Elsevier

Chemical Engineering Journal

Volume 226, 15 June 2013, Pages 336-347
Chemical Engineering Journal

Review
Adsorptive remediation of environmental pollutants using novel graphene-based nanomaterials

https://doi.org/10.1016/j.cej.2013.04.070Get rights and content

Highlights

  • Graphene-based materials present high adsorption capacity for water and air pollutants.

  • Graphene oxide exhibits high adsorption to basic and cationic compounds.

  • Strong π–π interaction plays an important role for graphene adsorption.

  • Graphene functionalised composites show enhanced performance in adsorption.

Abstract

Pollution of air, water and soil is a worldwide issue for the eco-environment and human society. Removal of various pollutants including inorganic and organic compounds from the environment is a big challenge. Adsorption techniques are usually simple and work effectively. However, the adsorption capacities of materials depend on their porous structure and surface properties. Graphene oxide and graphene are new carbonaceous nanomaterials. Graphene has a large theoretical specific surface area and graphene oxide has functional groups, indicating their potential for the adsorption processes. In the past few years, many investigations have been focused on the applications of graphene or composites in removal of pollutants from air and water. In this paper, we will review recent advances in graphene-related nanomaterials for adsorptive treatment of environmental pollution. Graphene oxide possesses several functional groups and strong acidity, exhibiting high adsorption for basic compounds and cations while graphene shows hydrophobic surface and presents high adsorption to chemicals due to strong π–π interaction. Modification of graphene oxide or graphene with metal oxides or organics can produce various nanocomposites, enhancing adsorption capacity and separation efficiency. Activation of graphene into porous carbonaceous material will be a promising way to further enhance adsorption capacity.

Introduction

Since the industrial revolution, rapid developments in industrialization, population expansion, and urbanization have largely contributed to the severe pollution to air, water and soil. A vast of pollutants discharged from industrial processes and households annually have caused significant effects on the eco-environment and human life. These pollutants include toxic gases (NOx, SOx, CO, NH3), heavy metals, organics and bio-toxics. A number of physical, chemical and biological technologies have been developed to control the pollution successfully [1], [2], [3], [4], [5], [6]. Among the various available technologies, adsorption process is widely used and considered as a simple and easy operation and it can effectively remove different types of pollutant from the environment [7], [8]. In addition, adsorption does not result in secondary pollution by producing harmful substances during the process.

For any adsorption process, an adsorbent having large surface area, pore volume, and proper functionalities is the key to success. Currently, many different porous materials have been developed, such as activated carbon, pillared clays, zeolites, mesoporous oxides, polymers and metal–organic frameworks, showing varying extent of effectiveness in removing the toxic pollutants from air, water and soil [8], [9], [10], [11], [12]. Among them, carbonaceous-based adsorbents including activated carbon, carbon nanotubes, and fullerene usually show high adsorption capacity and thermal stability [13], [14], [15], [16].

In the past a few years, graphene oxide (GO) and graphene nanosheets (GNs) have attracted tremendous interest in the world. Graphene is a two-dimensional carbon nanomaterial with single layer of sp2-hybridized carbon atoms arranged in six-membered rings. Graphene has strong mechanical, thermal, and electrical properties, with a theoretical value of specific surface area at 2630 m2/g [17]. GO is functionalized graphene with varying oxygen-containing groups. Several reviews have been reported on applications of GO and GNs in different areas such as physics, chemistry, biology, and materials science [17], [18], [19], [20], [21], however, few reviews on graphene-based materials as adsorbents for pollutant removal is available [22]. In this paper, we will review the research in graphene-based nanomaterials as adsorbents for removal of various types of contaminant in air and water systems.

Section snippets

Synthesis and structure of GO and GNs

Currently, most GO is synthesized by chemical oxidation and exfoliation of pristine graphite using either the Brodie, Staudenmaier, or Hummers method, or some variations of these methods. Brodie first found that the oxidizing mixture (KClO4 + fuming HNO3) could form GO only with graphitizable carbons that contain regions of graphitic structure [23]. Staudenmaier then reported the formation of GO when graphite was heated with H2SO4, HNO3, and KClO4 [24]. Later, Hummers and Offeman introduced a

Adsorptive removal of gas pollutants

Air pollutants include toxic gases and particulates. NOx, SOx, H2S, NH3, CO, and volatile organic compounds (VOCs) are the most important gaseous pollutants, which can cause significant damages to the eco-environment and human health. A traditional method for polluted air remediation is adsorption using solid adsorbents such as highly porous zeolites [37], [38], [39] and activated carbon [40], [41], [42], [43]. In the past years, it was found that GO, GNs and their modified forms can also be

Water treatment by GO or GNs adsorption

There are many pollutants in groundwater, surface water and wastewater systems. The important pollutants in water include anions and heavy metal cations as well as organic compounds. For removal of those pollutants, various carbon materials including activated carbon [59], [60], [61] and carbon nanotubes [13], [62] have been widely investigated in previous years and they show high adsorption capacity. Compared with activated carbon and carbon nanotubes, GO and GNs also present strong adsorption

Conclusion and perspectives

GO and GNs are new carbonaceous materials with high surface area and functional groups. These materials can be used as adsorbents to effectively remove various gaseous and aqueous pollutants. The adsorption depends on adsorbate forms, ionic or hydrophobic. As GO shows strong acidity and negative charges, it exhibits high adsorption of basic chemicals such as ammonia and cationic ions via reactive adsorption and ionic binding. On the contrary, due to loss of oxygen species, the π–π interaction

Acknowledgement

This project is partially supported by the Australian Research Council under Project no. DP130101319.

References (133)

  • H. Yi et al.

    Adsorption equilibrium and kinetics for SO2, NO, CO2 on zeolites FAU and LTA

    J. Hazard. Mater.

    (2012)
  • X. Zhou et al.

    Thermodynamics for the adsorption of SO2, NO and CO2 from flue gas on activated carbon fiber

    Chem. Eng. J.

    (2012)
  • M. Seredych et al.

    Removal of ammonia by graphite oxide via its intercalation and reactive adsorption

    Carbon

    (2007)
  • M. Seredych et al.

    Changes in graphite oxide texture and chemistry upon oxidation and reduction and their effect on adsorption of ammonia

    Carbon

    (2011)
  • M. Seredych et al.

    Graphite oxide/AlZr polycation composites: Surface characterization and performance as adsorbents of ammonia

    Mater. Chem. Phys.

    (2009)
  • M. Seredych et al.

    Manganese oxide and graphite oxide/MnO2 composites as reactive adsorbents of ammonia at ambient conditions

    Microporous Mesoporous Mater.

    (2012)
  • S. Wang et al.

    Volatile organic compounds in indoor environment and photocatalytic oxidation: state of the art

    Environ. Int.

    (2007)
  • Y. Matsuo et al.

    Introduction of amino groups into the interlayer space of graphite oxide using 3-aminopropylethoxysilanes

    Carbon

    (2007)
  • Y. Matsuo et al.

    Removal of formaldehyde from gas phase by silylated graphite oxide containing amino groups

    Carbon

    (2008)
  • A. Dabrowski et al.

    Adsorption of phenolic compounds by activated carbon – a critical review

    Chemosphere

    (2005)
  • D. Mohan et al.

    Activated carbons and low cost adsorbents for remediation of tri- and hexavalent chromium from water

    J. Hazard. Mater.

    (2006)
  • K.Y. Foo et al.

    Detoxification of pesticide waste via activated carbon adsorption process

    J. Hazard. Mater.

    (2010)
  • V.K.K. Upadhyayula et al.

    Application of carbon nanotube technology for removal of contaminants in drinking water: a review

    Sci. Total Environ.

    (2009)
  • S.-T. Yang et al.

    Folding/aggregation of graphene oxide and its application in Cu2+ removal

    J. Colloid Interface Sci.

    (2010)
  • Y.Q. He et al.

    Adsorption of graphene oxide/chitosan porous materials for metal ions

    Chin. Chem. Lett.

    (2011)
  • N. Zhang et al.

    Fabrication of highly porous biodegradable monoliths strengthened by graphene oxide and their adsorption of metal ions

    Carbon

    (2011)
  • L. Liu et al.

    Preparation and characterization of chitosan/graphene oxide composites for the adsorption of Au(III) and Pd(II)

    Talanta

    (2012)
  • Y.-C. Lee et al.

    Self-assembled flower-like TiO2 on exfoliated graphite oxide for heavy metal removal

    J. Ind. Eng. Chem.

    (2012)
  • M. Machida et al.

    Lead(II) adsorption onto the graphene layer of carbonaceous materials in aqueous solution

    Carbon

    (2006)
  • X. Deng et al.

    The adsorption properties of Pb(II) and Cd(II) on functionalized graphene prepared by electrolysis method

    J. Hazard. Mater.

    (2010)
  • L. Hao et al.

    SiO2/graphene composite for highly selective adsorption of Pb(II) ion

    J. Colloid Interface Sci.

    (2012)
  • T.S. Sreeprasad et al.

    Reduced graphene oxide–metal/metal oxide composites: facile synthesis and application in water purification

    J. Hazard. Mater.

    (2011)
  • Y. Ren et al.

    Graphene/δ-MnO2 composite as adsorbent for the removal of nickel ions from wastewater

    Chem. Eng. J.

    (2011)
  • A.K. Mishra et al.

    Functionalized graphene sheets for arsenic removal and desalination of sea water

    Desalination

    (2011)
  • K. Zhang et al.

    Graphene oxide/ferric hydroxide composites for efficient arsenate removal from drinking water

    J. Hazard. Mater.

    (2010)
  • Y. Li et al.

    Adsorption of fluoride from aqueous solution by graphene

    J. Colloid Interface Sci.

    (2011)
  • S.-T. Yang et al.

    Removal of methylene blue from aqueous solution by graphene oxide

    J. Colloid Interface Sci.

    (2011)
  • T. Liu et al.

    Adsorption of methylene blue from aqueous solution by graphene

    Colloids Surf. B-Biointerfaces

    (2012)
  • L. Sun et al.

    Graphene oxide adsorption enhanced by in situ reduction with sodium hydrosulfite to remove acridine orange from aqueous solution

    J. Hazard. Mater.

    (2012)
  • G.K. Ramesha et al.

    Graphene and graphene oxide as effective adsorbents toward anionic and cationic dyes

    J. Colloid Interface Sci.

    (2011)
  • P. Biswas et al.

    Control of toxic metal emissions from combustors using sorbents: a review

    J. Air Waste Manage. Assoc.

    (1998)
  • M.S. El-Geundi

    Adsorbents for industrial pollution control

    Adsorpt. Sci. Technol.

    (1997)
  • C. Kennes et al.

    Bioprocesses for air pollution control

    J. Chem. Technol. Biotechnol.

    (2009)
  • M.C. Delhomenie et al.

    Biofiltration of air: a review

    Crit. Rev. Biotechnol.

    (2005)
  • G.M. Gadd

    Biosorption: critical review of scientific rationale, environmental importance and significance for pollution treatment

    J. Chem. Technol. Biotechnol.

    (2009)
  • S.P. Dubey et al.

    Utility of adsorbents in the purification of drinking water: a review of characterization, efficiency and safety evaluation of various adsorbents

    J. Environ. Biol.

    (2009)
  • W.S.W. Ngah et al.

    Adsorption of dyes and heavy metal ions by chitosan composites: a review

    Carbohydr. Polym.

    (2011)
  • S. Sen Gupta et al.

    Adsorption of heavy metals on kaolinite and montmorillonite: a review

    Phys. Chem. Chem. Phys.

    (2012)
  • A.A. Adeyemo et al.

    Metal organic frameworks as adsorbents for dye adsorption: overview, prospects and future challenges

    Toxicol. Environ. Chem.

    (2012)
  • Y. Kim et al.

    Advances in environmental technologies via the application of mesoporous materials

    J. Ind. Eng. Chem.

    (2004)
  • Cited by (624)

    View all citing articles on Scopus
    View full text