals [27]. Moreover, the prepared magnetic graphene oxide composites showed good properties for water treatment [11, 12, 23, 28]. Recently, Lingamdinne et al. has been employed porous inverse spinel composite (MGO) and porous inverse magnetic-reduced GO (rMGO) nanocomposites using nickel ferrite and GO and applied for removal of As(III) and As(V) [29], Pb(II) and Cr(III) [30, 31]. They have been reported the as-prepared nanocomposites are shows considerably enhanced adsorption capacity for Pb(II), Cr(III), As(III), and As(V) compared to that of GO. They also conclude that the adsorption of reduced magnetic graphene oxide nanocomposite shows higher adsorption capacity than that of non-reduced magnetic graphene oxide nanocomposite for all metal ions. Summarized some of MGO’s used for heavy metal removal from water in Table1.

Table 1: Some of MGO’s used for removal of heavy metals.


Qmax (mg/g)


Graphene Oxide Nanosheets Decorated with

Fe3O4 Nanoparticles

Cu(II) –11.339


Ethylene diamine tetra acetic acid functionalized magnetic graphene oxide (EDTA-mGO)

Pb(II) - 508.4 @45o C

Hg(II) - 268.4 @45o C

Cu(II) - 301.2 @45o C


Ethylene diamine tri acetic acid graphene oxide (EDTA-GO)

Pb(II) – 479


Sulfonated magnetic graphene oxide composite (SMGO)

Cu(II) – 50.678 @ 10o C

Cu(II) – 56.857 @ 30o C

Cu(II) – 63.670 @ 50o C


Mn-doped Fe(III) oxide nanoparticle implanted graphene (GMIO)

Cd(II) – 87.2 @15o C

Cd(II) – 101.1 @30o C

Cd(II) – 117.3 @45o C

Cd(II) – 127.1 @60o C

Cu(II) – 129.7 @15o C

Cu(II) – 133.2 @30o C

Cu(II) – 140.3 @45o C

Cu(II) – 144.3 @60o C


Magnetic CoFe2O4 - reduced graphene oxide

Pb(II) - 299.4

Hg(II) - 157.9


Iron oxide nanoparticles immobilized sand material

Cu(II) - 1.2649

Cd(II) - 0.5282

Pb(II) - 2.0877


porous inverse spinel magnetic graphene oxide composite (MGO)

Pb(II) – 82.47

Cr(III) – 87.49


porous inverse magnetic graphene oxide nanocomposites (rMGO)

Pb(II) – 121.95

Cr(III) – 126.58



As(III) - 106.40

As(V) - 65.78


 Sun et al. have been developed the nanosize zero-valent iron-rGO (nZVI/RGO) for the removal of U(VI) [39]. Zong and co-workers [40] employed the removal of U(VI) using Fe3O4/GO prepared from natural flake graphite, and observed adsorption capacity of 69.49 mg/g. Zhao et al. [41] synthesized amidoximated magnetite/GO (AOMGO) composites, and successfully applied them to adsorption removal of U(VI) with high adsorption capacity (284.92 mg/g)[1]. They also concluded that the adsorption process was endothermic and spontaneous. MnO2–Fe3O4–rGO was successfully synthesized by Tan et al., [42] and utilized for the adsorption removal of U(VI), and exhibited 108.7 mg/g U(VI) removal. They also stated that the radionuclide loaded composite MnO2–Fe3O4–RGO can be efficiently recycled and reused. Recently, Lingamdinne et al. [43] have been synthesized nickel ferrite-GO nanocomposites for treatment of U(VI), and Th(IV). They reported that the synthesized nanocomposites exhibit high adsorption capacity for U(VI) and  Th(IV). They also observed that the reduction of magnetic nanocomposite enhances its adsorption capacity by almost double of bare materials adsorption capacity. The regeneration and reuse studies of the nanocomposites concluded that the prepared nanocomposites can be reused up to five cycles repeatedly. Finally, they conclude that the prepared MGO’s are efficient, promising, and easily recoverable by using an external magnetic field. And they achieved the EPA standard levels removal of radioactive ions from wastewater by using the MGO’s. Summarized some of MGO composites used for radioactive elements removal in Table 2.  Fig. 2  shows the schematic adsorption and removal, reusability process of MGO’s by using the external magnetic field.

Table 2: Some of MGO nanocomposites used for removal of U(VI) and Th(IV)[58]


 Maximum adsorption capacity, mg/g



Graphene oxide nanosheets [44]



Fe3O4/GO [45]



Reduced graphene oxide(RGO) [46]



GO@ sepiolite composites [47]



MnO2–Fe3O4–RGO [48]



Polyacrylamide grafted graphene oxide (PAM/GO) [49]



Amidoxime modified Fe3O4@SiO2 [4]



RGONF [43]



GONF [43]




Fig. 2 Schematic representation of MGO’s nanocomposites for adsorption and reusability [12].


  1. 1. Alvand M, Shemirani F (2016) Fabrication of Fe3O4@graphene oxide core-shell nanospheres for ferrofluid-based dispersive solid phase extraction as exemplified for Cd(II) as a model analyte. Microchim Acta 183:1749–1757. https://doi.org/10.1007/s00604-016-1805-82. Chung C, Kim Y-K, Shin D, Ryoo S-R, Hong BH, Min D-H (2013) Biomedical applications of graphene and graphene oxide. Acc Chem Res 46:2211–22243. Sreeprasad TS, Maliyekkal SM, Lisha KP, Pradeep T (2011) Reduced graphene oxide– metal/metal oxide composites: facile synthesis and application in water purification. J Hazard Mater 186:921–9314. Maaz K, Karim S, Mumtaz A, Hasanain SK, Liu J, Duan JL (2009) Synthesis and magnetic characterization of nickel ferrite nanoparticles prepared by co-precipitation route. J Magn Magn Mater 321:1838–18425. Gollavelli G, Chang C-C, Ling Y-C (2013) Facile synthesis of smart magnetic graphene for safe drinking water: heavy metal removal and disinfection control. ACS Sustain Chem Eng1:462–4726. Sarı A, Tuzen M, Soylak M (2007) Adsorption of Pb(II) and Cr(III) from aqueous solution on Celtek clay. J Hazard Mater 144:41–467. Hu X-J et al (2013) Removal of Cu(II) ions from aqueous solution using sulfonated magnetic graphene oxide composite. Sep Purif Technol 108:189–1958. Zhu J et al (2012) Magnetic graphene nanoplatelet composites toward arsenic removal. ECS J Solid State Sci Technol 1:M1–M59. Deng J-H, Zhang X-R, Zeng G-M, Gong J-L, Niu Q-Y, Liang J (2013) Simultaneous removal of Cd(II) and ionic dyes from aqueous solution using magnetic graphene oxide nanocomposite as an adsorbent. Chem Eng J 226:189–20010. Zhang W, Shi X, Zhang Y, Gu W, Li B, Xian Y (2013) Synthesis of water-soluble magnetic graphene nanocomposites for recyclable removal of heavy metal ions. J Mater Chem A 1:1745–175311. Koduru, J.R., Karri, R.R. and Mubarak, N.M., 2019. Smart Materials, Magnetic Graphene Oxide-Based Nanocomposites for Sustainable Water Purification. In Sustainable Polymer Composites and Nanocomposites (pp. 759-781). Springer, Cham.12. Lingamdinne, L.P., Koduru, J.R. and Karri, R.R., 2019. A comprehensive review of applications of magnetic graphene oxide based nanocomposites for sustainable water purification. Journal of environmental management, 231, pp.622-634.13. Lingamdinne LP, Choi Y-L, Kim I-S, Chang Y-Y, Koduru JR, Yang J-K (2016) Porous graphene oxide based inverse spinel nickel ferrite nanocomposites for the enhanced adsorption removal of arsenic. RSC Adv 6(77):73776–7378914. Hashim N et al (2016) A brief review on recent graphene oxide-based material nanocomposites: synthesis and applications. J Mater Environ Sci 7:3225–324315. Szabó T, Nánai L, Nesztor D, Barna B, Malina O, Tombácz E (2018) A Simple and Scalable Method for the Preparation of Magnetite/Graphene Oxide Nanocomposites under Mild Conditions Advances in Materials Science and Engineering 2018:1-1116. Baek S et al. (2011) A one-pot microwave-assisted non-aqueous sol–gel approach to metal oxide/graphene nanocomposites for Li-ion batteries RSC Advances 1:168717. She X, Zhang X, Liu J, Li L, Yu X, Huang Z, Shang S (2015) Microwave-assisted synthesis of Mn3O4 nanoparticles@reduced graphene oxide nanocomposites for high performance supercapacitors Materials Research Bulletin 70:945-95018. Ferrari AC et al. (2006) Raman Spectrum of Graphene and Graphene Layers Physical Review Letters 9719. Lingamdinne LP, Choi Y-L, Kim I-S, Yang J-K, Koduru JR, Chang Y-Y (2017) Preparation and characterization of porous reduced graphene oxide based inverse spinel nickel ferrite nanocomposite for adsorption removal of radionuclides Journal of Hazardous Materials 326:145-15620. Bai S, Shen X, Zhong X, Liu Y, Zhu G, Xu X, Chen K (2012) One-pot solvothermal preparation of magnetic reduced graphene oxide-ferrite hybrids for organic dye removal Carbon 50:2337-234621. Fan Z, Wang K, Wei T, Yan J, Song L, Shao B (2010) An environmentally friendly and efficient route for the reduction of graphene oxide by aluminum powder Carbon 48:1686-168922. Li, B., Cao, H., Shao, J., Qu, M., Warner, J.H., 2011d. Superparamagnetic Fe3O4 nanocrystals@ graphene composites for energy storage devices. J. Mater. Chem. 21, 5069.23. Xu, S., Zhang, F., Kang, Q., Liu, S., Cai, Q., 2009. The effect of magnetic field on the catalytic graphitization of phenolic resin in the presence of Fe–Ni. Carbon 47, 3233–3237.24. Muravyov, M.I., Fomchenko, N.V., Usoltsev, A.V., Vasilyev, E.A., Kondrat'eva, T.F., 2012. Leaching of copper and zinc from copper converter slag flotation tailings using H2SO4 and biologically generated Fe2(SO4)3. Hydrometallurgy 119–120, 40–46.25. Zhao, Z., Shuai, W., Zhang, J., Chen, X., 2013a. Sn(IV) anions adsorption onto ferric hydroxide: a speciation-based model. Hydrometallurgy 140, 135–14326. Lv, S., Chen, X., Ye, Y., Yin, S., Cheng, J., Xia, M., 2009. Rice hull/MnFe2O4 composite: preparation, characterization and its rapid microwave-assisted COD removal for organic wastewater. J. Hazard. Mater. 171, 634–639.27. Li, J., Guo, S., Zhai, Y., Wang, E., 2009. Nafion–graphene nanocomposite film as enhanced sensing platform for ultrasensitive determination of cadmium. Electrochem. Commun. 11, 1085–108828. Koo, H.Y., Lee, H.-J., Go, H.-A., Lee, Y.B., Bae, T.S., Kim, J.K., Choi, W.S., 2010. Graphene-based multifunctional iron oxide nanosheets with tunable properties. Chem. Eur J. 17, 1214–1219.29. Lingamdinne, L.P., Choi, Y.-L., Kim, I.-S., Chang, Y.-Y., Koduru, J.R., Yang, J.-K., 2016. Porous graphene oxide based inverse spinel nickel ferrite nanocomposites for the enhanced adsorption removal of arsenic. RSC Adv. 6, 73776–73789.30. Lingamdinne, L.P., Koduru, J.R., Choi, Y.-L., Chang, Y.-Y., Yang, J.-K., 2016. Studies on removal of Pb(II) and Cr(III) using graphene oxide based inverse spinel nickel ferrite nano-composite as sorbent. Hydrometallurgy 165, 64–72.31. Lingamdinne, L., Kim, I.-S., Ha, J.-H., Chang, Y.-Y., Koduru, J., Yang, J.-K., 2017. Enhanced adsorption removal of Pb(II) and Cr(III) by using nickel ferrite-reduced graphene oxide nanocomposite. Metals 7, 225.32. J. Li, S. Zhang, C. Chen, G. Zhao, X. Yang, J. Li, X. Wang, Removal of Cu(II) and Fulvic Acid by Graphene Oxide Nanosheets Decorated with Fe3O4 Nanoparticles, ACS Applied Materials & Interfaces, 4 (2012) 4991-5000.33. X.-j. Hu, Y.-g. Liu, H. Wang, A.-w. Chen, G.-m. Zeng, S.-m. Liu, Y.-m. Guo, X. Hu, T.-t. Li, Y.-q. Wang, L. Zhou, S.-h. Liu, Removal of Cu(II) ions from aqueous solution using sulfonated magnetic graphene oxide composite, Separation and Purification Technology, 108 (2013) 189-19534. L. Cui, Y. Wang, L. Gao, L. Hu, L. Yan, Q. Wei, B. Du, EDTA functionalized magnetic graphene oxide for removal of Pb(II), Hg(II) and Cu(II) in water treatment: Adsorption mechanism and separation property, Chemical Engineering Journal, 281 (2015) 1-10.35. C.J. Madadrang, H.Y. Kim, G. Gao, N. Wang, J. Zhu, H. Feng, M. Gorring, M.L. Kasner, S. Hou, Adsorption Behavior of EDTA-Graphene Oxide for Pb (II) Removal, ACS Applied Materials & Interfaces, 4 (2012) 1186-1193.36. D. Nandi, T. Basu, S. Debnath, A.K. Ghosh, A. De, U.C. Ghosh, Mechanistic Insight for the Sorption of Cd(II) and Cu(II) from Aqueous Solution on Magnetic Mn-Doped Fe(III) Oxide Nanoparticle Implanted Graphene, Journal of Chemical & Engineering Data, 58 (2013) 2809-2818.37. Y. Zhang, L. Yan, W. Xu, X. Guo, L. Cui, L. Gao, Q. Wei, B. Du, Adsorption of Pb (II) and Hg (II) from aqueous solution using magnetic CoFe2O4-reduced graphene oxide, Journal of Molecular Liquids, 191 (2014) 177-182.38. S.-M. Lee, C. Laldawngliana, D. Tiwari, Iron oxide nano-particles-immobilized-sand material in the treatment of Cu (II), Cd (II) and Pb (II) contaminated waste waters, Chemical Engineering Journal, 195 (2012) 103-111.39. Y. Sun, C. Ding, W. Cheng, X. Wang, Simultaneous adsorption and reduction of U(VI) on reduced graphene oxide-supported nanoscale zerovalent iron, Journal of Hazardous Materials, 280 (2014) 399-408.40. P. Zong, S. Wang, Y. Zhao, H. Wang, H. Pan, C. He, Synthesis and application of magnetic graphene/iron oxides composite for the removal of U(VI) from aqueous solutions, Chemical Engineering Journal, 220 (2013) 45-52.41. Y. Zhao, J. Li, S. Zhang, H. Chen, D. Shao, Efficient enrichment of uranium(vi) on amidoximated magnetite/graphene oxide composites, RSC Advances, 3 (2013) 18952.42. L. Tan, J. Wang, Q. Liu, Y. Sun, X. Jing, L. Liu, J. Liu, D. Song, The synthesis of a manganese dioxide–iron oxide–graphene magnetic nanocomposite for enhanced uranium (VI) removal, New Journal of Chemistry, 39 (2015) 868-876.43. L.P. Lingamdinne, Y.-L. Choi, I.-S. Kim, J.-K. Yang, J.R. Koduru, Y.-Y. Chang, Preparation and characterization of porous reduced graphene oxide based inverse spinel nickel ferrite nanocomposite for adsorption removal of radionuclides, Journal of Hazardous Materials, 326 (2017) 145-156.44. G. Zhao, T. Wen, X. Yang, S. Yang, J. Liao, J. Hu, D. Shao, X. Wang, Preconcentration of U (VI) ions on few-layered graphene oxide nanosheets from aqueous solutions, Dalton Transactions, 41 (2012) 6182-6188.45. P. Zong, S. Wang, Y. Zhao, H. Wang, H. Pan, C. He, Synthesis and application of magnetic graphene/iron oxides composite for the removal of U (VI) from aqueous solutions, Chemical Engineering Journal, 220 (2013) 45-52.46. N. Pan, J. Deng, D. Guan, Y. Jin, C. Xia, Adsorption characteristics of Th(IV) ions on reduced graphene oxide from aqueous solutions, Applied Surface Science, 287 (2013) 478-483.47. H. Cheng, K. Zeng, J. Yu, Adsorption of uranium from aqueous solution by graphene oxide nanosheets supported on sepiolite, Journal of Radioanalytical and Nuclear Chemistry, 298 (2013) 599-603.48. L. Tan, J. Wang, Q. Liu, Y. Sun, X. Jing, L. Liu, J. Liu, D. Song, The synthesis of a manganese dioxide–iron oxide–graphene magnetic nanocomposite for enhanced uranium(vi) removal, New Journal of Chemistry, 39 (2015) 868-876.49. W. Song, X. Wang, Q. Wang, D. Shao, X. Wang, Plasma-induced grafting of polyacrylamide on graphene oxide nanosheets for simultaneous removal of radionuclides, Physical Chemistry Chemical Physics, 17 (2015) 398-406.