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Preparation of Reduced Graphene Oxide Aerogel and Its Adsorption

for Pb(II)
Chunjuan Gao,* Zeliang Dong, Xiaocui Hao, Ying Yao, and Shuyuan Guo

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ABSTRACT: In this study, reduced graphene oxide (rGO) aerogels were successfully prepared using a facile hydrothermal method
and determined with Fourier transform infrared spectroscopy, X-ray diffraction spectroscopy, Raman spectroscopy, X-ray
photoelectron spectroscopy, Brunauer−Emmett−Teller surface area, and scanning electron microscopy. The rGO aerogels were
used to remove Pb(II) from aqueous solution, and the adsorption performance of rGO aerogels was investigated. In addition, the
adsorption−desorption cycle experiments were carried out to evaluate the recyclability and stability of rGO aerogels. The adsorption
data were consistent with the pseudo-second-order kinetic model and Langmuir isotherm model. The experimental results showed
that rGO aerogels have good adsorption capacity for Pb(II) and can be utilized for wastewater treatment.

■ INTRODUCTION
With the advancement of industrialization and economic
development, water pollution became an increasingly serious
problem.1,2 Heavy metal pollution in water attracted much
public attention because heavy metal ions were extremely toxic
even at low concentrations.3−5 As one of the major heavy metal
pollutants, lead seriously harmed human health and especially
had irreversible effects on children’s health and intelligence.6 It is
worse that lead is gradually accumulated in the human body and
is essentially nonbiodegradable.7,8 Hence, lead-containing
wastewater must be treated before being discharged into the
environment.
Lead-containing wastewater mainly came from the battery
industry, petroleum industry, nonferrous metal smelting, and
other industries. Because of its widespread use in industries, lead
is a common pollutant in wastewater. There are many
technologies and methods for heavy metal ions removal from
wastewater, such as chemical precipitation, membrane filtration,
ion-exchange, evaporation, concentration, and adsorption.9−14
Adsorption has the advantages of excellent separation efficiency,
easy to operate, and low cost, and is still an effective and widely
used method.5−18
It has been reported that various materials,19−25 including
activated carbon, sewage sludge ash, clay minerals, zeolite,
manganese oxides, peanut hulls, biomaterials, and polymeric
materials had the adsorption ability for heavy metal ions.
However, these materials had some common shortcomings such
as complex preparation process and poor recyclability.
Aerogel,26 a porous three-dimensional solid material with a
continuous pore network of nanometer scale, has special
properties such as high porosity, low density, and huge surface
area. The charming characteristics of aerogel makes it widely
applicable in the fields of adsorption, energy storage and
conversion, drug carriers, photocatalysis, and so forth.27−30 As
compared with the other carbonaceous materials, graphene had
many outstanding properties such as huge surface area, excellent
Received: January 14, 2020
Accepted: April 15, 2020

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optical, electrical, and mechanical properties, and especially spectrum. Meanwhile, the intensities of the vibrational bands of
good adsorption capacity for heavy metal ions.31−36 (−CO) and (−C−O) decreased in the rGO aerogel
In this work, the reduced graphene oxide (rGO) aerogels were spectrum, indicating the reduction of the functional groups
synthesized using a simple one-step hydrothermal reduction and the transformation from GO to rGO.
assembly method. The rGO aerogels had three-dimensional X-ray Diffraction. The phase structures of the samples were
network structures with nanoscale continuous pores and were measured by X-ray diffraction (XRD), as shown in Figure 2. The
used as adsorbents to remove Pb(II) in wastewater. The effects
of pH, contact time, and Pb(II) concentration on the adsorption
capacities of rGO aerogels were explored. The adsorption
kinetic and isotherm studies were also carried out to investigate
the adsorption behavior of rGO aerogel for Pb(II).

■ RESULTS AND DISCUSSION

Density. GO was reduced to rGO, and a three dimensional
network porous structure was formed by self-assembly. After
freeze-drying, the water in rGO hydrogels was replaced by air,
and the rGO aerogels were obtained. The densities of obtained
rGO aerogels were calculated.
There were some factors that had an influence on the
properties of rGO aerogels, including GO concentration,
hydrothermal temperature, and hydrothermal time. When the
concentration of GO was less than 1 mg/mL, the rGO hydrogel
shrunk drastically during the freeze-drying process, and its
volume decreased sharply. When the concentration of GO was
higher than 3 mg/mL, the structure of the rGO aerogel
remained almost constant during the freeze-drying process. Figure 2. XRD of GO and rGO aerogels (3 mg/mL, 140 °C, 8 h).
Increasing hydrothermal temperature and prolonging hydro-
thermal reaction time might have made the densities of prepared
rGO aerogels increased, resulting in the decrease of their sharp peak of GO at 2θ = 10.8° confirmed the presence of the
adsorption capacity. The rGO aerogel with a minimum density oxygen-containing functional groups, which was identical with
of 12.2 mg/cm3 was prepared successfully under the optimal the interlayer spacing of 0.8 nm. In comparison, a broad
reaction condition (GO concentration was 3 mg/mL, hydro- diffraction peak at about 24.72° along with the interlayer spacing
thermal temperature was 140 °C, and hydrothermal time was 8 of 0.35 nm appeared, corresponding to the characteristic
h). reflection peak of rGO aerogel. In addition, the peak at 2θ =
Fourier-Transform Infrared Spectra. Figure 1 shows the 10.8° disappeared significantly after reduction by the hydro-
characteristic peaks of GO and rGO aerogels. The absorption thermal synthesis method, suggesting that the oxygen-
containing groups of GO were diminished.
Raman Spectra. The Raman spectra of the samples were
measured as shown in Figure 3. It was observed that two obvious
peaks at 1335 and 1591 cm−1, which were clear indications
toward the characteristic D and G bands of GO, respectively. As

Figure 1. IR of GO and rGO aerogels (3 mg/mL, 140 °C, 8 h).

peak of GO at 3390 cm−1 testified the stretching vibrational

band of (−OH). The absorption peaks of GO at 1719, 1609,
1280, and 1040 cm−1 showed the stretching vibrational bands of
(−CO), (−CC), (−C−O), and (−O−), respectively. The Figure 3. Raman spectra of GO and rGO aerogels (3 mg/mL, 140 °C, 8
absorption peak of (−OH) disappeared in the rGO aerogel h).

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Figure 4. XPS survey spectra overlay of GO and rGO aerogels (a) and separate detailed C 1s spectra of GO (b) and rGO aerogel (c).

Figure 5. Nitrogen adsorption−desorption isotherm (a) and pore-size distribution curves based on BJH (b) of rGO aerogel.

compared with GO, the D band at 1332 cm−1 and the G band at proving the formation of the rGO aerogel after hydrothermal
1590 cm−1 became much stronger in the rGO aerogel, further treatment.
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X-ray Photoelectron Spectroscopy. X-ray photoelectron

spectroscopy (XPS) of GO and rGO aerogels are shown in
Figure 4. There were the O 1s peak and the C 1s peak, as shown
in Figure 4a, proving that graphite has been oxidized to GO.
Furthermore, the increase in the C/O ratio of rGO aerogel was
attributed to the reduction of the oxygen-containing groups.
Figure 4b shows the C 1s XPS spectra of GO in which the peaks
at 284.8, 286.82, and 288.17 eV were attributed to (C−C), (C−
O), and (CO), respectively. As shown in Figure 4c, the
intensities of peaks at 289.82 and 285.82 eV were significantly
decreased because of the efficient reduction of GO.
Brunauer−Emmett−Teller. The N2 adsorption−desorp-
tion isotherm and the distribution of pore diameter of rGO
aerogel were obtained through Brunauer−Emmett−Teller
(BET), and the curves are shown in Figure 5. The rGO aerogel
exhibited a typical IV isotherm accompanied by a hysteresis
loop, which could give information on the presence of
mesopores (Figure 5a). It is observed from Figure 5b that the
pore diameter of rGO aerogel calculated through the Barrett,
Joyner, and Halenda (BJH) model mainly was in the range
below 100 nm. As compared with those of graphene-based
materials, as shown in Table 1, the rGO aerogel showed a
relatively high BET surface area (136.7 m2/g), which was
favorable for the adsorption.

Table 1. BET Surface Areas of Different Materials Figure 6. SEM images of rGO aerogels with 10 mg/mL GO reduced
samples BET surface areas (m2/g) references (a−c) and with 2 mg/mL GO reduced (d−f).
GO aerogel 84.7 37
GO@TiO2 74.9 38
rGO−MnO/NC-2 38.9 39
rGO@Fe3O4 MNPs 58.0 40
rGO aerogel 136.7 present study

Scanning Electron Microscopy. The microstructure

images of rGO aerogels were observed by scanning electron
microscopy (SEM) (Figure 6). The SEM image in Figure 6a
showed that the rGO aerogel had multilayered structure, which
was formed with the rGO nanosheets through self-assembly. As
shown in Figure 6b,c, the rGO nanosheets were interconnected
continuously to form a three-dimensional porous network,
providing support and maintaining its shape during freeze-
drying.
With the decrease of the GO concentration, the overlapped
morphology in the rGO aerogel disappeared (Figure 6d). At the
same time, more micrometer-sized pores were distributed on the Figure 7. Effect of pH on the adsorption for Pb(II), conditions: Pb(II)
surface of the material, which provided more large surface area = 50 mg/L (25 mL), sorbent = 10 mg.
for the adsorption (Figure 6e,f). The continuous porous
structure was beneficial for the diffusion and adsorption of
Pb(II). It was virtually impossible to obtain the rGO aerogel
when the GO concentration was less than 1 mg/mL, which capacity of the rGO aerogel for Pb(II). As pH value increased,
revealed that the GO concentration played an important role in the adsorption efficiency of Pb(II) increased distinctly because
the formation of the rGO aerogel. H+ had lost its dominant position in the competition. The results
Effect of pH on the Adsorption Capacities of rGO suggested that the Pb(II) adsorption by rGO aerogel was
Aerogels for Pb(II). The pH value of solution was a critical sensitive to pH, and the most effective adsorption efficiency
parameter that greatly influenced the adsorption capacity of the could be achieved at pH 5.5. Therefore, the pH of the solution
adsorbents. Figure 7 reveals the effect of pH on the adsorption was maintained at 5.5 in the further studies.
capacities of rGO aerogels for Pb(II). It could be obviously Effect of Contact Time on Adsorption Capacities of
observed that the qe value was increased rapidly from 2.3 to 54.5 rGO Aerogels for Pb(II). The experiments with the different
mg/g as pH variated from 1 to 5.5 because of the competitive adsorption time were performed to investigate the influence of
adsorption of Pb(II) and H+ on the rGO aerogel. At a low pH contact time on the adsorption efficiency for Pb(II). As shown in
(pH < 3.0), more H+ might prevent the adsorption of Pb(II) Figure 8, the qt for Pb(II) increased rapidly within the initial 5
from the rGO aerogel, which would lead to the poor adsorption min of starting adsorption. As the extension of contact time, the
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Figure 8. Effect of contact time on the adsorption for Pb(II),
conditions: Pb(II) = 50 mg/L (25 mL), sorbent = 10 mg, pH = 5.5.
qt for Pb(II) increased gradually to a constant value at about 50
min, and the time was regarded as adsorption equilibrium time.
In order to further study how the contact time affected the
adsorption process, the experimental data were analyzed by the
pseudo-first-order model and the pseudo-second-order model.
The pseudo-first- and second-order models were expressed by
eqs 1 and 2
ln(qe − qt) = ln qe − k1t
t 1 t
= +
qt k 2qe 2 qe
where qe was the equilibrium adsorption capacity for Pb(II)
(mg/g), qt was the adsorption capacity for Pb(II) at t time, and
k1 and k2 were rate constant of pseudo-first-order kinetic
adsorption and pseudo-second-order kinetic adsorption,
respectively.
The linear fitting curve of the pseudo-second-order kinetic
model is shown in Figure 9. The corresponding fitted constants
calculated using the pseudo-first- and second-order kinetic
models are presented in Table 2. As seen from Table 2, the value
Figure 9. Linear fitting curves of pseudo-second-order kinetics.
Article
Table 2. Constants of Adsorption Kinetic Models
kinetic
models pseudo-first-order model pseudo-second-order model
constants R2 qe k1 R2 qe k2
0.9371 34.62 0.1409 0.9996 37.45 0.0061
of R2 of the pseudo-second-order kinetic model was higher than
that of the pseudo-first-order kinetic model, indicating that the
pseudo-second-order kinetic model was more suitable for the
adsorption of rGO aerogels toward Pb(II).
Effect of Pb(II) Concentration on Adsorption Capaci-
ties of rGO Aerogels for Pb(II). The effect of Pb(II)
concentration on adsorption was investigated, and the results
are shown in Figure 10. It was clearly observed that the value of q
(1)
(2)
Figure 10. Effect of the Pb(II) concentration on the adsorption for
Pb(II), conditions: sorbent = 10 mg, pH = 5.5.
gradually increased as the Pb(II) concentration increased. The
porous rGO aerogels could adsorb more ions at high Pb(II)
concentration as a result of the adsorption−desorption
equilibrium.
In order to investigate precisely the isotherm adsorption of
rGO aerogel for Pb(II), two most typical adsorption models, the
Langmuir and Freundlich isotherm models were used to fit the
adsorption data. The Langmuir and Freundlich isotherm models
were expressed as the following equations
Ce 1 C
= + e
qe klqm qm (3)
1
ln qe = ln k f + ln Ce
n (4)
where Ce was the equilibrium concentration for Pb(II) (mg/L),
qe was the equilibrium adsorption capacity for Pb(II) (mg/g),
qm was the maximum adsorption capacity for Pb(II) (mg/g),
and kl (L/mg), kf (L/mg), and 1/n were constants.
The fitted curves of two isotherm models are shown in Figure
11, and the isothermal constants which were calculated from the
experiment data are mentioned in Table 3. The R2 value of
Langmuir (Rl2 = 0.992) was higher than that of Freundlich (Rf2 =
0.986), indicating the adsorption isotherm of rGO aerogel for
Pb(II) was more suitable for the Langmuir isotherm model.
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Figure 11. Adsorption isotherms for Pb(II) onto rGO aerogel. Figure 12. Absorption recyclability and stability of rGO aerogel.

Table 3. Isothermal Constants for Pb(II) Adsorption

adsorption capacity percentages of the regenerated adsorbent
isotherm models Langmuir Freundlich for Pb(II) were 100, 96.5, 94.2, and 90.1% in the first four cycle
constants Rl2 kl qm Rf2 kf 1/n experiments, respectively. Subsequently, the adsorption capacity
0.998 0.02 58.04 0.986 2.513 0.614 percentages declined obviously in the fifth and sixth cycle. The
reduction of removal efficiency might be because of the
According to the Langmuir isotherm, the qm value of rGO destruction of active sites on the surface of the absorbent by
aerogel was calculated to be 58.04 mg/g and was compared with hydrochloric acid during desorption. The performance of the
other materials (Table 4). It was clear that the rGO aerogel rGO aerogel in the first four cycles revealed that the rGO aerogel
has an excellent recyclability and stability.
Table 4. Adsorption Capacities of Different Adsorbents for
Pb(II) ■ CONCLUSIONS
The rGO aerogels with porous structures were successfully
adsorption capacity prepared using a facile hydrothermal method without
adsorbents (mg/g) references
introducing any solid or aqueous activation agent, which were
rGO@Fe3O4 MNPs 49.00 40 confirmed by the results of structural analysis and morphology
magnetic graphene 6 41 test [i.e., Fourier-transform infrared (FT-IR) spectroscopy,
GO 81.3 42 XRD, XPS, SEM, and BET]. The results of adsorption
GT−rGO 6.945 42 experiments demonstrated that the rGO aerogels had shown
rGO−Fe3O4 30.68 43 good performance for the removal of Pb(II) and could be
NF−rGO 121.6 44 recycled at least four times. The adsorption data were in
Scenedesmus vacuolatus−rGO 95 45 accordance with the pseudo-second-order kinetic model and
chitosan-coated sand 12.32 46
Langmuir isotherm model, indicating that chemical adsorption
amino-BC 55.65 47
played a dominant role in the adsorption process. Therefore, the
Fe2O3−Al2O3 23.75 48
rGO aerogels could be used as promising adsorbents for
rGO aerogel 58.04 present study
wastewater treatment.

showed a better adsorption capacity for Pb(II) than these

materials such as magnetic graphene, rGO, rGO@Fe3O4 MNPs,
chitosan-coated sand, amino-BC, Fe2O3−Al2O3, and rGO−
Fe3O4. As compared to other adsorbents such as GO, NF−rGO,
and Scenedesmus vacuolatus−rGO, the adsorption capacity of
rGO aerogel was relatively lower. However, the synthesis of the
aforementioned materials was more complicated than that of the
rGO aerogel, and the rGO aerogel could be obtained using a
facile hydrothermal method.
Recyclability and Stability Studies. It was necessary to
test the adsorption ability of the regenerated rGO aerogel for the
sake of evaluating the economics and stability of the adsorbent.
The rGO aerogel was regenerated, and the adsorption
experiments were carried out using the regenerated adsorbent.
The aforementioned operation was repeated six times, and the
data are shown in Figure 12. As shown in Figure 12, the
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■ EXPERIMENTAL METHODS
Materials. Graphite powder was obtained from J & K
Chemical Ltd. Lead nitrate, nitric acid, sulfuric acid, potassium
permanganate, sodium nitrate, hydrochloric acid, hydrogen
peroxide, and other chemicals were purchased from Tianjin
Chemical Reagent Co. They were used without further
purification.
Synthesis of GO and rGO Aerogel. GO was synthesized
with graphite powder via a modified Hummer’s method.49
Concentrated H2SO4 (120 mL) was added into a 500 mL flask in
an ice bath, followed by the addition of 5.0 g of graphite power.
Then, 2.5 g of NaNO3 was slowly added under stirring, and the
mixture was continuously stirred for 2 h. After that, 15 g of
KMnO4 was slowly added to the mixture, and the mixture was
stirred for another 2 h at <20 °C. Next, the ice bath was removed,
and the mixture was stirred for 0.5 h at 35 °C. Deionized water
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(150 mL) was then poured into the mixture, and the solution
was stirred for 0.5 h at 90 °C, and then, 30% H2O2 was gradually
added until the solution turned bright yellow. After filtration
while still warm, the product was washed with 5% HCl to
remove metal ions, followed which the acid was washed off using
deionized water. Finally, the product was dried and dispersed to
obtain the GO suspension aqueous solution.
The effects of reaction parameters such as the concentration
of GO (2−10 mg/L), reaction time (8−24 h), and reaction
temperature (140−180 °C) on the preparation of rGO aerogel
were studied. To synthesize the rGO aerogel, a certain amount
of the GO suspension was weighed, diluted with purified water
to different concentrations, and ultrasonicated for 0.5 h. Then,
the dispersed homogeneous GO suspension was added into a 50
mL Teflon reactor. The Teflon reactor was sealed and heated in
an electrical oven at a specific temperature for a certain time to
obtain the rGO hydrogel. Next, the rGO hydrogel was removed
from the Teflon reactor and was immersed in a 10% aqueous
alcohol solution for more than 6 h. Finally, it was placed in a
refrigerator for freezing overnight and was freeze-dried at −60
°C for 24 h under vacuum (<12 Pa) to obtain the rGO aerogel.
FT-IR Analysis. FT-IR measurement was performed on a
Bruker VERTEX70 infrared analyzer.
XRD Analysis. The XRD studies of GO and rGO aerogels
were characterized on a Philips PW1840 X-ray diffractometer
with Cu Kα radiation (λ = 0.154 nm), which operated at (40 kV,
40 mA).
Raman Analysis. Raman spectroscopy was conducted on
Thermo Scientific DXR equipped with EZ OMNIC software to
analyze the structure of GO and rGO aerogels.
XPS Analysis. Surface composition of GO and rGO aerogels
were performed on a Thermo Fisher Scientific X-ray photo-
electron spectrometer with monochromatic Al Kα radiation at
1486.6 eV.
BET Analysis. N2 adsorption and desorption isotherms of
GO and rGO aerogels were determined by an ASAP2020 HD88
instrument at 78 K.
SEM Analysis. The SEM images of rGO aerogels were
obtained by a Zeiss EM900 scanning electron micrography at 30
kV.
Adsorption Experiments. The effects, including contact
time (10−120 min), pH value (1−5), and the initial
concentration (6−100 mg/L) on the adsorption efficiency of
rGO aerogels for Pb(II) were investigated. A 1000 mg/L Pb(II)
stock solution was prepared using Pb(NO3)2 and diluted by
adding deionized water to achieve the desired concentration.
The initial pH value of each sample solution was adjusted by
adding 0.001−2 mol/L of HNO3 or NaOH solution. The
adsorption experiments of Pb(II) were carried out by adding
absorbent (10 mg) to the experimental solution of the known
concentration (25 mL) under shaking condition (100 rpm).
After adsorption equilibrium, the adsorption solution was
filtered to separate the supernatant. The concentration of
Pb(II) in aqueous solution was analyzed by an inductive coupled
plasma emission spectrometer (180−80, Hitachi, Japan).
The equilibrium adsorption capacity of Pb(II) [qe (mg/g)]
was calculated using the following eq 5.
(Co − Ce)V
qe =
W (5)
where Co was the initial concentration of Pb(II) (mg/L); Ce
was the equilibrium concentration of Pb(II) (mg/L); V (L) was
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the volume of the adsorption solution; and W (g) was the weight
of the adsorbent.
■
AUTHOR INFORMATION
Corresponding Author
Chunjuan Gao − Institute of Seawater Desalination and
Multipurpose Utilization, MNR(Tianjin), Tianjin 300192, P. R.
China; orcid.org/0000-0002-2958-4674;
Email: liuxing326@163.com
Authors
Zeliang Dong − Institute of Seawater Desalination and
Multipurpose Utilization, MNR(Tianjin), Tianjin 300192, P.
R. China
Xiaocui Hao − Institute of Seawater Desalination and
Multipurpose Utilization, MNR(Tianjin), Tianjin 300192, P.
R. China
Ying Yao − Institute of Seawater Desalination and Multipurpose
Utilization, MNR(Tianjin), Tianjin 300192, P. R. China
Shuyuan Guo − Institute of Seawater Desalination and
Multipurpose Utilization, MNR(Tianjin), Tianjin 300192, P.
R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.0c00183
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors are grateful for financial support from the National
Natural Science Foundation of China (51602069), the Tianjin
Science and Technology Supports Key Proje cts
(18YFZCSF00350), the Guangdong Province Zhanjiang Bay
Laboratory Project (012S19005-005), and the Haikou City’s
Marine Economic Innovation and Development Demonstration
City Project (HHCL201810).
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