Graphene oxide-manganese ferrite (GO-MnFe2O4) nanocomposite: One-pot hydrothermal synthesis and its use for adsorptive removal of Pb2+ ions from aqueous medium

https://doi.org/10.1016/j.molliq.2020.113769Get rights and content

Highlights

  • GO-MnFe2O4 nanocomposite synthesized using one-pot hydrothermal

  • A better enhancement in the Pb2+ adsorption occurs in aqueous solution.

  • Maximum adsorption capacity was found to be 621.11 mg/g.

  • Adsorption equilibrium occurs after 30 min, and followed to the pseudo-second order kinetic model.

  • Adsorption followed to Langmuir isotherm model (monolayer adsorption)

Abstract

Herein, we showed that the graphene oxide with manganese ferrite (GO-MnFe2O4) possess great adsorption properties for the selective Pb2+ ions removal from the aqueous medium. Nanocomposite adsorbent was developed by one-pot hydrothermal method, using graphene oxide as a supporting material to minimize the aggregation of MnFe2O4. Also, GO possesses important role in the adsorption mechanism of Pb2+ through electrostatic/ionic interactions. The characterizations such as FT-IR, XPS, P-XRD, FE-SEM, and BET of the synthesized nanocomposite were carried out to assess the different properties such as functionalities, crystallinity, morphology, and surface area value, respectively. Thereafter, the adsorption performance of GO-MnFe2O4 nanocomposite was tested for the Pb2+ at various adsorption parameters including to contact time, solution pH, adsorbent dose, and concentration of initial Pb2+ in order to measure the optimum adsorption condition. Kinetic experiments suggest that the equilibrium attained in 30 min and followed a pseudo-second-order kinetic model. Adsorption isotherm model followed to Langmuir isotherms and gives a maximum adsorption capacity of 621.11 mg/g. The reusability tests exhibited good durability and good efficiency for repeated Pb2+ adsorptions with GO-MnFe2O4 nanocomposite. These results demonstrated that the GO-MnFe2O4 nanocomposite may be an attractive adsorbent having low-cost for the effectively Pb+2 removal of from the polluted water.

Introduction

In the recent decades, the environmental pollution accompanied by growing global industrialization and agricultural/domestic activities such as the presence of heavy metals (e.g., arsenic, cadmium, mercury, lead, chromium, selenium etc.) in aquifer systems exerted potential negative effects on human health and ecological systems. Among various heavy metal ions, lead (Pb2+) is a non-biodegradable, highly toxic and wide spread contaminant in aqueous solutions which has the ability to produce disorders related with genotoxic, neurological carcinogenic, and reproductive defects in the human [1]. It is among top 20 hazardous pollutants which has been identified by United States Environmental Protection Agency (USEPA) and Agency for Toxic Substances and Disease Registry (ATSDR) [2]. The maximum acceptance limit of Pb2+ is 0.05 mg/L and 0.015 mg/L according to Bureau of Indian Standards (BIS) and World Health Organization (WHO), respectively, in potable water [3]. Therefore, effectively Pb2+ removal from aqueous solutions is a challenging task for the scientific community to prevent the adverse effects on the human health and environment.

A number of different technologies such as chemical oxidation/reduction [4] membrane separation [5], electrochemical treatment [6], coagulation/flocculation [7], chemical precipitation [8], ion exchange [9], and adsorption [10,11] have been successfully applied for the Pb2+ removal from aqueous medium. Among them, the adsorption is one of the effective technique for this purpose as it is cost effective, simple and rapid, produce minimum sludge, highly efficient and reproducible [12,13].

Literature survey revealed the use of different type of materials including activated carbons [14], polymers [15], and nanomaterial based adsorbent for example carbon nanotubes, graphene, metal oxides/magnetic nanoparticles and their composite/hybrid [[16], [17], [18]] for the pollutants removal from the aqueous medium. Among them, activated carbon is most widespread and accepted materials for wastewater treatment among the different adsorbents. This is due to having porous structure which resulted in high surface area for pollutants removal. However it is restricted due to energy intensiveness as 500–900 °C required for the regeneration and it also have limited removal efficiency for many hydrophilic micropollutants [19]. Different types of spinel ferrites (MFe2O4 where M = Fe2+, Mn2+, Ni2+, Co2+etc.) nanocomposite have been reported for the effectively heavy metal ions removal [20]. The efficiency of such spinel nanocomposites are limited for heavy metal ions removal from aqueous solutions due to their aggregation tendency which does not allowed them for practical applications [21,22]. Hence, the modification in spinel nanocomposites is required for the acceptable heavy metal ions removal with fast adsorption rate. Recently, a single layer carbon sheet of graphene having a hexagonal packed lattice structure showed interesting physio-chemical properties because of large theoretical specific surface area value (2630 m2/g) [23]. Graphene oxide (GO), a oxidise form of graphene based material has been reported to have large number of oxygenated functionalities, non-toxic nature and low cost which makes them an impressive modifier for the heavy metals removal [24,25]. Some researchers have reported the removal of different heavy metals such as As3+, As5+, Cd2+, Pb2+ and rare earth elements (La3+ and Ce3+) using GO-MnFe2O4 nanocomposite from the contaminated water. For example, Kumar et al. reported the hybrid single-layer graphene oxide with magnetic MnFe2O4 nanoparticles synthesized via the coprecipitation technique for the adsorptive removal of As3+ and As5+ from the contaminated water with maximum adsorption capacity 146 and 207 mg/g, respectively [26]. Chella et al. reported the solvothermal synthesis of MnFe2O4-graphene composite for the Pb2+ and Cd2+ removal with adsorption capacity of 100 mg/g and 76.90 mg/g, respectively at pH 5 and 7 [27]. Peng et al. reported the synthesis of graphene oxide/MnFe2O4 motor via green route and found 100 mg/g adsorption capacity for both Pb2+ and Cd2+ heavy metals for the removal of Pb2+ and Cd2+ heavy metals [28]. Xu et al. were reported the synthesis of GO/MnFe2O4 via hydrothermal process and found the adsorption capacity 133.3 mg/g for Pb2+ through Langmuir isotherm model [29]. Ghobadi and co-workers reported the removal of La3+ and Ce3+ at room temperature using MnFe2O4-GO with 1001 and 982 mg/g adsorption capacity, respectively [30]. However, synthesis of GO-MnFe2O4 via one-pot hydrothermal nanocomposite and it's use for selective Pb2+ removal from aqueous solution have never been reported to the best of our knowledge. Therefore, we reported here the synthesis of GO-MnFe2O4 nanocomposite via one-pot hydrothermal process for Pb2+ removal. It also includes the investigation on its adsorption efficiency for the Pb2+ ions removal in relation to adsorption related parameters.

Section snippets

Materials

All the chemicals were used of analytical grade: natural graphite powder (200 mesh), concentrated sulfuric acid (H2SO4, 98%) and ethanol (C2H5OH), sodium nitrate (NaNO3), hydrogen peroxide (H2O2, 30%), permanganate (KMnO4, 99.9%), ferrous sulfate hexahydrate (FeCl3·6H2O, ≥99%), manganese (II) sulfate tetrahydrate (MnCl2·4H2O, ≥99%), hydrogen chloride (HCl, 37%), sodium hydroxide (NaOH, 99%) and lead nitrate (PbNO3) were procured from Merck India Ltd., Mumbai, India.

Synthesis of GO

Modified Hummer's method was

Characterization of GO-MnFe2O4 nanocomposite

The phase purity and crystalline structure of the prepared GO-MnFe2O4 nanocomposite has shown in Fig. 1. All the diffraction patterns ensured the well-crystallized structure of spinel type MnFe2O4 phase. The diffraction peaks appeared at 2θ values of 30.52, 33.61, 36.21, 41.27, 50.13, 54.35, 62.98, 64.36 and 72.47° correspond to the (220), (311), (222), (400), (422), (511), (440), (531) and (533) crystal plan of MnFe2O4 respectively of the P-XRD pattern of GO-MnFe2O4 suggest the presence of

Conclusion

The present study summarized a facile process for the preparation of GO-MnFeO4 nanocomposite in one-pot using hydrothermal process. The GO-MnFeO4 nanocomposite were used for the adsorptive removal of Pb2+ ions from water. The powder XRD, and FE-SEM analysis were used for the structural and surface morphology of synthesized nanocomposite showed a cubic spinel structure. The results of adsorption experiments suggest that the optimum adsorption for Pb2+ removal can be achieved at pH = 6, adsorbent

CRediT authorship contribution statement

Monu Verma: Conceptualization, Writing - original draft. Ashwani Kumar: Data curation. Krishna Pal Singh: Investigation. Ravi Kumar: Writing - original draft. Vinod Kumar: Writing - original draft. Chandra Mohan Srivastava: Investigation. Varun Rawat: Investigation. Gyandeshwar Rao: Investigation. Sujata Kumari: Investigation. Pratibha Sharma: Investigation. Hyunook Kim: Writing - review & editing.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgement

The authors gratefully acknowledge to National Research Foundation of Korea (NRF) to provide the funding for research under the Korea Research Fellowship (KRF) program having grant number 2019H1D3A1A01102657. Authors are also grateful to Dr. Ramesh Chandra, Institute Instrumentation Centre (IIC), IIT Roorkee for providing FE-SEM and XPS facilities.

References (58)

  • M. Siahkamari et al.

    Removal of lead(II) ions from aqueous solutions using biocompatible polymeric nano-adsorbents: a comparative study

    Carbohydr. Polym.

    (2017)
  • P.C. Chiang et al.

    Comparison of chemical and thermal regeneration of aromatic compounds on exhausted activated carbon

    Water Sci. Technol.

    (1997)
  • D.H.K. Reddy et al.

    Spinel ferrite magnetic adsorbents: alternative future materials for water purification?

    Coord. Chem. Rev.

    (2016)
  • N.C. Feitoza et al.

    Fabrication of glycine-functionalized maghemite nanoparticles for magnetic removal of copper from wastewater

    J. Hazard. Mater.

    (2014)
  • Q.U. Ain et al.

    Application of magnetic graphene oxide for water purification: heavy metals removal and disinfection

    J. Water Process Eng.

    (2020)
  • S. Chella et al.

    Solvothermal synthesis of MnFe2O4-graphene composite-investigation of its adsorption and antimicrobial properties

    Appl. Surf. Sci.

    (2015)
  • W. Xu et al.

    Novel ternary nanohybrids of tetraethylenepentamine and graphene oxide decorated with MnFe2O4 magnetic nanoparticles for the adsorption of Pb(II)

    J. Hazard. Mater.

    (2018)
  • M. Ghobadi et al.

    MnFe2O4-graphene oxide magnetic nanoparticles as a high-performance adsorbent for rare earth elements: synthesis, isotherms, kinetics, thermodynamics and desorption

    J. Hazard. Mater.

    (2018)
  • M. Verma et al.

    Adsorptive removal of Pb (II) ions from aqueous solution using CuO nanoparticles synthesized by sputtering method

    J. Mol. Liq.

    (2017)
  • P. Marin et al.

    Synthesis and characterization of graphene oxide functionalized with MnFe2O4 and supported on activated carbon for glyphosate adsorption in fixed bed column

    Process. Saf. Environ. Prot.

    (2019)
  • Y. Zhou et al.

    Photo-Fenton degradation of ammonia via a manganese-iron double-active component catalyst of graphene-manganese ferrite under visible light

    Chem. Eng. J.

    (2016)
  • K.C. Barick et al.

    Porosity and photocatalytic studies of transition metal doped ZnO nanoclusters

    Microporous Mesoporous Mater.

    (2010)
  • Ö. Gerçel et al.

    Adsorption of lead(II) ions from aqueous solutions by activated carbon prepared from biomass plant material of Euphorbia rigida

    Chem. Eng. J.

    (2007)
  • S. Hokkanen et al.

    Removal of heavy metals from aqueous solutions by succinic anhydride modified mercerized nanocellulose

    Chem. Eng. J.

    (2013)
  • Y.S. Ho et al.

    Pseudo-second order model for sorption processes

    Process Biochem.

    (1999)
  • S. Figaro et al.

    Adsorption studies of molasse's wastewaters on activated carbon: Modelling with a new fractal kinetic equation and evaluation of kinetic models

    J. Hazard. Mater.

    (2009)
  • F. Zhao et al.

    Adsorption of Cd(II) and Pb(II) by a novel EGTA-modified chitosan material: kinetics and isotherms

    J. Colloid Interface Sci.

    (2013)
  • F. Ge et al.

    Effective removal of heavy metal ions Cd2+, Zn2+, Pb2+, Cu2+ from aqueous solution by polymer-modified mag netic nanoparticles

    J. Hazard. Mater.

    (2012)
  • S. Mishra et al.

    Carbon gel-supported Fe-graphene disks: synthesis, adsorption of aqueous Cr(VI) and Pb(II) and the removal mechanism

    Chem. Eng. J.

    (2017)
  • Cited by (64)

    View all citing articles on Scopus
    View full text