Journal of Molecular Liquids 211 (2015) 957964

Contents lists available at ScienceDirect

Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Application of graphene oxides for the removal of Pb(II) ions from

aqueous solutions: Experimental and DFT calculation
Xiangxue Wang a,b,, Zhongshan Chen a, Shubing Yang a,b,c,
a
b
c

School of Chemistry and Environment, North China Electric Power University, Beijing 102206, PR China
Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, PR China
School for Radiological and Interdisciplinary Sciences, Soochow University, 215123 Suzhou, PR China

a r t i c l e

i n f o

Article history:
Received 15 May 2015
Received in revised form 24 June 2015
Accepted 8 August 2015
Available online xxxx
Keywords:
Graphene oxides
Sorption
Pb(II) ions
Interaction mechanism
DFT calculation

a b s t r a c t
Graphene oxides (GOs) have attracted intense multidisciplinary study because of their special physicochemical
properties and their possible applications. The large amount of oxygen-containing functional groups on GO surfaces makes it possible to form strong surface complexes with metal ions. Herein, the GOs are synthesized by
modied Hummers method and characterized by SEM, TEM, FTIR, XRD, XPS and Raman spectroscopy techniques
in detail. The results show that large amount of oxygen-containing functional groups is generated on GO surfaces
during the synthesis process. The GOs are applied as adsorbents to remove Pb(II) ions from aqueous solutions and
the sorption of Pb(II) is strongly dependent on pH and the sorption of Pb(II) is mainly attributed to the formation
of strong surface complexes. Comparing the sorption capacities of Pb(II) on different materials, the GOs have the
highest sorption capacity among todays' materials. The results of far infrared spectroscopy analysis and the DFT
calculation also indicate that the binding of Pb(II) on GOs is mainly attributed to the COOH groups rather than
other functional groups. The GOs may be suitable materials for the preconcentration of heavy metal ions from
large volume of aqueous solutions in the near future if GOs could be synthesized in large scale at low price.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Graphene oxides (GOs), a one or several atomic layers of graphite,
have unique two-dimensional (2D) structures and special physicochemical properties, and have attracted intense multidisciplinary research areas [14]. GOs are exfoliated by strong oxidants, and consist
of a hexagonal network of covalently linked carbon atoms with
oxygen-containing functional groups. Considering the basal planes decorated with functional groups, GOs are also regarded as very suitable
materials for the preconcentration of pollutants due to their excellent
sorption ability [5,6]. From this viewpoint, GOs are ideal adsorbent materials to eliminate heavy metal ions from large volumes of aqueous solutions. In the solidwater interface science, theoretical calculation of
metal ion sorption on GOs has been carried out extensively in the last
decade. Density functional theory (DFT) is a powerful and useful tool
for describing the chemical and physical interaction properties of
metal ions with GOs [7]. Besides DFT calculation, the extended X-ray absorption uorescence spectroscopy (EXAFS) technique is also a very
good method to study the interaction mechanism. The microstructures
and species of heavy metal ions can be achieved from the EXAFS spectra
analysis [811]. Wu et al. [12,13] studied the interaction of uranium,
Corresponding authors at: School of Chemistry and Environment, North China Electric
Power University, Beijing 102206, PR China.
E-mail addresses: wang730304@163.com (X. Wang), sdysb2006@163.com (S. Yang).

http://dx.doi.org/10.1016/j.molliq.2015.08.020
0167-7322/ 2015 Elsevier B.V. All rights reserved.

neptunium and plutonium with GOs using DFT calculation and found
that the radionuclides could form strong inner-sphere surface complexes on GOs. Yang et al. [14] compared the interaction of Pb(II),
Ni(II) and Sr(II) with GOs by DFT calculation and found that the interaction of Pb(II) with GOs was much stronger than that of Ni(II) and Sr(II)
with GOs. Zhao et al. [15] found that the sulfonated graphene had the
adsorption capacity of ~ 2.32.4 mmol/g naphthalene and 1-naphthol,
which was the highest capability of today's nanomaterials for organic
pollutants. Zhao et al. [16] also found that the maximum sorption capacities of Cd(II) and Co(II) ions on GO nanosheets were about 106.3 and
68.2 mg/g, respectively, at pH ~ 6.0 and T = 303 K, which were also
much higher than those of Cd(II) and Co(II) on other materials. Sitko
et al. [17] studied the sorption of Pb(II) on aminosilanized GOs and
found the sorption capacity of 96 mg/g at pH 6. Shao et al. [18] synthesized polyaniline-GO composites and applied them to preconcentrate
U(VI) from solutions with maximum sorption capacity of 1960 mg/g
at pH 5.0, which are ideal materials for the selective removal of U(VI)
from solutions. Zhang et al. [19] synthesized CoFe2O3-GO composites
and found that the maximum sorption capacity of Pb(II) was
299.4 mg/g at pH 5.3. Madadrang et al. [20] successfully modied GOs
with EDTA and found that the EDTA-GO had the sorption capacity of
479 mg/g for Pb(II) ions at pH 6.8. From the published papers mentioned above, one can see that most papers mentioned above focused
on the sorption of heavy metal ions on GOs or GO-based composites,
and few works focused on the theoretical calculation of metal ion

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X. Wang et al. / Journal of Molecular Liquids 211 (2015) 957964

interaction with GOs. No report is available to understand the interaction of metal ions with GO from batch experiments and DFT calculations, which are crucial to understand which group is mainly
responsible for the sorption of metal ions on GOs.
Lead ions are detrimental to human health and living things. Longterm drinking water polluted by lead would cause serious disorders,
such as anemia, cancer, kidney disease and metal retardation [21]. Because of their high toxicity, it is necessary to eliminate Pb(II) ions from
aqueous solutions before the wastewater is released into the natural environment. Many methods have been applied to eliminate Pb(II) ions
from large volumes of aqueous solutions such as membrane ltration,
ion exchange, chemical precipitation, and sorption. [2225]. Among
these methods, sorption technique has been widely used in the elimination of metal ions from aqueous solutions due to its easy-operation,
low-cost and wide adaptability [26]. Although the sorption of Pb(II)
ions on GOs and other materials has been studied extensively, all
these works were performed by experiments and no work focused on
the comparison of Pb(II) interaction with GOs from experiments and
computational calculations to understand which functional group is
crucial to form complexes with Pb(II) ions.
In this paper, we rstly studied the sorption properties of Pb(II) on
GOs under different experimental conditions and applied DFT to calculate the possible binding energy of Pb(II) with different oxygencontaining functional groups. The interaction mechanism between
Pb(II) ions and GOs was discussed based on the experimental results
and theoretical calculations. The ndings are important and useful for
us to understand the mechanism of heavy metal ion interaction with
GOs and to synthesize suitable functionalized GOs in environmental
pollution cleanup.

The analytical-grade lead nitrate was used to prepare Pb(II) stock solution. The sorption of Pb(II) on GOs was carried out in polyethylene test
tubes. The stock suspensions of GOs, Pb(II) and NaClO4 solutions were
added into the polyethylene test tubes to achieve the desired concentrations of different components. Because the sorption of Pb(II) on GOs was
carried out in NaClO4 solutions, the pH values were adjusted by adding
negligible volumes of 0.1 or 0.01 mol/L HClO4 or NaOH. After the suspensions were shaken for 24 h to achieve the sorption equilibrium, the solid
phase was separated from the solution by centrifugation at 12,000 rpm
for 30 min and then the supernatant was passed through 0.22 m membrane lters to separate other small particles. The concentration of Pb(II)
in the ltrate was determined by spectrophotometry at the wavelength
of 616 nm using Pb(II)chlorophosphonazo(III) complex. All the experimental data were the average of duplicate experiments, and the relative
errors were about 5%. The amount of Pb(II) adsorbed on GOs was calculated from the difference between the initial concentration (C0) and the
equilibrium one (Ce) (Sorption% = (C0 Ce)/C0 100%, and Cs =
(C0 Ce)/m V, where Cs is the amount of Pb(II) adsorbed on GOs, V
is the volume of the suspension, and m is the mass of GOs in solution).
For the desorption experiments, after the sorption equilibrium of
Pb(II) on GOs, half volume of the supernatant was pipetted and the
same volume solution containing 0.01 M NaClO4 with the same pH as
the sorption experiments was added into the suspension. Then the
mixtures were shaken and centrifuged at the same conditions as the
sorption experiments. Finally, the concentration of Pb(II) in the supernatant was measured and the Cs values were deduced from the difference of Pb(II) in the supernatant.

2. Experimental

3. Results and discussion

2.1. Materials

3.1. Characterization of FGO

The GOs were synthesized from the natural powdered ake graphite
(400 mesh, 99.96% purity, Qingdao Tianhe Graphite Company, China)
by a modied Hummers method. Briey, the mixture of the graphite
powder and NaNO3 (A.R.) was added into the concentrated H2SO4 solution in an icewater bath. Then the KMnO4 was gradually added into the
suspension and the suspension was vigorously stirred in the icewater
bath for 2 h and then continually stirred for 5 days at room temperature.
The mixture was diluted with Milli-Q water (Millipore, Billerica, MA,
USA), and a certain amount of 30% H2O2 was put into the suspension. Finally, the GOs were obtained by rinsing with Milli-Q water and centrifugation. The desired material was dried in a vacuum tank at room
temperature, and thus achieved GO material was characterized and
used in the following sorption experiments.

Fig. 1 shows the SEM and TEM images of the as-synthesized GOs.
From the SEM image, one can see that the GOs have lateral dimensions
of several micrometers. Some tiny holes are found in the SEM image,
which is caused by the overexposure to sonication in the preparation
processes. The GOs are partially transparent, suggesting that the fewlayered graphene oxides are formed, although the layer number cannot
be estimated from the SEM image exactly. The SEM image shows that
the GOs are high quality with few layers. The TEM image (Fig. 1B)
shows that the graphene oxides are transparent, and the aggregation
of GOs is also observed for the bare GOs. The transparent image also suggests that the synthesized GOs are few-layered, indicating the successful
synthesis of few-layered GOs by the Hummers method.
Fig. 2A shows the XRD patterns of GOs and graphite. The diffraction
peak at 2 = 26.4 (d = 0.34 nm) corresponding to the normal graphite
spacing (002) of graphite plane, disappears in the XRD pattern of the assynthesized GOs. The broad and relatively weak diffraction peak at
2 = 10.03 with d = 0.87 nm corresponds to the typical diffraction
peak of GOs, which is the typical (002) plane of GOs. From the XRD
patterns, one can see that the c-axis spacing increases from 0.34 nm
(for graphite) to 0.87 nm (for the as-synthesized GOs) during the oxidation process, which may be due to the generation of the oxygencontaining functional groups on GO surfaces [27,28], which are also
evidenced by the XPS analysis in the following section.
Fig. 2B shows the FTIR spectrum of GOs. Different oxygen-containing
functional groups such as COC group at 1217 cm1 and 1047 cm1,
COOH group at 1726 cm1 and C = C group at 1618 cm1 are found
on GO surfaces. The broad peak at 3400 cm1 is attributed to the vibration of COOH group [29,30]. The FTIR spectrum indicates that large
amounts of oxygen-containing functional groups are formed on the surface of GOs during the synthesis process.
Fig. 2C shows the high deconvoluted C 1s XPS spectrum of GOs,
which indicates a considerable degree of oxidation with different

2.2. Characterization
The synthesized GOs were characterized by using scanning electron
microscopy (SEM), transmission electron microscopy (TEM), Fourier
transformed infrared spectroscopy (FT-IR), powder X-ray diffraction
(XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.
The morphology of GOs was investigated by SEM (FEI-JSM 6320F) by dispensing a small amount of suspension on a 1 1 cm section of silicon
wafer. The TEM image was employed with a JEM-2010. The functional
groups on the surfaces of GOs were measured by using FTIR (PerkinElmer
Spectrum 100 system spectrometer) and XPS (Thermo ESCALAB 250 electron spectrometer). The FTIR spectrum was recorded in pressed KBr pellets (Aldrich, 99%, analytical reagent) at room temperature. The XPS
spectrum was conducted at 10 kV and 5 mA under 108 Pa residual pressure. The peak energy was corrected with C 1s peak at 284.6 eV as a reference. The XRD pattern was measured on a D/max2500 with a Cu K
source ( = 1.541 ). Raman spectrum was recorded with a Renishew
in Via Raman spectrometer (Renishawplc, UK).

2.3. Sorption and desorption experiments

X. Wang et al. / Journal of Molecular Liquids 211 (2015) 957964

959

Fig. 1. SEM (A) and TEM (B) images of the as-synthesized GOs.

types of oxygen-containing functional groups, i.e., the non-oxygenated

ring CC (284.5 eV), the C atom in CO bond (286.2 eV), and the carboxylate carbon (OC_O) (289.0 eV). The relative contents of the oxygencontaining functional groups from the curve tting are also given in
Fig. 2C. From the C 1s spectrum, one can see the high oxygencontaining functional groups on GO surfaces, indicating the high oxidation of the GOs by the oxidant in the synthesis process [31]. The main
oxygen-containing groups are CO and OC_O groups, which can
form strong surface complexes with Pb(II) ions on GO surfaces. It is
also important to say that the GOs have very high dispersion properties
in aqueous solutions, which could make the oxygen-containing functional groups of GOs form strong surface complexes with Pb(II) ions
easily.
Fig. 2D shows the Raman spectrum. The obvious band at around
1350 cm1 is assigned to the D band which is related to the vibrations
of sp3 carbon atoms of defects and disorder of GOs, and the band at
around 1580 cm1 is generally assigned to the G band which is

associated with the vibration of sp2 carbon atoms in a graphitic 2D hexagonal lattice of GOs. These strong bands are also found in some published papers [3234]. The weak and broad 2D peak at around
2700 cm1 is another indication of disorder due to an out of plane vibrational mode. The weak S3 peak at around 2950 cm1 is attributed
to the cooperation between the D and G peaks. Both of the 2D and S3
peaks are very similar with the results reported in the previous papers
[3234].
3.2. Effect of contact time
The sorption of Pb(II) on GOs as a function of contact time is studied
and the results are shown in Fig. 3. One can see that the sorption increases quickly with increasing contact time at the initial contact time,
and then the sorption increases very slowly with increasing contact
time. The fast sorption suggests that chemical sorption rather than
physical sorption contributes Pb(II) sorption to GOs. From the results,

Fig. 2. Characterization of GOs. A: XRD patterns; B: FTIR spectrum; C: C 1s XPS spectrum; D: Raman spectrum.

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X. Wang et al. / Journal of Molecular Liquids 211 (2015) 957964

Fig. 3. The effect of contact time on Pb(II) sorption to GOs. m/V = 0.3 g/L, pH = 5.2, T =
293 K, C[Pb(II)] = 4.6 104 mol/L.

it is clear that several hours are enough to achieve the sorption equilibrium. In the following experiments, the contact time is xed to 24 h to
assure the sorption equilibrium.

3.3. Effect of pH and NaClO4 concentrations

The sorption of Pb(II) ions on GOs as a function of pH in 0.001 M,
0.01 M and 0.1 M NaClO4 solutions is investigated (Fig. 4). One can see
that the sorption of Pb(II) ions on GOs increases with pH increasing
from 1.0 to 6.0, maintains the high level at the pH range of 68, and
then decreases with pH increasing at pH N 8. Herein we have to notice
that the pH values in Fig. 4 are the pH values of the suspensions after
Pb(II) sorption to GOs reaching sorption equilibrium. The solution pH
decreases a little after the sorption of Pb(II) on GOs, suggesting that
part of H+ ions is released into the solution during the sorption process.
During the sorption processes, the oxygen-containing functional groups
on GO surfaces can be deprotonated, and part of H+ ions is released into
the solution. The deprotonation reaction can be expressed as S
OH S O + H+, where S represents the GOs, and OH represents the oxygen-containing functional groups [35]. At low pH values,

Fig. 4. Sorption of Pb(II) on GOs as a function of pH in different NaClO4 solutions. m/V =

0.3 g/L, T = 293 K, C[Pb(II)] = 4.6 104 mol/L.

the sorption of Pb(II) is partly attributed to the ion exchange of Pb2+

with H+/Na+ on GO surfaces, and thereby the exchanged H+/Na+
ions are released into the solution. The released H+ ions can then result
in the decrease of solution pH. At high pH values, the oxygen-containing
functional groups are progressively deprotonated, and the surface
charge of GOs becomes negative [36]. The relative distribution of
Pb(II) species at ionic strength of 0.01 mol/L NaClO4 was calculated
from the hydrolysis constants (logk1 = 6.48, logk2 = 11.16, logk3 =
14.16) [37]. The results demonstrated that Pb(II) species are present
in the forms of Pb2+, Pb(OH)+, Pb(OH)02 and Pb(OH)
3 at various pH
values (Fig. 5). From the relative distribution of Pb(II) species in aqueous solution, the Pb(II) ions are negatively charged at high pH values,
and thereby the negatively charged Pb(II) species is difcult to be
adsorbed onto the negatively charged GOs. With increasing pH, the surface charge of GOs is more negative, and the electrostatic repulsion becomes more stronger, thereby resulting in the decrease sorption of
Pb(II) on GOs at high pH values.
From Fig. 4, one can also see that the sorption curve of Pb(II) on GOs
is shifted to lower pH values in 0.001 M NaClO4 solutions at pH b 6. The
sorption of Pb(II) ions on GOs is dependent on pH and ionic strength at
pH b 6, and independent of ionic strength at pH N 6. The results suggest
that the sorption of Pb(II) ions on GOs is mainly dominated by outersphere surface complexation or ion exchange at pH b 6, and by innersphere surface complexation at pH N 6 [38,39]. From the precipitation
constant of Pb(OH)2(s) (1.2 1015) [21], the Pb(II) ions begin to
form precipitation at pH ~ 8.2 at Pb(II) initial concentration of
4.6 10 4 mol/L. From the sorption curves, one can see that more
than 96% Pb(II) ions are adsorbed on GOs at pH N 6. Thereby, the contribution of Pb(II) precipitation on Pb(II) sorption to GOs is negligible. The
oxygen-containing functional groups on GO surface can form strong
surface complexes with Pb(II) ions, which contributes to the high sorption of Pb(II) ions on GOs.
3.4. Sorption and desorption isotherms
The sorption isotherms of Pb(II) ions on GOs at pH 3.0 and 5.0, and
T = 293 K are shown in Fig. 6A. The sorption isotherm at pH 5.0 is
much higher than that at pH 3.0, suggesting that the sorption of Pb(II)
on GOs is strongly dependent on pH values, which is in good agreement
with the results shown in Fig. 4. The sorption isotherm is highest at T =
323 K and is lowest at T = 293 K (Fig. 6B), suggesting that the sorption
of Pb(II) on GOs is promoted at higher temperature. In order to simulate
and to understand the sorption mechanism, the widely used Langmuir

Fig. 5. The relative distribution of Pb(II) in aqueous solution.

X. Wang et al. / Journal of Molecular Liquids 211 (2015) 957964

961

Fig. 6. Sorption and desorption isotherms of Pb(II) on GOs at different pH values (A) and different temperatures (B). I = 0.01 M NaClO4, m/V = 0.3 g/L.

and Freundlich models are used to simulate the sorption isotherms. The
Langmuir and Freundlich models are expressed as:
Cs

Csmax  KL  Ce
1 KL  Ce

Cs K F  Ce 1=n

where Ce is the equilibrium concentration of Pb(II) ions in aqueous solution (mmol/L), Cs is the amount of Pb(II) ions adsorbed on GO
(mmol/g), Csmax is the maximum sorption capacity, KL is the Langmuir
constant, KF and n are the Freundlich constants which are related to
the adsorption capacity and adsorption intensity, respectively.
The experimental data are simulated by the Langmuir and
Freundlich isotherm models, respectively. The results indicated that
the Langmuir model simulated the sorption isotherms much better
than the Freundlich model (data not shown), suggesting that the sorption of Pb(II) on GO surfaces is monolayer coverage. The maximum
sorption capacities (Csmax) of Pb(II) ions on GOs at 293, 308, and
323 K are calculated to be 2.27, 2.76, and 3.27 mmol/g, respectively.
The sorption of Pb(II) ions on GOs is strongly dependent on temperature. Compared to the sorption of Pb(II) ions on other kinds of materials,
the sorption capacity of Pb(II) ions on GOs is the highest among today's
manmade nanomaterials and natural materials (Table 1). The sorption
capacity of Pb(II) on GOs is a little higher than those of Pb(II) on
Table 1
The maximum adsorption capacities of Pb(II) ions on different kinds of materials.
Adsorbents

Experimental
Csmax
(mmol/g) conditions

References

Activated carbon
Sawdust
Iron oxide
GMZ bentonite
Hazelnut shell
Oxidized MWCNTs
Functionalized graphene
GOs
2- or 3-layered graphene
Magnetic chitosan/graphene oxide
Composites
GO
EDTA-RGO
Amino-functionalized carbon nanotubes
Chitosan/alginate composite beads
MnFe2O4 nanoparticles
Peanut husk
Chitosan beads
Multiwalled carbon
nanotubes/polyacrylamide
composites
Epichlorohydrin-crosslinked chitosan

0.09
0.14
0.15
0.10
0.12
0.01
1.69
2.27
1.67
0.37

pH 6.0, T 303 K
pH 7.0, T 303 K
pH 5.5, T 298 K
pH 5.2, T 293 K
pH 6.0, T 298 K
pH 6.0, T 293 K
pH 5.1, T 293 K
pH 5.0, T 293 K
pH 6.0, T 293 K
pH 5.0, T 303 K

[47]
[48]
[49]
[50]
[44]
[45]
[46]
This work
[21]
[51]

1.58
0.99
0.28
0.29
2.36
0.14
0.17
0.18

pH 6.8, T 298 K
pH 6.8, T 298 K
pH 6.2, T 318 K
pH 4.5, T 298 K
pH 5.0, T 300 K
pH 4.0, T 298 K
pH 4.5, T 298 K
pH 5.0, T 293 K

[52]
[42]
[53]
[54]
[55]
[56]
[54]
[16]

0.16

pH 6.0, T 298 K [57]

functionalized GOs (1.69 mmol/g, pH 5.1, T = 293 K) [46] and on 2or 3-layered graphene (1.67 mmol/g, pH 6.0, T = 293 K) [21]. The
high sorption capacity of Pb(II) on GOs may be attributed to the high
amount of oxygen-containing functional groups on GO surfaces, which
can form strong surface complexes with Pb(II) ions on GO surfaces.
The sorptiondesorption isotherms of Pb(II) on GOs at pH 3.0 and
pH 5.0, respectively, are also shown in Fig. 6A, and those of Pb(II) on
GOs at the temperatures of 293 K, 308 K and 323 K, respectively, are
shown in Fig. 6B. The amounts of Pb(II) adsorbed on GOs in the sorption
and desorption experiments were calculated from the following
equations:
Cs Cini Ce 

V
m


0
1
V
e
Cs Cs Ce 0 Ce 
2
m

where Cini was the initial concentration of Pb(II) in suspension, Ce was

the equilibration concentration of Pb(II) in supernatant after sorption
experiment, Ce was the nal concentration of Pb(II) in supernatant
after the desorption experiment, V was the volume and m was the
mass of GOs. Cs was the amount of Pb(II) adsorbed on GOs after the
sorption experiment, and Cs was the amount of Pb(II) still adsorbed
on GOs after desorption re-equilibration.
From Fig. 6, one can see that all the desorption isotherms are higher
than the sorption isotherms, suggesting that the sorption of Pb(II) on

Fig. 7. The single and competitive sorption of Pb(II), Ni(II) and Cs(I) on GOs. m/V = 0.3 g/L,
pH = 5.5, T = 293 K, C[Pb(II)] = C[Ni(II)] = C[Cs(I)] = 4.6 104 mol/L.

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X. Wang et al. / Journal of Molecular Liquids 211 (2015) 957964

~65%, ~71% and ~55%, respectively. For the competitive sorption, the removal percentages of Pb(II), Ni(II) and Cs(I) on GOs were ~60%, ~66%
and ~ 34%, respectively. One can see that the single sorption of the
three metal ions is higher than the competitive sorption of the metal
ions, suggesting that the presence of other heavy metal ions can inhibit
the sorption of Pb(II) onto GOs. However, in the presence of the three
metal ions, it is clear that the total sorption of Pb(II), Ni(II) and
Cs(I) on GOs is much higher than the sorption of single metal ions.
The results suggest that the GOs are very suitable materials for the
preconcentration of different kinds of metal ions from aqueous solutions in real applications.
3.5. Far infrared spectroscopy analysis and DFT calculation

Fig. 8. The FIR spectra of GOs before and after Pb(II) sorption.

GOs is irreversible. When the Pb(II) concentration in solution is decreased, the distribution of Pb(II) on solidwater interface is destroyed,
the surface adsorbed Pb(II) cannot be desorbed from the GOs. From the
sorptiondesorption isotherms, it is clear that the irreversible sorption
of Pb(II) on GOs suggests that Pb(II) forms strong surface complexes
on GOs and cannot be easily transferred from GOs to solution after the
experimental condition changes. Li et al. [40] studied the sorption
desorption of metal ions from carbon nanotubes and found that the
oxygen-containing functional groups contributed importantly to the
sorption of metal ions. For the outer-sphere surface complexes, the
Pb(II) ions are weakly bounded on GO surface and can be desorbed
when the solution conditions change. For the inner-sphere surface complexes, the Pb(II) ions are strongly bounded on GO surfaces, which is difcult to be desorbed from solid particles. From the sorptiondesorption
isotherms, one can see that the Pb(II) ions form strong surface complexes with oxygen-containing functional groups on GO surfaces.
The understanding of the competitive sorption of metal ions on GOs
is important for the application of GOs in the removal of heavy metal
ions from aqueous solutions. Herein, the single sorption of Pb(II),
Ni(II) and Cs(I) on GOs, and the competitive sorption of Pb(II), Ni(II)
and Cs(I) on GOs are studied and the results were shown in Fig. 7. The
removal percentages of Pb(II), Ni(II) and Cs(I) for single sorption were

The FT-IR spectra (Fig. 8) of GOs before and after Pb(II) sorption are
collected in the far-infrared region using far infrared (FIR) spectroscopy.
Based on the previous work [41], the characteristic vibration of Pb(II)
ion adsorbed on GOs can be observed at 300 cm1. Compared to the
spectrum of GOs before Pb(II) sorption, one can see that a peak at
137 cm1 is observed in the FIR spectrum of GOs after Pb(II) sorption.
The peak is assigned to the stretching vibration of PbO bonds [42].
The result indicates that Pb(II) ions tend to form stable bond with
oxygen-containing functional groups of GOs. As COC group is difcult
to form stable bond with Pb(II) ions, thereby, the most sorption sites for
the binding of Pb(II) ions on GOs are attributed to COOH group.
From the XPS and FTIR analyses, the COOH and COC are the main
oxygen-containing functional groups on GO surfaces. The FIR spectroscopy analysis also indicates that the binding of Pb(II) is mainly attributed to
the formation of Pb(II) with COOH groups. Casabianca et al. [43] showed
that the COOH and epoxide (COC) carbons of GO structure were directly
bonded. Based on the results, the structures of GOs with COC and COOH
groups were employed to describe the sorption of Pb(II) on GOs by the
DFT calculation. Thereby, the interactions of Pb2+ with COOH and COC
were calculated to understand the interaction of Pb2+ with GOs, and to
reveal which group (i.e., COOH or COC) is mainly responsible for the
sorption of Pb2 + on GOs. The binding energy (Ebd) of Pb2+ with one
COC group is 1.3 kcal/mol, and with two COC groups is 16.5 kcal/mol,
which increases signicantly. The Ebd of Pb2+ with one COOH group is
14.7 kcal/mol, and with two COOH groups is 18.7 kcal/mol. One can
see that the Ebd of Pb2+ with COOH groups is much higher than that
with COC groups, indicating that Pb2+ ions prefer to bind with COOH
groups on GO surfaces. These results indicate the highly oxidized GOs
have strong sorption capability of Pb(II). The stable species of Pb(II) on
GOs calculated from the DFT calculation is shown in Fig. 9. The Pb2+

Fig. 9. The stable species of Pb(II) sorption on GO surface.

X. Wang et al. / Journal of Molecular Liquids 211 (2015) 957964

963

References

Fig. 10. The recycling sorption of Pb(II) on GOs. m/V = 0.3 g/L, pH = 5.5, T = 293 K,
C[Pb(II)] = 4.6 104 mol/L.

ions can form strong complexes on GO surfaces through the formation of

Pb2+ with COOH functional groups.

3.6. Regeneration and reuse property

The regeneration and reuse property of the adsorbent are important
for the real application in the removal of heavy metal ions from aqueous
solutions. Herein, after the sorption equilibrium, the GOs were treated
with 1.0 M HNO3 to desorb the Pb(II) ions from GOs and then rinsed
with Milli-Q water. The recycling experiments of GOs in the recovery
of Pb(II) are studied for the contact time of 6 h and the results were
shown in Fig. 10. The results demonstrated a satised sorption proportion after six circles, suggesting that the GOs could be employed repeatedly in Pb(II) sorption processes. The experimental results of the
regeneration and reuse ability demonstrated that the GOs possess a
wide application perspective for the cost-effective removal of Pb(II)
from aqueous solutions.

4. Conclusion
Based on the characterization of GOs and the sorption results of
Pb(II) on GOs at different pHs and ionic strength conditions, one can
draw the following conclusion: 1) The few-layered GOs are successfully
synthesized through the Hummers method, and the as-prepared GOs
are highly oxidized and there are large amounts of oxygen-containing
functional groups on GO surfaces; 2) The sorption of Pb(II) on GOs is
strongly dependent on pH values. The sorption of Pb(II) on GOs is mainly attributed to the oxygen-containing functional groups on GO surfaces; 3) The binding of Pb(II) on GOs is mainly attributed to the
COOH groups, which is evidenced by the far infrared spectroscopy analysis and the DFT calculation; and 4) The GOs have very high sorption capacity in the preconcentration of Pb(II) ions from aqueous solutions.
The GOs have the highest sorption capacity among todays' manmade
nanomaterials and natural materials. The GOs may be suitable materials
in environmental pollution cleanup in the near future if GOs could be
synthesized in large scale at low price with the development of
technology.

Acknowledgment
Financial support from the National Natural Science Foundation of
China (21225730) is acknowledged.

[1] V.C. Tung, M.J. Allen, Y. Yang, R.B. Kaner, High-throughput solution processing of
large-scale graphene, Nat. Nanotechnol. 4 (2009) 2529.
[2] Q. Wang, X.K. Wang, Z.F. Chai, W.P. Hu, Low-temperature plasma synthesis of carbon nanotubes and graphene based materials and their fuel cell applications,
Chem. Soc. Rev. 42 (2013) 88218834.
[3] G.X. Zhao, T. Wen, C.L. Chen, X.K. Wang, Synthesis of graphene-based nanomaterials
and their application in energy-related and environmental-related areas, RSC Adv. 2
(2012) 92869303.
[4] K. Lv, G. Zhao, X. Wang, A brief review of graphene-based material synthesis and its
application in environmental pollution management, Chin. Sci. Bull. 57 (2012)
12231234.
[5] Y. Sun, S. Yang, G. Zhao, Q. Wang, X. Wang, Adsorption of polycyclic aromatic hydrocarbons on graphene oxides and reduced graphene oxides, Chem. Asian. J. 8 (2013)
27552761.
[6] T. Wen, X. Wu, X. Tan, X. Wang, A. Xu, One-pot synthesis of water-swellable mgal
layered double hydroxides and graphene oxide nanocomposites for efcient removal of As(V) from aqueous solutions, ACS Appl. Mater. Interfaces 5 (2013)
33043311.
[7] Y. Peng, J. Li, Ammonia adsorption on graphene and graphene oxide: a rstprinciples study, Front. Environ. Sci. Eng. 7 (2013) 403411.
[8] G.D. Sheng, S.T. Yang, Y.M. Li, X. Gao, Y.Y. Huang, X.K. Wang, Retention mechanisms
and microstructure of Eu(III) on manganese dioxide studied by batch and high resolution EXAFS technique, Radiochim. Acta 102 (2014) 155167.
[9] G.D. Sheng, Q. Yang, F. Peng, H. Li, X. Gao, Y.Y. Huang, Determination of colloidal pyrolusite, Eu(III) and humic substance interaction: a combined batch and EXAFS approach, Chem. Eng. J. 245 (2014) 1016.
[10] G.D. Sheng, H.P. Dong, R.P. Shen, Y.M. Li, Microscopic insights into the temperaturedependent adsorption of Eu(III) onto titanate nanotubes studied by FTIR, XPS, XAFS
and batch technique, Chem. Eng. J. 217 (2013) 486494.
[11] G.D. Sheng, R.P. Shen, H.P. Dong, Y.M. Li, Colloidal diatomite, radionickel and humic
substance interaction: a combined batch, XPS and EXAFS investigation, Environ. Sci.
Pollut. Res. 20 (2013) 37083717.
[12] Q.Y. Wu, J.H. Lan, C.Z. Wang, C.L. Xiao, Y.L. Zhao, Y.Z. Wei, Z.F. Chai, W.Q. Shi, Understanding the bonding nature of uranyl ion and functionalized graphene: a theoretical study, J. Phys. Chem. A 118 (2014) 21492158.
[13] Q.Y. Wu, J.H. Lan, C.Z. Wang, Y.L. Zhao, Z.F. Chai, W.Q. Shi, Understanding the interactions of neptunium and plutonium ions with graphene oxide: scalar-relativistic
DFT Investigations, J. Phys. Chem. A 118 (2014) 1027310280.
[14] S. Yang, C. Chen, Y. Chen, J. Li, D. Wang, X. Wang, W. Hu, Competitive adsorption of
Pb(II), Ni(II) and Sr(II) ions on graphene oxides: a combined experimental and theoretical study, ChemPlusChem 80 (2015) 480484.
[15] G.X. Zhao, L. Jiang, Y.D. He, J.X. Li, H.L. Dong, X.K. Wang, W.P. Hu, Sulfonated graphene
for persistent aromatic pollutant management, Adv. Mater. 23 (2011) 39593963.
[16] G.X. Zhao, J.X. Li, X.M. Ren, C.L. Chen, X.K. Wang, Few-layered graphene oxide nanosheets as superior sorbents for heavy metal ion pollution management, Environ. Sci.
Technol. 45 (2011) 1045410462.
[17] R. Sitko, P. Janik, B. Feist, E. Talik, A. Gagor, Suspended aminosilanized graphene
oxide nanosheets for selective preconcentration of lead ions and ultrasensitive determination by electrothermal atomic absorption spectrometry, ACS Appl. Mater.
Interfaces 6 (2014) 2014420153.
[18] D.D. Shao, G.S. Hou, J.X. Li, T. Wen, X.M. Ren, X.K. Wang, PANI/GO as a super adsorbent for the selective adsorption of uranium(VI), Chem. Eng. J. 255 (2014) 604612.
[19] Y.K. Zhang, L.G. Yan, W.Y. Xu, X.Y. Guo, L.M. Cui, L. Gao, Q. Wei, B. Du, Adsorption of
Pb(II) and Hg(II) from aqueous solution using magnetic CoFe2O3-reduced graphene
oxide, J. Mol. Liq. 191 (2014) 177182.
[20] C.J. Madadrang, H.Y. Kim, G.H. Gao, N. Wang, J. Zhu, H. Feng, M. Gorring, M.L. Kasner,
S.F. Hou, Adsorption behavior of EDTA-graphene oxide for Pb(II) removal, ACS Appl.
Mater. Interfaces 4 (2012) 11861193.
[21] G. Zhao, X. Ren, X. Gao, X. Tan, J. Li, C. Chen, Y. Huang, X. Wang, Removal of Pb(II)
ions from aqueous solutions on few-layered graphene oxide nanosheets, Dalton
Trans. 40 (2011) 1094510952.
[22] M.M. Matlock, B.S. Howerton, D.A. Atwood, Chemical precipitation of lead from lead
battery recycling plant wastewater, Ind. Eng. Chem. Res. 41 (2002) 15791582.
[23] S. Yang, J. Hu, C. Chen, D. Shao, X. Wang, Mutual effect of Pb(II) and humic acid adsorption onto multiwalled carbon nanotubes/poly(acrylamide) composites from
aqueous solution, Environ. Sci. Technol. 45 (2011) 36213627.
[24] Y. Sun, Q. Wang, C. Chen, X. Tan, X. Wang, Interaction between Eu(III) and graphene
oxide nanosheets investigated by batch and extended X-ray absorption ne structure
spectroscopy and by modeling techniques, Environ. Sci. Technol. 46 (2012) 60206027.
[25] Y. Sun, D. Shao, C. Chen, S. Yang, X. Wang, Highly efcient enrichment of radionuclides on graphene oxide supported polyaniline, Environ. Sci. Technol. 47 (2013)
99049910.
[26] R. Hu, D. Shao, X. Wang, Graphene oxide/polypyrrole composites for highly selective enrichment of U(VI) from aqueous solutions, Polym. Chem. 5 (2014)
62076215.
[27] X. Fan, W. Peng, Y. Li, X. Li, S. Wang, G. Zhang, F. Zhang, Deoxygenation of exfoliated
graphite oxide under alkaline conditions: a green route to graphene preparation,
Adv. Mater. 20 (2008) 44904493.
[28] X. Meng, D. Geng, J. Liu, M.N. Banis, Y. Zhang, R. Li, X. Sun, Non-aqueous approach to
synthesize amorphous/crystalline metal oxide-graphene nanosheet hybrid composites, J. Phys. Chem. C 114 (2010) 1833018337.
[29] N.A. Kumar, H.J. Choi, Y.R. Shin, D.W. Chang, L. Dai, J.B. Baek, Polyaniline-grafted reduced graphene oxide for efcient electrochemical supercapacitors, ACS Nano 6
(2012) 17151723.

964

X. Wang et al. / Journal of Molecular Liquids 211 (2015) 957964

[30] Y. Sun, S. Yang, Y. Chen, C. Ding, W. Cheng, X. Wang, Adsorption and desorption of
U(VI) on functionalized graphene oxides: a combined experimental and theoretical
study, Environ. Sci. Technol. 49 (2015) 42554262.
[31] W. Song, D. Saho, S. Lu, X. Wang, Simultaneous removal of uranium and humic acid
by cyclodextrin modied graphene oxide nanosheets, Sci. China Chem. 57 (2014)
12911299.
[32] C. Valls, C. Drummond, H. Saadaoui, C.A. Furtado, M. He, O. Roubeau, L. Ortolani, M.
Monthioux, A. Pnicaud, Solutions of negatively charged graphene sheets and ribbons, J. Am. Chem. Soc. 130 (2008) 1580215804.
[33] G. Eda, M. Chhowalla, Chemically derived graphene oxide: towards large-area thinlm electronics and optoelectronics, Adv. Mater. 22 (2010) 23922415.
[34] D. Shao, J. Li, X. Wang, Poly(amidoxime)-reduced grapheme oxide composites as adsorbents for the enrichment of uranium from seawater, Sci. China Chem. 57 (2014)
14491458.
[35] S. Yang, G. Sheng, X. Tan, J. Hu, J. Du, G. Montavon, X. Wang, Determination of Ni(II)
sorption mechanisms on mordenite surfaces: a combined macroscopic and microscopic approach, Geochim. Cosmochim. Acta 75 (2011) 65206534.
[36] Y. Sun, J. Li, X. Wang, The retention of uranium and europium onto sepiolite investigated by macroscopic, spectroscopic and modeling techniques, Geochim.
Cosmochim. Acta 140 (2014) 621643.
[37] C.H. Weng, Modeling Pb(II) adsorption onto sandy loam soil, J. Colloid Interface Sci.
272 (2004) 262270.
[38] S. Yang, G. Sheng, G. Montavon, Z. Guo, X. Tan, B. Grambow, X. Wang, Investigation
of Eu(III) immobilization on -Al2O3 surfaces by combining batch technique and
EXAFS analysis: role of contact time and humic acid, Geochim. Cosmochim. Acta
121 (2013) 84104.
[39] G. Sheng, S. Yang, J. Sheng, J. Hu, X. Tan, X. Wang, Macroscopic and microscopic investigation of Ni(II) sequestration on diatomite by batch, XPS and EXAFS techniques, Environ. Sci. Technol. 45 (2011) 77187726.
[40] J. Li, C. Chen, S. Zhang, X. Wang, Comparison of adsorptiondesorption hysteresis of
metal cation and anion ions from carbon nanotubes, Environ. Sci. Nano 1 (2014)
488495.
[41] G.L. Saot, P. Simon, F. Fayon, A. Blin, Y. Vaills, Raman and infrared study of
(PbO)x(P2O5)(1 x) glasses, J. Raman Spectrosc. 33 (2002) 740746.
[42] L.P. Liu, Infrared spectroscopy on lead silicate glass, Z. Phys. B 90 (1993) 393399.
[43] L.B. Casabianca, M.A. Shaibat, W.W. Cai, S.J. Park, R. Piner, R.S. Ruoff, Y. Ishii, NMRbased structural modeling of graphite oxide using multidimensional 13C solidstate NMR and ab initio chemical shift calculations, J. Am. Chem. Soc. 132 (2010)
56725676.

[44] E. Pehlivan, T. Altun, S. Cetin, M. Iqbal Bhanger, Lead sorption by waste biomass of
hazelnut and almond shell, J. Hazard. Mater. 167 (2009) 12031208.
[45] D. Xu, X. Tan, C. Chen, X. Wang, Removal of Pb(II) from aqueous solution by
multiwalled carbon nanotubes, J. Hazard. Mater. 154 (2008) 407416.
[46] X. Deng, L. L, H. Li, F. Luo, The adsorption properties of Pb(II) and Cd(II) on functionalized graphene prepared by electrolysis method, J. Hazard. Mater. 183 (2010)
923930.
[47] M.M. Rao, D.K. Ramana, K. Seshaiah, M.C. Wang, S.W.C. Chien, Removal of some
metal ions by activated carbon prepared from Phaseolus aureus hulls, J. Hazard.
Mater. 166 (2009) 10061013.
[48] M. Rafatullah, O. Sulaiman, R. Hashim, A. Ahmad, Adsorption of copper(II),
chromium(III), nickel(II) and lead(II) ions from aqueous solutions by meranti sawdust, J. Hazard. Mater. 170 (2009) 969977.
[49] N.N. Nassar, Rapid removal and recovery of Pb(II) from wastewater by magnetic
nanoadsorbents, J. Hazard. Mater. 184 (2010) 538546.
[50] S. Wang, Y. Dong, M. He, L. Chen, X. Yu, Characterization of GMZ bentonite and its
application in the adsorption of Pb(II) from aqueous solutions, Appl. Clay Sci. 43
(2009) 164171.
[51] L. Fan, C. Luo, M. Sun, X. Li, H. Qiu, Highly selective adsorption of lead ions by waterdispersible magnetic chitosan/graphene oxide composites, Colloids Surf. B. 103
(2013) 523529.
[52] C.J. Madadrang, H.Y. Kim, G. Gao, N. Wang, J. Zhu, H. Feng, M. Gorring, M.L. Kasner, S.
Hou, Adsorption behavior of EDTA-graphene oxide for Pb(II) removal, ACS Appl.
Mater. Interfaces 4 (2002) 11861193.
[53] G.D. Vukovi, A.D. Marinkovi, S.D. kapin, M.. Risti, R. Aleksi, A.A. Peri-Gruji,
P.S. Uskokovi, Removal of lead from water by amino modied multi-walled carbon
nanotubes, Chem. Eng. J. 173 (2011) 855865.
[54] W.S. Wan Ngah, S. Fatinathan, Pb(II) biosorption using chitosan and chitosan derivatives beads: equilibrium, ion exchange and mechanism studies, J. Environ. Sci. 22
(2010) 338346.
[55] S. Kumar, R.R. Nair, P.B. Pillai, S.N. Gupta, M.A.R. Iyengar, A.K. Sood, Graphene oxide
MnFe2O4 magnetic nanohybrids for efcient removal of lead and arsenic from
water, ACS Appl. Mater. Interfaces 6 (2014) 1742617436.
[56] Q. Li, J.P. Zhai, W.Y. Zhang, M.M. Wang, J. Zhou, Kinetic studies of adsorption of
Pb(II), Cr(III) and Cu(II) from aqueous solution by sawdust and modied peanut
husk, J. Hazard. Mater. 141 (2007) 163167.
[57] A.H. Chen, S.C. Liu, C.Y. Chen, C.Y. Chen, Comparative adsorption of Cu(II), Zn(II), and
Pb(II) ions in aqueous solution on the crosslinked chitosan with epichlorohy, J.
Hazard. Mater. 154 (2008) 184191.