Open Access

Thiol-functionalized magnetite/graphene oxide hybrid as a reusable adsorbent for Hg2+ removal

Nanoscale Research Letters20138:486

DOI: 10.1186/1556-276X-8-486

Received: 25 October 2013

Accepted: 12 November 2013

Published: 19 November 2013


A thiol-functionalized magnetite/graphene oxide (MGO) hybrid as an adsorbent of Hg2+ was successfully synthesized by a two-step reaction. It exhibited a higher adsorption capacity compared to the bare graphene oxide and MGO due to the combined adsorption of thiol groups and magnetite nanocrystals. Its capacity reached 289.9 mg g-1 in a solution with an initial Hg2+ concentration of 100 mg l-1. After being exchanged with H+, the adsorbent could be reused. The adsorption of Hg2+ by the thiol-functionalized MGO fits well with the Freundlich isotherm model and followed pseudo-second-order kinetics.


Mercury ion Magnetite Adsorption capacity Graphene oxide Hybrid


Due to the development and expansion of industry, pollution of heavy metals in water supplies increases in the recent years. The pollution is seriously threatening the ecological systems as well as human health. Among them, mercury is one of the most hazardous elements due to its toxicological and biogeochemical behavior[1, 2]. A lot of adsorbents have been employed to extract Hg2+ from the industrial wastewaters. For example, thiol-functionalized adsorbents exhibited a specific binding capability toward highly toxic heavy metal ions including Hg2+ due to the existence of the thiol groups[36]. While for iron oxides, their adsorption mechanism was attributed to the complexation of Hg2+ and surface hydroxyl group at the iron oxide/water interface[79]. Iron oxide nanocrystals can further enhance the adsorption capacities because of their high specific surface area[6, 10]. Another advantage of using iron oxide-based adsorbents is that they can be easily extracted from wastewater by applying an external magnetic force. However, few research works have reported on adsorbents with both adsorption effects. The emergence of graphene oxide makes such combination possible due to its abundant functional moieties (hydroxyl and carboxyl groups)[11, 12], which enable possible metal oxide deposition and functional organic group grafting on its surface[1315]. In this work, we deposited Fe3O4 nanoparticles on graphene oxide and then grafted thiol groups on the Fe3O4/graphene oxide (MGO). The thiol-functionalized MGO exhibited relatively high Hg2+ adsorption capacity. The adsorbent could be separated from the water solutions easily and reused after it was exchanged with H+.


Chemicals and materials

Natural graphite (500 mesh), 98 wt.% H2SO4, 5 wt.% HCl aqueous solution, 30 wt.% H2O2 aqueous solution, acetone, and Na2CO3 were purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). 1-Methyl-2-pyrrolidone (NMP), ferric acetylacetonate (Fe(acac)3), potassium permanganate (KMnO4), NaHCO3, 1-ethy-3-(3-dimethyllaminopropyl) carvodiimide hydrochloride (EDC), and 2-mercaptoethylamine (MEA) were purchased from Aladdin Reagent Company (Shanghai, China). Other reagents used were of analytical grades without further purification. Deionized water was used in all the processes of aqueous solution preparations.

Preparation of MGO

Graphene oxide (GO, 100 mg) was dispersed in 30 ml of NMP by ultrasonication at room temperature, and the mixture was heated to 190°C under an argon atmosphere. Fe(acac)3 (1.413 g, 4 mmol) was dissolved in 20 ml of NMP and added dropwise in about 1 h to the GO/NMP solution under vigorous stirring. The stirring was continued for another 4 h after the dropping was finished. After being cooled to room temperature, the mixture was washed three times using acetone and water alternatively. The precipitate was collected by magnetic separation and was then dispersed in water by ultrasonication. The resulting black powder was collected by freeze-drying.

Synthesis of thiol-functionalized MGO

MGO (10 mg) was dispersed in 10 ml of deionized water by ultrasonication in an ice bath. EDC of 50 ml and a Na2CO3-NaHCO3 (1:9) buffer solution were added to adjust the pH of the system to approximately 9. After carboxyl groups on MGO were activated in 1 h, a solution containing 100 mg of MEA was added dropwise to the system. With the protection of argon, the reaction lasted for 24 h. The precipitate was collected by magnetic separation and was then dispersed in water by ultrasonication. The resulting black powder was collected by freeze-drying.

Adsorption experiment

The effects of the initial concentration of Hg2+ and adsorption time on the final adsorption capacity were tested to obtain the saturated adsorption capacity and dynamic adsorption curve. Thiol-functionalized MGO powder was added to 25 ml of water solution with different concentrations of Hg2+. NaOH was used to adjust the pH of the solution. While the temperature was kept stable by using a water bath, the samples were placed on a standard rocker and oscillated for given hours. The supernate was collected by magnetic separation for reproducibility test. After washing with diluted HCl (0.25 N), the thiol-functionalized MGO was re-immersed in the solution with an initial Hg2+ concentration of 100 mg l-1 and oscillated for 48 h.


The X-ray diffraction (XRD) pattern was taken on a D/MAX-RB diffractometer using Cu Kα radiation. Investigation of the microstructure was performed by transmission electron microscopy (TEM, JEOL JEM-2010 F, JEOL Ltd., Akishima, Tokyo, Japan). Water bath sonication was performed with a JYD 1800 L sonicator (100 to 2,000 W, ZhiXin Instrument Co., Ltd, Shanghai, China). Hg2+ concentration was determined by using a DMA-80 direct mercury analyzer (Milestone S.r.l., Sorisole, Italy).

Results and discussion

GO was prepared from natural graphite using modified Hummer's method[16, 17]. Fe3O4 nanoparticles were deposited on graphene oxide by decomposition of Fe(acac)3 in NMP solution (Figure 1, step A) at 190°C[18]. Figure 2a shows the XRD pattern of the product. The peaks at 30.2°, 35.5°, 43.1°, 53.5°, 57.0°, 62.4° in the pattern could be ascribed to diffraction of (220), (311), (400), (422), (511), and (440) crystal planes of Fe3O4 (magnetite, JCPDS no. 75–0033). Based on the Scherrer analysis of the pattern, the crystallite size of Fe3O4 was estimated to be 13.0 nm. The appearance of the magnetite phase was consistent with the electron diffraction pattern (inset in Figure 2b). The TEM image (Figure 2b) of the product showed that GO was decorated with magnetite aggregates with a size of several tens of nanometers. In the synthesis process, carbon monoxide was generated at a relatively high temperature and partially reduced Fe3+ to Fe2+. Then, the magnetite nanocrystals nucleated and grew at the oxygen-containing defects sites such as carboxyl, hydroxyl, and epoxy groups[14]. Finally, MGO was obtained. Thiol functional groups were grafted on the MGO by the reaction between MEA and carboxyl groups on GO activated by EDC (Figure 1, step B). Energy-dispersive X-ray spectroscopy (EDAX) analysis (Figure 2c) indicated the appearance of the sulfur element, indicating that the thiol groups were successfully grafted on MGO. Thus, the thiol-functionalized MGO was obtained after the reaction. The magnetic properties of the thiol-functionalized MGO were investigated using a superconducting quantum interference device (SQUID) magnetometer. Figure 3 shows the hysteresis loop of the thiol-functionalized MGO hybrids at room temperature (300 K). The saturation magnetization was 22.0 emu g-1, which was much smaller than 92.0 emu g-1, the saturation magnetization of bulk Fe3O4[19]. The reduction in the value of saturation magnetization could be attributed to the rather small size of magnetite and GO in the hybrids[20, 21]. The remnant magnetization and coercivity for thiol-functionalized MGO were 0.74 emu g-1 and 11.89 Oe, respectively, which were ascribed to the superparamagnetic state of magnetite nanocrystals due to the size effect. Such superparamagnetic state of the adsorbent with small remnant magnetization and coercivity at room temperature could enable the adsorbent to be readily attracted and separated by even a small external magnetic field[22]. In fact, the thiol-functionalized MGO dispersed in water solution was easily extracted from water with a magnet (Figure 3b).
Figure 1

Schematic of synthesis of thiol-functionalized MGO from graphene oxide.
Figure 2

XRD pattern, TEM image, and EDAX analysis. (a) XRD pattern of MGO, (b) TEM image of MGO (inset, the electron diffraction pattern of MGO), and (c) EDAX analysis of thiol-functionalized MGO.
Figure 3

Hysteresis loop and extraction of the thiol-functionalized MGO. (a) Hysteresis curve of thiol-functionalized MGO (inset, close view of hysteresis loops) and (b) the water solution dispersed with thiol-functionalized MGO and magnetic separation.

The adsorption kinetics of Hg2+ by the thiol-functionalized MGO is shown Figure 4a. The initial Hg2+ concentration was 10 mg l-1. The adsorbed capacity (Q) of Hg2+ per unit mass was calculated using the following equation:
Q = C 0 - C t × V W
where, Q (mg g-1) is the amount of Hg2+ adsorbed per unit of adsorbent (mg g-1); C0 (mg l-1) and C t (mg l-1) refer to the initial concentration of Hg2+ and the concentration of Hg2+ after the adsorption, respectively; W (g) is the weight of thiol-functionalized MGO; V (ml) is the volume of the whole solution system. After a 48-h adsorption, the solution reached a state of equilibrium. Even GO alone had a certain adsorption capacity of Hg2+, which was due to the formation of exchanged metal carboxylates on the surface of GO[23], while the adsorption capacity of thiol-functionalized MGO was higher than those of GO and MGO. The improved adsorption capacity of thiol-functionalized MGO could be attributed to the combined affinity of Hg2+ by magnetite nanocrystals and thiol groups. To determine the mechanism of Hg2+ adsorption from an aqueous solution by thiol-functionalized MGO, the pseudo-first-order and pseudo-second-order kinetic models were applied to interpret the adsorption data. The pseudo-second-order kinetics was presented as[24]
t Q t = 1 K 2 Q e 2 + t Q e
where K2 is the pseudo-second-order rate constant (g mg-1) and Q t is the amount of Hg2+ adsorbed per unit of adsorbent (mg g-1) at time t. The t/Q t versus t plot shown in Figure 4b indicated that the adsorption of Hg2+ by thiol-functionalized MGO followed the pseudo-second-order kinetic model, but not the pseudo-first-order kinetic model (Additional file1: Figure S1a). K2 and Qe were calculated to be 6.49E - 4 g mg-1 min-1 and 30.94 mg g-1, respectively. To understand how Hg2+ interacted with thiol-functionalized MGO, different adsorption isotherm models were used to fit the adsorption data. The data of Hg2+ adsorption were fit with the Freundlich isotherm model, which can be expressed as[25]
log Q e = log K + 1 n log C e
where K and n are the Freundlich adsorption isotherm constants, which are related to the relative adsorption capacity of the adsorbent and the degree of nonlinearity between solution concentration and adsorption, respectively. K and 1/n values can be calculated from the intercept and slope of the linear plot between logC e and logQ e . Based on the plot shown in Figure 5a, n and K were calculated to be 1.02 and 10.54, respectively. However, the data did not fit the Langmuir isotherm model very well (Additional file1: Figure S1b), indicating that the adsorption of Hg2+ by the adsorbent was not restricted to monolayer formations[26]. To test the reproducibility of the adsorbents, they were immersed in an aqueous solution with an initial Hg2+ concentration of 100 mg l-1 for 48 h with oscillation. The adsorption capacity for the first-time immersion was calculated to be 289.9 mg g-1. After being washed with diluted HCl, thiol-functionalized MGO was applied to repeat the exact same adsorption test. The obtained adsorption capacities were 282.4, 276.8, and 258.1 mg g-1 for the second-, third-, and fourth-time immersion, respectively, which were corresponding to 97.4%, 95.5%, and 89.0% of initial adsorption capacity. It indicated that the adsorbents could be reused.
Figure 4

Adsorption kinetics. (a) Hg2+ adsorption kinetics of GO, MGO, and thiol-functionalized MGO, respectively. (b) The adsorption kinetics of thiol-functionalized MGO fits with the pseudo-second-order kinetics (initial concentration, 10 mg l-1).
Figure 5

Adsorption isotherms and adsorption capacity. (a) Adsorption isotherms fitted with the Freundlich model (red line) for adsorption of Hg2+ on thiol-functionalized MGO and (b) adsorption capacity versus the cycling number with the initial concentration of 100 mg l-1 Hg2+.


Thiol-functionalized MGO with magnetite nanoparticles was successfully synthesized using a two-step reaction. Thiol-functionalized MGO exhibited higher adsorption capacity compared to the bare graphene oxide and MGO. Its capacity reached 289.9 mg g-1 in the solution with an initial Hg2+ concentration of 100 mg l-1. The improved adsorption capacity could be attributed to the combined affinity of Hg2+ by magnetite nanocrystals and thiol groups. After being exchanged with H+, the adsorbent could be recycled. The adsorption of Hg2+ by thiol-functionalized MGO fits well with the Freundlich isotherm model and followed pseudo-second-order kinetics. The scheme reported here enables rational design of the surface properties of graphene oxide and can be used to synthesize other functionalized composites for environmental applications.



Ferric acetylacetonate


Graphene oxide


Potassium permanganate




Magnetite/graphene oxide




Superconducting quantum interference device


X-ray diffraction.



This work was supported by the Jiangsu Environmental Protection Project (no. 2012005).

Authors’ Affiliations

Jiangsu Provincial Academy of Environmental Science
Shanghai Key Laboratory of Special Artificial Microstructure Materials and Technology, Tongji University


  1. Kelly C, Rudd JW, Holoka M: Effect of pH on mercury uptake by an aquatic bacterium: implications for Hg cycling. Environ Sci Technol 2003, 37: 2941–2946. 10.1021/es026366oView ArticleGoogle Scholar
  2. World Health Organization: IPCS Environmental Health Criteria 101: Methylmercury. International Programme of Chemical Safety. Geneva: World Health Organization; 1990.Google Scholar
  3. Vieira FSE, de Simoni JA, Airoldi C: Interaction of cations with SH-modified silica gel: thermochemical study through calorimetric titration and direct extent of reaction determination. J Mater Chem 1997, 7: 2249–2252. 10.1039/a704286hView ArticleGoogle Scholar
  4. Feng X, Fryxell G, Wang L-Q, Kim AY, Liu J, Kemner K: Functionalized monolayers on ordered mesoporous supports. Science 1997, 276: 923–926. 10.1126/science.276.5314.923View ArticleGoogle Scholar
  5. Bibby A, Mercier L: Mercury (II) ion adsorption behavior in thiol-functionalized mesoporous silica microspheres. Chem Mater 2002, 14: 1591–1597. 10.1021/cm0112082View ArticleGoogle Scholar
  6. Yavuz CT, Mayo J, William WY, Prakash A, Falkner JC, Yean S, Cong L, Shipley HJ, Kan A, Tomson M: Low-field magnetic separation of monodisperse Fe3O4 nanocrystals. Science 2006, 314: 964–967. 10.1126/science.1131475View ArticleGoogle Scholar
  7. Kinniburgh D, Jackson M: Adsorption of mercury (II) by iron hydrous oxide gel. Soil Science Society of America Journal 1978, 42: 45–47. 10.2136/sssaj1978.03615995004200010010xView ArticleGoogle Scholar
  8. Tiffreau C, Lützenkirchen J, Behra P: Modeling the adsorption of mercury (II) on (hydr) oxides I. Amorphous iron oxide and α-quartz. J Colloid Interface Sci 1995, 172: 82–93. 10.1006/jcis.1995.1228View ArticleGoogle Scholar
  9. Kim CS, Rytuba JJ, Brown GE Jr: EXAFS study of mercury (II) sorption to Fe-and Al-(hydr) oxides: I Effects of pH. J Colloid Interface Sci 2004, 271: 1–15. 10.1016/S0021-9797(03)00330-8View ArticleGoogle Scholar
  10. Chandra V, Park J, Chun Y, Lee JW, Hwang I-C, Kim KS: Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. ACS Nano 2010, 4: 3979–3986. 10.1021/nn1008897View ArticleGoogle Scholar
  11. He H, Klinowski J, Forster M, Lerf A: A new structural model for graphite oxide. Chemical Physics Letters 1998, 287: 53–56. 10.1016/S0009-2614(98)00144-4View ArticleGoogle Scholar
  12. Hontoria-Lucas C, Lopez-Peinado A, López-González JD, Rojas-Cervantes M, Martin-Aranda R: Study of oxygen-containing groups in a series of graphite oxides: physical and chemical characterization. Carbon 1995, 33: 1585–1592. 10.1016/0008-6223(95)00120-3View ArticleGoogle Scholar
  13. Dreyer DR, Park S, Bielawski CW, Ruoff RS: The chemistry of graphene oxide. Chem Soc Rev 2010, 39: 228–240. 10.1039/b917103gView ArticleGoogle Scholar
  14. Wang H, Robinson JT, Diankov G, Dai H: Nanocrystal growth on graphene with various degrees of oxidation. J Am Chem Soc 2010, 132: 3270–3271. 10.1021/ja100329dView ArticleGoogle Scholar
  15. Wang X, Tabakman SM, Dai H: Atomic layer deposition of metal oxides on pristine and functionalized graphene. J Am Chem Soc 2008, 130: 8152–8153. 10.1021/ja8023059View ArticleGoogle Scholar
  16. Moon IK, Lee J, Ruoff RS, Lee H: Reduced graphene oxide by chemical graphitization. Nat Commun 2010, 1: 73.View ArticleGoogle Scholar
  17. Hummers WS Jr, Offeman RE: Preparation of graphitic oxide. J Am Chem Soc 1958, 80: 1339. 10.1021/ja01539a017View ArticleGoogle Scholar
  18. Li Z, Sun Q, Gao M: Preparation of water‒soluble magnetite nanocrystals from hydrated ferric salts in 2‒pyrrolidone: mechanism leading to Fe3O4. Angew Chem Int Ed 2005, 44: 123–126. 10.1002/anie.200460715View ArticleGoogle Scholar
  19. Zaitsev VS, Filimonov DS, Presnyakov IA, Gambino RJ, Chu B: Physical and chemical properties of magnetite and magnetite-polymer nanoparticles and their colloidal dispersions. J Colloid Interface Sci 1999, 212: 49–57. 10.1006/jcis.1998.5993View ArticleGoogle Scholar
  20. Berkowitz AE, Schuele WJ, Flanders PJ: Influence of crystallite size on the magnetic properties of acicular γ-Fe2O3 particles. J Appl Phys 1968, 39: 1261–1263. 10.1063/1.1656256View ArticleGoogle Scholar
  21. Chen J, Sorensen C, Klabunde K, Hadjipanayis G, Devlin E, Kostikas A: Size-dependent magnetic properties of MnFe2O4 fine particles synthesized by coprecipitation. Physical Review B 1996, 54: 9288. 10.1103/PhysRevB.54.9288View ArticleGoogle Scholar
  22. Wang X, Yang D-P, Huang G, Huang P, Shen G, Guo S, Mei Y, Cui D: Rolling up graphene oxide sheets into micro/nanoscrolls by nanoparticle aggregation. J Mater Chem 2012, 22: 17441–17444. 10.1039/c2jm32810kView ArticleGoogle Scholar
  23. Karabulut S, Karabakan A, Denizli A, Yürüm Y: Batch removal of copper (II) and zinc (II) from aqueous solutions with low-rank Turkish coals. Sep Purif Technol 2000, 18: 177–184. 10.1016/S1383-5866(99)00067-2View ArticleGoogle Scholar
  24. Ho Y-S, McKay G: Pseudo-second order model for sorption processes. Process Biochem 1999, 34: 451–465. 10.1016/S0032-9592(98)00112-5View ArticleGoogle Scholar
  25. Freundlich H: Uber die adsorption in lasugen. Z Phys Chem 1906, 57: 385–470.Google Scholar
  26. Langmuir I: The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc 1918, 40: 1361–1403. 10.1021/ja02242a004View ArticleGoogle Scholar


© Bao et al.; licensee Springer. 2013

This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.