Environmental Pollution 252 (2019) 62e73

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Graphene oxide-based materials for efficient removal of heavy metal

ions from aqueous solution: A review
Xiaolu Liu a, Ran Ma a, Xiangxue Wang a, *, Yan Ma a, Yongping Yang b, Li Zhuang a,
Sai Zhang a, Riffat Jehan a, Jianrong Chen c, Xiangke Wang a
a
MOE Key Laboratory of Resources and Environmental Systems Optimization, College of Environmental Science and Engineering, North China Electric
Power University, Beijing, 102206, PR China
b
College of Chemical Engineering and Technology, Yanshan University, Qinhaungdao, 066044, PR China
c
College of Geography and Environmental Science, Zhejiang Normal University, Jinhua, 321004, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Graphene with atomic layer of sp2-hybridized carbon atoms in a hexagonal structure has attracted
Received 27 January 2019 multidisciplinary attention since its discovery. Due to the inherent advantages of large specific surface
Received in revised form area and abundant functional groups, its derivative graphene oxide (GO) nanomaterials have achieved
12 April 2019
large-scale development in effective pollution treatment. In the past few years, novel GO-based nano-
Accepted 10 May 2019
materials through coupling with other nanomaterials have been synthesized with significant process and
Available online 16 May 2019
applied for efficient elimination of different kinds of pollutants. This paper aims to summarize recent
research results on the excellent removal ability of GO-based nanomaterials for various heavy metal ions
Keywords:
Graphene
in aqueous solutions. The synthesis, adsorption process characteristics and interaction mechanism of the
Adsorbent adsorbent are emphasized and discussed. The effects of various environmental conditions are outlined.
Pollution treatments At last, a brief summary, perspective and outlook are presented. This review is intended to provide some
Environmental conditions thrilling information for the design and manufacture of GO-based nanomaterials for the elimination of
Interaction mechanism heavy metal ions from wastewater in environmental pollution management.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction precipitation has the advantage of low-cost and simple operation,

Water pollution is among the most paramount issues of the
whole world, especially the toxic heavy metal ions’ pollution is one
of the most severe environmental challenge that threatens hu-
manity all over the world (Wu et al., 2018, 2019; Yao et al., 2011).
Heavy metal ions released from electroplating and metal-finishing
plants can be accumulated through food chain organisms and have
serious impacts on environmental ecosystem and human health by
the physicochemical properties of highly virulent, hardly degraded
and widely dispersed in water (Khan et al., 2017; Simonovic, 2002).
At present, many treatment techniques have been used for the
elimination of heavy metal ions from wastewater, such as chemical
precipitation, membrane separation, ion-exchange and electro-
chemical treatment etc. (Yu et al., 2018a; Zhao et al., 2018a).
However, each method has its advantages and disadvantages
(Efome et al., 2018; Gu et al., 2018). For instance, chemical
* Corresponding author.
E-mail address: wang730304@163.com (X. Wang).
but large amounts of chemical products are produced, resulting in
landfill problems. Membrane separation method has the advan-
tages of high separation efficiency in removing heavy metal ions,
yet low economic feasibility and high maintenance cost restrict its
application in large scale. Sorption technology, which is easy to
perform, remarkable effect and low-cost, is considered as a fast and
relatively inexpensive approach for wastewater treatment (Li et al.,
2018; Yu et al., 2018b). To date, many materials including activated
carbons (Ren et al., 2013), clay minerals (Zhao et al., 2010a), poly-
mers (Huang et al., 2014; Hu et al., 2014), zeolites (Gupta and
Bhattacharyya, 2012), mesoporous materials (Kim and Yi, 2004)
have been widely adopted for wastewater treatment. However,
most of the above-mentioned materials suffered the problems of
low sorption capacity or unstable at low or high pH values. In recent
years, graphene oxide (GO), one of the representative carbon
nanomaterials by virtue of its strong adsorption capacity and high
surface area, has become a hot spot for environmental experts
around the world (Novoselov et al., 2004; Yu et al., 2017).
Graphene, with a single-atom-thick sheet of carbon atoms as

https://doi.org/10.1016/j.envpol.2019.05.050
0269-7491/© 2019 Elsevier Ltd. All rights reserved.
 X. Liu et al. / Environmental Pollution 252 (2019) 62e73
hexagonally arrayed sp2 structures, has a thickness of 0.334 nm and
a theoretical maximum surface area of 2630 m2 g-1 (Schedin et al.,
2007). Being one of the important graphene derivatives, graphene
oxide (GO) was proved to be a prospective material for the pre-
concentration of heavy metal ions on account of its relatively large
specific area, abundant functional groups and extraordinary me-
chanical strength (Chandra et al., 2010; Hao et al., 2012). Especially,
GO has a very extensive advantage in eliminating various heavy
metal ions from aqueous solutions, such as lead (Pb(II)) (Weng
et al., 2019), copper (Cu(II)) (Fu and Huang, 2018), cobalt (Co(II))
(Wang et al., 2018), cadmium (Cd(II)) (Pakulski et al., 2018), chro-
mium (Cr(VI)) (Zheng et al., 2019). Nonetheless, there is a strong
inter-functional bond between graphene sheets, which leads to
inactive surface chemical properties, decreased surface area, and
poor dispersion and agglomeration in aqueous solutions, restricting
the performance of its adsorption ability and further application in
wastewater treatment (Ramesha et al., 2011). To amend this
disadvantaged, GO-based materials, including chemical modifica-
tion of GO (Mishra and Ramaprabhu, 2011), fabrication of GO/metal
oxide composites (Wan et al., 2018), GO/organic compound com-
posites (Ma et al., 2012), GO/photocatalytic composites
(Wojtoniszak et al., 2012), have been systematically synthesized as
excellent adsorbents with high efficiency to enrich and to remove
various heavy metal ions from wastewater. Although those
remarkable progresses are achieved, GO-based composites still
suffer from some key challenges: (i) the interaction mechanism of
GO-based composites with heavy metal ions is still unclear because
of the different surface properties of different GO-based compos-
ites; (ii) tremendous efforts are needed in the recovery and reus-
ability of GO-based composites because of the high dispersion in
aqueous solutions and strong interaction of metal ions with func-
tional groups; (iii) really aware of low cost, high volume and
environmentally friendly manufacturing processes still remains a
challenging task, as low prices and large scale synthesis are critical
to practical applications.
This paper presents a brief review on several typical GO-based
materials, i.e., chemical modified GO, GO/metal oxide composites,
GO/organic compound composites, and GO/photocatalytic com-
posites, including their synthesis and applications toward heavy
metal ions’ elimination from wastewater under varying environ-
mental conditions (i.e., foreign ions, pH, ionic strengths, tempera-
tures and contact time). The underlying mechanisms of heavy
metal ions interaction with these composites are also discussed in
detail. It is anticipated that this systematic review will present
serviceable clues for designing of GO-based materials with highly
efficient and provides significant information for the statement of
various heavy metal ions adsorption processes in environmental
pollution cleanup.
2. Preparation of GO
Since graphene was firstly discovered in 2004 (Novoselov et al.,
2004), its unique properties have triggered great interest from
different research fields. GO is the derivate of graphene, which has
attracted great attention in environmental pollution treatment. Up
to date, the preparation methods of GO mainly include Brodie
method (Brodie, 1859), Staudenmaier method (Staudenmaier,
1898), and Hummers' method (Hummers and Offeman, 1958), or
some variations of these methods.
The first synthesis of GO was demonstrated in 1859 by Brodie at
the University of Oxford. In the preparation, a certain amount of
graphite was intimately mixed with potassium chlorate (the weight
ratio was 1:3), and the mixture was placed in a distiller. Then, an
adequate amount of the strongest fuming nitric acid was added, to
render the whole fluid. The distiller was placed in a water-bath, and
63
kept for some times at 60
C until no yellow vapors were evolved.
After that, the substance was thrown into a sufficient quantity of
deionized water, and washed by decantation nearly free from salt
and acid. It was dried in a water bath, and the oxidizing operation
repeated with the same proportion of potassium chlorate and nitric
acid until no further change was observed. The obtained GO was
ultimately dried in vacuo at 100
C.
Almost 40 years later, Staudenmaier (1898) improved Brodie's
method by using fuming nitric acid as well as concentrated sulfuric
acid to increase the acidity of the mixture and adding the potassium
chlorate in multiple aliquots over the process of the reaction. This
subtle alteration in the fabrication process caused an overall extent
of oxidation similar to Brodie's approach (C: O ¼ 2 : 1), but
exhibited more practically and pragmatically in a single reaction
vessel. However, a large number of investigations found that the
Staudenmaier method was hazardous and time consuming.
Almost 60 years later, Hummers and Offeman (1958) reported
the commonly used method to synthesize GO using concentrated
sulfuric acid and potassium permanganate. Generally, a certain
amount of graphite, sodium nitrate and concentrated sulfuric acid
were mixed in a flask that had been cooled to 0
in an ice-bath.
Then, a given mass of potassium permanganate was slowly added
to the suspension under the vigorous agitation. After that, the ice-
bath was removed, and the temperature of the mixture brought to
35
and maintained for 30 min. Then, the temperature was
increased to 98
and maintained for 15 min. After that, the sus-
pension was treated with 3% hydrogen peroxide to reduce the re-
sidual manganese dioxide and permanganate to colorless soluble
manganese sulfate. The yellowish-brown filter cake was washed
several times with distilled water and then dispersed in distilled
water.
Though other researchers had fabricated slightly changed
methods, these three versions comprise the main pathways for
forming GO, and almost unchanged about them. Importantly, it has
since been proved that the prepared materials of these reactions
exhibited strong differences, depending not only on the reaction
conditions used, but also on the oxidants and graphite source.
Despite of those eminent advances achieved, to really achieve the
low-cost, high quality and environmentally friendly manufacturing
process is a challenging task.
3. Removal of metal ions from solutions by GO-based
nanomaterials
With the quick growth of industrialization, large amounts of
toxic heavy metal ions have been generated and lead to serious
environmental problem. Therefore, efficient separate and removal
of heavy metal ions is significant for human safety and environ-
mental stability. Recently, GO and GO-based nanomaterials with
unique physicochemical properties including high surface area and
abundant oxygen-containing functional groups are applied as high
efficiency adsorbent to elimination of heavy metal ions. The main
adsorption properties between GO-based materials and heavy
metal ions are summarized in Table 1.
3.1. Pristine GO
GO, which is regarded as the oxidized graphene, contain hy-
droxyl, carboxylic, and epoxide functional groups on the surfaces.
Considering the high surface area and abundant functional groups
on the GO surfaces, the material showed high adsorption capacity
in the removal of heavy metal ions from aqueous solutions. Zhao
et al. (2011) prepared few-layered GO (FGO) by modified Hum-
mers’ method. As shown in Fig. 1, the c-axis spacing of graphite
increased from 0.34 to 0.87 nm during the oxidation process, which
64 X. Liu et al. / Environmental Pollution 252 (2019) 62e73

Table 1
Graphene oxide-based nanomaterials for the removal of heavy metal ions.

Adsorbent Adsorbate Environmental conditions Maximum Interaction mechanism Ref.

adsorption
m/V (g/L) C0 (mg/L) pH Time (h) T (K)
capacity (mg/g)

GO Am(III) 0.1 3.5 0.08 298 8.5 Romanchuk et al. (2013)

GO Au(III) 0.3 50 6.0 7 298 108 Liu et al. (2012c)
GO/chitosan 0.2 80 4.0 16 298 1077 Ionic interaction Liu et al. (2012b)
RGO/Fe3O4/MnO2 As(III) 0.5 5 7.0 24 298.5 14 Luo et al. (2012)
RGO/Fe3O4/MnO2 As(IV) 0.5 5 7.0 24 298.5 12 Luo et al. (2012)
GO Co(II) 0.1 30 6.0 24 303 68 Electrostatic interaction Zhang et al., 2011b
GO/Fe3O4 0.4 10 6.8 24 303 13 Inner-sphere surface complexation Liu et al. (2011)
GO/b-CD 0.1 10 6.0 24 303 72 Surface complexation Song et al. (2013)
GO Cd(II) 0.1 20 6.0 24 303 106 Electrostatic interaction Zhang et al., 2011b
GO 0.1 1 6.0 2 298 530 Surface complexation Sitko et al. (2013)
Tri-amino-RGO 1 7.0 236 Sayar et al. (2014)
GO/Fe3O4/b-CD Cr(VI) 1 100 3.0 1 120 Surface complexation Fan et al., 2012b
RGO/CTAB 8 50 2.0 0.7 293 22 Wu et al. (2013b)
GO Cu(II) 0.5 3.2 5.0 12 298 47 Coordination and electrostatic interaction Yang et al. (2010)
GO 0.1 1 5.0 2 298 294 Surface complexation Sitko et al. (2013)
GO 1.0 50 5.3 2.5 298 118 Surface complexation, ion exchange, Wu et al. (2013a)
and electrostatic attraction
GO/Fe3O4 0.4 10 5.3 24 298 18 Electrostatic interaction, complexation Li et al. (2012b)
GO/Chitosan 0.6 19.2 6.0 8 303 25.4 Yu et al. (2013)
RGO/b-MnO2 1 50 6.0 3 298 103 Surface adsorption and intraparticle Ren et al. (2012)
diffusion
GO Eu(III) 0.2 50 6.0 24 298 175 Inner-sphere surface complexation Sun et al., 2012
RGO Fe(II) 1 20 6.0 24 299 Electrostatic interaction Chang et al. (2013)
RGO/CoFe2O4 Hg(II) 0.14 5 4.6 2 298 158 Zhang et al. (2014)
RGO/polypyrrole 0.2 233 3.0 3 293 980 Complexation Chandra and Kim, 2011
RGO/polyaniline 0.2 10 4.0 5 1000 Group coordination and chelation Lin et al., 2013c
RGO/b-MnO2 Ni(II) 50 7.0 2 298 47 Surface complexation Ren et al. (2011)
GO Cd(II) 0.1 20 6.0 24 303 106.3 Electrostatic interaction Zhang et al., 2011b
GO Pb(II) 0.1 1 3e7 2 298 1119 Surface complexation Sitko et al. (2013)
EDTA-GO 0.1 100 6.8 24 298 479 Surface complexation and electrostatic Madadrang et al. (2012)
attraction
GO/poly(acrylamide) 0.9 1500 6.0 0.7 298 1000 Yang et al., 2013b
GO/chitosan 50 298 100 He et al. (2011)
GO/SiO2 0.3 20 6 1 298 114 Electrostatic interaction Hao et al. (2012)
GO/Fe3O4/chitozan 0.2 5 1 303 77 Fan et al. (2013)
RGO/b-MnO2 1 51 6 3 298 162 Interglobular complexation Ren et al. (2012)
RGO/CoFe2O4 0.14 20 5..3 2 298 299 Zhang et al. (2014)
GO Pt(IV) 0.3 30 6.0 10 298 71 Liu et al. (2012c)
GO Sr(II) 0.1 6.5 24 Romanchuk et al. (2013)
GO U(VI) 0.1 5.0 28 Romanchuk et al. (2013)
GO U(VI) 0.06 98 5.0 24 293 98 Inner sphere surface complexation Zhao et al. (2012b)
GO U(VI) 0.4 119 4.0 24 298 299 Inner sphere surface complexation Li et al. (2012c)
GO Th(IV) 0.1 58 3.0 2 298 411 Pan et al. (2013)
GO Zn(II) 0.1 1 5e8 2 298 345 Surface complexation Sitko et al. (2013)

was attributed to the formation of the oxygen-containing func-
tional groups (e.g. C-O and C¼O) on the surfaces of FGO. The
maximum removal capacity of Pb(II) on FGO at 293 K was
842 mg g1. However, the pristine GO can incur irreversible ag-
gregation in aqueous solution, which may reduce the surface areas
and further hinder effective elimination behaviors. Therefore,
different modified GO materials were fabricated and applied to the
efficient removal of heavy metal ions.
3.2. Chemical modified GO
GO tends to aggregate rapidly in aqueous solutions owing to the
strong p-p forces and inert surface chemistry (Mao et al., 2013),
which reduces the GO interaction with target contaminants and
thereby limits their further applications in environmental pollution
management. In order to enhance its dispersibility and to reduce
the aggregation of GO, all kinds of surface-modified GO were syn-
thesized via chemical modification or attaching a stabilizer such as
a soluble polymer or a surfactant to graft different functional
groups on the surfaces (Lee et al., 2009; Park et al., 2008).
Introduction of substituted amines is one of the most useful and
popular methods of covalent functionalization, Kumar et al. (2013)
prepared trioctylamine impregnated GO (TOA-EGO) by improved
Hummers’ method and applied for the removal of Cr(VI). As shown
in Fig. 2A and B, the interaction mechanisms between Cr(VI) and
TOA-EGO were cation-p, lone pair-p and electrostatic interactions.
Ma et al. (2012) prepared ethylenediamine-reduced graphene ox-
ides (ED-RGO) by reacting ethylenediamine (ED) with GO. In order
to develop new GO-based composite materials for the enrichment
of toxic environmental pollutants, Zhang et al. (2013a,b) combined
GO with dimethyl form amide solvent via a simple and green
approach, and successfully modified GO with functional groups.
Notably, various organic molecules functionalized GO materials
via non-covalent forces have already fabricated and applied in
different areas. As shown in Fig. 2C, Lv et al. (2018) fabricated 1-OA
(octadecylamine (OA) and tetrazolyl derivative (1)) modified GO
(GO/1-OA) and the adsorbent not only to eliminate dyes, BPA, CIP
and Cu2þ in their single system, but also to simultaneous co-adsorb
their binary, ternary and quaternary pollutants mixture. To efficient
remove ultralow concentrations of heavy metal ions in water, Yap
et al. (2019) designed cysteamine functionalized reduced gra-
phene oxide (Cyst-prGO) by thiol-ene click reaction (Fig. 2D) and
 X. Liu et al. / Environmental Pollution 252 (2019) 62e73 65

Fig. 1. XRD patterns of FGO and graphite (A); XPS C 1S spectra of graphite (B) and FGO (C); a Raman spectrum of FGO (D) (Zhao et al., 2011).

Fig. 2. Conceptual illustration of the affinity between (A) EGO and trioctylamine (B) TOA-EGO and chromium(VI) (Kumar et al., 2013). (C) Illustration of the synergistic non-covalent
interactions between GO, 1-OA and MG (Lv et al., 2018). (D) Schematic illustration of the functionalization of GO with thiol-ene click reaction to achieve a graphene composite with
multifunctional binding chemistry for high performing adsorption of mercury (Yap et al., 2019).

applied to the removal of mercury (Hg(II)). The high elimination
capacity (169 ± 19 mg g1), high selectivity and high regeneration
ability were achieved. No doubt that chemical-modification of GO
with different functional groups have shown high adsorption ca-
pacity, fast adsorption kinetics, and superior selectivity in the
preconcentration of heavy metal ions from wastewater (Dreyer
et al., 2014; Huang et al., 2011; Li et al., 2009). However, a great
challenge is that the high water solubility and small size of these
functionalized GO materials make them extremely difficult to be
separated from wastewater after heavy metal ions adsorption.
3.3. GO/metal oxide composites
As a kind of metal oxide, Fe3O4 with large specific surface area,
biocompatible property and outstanding magnetic property, has
been widely applied to water treatment (Chen et al., 2018;
Nizamuddin et al., 2019). However, Fe3O4 tends to aggregate
easily due to its small particle size and easily oxidization to form a/
g-Fe2O3 (Chandra et al., 2010; Koduru et al., 2019). To overcome this
deficiency, Fe3O4 was compounded with GO to form magnetic
graphene/iron oxide composites (Fe3O4/GO) which showed the
advantages of both Fe3O4 and GO nanomaterials with high sorption
66 X. Liu et al. / Environmental Pollution 252 (2019) 62e73
capacity and separation efficiency (Zong et al., 2013a; Wu et al.,
2011). The synthesis of GO@Fe3O4 is shown in Fig. 3A. More and
more attentions have been paid to the synthesis and application of
magnetic graphene composites in environmental pollution man-
agement. The Fe3O4/GO nanoparticles showed the removal effi-
ciency (approximately 100%) of arsenic (As(III)) ions at the
concentration of 1 ppb (Chandra et al., 2010). Bhunia et al. (2012)
reported that the maximum adsorption capacity of RGO-Fe(0)-
Fe3O4 for As(III) is as high as 44 mg g-1, followed by RGO-Fe(0)
(37 mg g-1), this material can also adsorb other heavy metal ions
like Cr(VI), Cd(II), Pb(II), and Hg(II) ions from wastewater. Addi-
tionally, Fe3O4/GO can be conveniently separated from aqueous
solution by external magnetic field, which is facilitated for its
application in large scale. Liu et al. (2013) synthesized the porous
hollow Fe3O4/GO composites by a facile self-assembly approach
using positively charged Fe3O4 hollow microspheres and negatively
charged GO sheets. The XRD patterns and the Raman spectra of GO
and Fe3O4/GO (Fig. 3B) showed the successful synthesis of the
nanomagnetic composites. The application of the nanomagnetic
composites for Cr(VI) adsorption implied the adsorption capacity of
32.33 mg g-1, much higher than that of Fe3O4 microspheres.
In addition, GO can also interact with other commonly used
metal oxides such as MnO2, SiO2, ZnO, and ZrO2, and thereby can
form composites for the application in wastewater treatment
(Wang et al., 2012; Zong et al., 2013b). Luo et al. (2012) prepared
GO-ZrO(OH)2 by hydrothermal co-precipitation and the adsorption
capacities for As(V) and As(III) were 84.89 and 95.15 mg g-1,
respectively, which were 4.64 and 3.54 times higher than that of
ZrO(OH)2 nanoparticles. According to the results reported by Ren
et al. (2012), graphene/d-MnO2, which was synthesized by
oxidation-reduction processes, had the adsorption capacity of
46.6 mg g-1 for Ni(II). Under optimal conditions, the maximum
adsorption of Ni(II) over the graphene/d-MnO2 composites were 1.5
and 15 times higher than those of d-MnO2 and graphite nanosheet,
respectively. Fig. 3C showed the hypothetical mechanism of d-
MnO2/graphene composites with Cu(II) and Pb(II) ions. The EDAX
spectrum and elemental mapping of RGO-MnO2 sample after the
Fig. 3. (A) Synthesis of the GO@NanoFe3O4 hybrid nanoparticles (Kassaee et al., 2011);
(B) The Raman spectra (a) and the XRD patterns (b) of GO and Fe3O4/GO (Li et al.,
2013a); (C) Possible tetradentate configurations after Cu(II) and Pb(II) sorption: (a)
monodentate, (b) bidentate mononuclear, (c) bidentate binuclear, (d) multidentate,
and (e) proposed tetradentate monodentate complexes on GNS/MnO2 surface and
MnO2 layer in actual solution (Ren et al., 2012); (D) EDAX spectrum and elemental
mappings of RGO-MnO2 sample after adsorption of Hg(II) (Sreeprasad et al., 2011). (E)
Schematic illustration of the fabrication process of GO@SiO2 and RGO@SiO2 composites
(Zhang et al., 2013a,b).
adsorption of Hg(II) is shown in Fig. 3D. One can see that the Hg(II)
ions are homogeneously distributed on the composites, which is in
good agreement with the distribution of O and Mn ions in the
composites. The results suggest that the adsorption of Hg(II) is
related to O and Mn ions through the formation of surface com-
plexes. Fig. 3E shows the schematic of the manufacturing process of
GO@SiO2 and RGO@SiO2 composites. These composites not only
have good adsorption properties, but also have high selectivity to
some metal ions (Zhao et al., 2012a). However, compared with
other nanomaterials, it is still a challenging task of improving the
removal efficiency of GO/metal oxide composites.
3.4. GO/organic compound composites
GO/organic compound composites have excellent adsorption
properties for heavy metal ions. The active functional groups from
GO and organic compounds can interact with heavy metal ions
through ion exchange, surface complexation and chelation, the
high specific surface area can also provide enough adsorption sites
and thereby enhances the adsorption capacity of GO/organic
compound composites for the binding of heavy metals (Li et al.,
2012a). The preparation of the GO-organic compound nano-
composites was not complicated and the surface grafted organic
compound could provide more active sites and oxygen-containing
functional groups, which were favorable for the formation of sur-
face complexes with metal ions and thereby enhanced the sorption
capacity of the composites. Another advantage of such composites
is that the surface grafted organic compounds could prevent the
aggregation of the GO-organic compound composites in aqueous
solutions, which is also favorable to provide more functional groups
and active sites for the binding of metal ions to the composites.
b-cyclodextrin (b-CD), a truncated cone of cyclic oligosaccha-
rides, can form cylindrical chambers, which are completely insol-
uble in water (Arkas et al., 2006). Song et al. (2013) synthesized b-
CD modified GO (b-CD-GO) and applied as adsorbent for the
elimination of Co(II) from wastewater. At pH ¼ 6.0 ± 0.1 and
T ¼ 303 K, the maximum adsorption capacity of b-CD-GO for Co(II)
(72.4 mg g-1) exceeded GO (47.39 mg g-1) and other adsorbents. b-
CD-GO had a high pH dependence on the adsorption process of
Co(II), which was independent of ionic strength. Thermodynamic
data suggested that the adsorption of Co(II) on b-CD-GO was
spontaneous and endothermic processes. The Langmuir model
described well the adsorption isotherms. Furthermore, the main
mechanism of b-CD-GO adsorption of Co(II) is the inner-sphere
surface complexation with metal ions and a large number of
oxygen-containing functional groups on the surface of b-CD-GO.
Chitosan (CS), one of the most prospective materials for elimi-
nating heavy metal ions from aqueous solutions, possesses high
adsorption abilities for the elimination of heavy metal ions (Chen
et al., 2008; Liu et al., 2008). For example, He et al. (2011) pre-
pared highly porous GO/CS (PGOC) materials via unidirectional
freeze-drying method and used for the removal of Pb(II) from
wastewater. When 5% GO was incorporated in the composites, the
maximum adsorption capacity of Pb(II) reached up to 99 mg g-1. The
most important property of the composites was its high reusability
and stability. Adsorption capacity remained as high as 80.2 mg g-1
after five cycles of adsorption-desorption reusability. In recent
years, owing to the admirable adsorption performance, high sep-
aration efficiency and good reproducibility, magnetic CD-CS/GO
(CCGO) composites have become promising materials in terms of
removing heavy metal ions from aqueous solutions. Li et al. (2013a)
reported that CCGO had the maximum sorption capacity of
67.66 mg g-1 for Cr(VI), much higher than other sorbents such as
Fe@Fe2O3 nanowires (7.78 mg g-1) (Ai et al., 2008), elaeagnus tree
leaves (10.94 mg g-1) (Dong et al., 2010), amino starch (12.12 mg g-1)
 X. Liu et al. / Environmental Pollution 252 (2019) 62e73
(Alvarez et al., 2011), polyethyleneimine modified activated carbon
(20.05 mg g-1) (Owlad et al., 2010), mesoporous TiO2 (33.9 mg g-1)
(Asuha et al., 2010), poly (4-vinylpyridine) modified activated car-
bon (53.7 mg g-1) (Fang et al., 2007), ethylenediamine functional-
ized Fe3O4 (61.35 mg g-1) (Zhao et al., 2010b). The experimental
kinetic data was well simulated by the pseudo second-order model,
with a correlation coefficient of 0.9914, suggesting a chemisorption
process for the rapid sorption of Cr(VI) to CCGO. Moreover, the
Cr(VI)-adsorbed CCGO was easily separated from aqueous solutions
by a permanent magnetite, which is helpful for its application in
large scale. In particular, the adsorption amount of Cr(VI) only
decreased less than 5% after five adsorption-desorption cycles, and
the structure was not destroyed after the long-term reusability,
suggesting the high stability and reusability in the efficient elimi-
nation of Cr(VI) from aqueous solutions.
Other organics, such as polyacrylamide (PAM) and polypyrrole,
can be modified to GO to provide more functional groups and
surface sites for the elimination of heavy metal ions from waste-
water (Blindauer et al., 2002). Yang et al. (2013) reported the syn-
thesis of PAM chains on RGO nanosheets by free radical
polymerization and their application for the adsorption of Pb(II)
ions from aqueous solutions. The results indicated that the surface
grafted PAM chains can act as different “trees” on the surface of
RGO and provided more “leaves” and “branches” to form surface
complexes with Pb(II) ions, thus promoted the adsorption ability of
RGO. Compared with the inorganic materials, the greatest strength
of organic polymer materials is that they possess chelating groups,
which are selective and favorable to bind heavy metal ions, so as to
effectively eliminate heavy metal ions from aqueous solution. But
the disadvantage is that the GO/organic compound composites
have poor recyclability and reproducibility.
3.5. GO/metal oxide photocatalytic composites
Photocatalytic degradation technology is also widely applied for
the elimination of heavy metal ions, especially for Cr(VI) and U(VI).
Some conventional photocatalysts such as TiO2 and ZnO, showed
higher catalytic activity for the degradation of Cr(VI) than pure TiO2
and ZnO when they were combined with GO-based nanomaterials.
To date, GO/metal oxide photocatalytic composites have been re-
ported frequently and achieved hot attentions (Zhang et al., 2010;
Liang et al., 2010; Wang et al., 2010; Yoo et al., 2011; Zhu et al.,
2010; Tang et al., 2010). For example, Jiang et al. (2011) synthe-
sized two-dimensional (2D) porous graphene/TiO2 nano-
composites by in-situ depositing of TiO2 nanoparticles on GO
nanosheets and then calcined at 200
C. As expected, the photo-
catalytic reduction of Cr(VI) over the composites was superior to
that of chemically bonded TiO2 (P25). The reason was due to the
thin 2D GO nanosheets, large surface area and high adsorption
capacity, and the strong electron transfer ability of the thermally
RGO in the composites. Similarity, ZnO-doped RGO (ZnO-RGO)
nanocomposites had the highest removal rate of Cr(VI) (~96%)
under UV light irradiation as compared with pure ZnO (67%), which
was attributed to the increased light absorption efficiency and the
reduction of electron-hole pair recombination in ZnO with the
introduction of RGO (Liu et al., 2012d).
The interaction between different GO-based nanomaterials and
heavy metal ions on were compared in Table 1. It is clear that the
sorption capacities of different materials are quite different, and the
sorption of different metal ions on the same material is also
different. The difference in the sorption capacities is attributed to
the following reasons: 1) the surface properties of different nano-
materials are different; 2) the properties of different metal ions are
different under similar experimental conditions; 3) the
protonation-deprotonation reactions at different pH values results
67
in the difference of surface properties at different pH values; 4) the
electronic layers and properties of materials are quite different at
different ionic strength conditions; 5) the binding of different
functional groups with metal ions is quite different; 6) the pore
volume of different nanomaterials is quite different, which affects
the diffusion of metal ions from the solution to material surface and
then diffuse from surface to inner channel of the nanomaterials;
and 7) other parameters such temperature which affects the ther-
modynamic movements in solutions and also binding on material
surfaces, solid-liquid ratio which affects the efficient binding sites
and functional groups because of the aggregation of nanomaterials
in solutions, coexisting metal ions or organic materials which
competes the interaction of metal ions on solid particle surfaces etc.
4. Effects of wastewater parameters
In general, environmental factors such as the solution pH,
temperature, and contact time, are the important parameters that
finally affect the interaction mechanism of heavy metal ions with
graphene-based nanocomposites (Yu et al., 2015). Thereby, it is
necessary to discuss the influencing factors to find the suitable
experimental conditions for the elimination of heavy metal ions in
pollution management. For example, the solution pH value, tem-
perature, contact time, initial concentration of heavy metal ions
and other factors have a great impact on the surface characteristics
of adsorbents and the species of heavy metal ions; therefore affect
the sorption properties of metal ions on solid particles. In this
section, the effect of these factors on heavy metal ion sorption was
generally discussed.
4.1. Effect of pH
Solution pH value has been identified as one of the most
important parameters which governs heavy metal ion adsorption
to solid particles, which would affect the relative distribution of
metal ion species and the surface potential properties of GO-based
nanomaterials (Fig. 4A and B), especially the protonation-
deprotonation reactions at different pH values (Yu et al., 2019).
Madadrang et al. (2012) reported that the GO surface is negatively
charged when the solution pH > 2.0. As shown in Fig. 4A, the
adsorption capacity of GO-based nanomaterials for Cr(VI) is pH-
responsive and they were markedly increased with increasing the
pH value from 1.0 to 2.0 and then decreased from 2.0 to 6.0. At low
pH values, the high concentrations of Hþ and H3Oþ in solution
would compete with heavy metal ions to attach to the available
binding sites of GO and GO-based nanomaterials, which reduced
the adsorption of metal ions at low pH (Gercel and Gercel, 2007).
On the one hand, the oxygen-containing functional groups on GO-
based material surfaces were easily protonated at high pH values.
More sites and ligands can be provided for the binding of metal ions
(Wang et al., 2015). On the other hand, as the pH of the solution
increases, electrostatic interaction between the positively charged
metal ions and the negatively charged surfaces of GO nanosheets
was enhanced, which was another motivation for the increase in
adsorption capacity (Gu and Fein, 2015). Furthermore, all kinds of
heavy metal ions in wastewater may be presented in the species of
þ
M(OH)2 -
nþ2, M(OH)nþ1, M(OH)n-1, M(OH)n, and M
nþ
etc., at different
pH values owing to the hydrolysis reactions at different pH values
(Xu et al., 2008). At higher pH range, the adsorption capacity of
metal ions reduced again with pH increasing because of electro-
static repulsion between M(OH)-nþ1, M(OH)2 nþ2 and the negatively
charged oxygenous functional groups on the surfaces of GO or GO-
based nanomaterials (Wang et al., 2015). Owing to differences in
the electronegativity of metal ions, the standard reduction poten-
tial value of metal ions, and the first stable constant of related metal
68 X. Liu et al. / Environmental Pollution 252 (2019) 62e73
Fig. 4. Effect of pH on adsorption capacity (A) and zeta potential (B) of GO-HBP-NH2-
DETA, GO-HBP-NH2-TETA and GO-HBP-NH2-TEPA (Kong et al., 2019). (C) Adsorption
isotherms of U(VI) on LGO at different temperature (Liu et al., 2019). (D) Influence of
contact time and initial concentration on the adsorption amount of Cd2þ by MGO@-
poly(b-CD) (Wang et al., 2019).
hydroxides, the optimum solution pH for adsorbing different metal
ions to different materials should be different (Gu and Fein, 2015).
The sorption behaviors of different kinds of metal ions on different
kinds of GO-based nanomaterials are dependent on metal ion
species, surface functional groups and surface properties of GO-
based nanomaterials which are generally affected by solution pH
values obviously (Lim et al., 2018a, 2018b). In the real applications
of GO-based nanomaterials in the elimination of metal ions, the
solution pH should be firstly considered as the elimination effi-
ciency is strongly dependent on solution pH values.
4.2. Effect of ionic strength
The presence of foreign ions could impact the binding of
adsorbing species through affecting the electrical double layers and
structures of hydrated particulate remarkably. The main reasons for
the influence of ionic strength on metal ion adsorption to GO or GO-
based nanomaterials are as follows: (1) the affinity between the
ionic species and the adsorbent affects the binding of metal ion to
solid particles, the foreign ions will compete with the pollutants for
a finite reaction site on solid particle surfaces, which reduces the
adsorption capacity of the adsorbent; (2) the concentration of
foreign ions could remarkably affect the electrostatic interactions,
which would then impact the particle aggregation; (3) the con-
centration of other metal ions affects the activity coefficients of the
pollutants, thereby limiting the transfer of pollutants from aqueous
solutions to adsorbent surfaces (Zhao et al., 2011). The influence of
foreign ions on the sorption of pollutants to nanomaterials has been
studied extensively (Wu et al., 2019; Gu et al., 2018). Generally, the
sorption of high valent pollutants is weakly affected by ionic
strength whereas the sorption of low valent pollutants is influ-
enced by ionic strength obviously. If the pH dependence of the
adsorption process is low and the ionic strength is irrelevant, the
adsorption is mainly determined by the inner-sphere surface
interaction. However, if the adsorption process is affected by ionic
strength strongly and by pH weakly, then the sorption is mainly
dominated by outer-sphere surface complexation. Generally, if the
adsorption is affected by ionic strength obviously, then the total
concentration of other different metal ions in wastewater should be
considered before the nanomaterials are applied in real
applications. Otherwise, one can just consider the pH of wastewater
and is not necessary to take into account of other kinds of metal
ions in real applications.
4.3. Effect of temperature
Among the factors that have a significant impact on the
adsorption process, temperature is also critical. So far, the adsorp-
tion of metal ions on GO and GO-based nanocomposites can be
simulated by various isothermal models such as Dubinin-
Radushkevich (D-R), Freundlich, Langmuir and Sips sorption
models (Chen et al., 2017). Temperature affects the kinetics process
by alternating the solubility of metal ions and molecular in-
teractions with solid particles (Ahmaruzzaman and Sharma, 2005).
The increase in temperature not only leads to an increase in the
available of sorption sites on GO or GO-based nanomaterial sur-
faces, but also increases the rate of metal ion diffusion from solu-
tion to the graphene surfaces, thereby increasing the adsorption
rate. Generally, the sorption capacity of metal ions on GO or GO-
based nanocomposites increased with the increase of tempera-
ture (Fig. 4C), indicating the spontaneous and endothermic pro-
cesses. For the real application of GO or GO-based nanomaterials in
the removal of metal ions from wastewater, it is not necessary to
consider the effect of temperature as the control of wastewater
temperature is generally more difficult and needs more energy,
which is not environmental friendly. Generally, the operation at
room temperature under ambient conditions is suitable for the
preconcentration of metal ions from aqueous solution to GO or GO-
based nanomaterials.
4.4. Effect of contact time
Time is an important factor which affects the mass transfer rate
of pollutants during the adsorption process. For most metal ions,
the removal efficiency initially increases dramatically and then
increases slowly until the contact time is extended to reach equi-
librium (Fig. 4D). This phenomenon is attributed to the fact that the
available adsorption sites on GO surfaces are sufficient at the initial
time. The available sites on GO or GO-based nanomaterial surfaces
and the driving force for metal ions to the binding sites decrease
with the contact time increasing, resulting in slow adsorption
behavior and ultimately reaching the saturated adsorption capacity
(Chen et al., 2015). It is necessary to note that the time to reach
sorption equilibrium is a very important parameter for the appli-
cation of nanomaterials in real applications. The shorter time to
reach sorption equilibrium suggests the higher efficiency and more
economic of the nanomaterial application in wastewater treatment.
5. Interaction mechanism
Understanding the interaction mechanism between adsorbents
and heavy metal ions is imperative for the fabrication of high ef-
ficiency materials for pollutants removal. A range of interaction
mechanisms, such as ion exchange, surface complexation, and
precipitation, may play a major role in controlling the heavy metal
ions elimination process taking place at the solid-liquid interfaces.
However, macroscopic batch experiments cannot definitively and
sufficiently supply a microscopic understanding of interaction
mechanism. Therefore, spectroscopic approaches including
Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelec-
tron spectroscopy (XPS) and X-ray absorption fine structure (XAFS)
and computational approaches are proposed and utilized to
investigate the reaction mechanism in great detail (Gao et al.,
2018a; Zhao et al., 2017; 2018b). Combined with the experiment
results allows an accurate and systematic validation and
 X. Liu et al. / Environmental Pollution 252 (2019) 62e73
interpretation of interaction mechanisms between heavy metal
ions and GO-based nanomaterials.
FT-IR and XPS spectroscopy are extensively used surface
chemical analysis technique that can offer molecular information
(e.g. bonding relationships, elemental composition, chemical state
of the elements) of materials with a high spatial resolution at
molecular level. The FT-IR spectra of GO before and after carrying
different metal ions are shown in Fig. 5A. The results indicated that
metal cations can binding with GO's oxygen functional groups via
surface complexation and with GO's aromatic framework through
cation-p interactions (Gao et al., 2018b). Fig. 5B shows XPS survey
spectra of the fresh GO-CS, U_pH 5.0, and U_pH 8.3. Huang et al.
(2017) reported that the adsorption processes were mainly domi-
nate by the inner-sphere surface coordination between U(VI) and
-NH2, -COO-, and -OH groups of the GO-CS. From the EXAFS analysis
(Fig. 5C and D), Hu et al. (2017) found that the outer-sphere com-
plexes of Cu(II) on LDH were transformed to inner-sphere com-
plexes on LDH_GO. Wang et al. (2018) investigated the interaction
mechanism between Co(II) and different GO-based nanomaterials
by the theoretical calculated partial density of states (PDOS) and
total density of states (TDOS). Based on the results of Fig. 6, one can
draw a conclusion that the interaction of heavy metal ions with
oxygen-containing surface groups was stronger than nitrogen-
containing surface groups. Clearly, it is highly recommended to
use combined multiple approaches including experimental, spec-
troscopic and theoretical investigations to gain deep insight into
the interaction process of heavy metal ions on GO-based nano-
materials, which allow a more accurate and reliable elucidation for
heavy metal ions environmental behavior and removal efficiency of
adsorbents.
6. Desorption and regeneration
Cyclic regeneration of the adsorbent is very important for highly
Fig. 5. (A) FT-IR spectra of GO before and after reaction with Zn(II), Co(II) and Cd(II)
(Gao et al., 2018b). (B) XPS survey scans of the fresh GO-CS hydrogel, U_pH5.0, and
U_pH8.3 samples (Huang et al., 2017). The k3-weighted EXAFS spectra (C) and the
corresponding RSF magnitudes (D) of sorption samples for GO_Cu(II) and LDH_GO_-
Cu(II) systems (Hu et al., 2017).
69
efficient applications in wastewater treatment. The excellent
adsorbent should possess high adsorption capacity and good
adsorption-desorption performance, which is of great significance
for improving adsorption efficiency and reducing cost. For efficient
desorption, the choice of a suitable eluent is generally dependent
on the adsorption mechanism, the nature of the adsorbates and the
nature of the adsorbent. In general, the most commonly used
desorption solution is an alkaline solution and/or an acid solution
for eluting metal ions from the supported adsorbent. For example,
with 0.1 M HCl, the desorption rate of Zn(II) from spent GO was
91.6%, which indicated that HCl has excellent elution ability (Wang
et al., 2013). In addition, EDTA (Leng et al., 2012) and thiourea-HCl
(Liu et al., 2012c) were also used as high-efficiency eluents for the
elution of adsorbed pollutants from spent adsorbents. The
adsorption properties of recycled GO for Cu(II) ions can maintain
more than 95% of its initial performance after 5 cycles, and can
maintain more than 90% even after 10 cycles (Wu et al., 2013a). The
adsorption capacities of GO membrane after 6th cycles decreased
only to approximately 10% for Cu(II) ions, 12% for Cd(II) ions and 21%
for Ni(II) ions (Tan et al., 2015). However, it should be mentioned
that systematic studies on other optimal conditions for example
eluent, pH, desorption time, temperatures and recovery efficiency
have not been extensively studied and should be further advanced
in future work. For real applications, the less volume eluent is used,
the better economy benefit is achieved. The post-treatment of the
eluent is also an important parameter for the application of the
nanomaterials.
7. Conclusions and future perspectives
In this review, the preparation and development of GO-based
nanocomposites and their efficient application for the removal of
heavy metal ions from aqueous solutions under different environ-
mental conditions were summarized. Moreover, GO-based com-
posite materials have been extensively studied as novel adsorbent
materials due to their high efficiency and strong affinity for various
metal ions. In spite of those extraordinary progresses achieved, as a
hot research topic in the field of the environment, GO-based
composites and their corresponding wastewater control still
remain some key problems to be solved. 1) Efforts should be made
to develop various effective methods for designing GO-based
composite materials with high adsorption properties. Neverthe-
less, theoretical guidance and engineering practice are essential; 2)
In-depth study of adsorption and selective adsorption of various
metal ions under complicated conditions should be further
explored; 3) Further optimization of the synthesis process of GO-
based composites and simplification of the preparation process;
4) For the high selective removal of different metal ions under
complicated conditions, the selective of materials with special
functional groups for the binding of metal ions is crucial to syn-
thesize the nanocomposites; 5) The stability of the nanocomposites
at extreme conditions; 6) Easy and fast separation of the nano-
composites from aqueous solutions; 7) Reduction of the prepara-
tion cost in simple processes and in large scale by environmental
friendly method; 8) The environmental friendship of nanomaterial
itself in the natural environment; 9) Other parameters such as high
recyclability, easy operation, even the irreversibility for some spe-
cial metal ions etc. Such problems should be considered for the
preparation and application of GO-based nanomaterials in future.
Although there are still many problems in the synthesis of GO-
based nanomaterials and their application in environmental
pollution cleanup, through the efforts of the researchers, it is
believed that GO-based composites can be used in the field of
wastewater treatment in real application in near future.
70 X. Liu et al. / Environmental Pollution 252 (2019) 62e73

Fig. 6. (A-C) The DOS plots of GO(-COOH)/Co, GO(-OH)/Co and NGO/Co complexes. (D-F) The charge density difference plots of GO(-COOH)/Co, GO(-OH)/Co and NGO/Co complexes.
The yellow and cyan isosurfaces (þ0.006 and 0.006 a.u., respectively) represented the region in which electron density was increased and decreased after Co(II) coordinated to GO
or NGO (Wang et al., 2018).

Acknowledgements Research Funds for Central Universities (2017MS045, 2017XS094,

2018ZD11, 2018MS114), NCEPU“Double First-Class” Graduate Talent
Support from National Key Research and Development Program Cultivation Program and Guangdong Provincial Key Laboratory of
of China (2017YFA0207002), Science Challenge Project Environmental Pollution and Health (No. GZKLEPH201815) are
(TZ2016004), NSFC (21876048, 21836001, 21607042), Fundamental acknowledged.
 X. Liu et al. / Environmental Pollution 252 (2019) 62e73 71

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