Applied Surface Science 467–468 (2019) 1122–1133

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Applied Surface Science

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

Full Length Article

Green synthesis of amino-functionalized carbon nanotube-graphene hybrid T

aerogels for high performance heavy metal ions removal
⁎
Wenwei Zhana, Liang Gaob, Xue Fua, Sajid Hussain Siyala, Gang Suia, , Xiaoping Yanga
a
State Key Laboratory of Organic-Inorganic Composites, College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
b
AVIC Composite Corporation LTD, Beijing 101300, China

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, the ultra-lightweight and robust three-dimensional graphene/polydopamine modified multiwalled
Graphene aerogel carbon nanotube (MWCNT-PDA) hybrid aerogels were prepared via a viable green route and applied to highly
Polydopamine efficient heavy metal ions adsorption. No additional reducing agents were required during the molding of the
Carbon nanotubes hybrid aerogel, thus greatly reducing the environment pollution emissions. The MWCNT-PDA in right amounts
Adsorption
provided the hybrid aerogels with satisfying structure stability and effectively prevented the stacking of GO
Heavy metal ions
sheets, as well as exposed more active sites to improve the adsorption of heavy metal ions. Benefiting from the
large specific surface area, porous structure and competent active sites, the resulting hybrid aerogels showed
superior adsorption performance for heavy metal ions, and the saturated adsorption capacities were as large as
318.47 and 350.87 mg g−1 for Cu(II) and Pb(II), respectively, calculated by the Langmuir isotherm model. The
research revealed that the synergistic effects of the surface complexation and chelation between active sites in
hybrid aerogels and heavy metal ions were the dominant adsorption mechanisms. High adsorption capacity and
easy separation from water after adsorption make the hybrid aerogels an ideal choice for heavy metal ions
treatment in practical application.

1. Introduction
Water pollution caused by heavy metal ions has a deleterious impact
on human being health and ecological environment [1,2], and a sui-
table technology is needed to effectively treat heavy metal ions in
contaminated water. Up till now, various methods have been taken to
remove metal ions in wastewater, including chemical precipitation [3],
ion exchange [4], membrane filtration [5], biological treatment [6] and
adsorption [7]. Among them, the adsorption method is regarded as the
most effective method due to its reasonably wide adaptability, simple
handling, low cost and little secondary pollution. Traditional adsorbent,
such as zeolite [8], activated carbon [9], silica [10], metal oxide [11]
and polymer resin [12], suffers from either low adsorption capacity or
low efficiency. Therefore, it is significant to find new ideal adsorbent
with high adsorption capacity and excellent adsorption selectivity.
Recently, some nanostructured adsorbents have been applied to
remediate contaminants from wastewater because of their huge specific
surface area and abundant active sites. As one of the most promising
nanomaterials, carbon-based nanomaterials, like carbon nanotube [13],
graphene [14] and carbon aerogel [15], have been used as adsorbents
to remove organic pollutants and heavy metal ions. Among them,
graphene oxide (GO) has drawn extensive attention to potential for the
removal of heavy metal ions due to its numerous negatively charged
active adsorption sites [16]. The abundant oxygen-containing groups
(eOH, eCOOH and epoxy groups) on the basal and edges planes of GO
can provide negative charge to combine positively charged heavy metal
ions through electrostatic interaction or constitute complexes with
heavy metal ions [17,18]. However, GO is prone to restack or ag-
glomerate because of the strong van der Waals interactions and π-π
stacking [19,20], which can consume a large number of active sites.
Further, the oxygen functional groups on GO sheet can enable it to
disperse well in water [21], so it needs high-speed centrifugation to
gather together. Obviously, the high-speed centrifugation is unreason-
able for wastewater treatment, owing to the large amounts of waste-
water and operation cost. Thus, an appropriate technology, through
which could separate GO and water once the adsorption is finished
without losing its high adsorption capacity, needs to be explored.
Fortunately, the assembly of GO nanosheets into 3D graphene
aerogel (GA) is considered one of the most promising strategies to
overcome the problems mentioned above. As a newly emerging porous
material, GA exhibits special mechanical property, low density and high
internal surface area [22,23]. The integration of individual GO sheet

⁎
Corresponding author.
E-mail address: suigang@mail.buct.edu.cn (G. Sui).

https://doi.org/10.1016/j.apsusc.2018.10.248
Received 7 July 2018; Received in revised form 25 October 2018; Accepted 29 October 2018
Available online 30 October 2018
0169-4332/ © 2018 Elsevier B.V. All rights reserved.
W. Zhan et al. Applied Surface Science 467–468 (2019) 1122–1133

Fig. 1. Schematic illustration of the synthesis process of as-prepared carbon nanotube-graphene hybrid aerogels.

Fig. 2. The SEM images of the hybrid aerogels with different GO/MWCNT-PDA mass ratio: (a) 1:1, (b) 2:1, (c) 3:1 and (d) 4:1.

into graphene aerogel can not only maximally preserve the specific
properties inherited from GO, but also exhibit the peculiar three-di-
mensional porous network structure consisting of interconnected
macro-pores and micro-pores. The unique structure prevents aggrega-
tion of GO, promotes the free diffusion of heavy metal ions and en-
hances the probability of contact between heavy metal ions and active
sites [24–26]. Thus, 3D graphene aerogels reveal high adsorption ca-
pacity for the removal of heavy metal ions. However, GA is difficult to
maintain high structure stability and high effective active site exposure
at the meantime [27,28]. The high structure stability of GA mostly
depends on the high compactness, but it will limit the metal ion dif-
fusion and result in adsorption site deactivation [29,30]. On the con-
trary, reducing the compactness of GA to expose more active sites may
reduce the structure stability.
At present, the hybrid materials combining carbon nanotubes
(CNTs) and 3D architecture of graphene have been reported to prepare
hybrid material for widespread applications including water purifica-
tion [31], shape memory [32], selective oil/water separation [33], solar
steam generation [34] and removal of formaldehyde [35]. In-
corporating CNTs into the GA can improve its mechanical properties
and structure stability [36]. The CNTs in the graphene interlayer can
hinder from the restacking of graphene nanosheets and provide more
accessible surface area.
CNTs have been served as high-efficiency adsorbent in the adsorp-
tion field because of their large specific surface area, low density and
strong interaction with metal ions. The assembly of graphene and CNTs

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Fig. 3. (a) FT-IR spectra, (b) Raman spectra and (c) XRD patterns of GO, MWCNT-PDA and hybrid aerogel; (d) BET analysis of hybrid aerogel.
hybrid aerogels, which can combine the outstanding properties of CNTs
and graphene, as well as the unique characteristics of aerogels, will
produce new porous materials with desired structures and peculiar
adsorption properties. So far, CNTs/graphene hybrid aerogels are
mainly prepared by chemical vapor deposition (CVD), chemical re-
duction and hydrothermal reduction process [37–41]. The CVD method
requires expensive reagents and complicated instruments, which limits
its applications. The other two methods seem more plausible, but the
high-energy consumption and heavy use of chemical reagents virtually
violate the concept of environmental protection.
Recently, bio-inspired polydopamine (PDA) has received extensive
attention and has become one of the focal points in the field of surface
modification of material [42–44]. Dopamine (DA) can be spontaneously
oxidized and self-polymerized in Tris-HCl buffer solutions (pH = 8.5),
and firmly adhere to almost all substrates [45,46]. Besides, PDA has
plentiful catechol and amine functional groups, which can become the
active sites for heavy metal ions through electrostatic interactions,
hydrogen bonding interactions, or bidentate chelating [47–49]. Con-
sidering these fascinating properties of PDA, this paper creatively in-
troduces PDA functionalized multi-walled carbon nanotubes (MWCNT-
PDA) into the structure of GA. The whole forming process of MWCNT-
PDA/GO hybrid aerogels was carried out under mild conditions without
additional reducing agents. The abundant catechol and amine func-
tional groups of MWCNT-PDA can increase the amount of active sites on
the hybrid aerogels surface bonding with heavy metal ions. The ag-
gregation effect of GO sheets was also subdued with the introduction of
MWCNT-PDA to expose more adsorption sites available, and the
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adsorption ability for heavy metal ions was enhanced significantly.
Moreover, the hybrid aerogels showed mechanical behavior like a
sponge, which facilitated recycling of aerogel after water remediation
and minimized potential environmental threats caused by discarded
graphene nanosheets. The proposed hybrid aerogels with porous
structure showed the prospect of highly efficient removal of heavy
metal ions, oil contamination, and toxic dyes from wastewater.
2. Experimental section
2.1. Materials
Natural flake graphite, carboxylic multiwalled carbon nanotube
(MWCNT-COOH) were obtained from Xianfeng Nanomaterials Co. Ltd.,
Nanjing, China. Pb(NO3)2·3H2O, Cu(NO3)2·3H2O, dopamine hydro-
chloride, and tris (hydroxyethyl) aminomethane were provided by
Aladdin Co. Ltd., Shanghai, China. Potassium permanganate power
(KMnO4, ≥99.5%) and sulfuric acid (H2SO4, 98%) were purchased
from Sinopharm Chemical Reagent Co. Ltd., Shanghai, China.
2.2. Preparation of samples
2.2.1. Preparation of GO
GO was prepared by the oxidation of natural flake graphite through
a modified hummers method [50]. Briefly, flake graphite (5 g) and
NaNO3 (2.5 g) were added to a cooled of H2SO4 (120 ml) under stirring
in an ice bath. 15 g of KMnO4 were slowly added into the mixture. Then
W. Zhan et al.
Fig. 4. (a) XPS survey spectra of GO, MWCNT-PDA and hybrid aerogel; High-resolution XPS spectra of (b) C 1s, (c) O 1s and (d) N 1s peaks for hybrid aerogel.
the mixture was heated at 35 °C for 12 h. Afterward, the ice water
(400 ml) and H2O2 (15 ml) were added to remove excess permanganate
ions and manganese dioxide. Next, the graphite oxide solution was
ultra-sonicated for 2 h in order to peel it into graphene oxide na-
nosheets. The pH value of graphene oxide solution was adjusted to
neutral by several days dialysis. Finally, the mixture was purified by
repeated centrifugation and the supernatant is collected to obtain the
graphene oxide suspension.
2.2.2. Preparation of MWCNT-PDA
The preparation of MWCNT-PDA was based on our previous work
[51]. 100 mg MWCNT-COOH and 200 mg dopamine hydrochloride
were mixed into 200 ml Tris-HCl buffer solution (pH = 8.5). The solu-
tion was then stirred at room temperature for 48 h and the resultant was
centrifuged several times with deionized water. Finally, the MWCNT-
PDA was frozen at −50 °C for 3 h, followed by freeze drying process
(24 h, 30 Pa).
2.2.3. Preparation of 3D MWCNT-PDA/GO hybrid aerogels
The MWCNT-PDA/GO hybrid aerogels were synthesized through
hydrothermal reduction of the mixture of GO and MWCNT-PDA. The
GO and MWCNT-PDA with different mass ratios (1:1, 2:1, 3:1, 4:1) were
dispersed in a 20 ml vial. After sonicated for 2 h and stirred for 1 h, the
black mixture was heated at 90 °C for 12 h to obtain the hybrid hy-
drogel. Then the hydrogels were washed using deionized water for at
least 12 h to remove the impurities. Finally, the hybrid aerogels were
formed after the freeze-drying process (−50 °C) for 48 h.
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2.3. Material characterization
The morphologies and structures of hybrid aerogels were observed
using a field-emission scanning electron microscope (FE-SEM, S-4700,
Hitachi, Japan) and transmission electron microscope (TEM,
JEM100CX, Leica, USA) operating at an accelerating voltage of 200 kV.
Fourier transform infrared (FTIR) spectra was measured with a
PerkinElmer Spectrum 400. X-ray diffractometer (XRD) pattern was
collected on a Rigaku D/Max 2500 diffractometer with 2 theta ranging
from 5 to 80° using Cu Kα radiation (40 KV and 40 mA, λ = 0.154 nm).
The interplanar spacing of graphene sheets was calculated by the Bragg
equation (2dsinθ = nλ). The Raman spectroscopy was performed on
Raman spectroscope (Renishaw inVia laser) with 514 nm laser excita-
tion wavelength. The specific surface areas were measured by using
Brunauer-Emmett-Teller (BET) on a Micromeritics ASAP 2460 instru-
ment. X-ray photoelectron spectroscopy (XPS, ESCALAB 250 spectro-
graph) was used to identify the chemical composition of hybrid aero-
gels. The inductively Coupled Plasma Optical Emission Spectrometer
(ICP-OES, Thermo Fisher Scientific, USA) was used to determine the
metal ion content in water.
Adsorption experiments at room temperature were used to in-
vestigate the adsorption behavior of hybrid aerogels towards Cu(II) and
Pb(II). The impact of different parameters such as pH value, heavy
metal ion concentration and adsorption time on adsorption capacity
was studied. Heavy metal ion solutions were prepared by dissolving
lead nitrate (1 g L−1) and cadmium nitrate (1 g L−1) in deionized water.
The effect of pH value was investigated by adjusting the initial pH value
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Fig. 5. (a) TEM images of MWCNTs-PDA samples; (b) TEM images of the hybrid aerogel; (c) Low-magnification and (d) High-magnification SEM images of hybrid
aerogel.
of the experimental solutions between 2.0 and 7.0. In the adsorption
isotherm experiments, a solution with different metal ion concentra-
tions (50, 100, 150, 200, 300 and 400 mg L−1) were obtained by di-
luting the stock solution (1 g L−1). 25 mg of hybrid aerogels were added
to 50 ml solution with different initial concentration. Then the mixture
was shaken on a vibrator for 24 h. In the adsorption kinetic experi-
ments, 50 mg of hybrid aerogels were added into 100 ml solution with
initial metal ion concentration of 300 mg L−1 (pH = 6), respectively.
Each solution was agitated for 5, 10, 20, 40, 60, 90, 120, 180, 240, 360,
480 and 600 min, respectively, at 200 rpm in water bath shaker under
25 °C to achieve adsorption equilibration. The competitive adsorption
experiments of Cu(II) and Pb(II) in hybrid aerogels were carried out by
adding 50 mg of hybrid aerogels into a solution containing a mixture of
Cu(II) and Pb(II). The initial concentration of both Cu(II) and Pb(II) was
300 mg L−1 (pH = 6). The remaining concentration of Cu(II) and Pb(II)
in the filtrated solutions was measured by using ICP-OES.
The final adsorption capacity (Q) of the hybrid aerogel was ana-
lyzed using the following equation [52]:
Q= (C0 − Ce) V/m (1)
where V (mL) is the volume of the heavy metal ions solution, m (mg) is
the mass of the adsorbent, respectively. C0 is the initial concentrations
and Ce is the equilibrium concentrations of the heavy metal ions
(mg L−1).
3. Results and discussion
3.1. Characterization of the MWCNT-PDA/GO hybrid aerogel
Fig. 1 elucidates a general formation routine of the 3D hybrid
aerogel. Firstly, the MWCNT-PDA and GO were fully mixed and soni-
cated to obtain a uniform mixture solution. The abundant catechol and
amine groups of polydopamine on the MWCNT surface can easily form
hydrogen bonds with water molecules and exhibited strong affinity for
water molecules. Therefore, MWCNT-PDA showed outstanding water-
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Applied Surface Science 467–468 (2019) 1122–1133
solubility and dispersion stability in water. Then, the mixture was
moved to a screw bottle and heated at 90 °C for 12 h to obtain MWCNT-
PDA/GO hybrid hydrogel. There was no need for additional reducing
agents in the entire formation process of hybrid hydrogel, which greatly
reduced environmental damage. Herein, the polydopamine was si-
multaneously used as reducing agent and crosslinking agent during the
assembly process of the graphene oxide sheets, which could effectively
shorten reaction time and lower reaction temperature. The GO sheets
can retain a mass of oxygen functional groups due to the weak reduc-
tion of polydopamine and the low reaction temperature during the
hydrothermal process. Finally, the hydrogels were freeze-dried to ob-
tain the corresponding aerogel.
Fig. S1† shows the differences in the macroscopic morphology of
hybrid hydrogels and aerogels with different mass ratios. The ultra-light
characteristic (samples density of 4.3–9.2 mg cm−3) of the hybrid
aerogel was proved by placing it above the dandelion without de-
forming (Fig. S2†). The addition of different amounts of MWCNT-PDA
significantly influenced the macroscopic and microscopic structure of
the hybrid aerogel. Excessive amounts of MWCNT-PDA could induce
their aggregation, and damage the structure uniformity. After freeze-
drying, the morphology of the hybrid aerogel (GO:MWCNT-PDA = 1:1)
had collapsed and the obvious cracks appeared on the surface of the
hybrid aerogel. The aerogels with other proportions of GO and
MWCNT-PDA exhibited a low volume shrinkage and maintained a good
morphology. Fig. 2 shows the SEM images of hybrid aerogels with
different mass ratios. It can be seen that the micro-pores of the hybrid
aerogel (1:1) were randomly distributed and lacked clear inter-
connectivity (Fig. 2a). By reducing the MWCNT-PDA content in hybrid
aerogels, the graphene sheets started to assemble into a honeycomb-like
structure, in which the high density of well-packed and equi-size pores
can be observed (Fig. 2b–d). As the amount of MWCNT-PDA decreased,
the pore sizes became larger. The MWCNT-PDA can cross-link nearby
GO nanosheets and facilitate their self-assembly, the reduction degree
of GO was increased with the rising MWCNT-PDA content at the same
reaction temperature. In the process of assembly and molding of hybrid
W. Zhan et al. Applied Surface Science 467–468 (2019) 1122–1133

Fig. 6. (a) Effects of pH value on the adsorption capacities of Cu(II) and Pb(II); (b) Zeta-potentials of MWCNT-PDA and GO under different pH values; (c) The effect of
initial metal ion concentration on Cu(II) and Pb(II) adsorption; (d) Effect of contact time on Cu(II) and Pb(II) adsorption.

Fig. 7. Langmuir (a) and Freundlich (b) adsorption isotherm for Cu(II) and Pb(II) on hybrid aerogel.

aerogels, MWCNT-PDA can act as a supporting skeleton to build the
porous structure, and when an appropriate amount of MWCNT-PDA
was introduced, the overall pore structure can be formed. In addition,
the plentiful functional groups particularly catechol and amino groups
of MWCNT-PDA can be served as active adsorption sites to bind metal
ions by electrostatic attraction and bidentate chelating. Therefore, the
hybrid aerogel with GO/MWCNT-PDA mass ratios of 2:1 was selected to
explore the adsorption capacity and adsorption mechanism for heavy
metal ions.
The FT-IR spectra of GO, MWCNT-PDA and hybrid aerogel with GO/
MWCNT-PDA mass ratio of 2:1 (Fig. 3a). The characteristic peaks of GO
appeared at 1085, 1406 and 1734 cm−1 which corresponded to the
CeO stretching vibration in the alkoxy groups, OeH deformation vi-
brations and C]O stretching vibration in the carbonyl and carboxyl
groups. This clearly confirmed that various oxygen functional groups
existed on GO sheets. After weak chemical reduction of polydopamine
and thermal reduction, the corresponding adsorption peaks of the
oxygen functional groups was merely weakened to a certain extent,

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Table 1
Adsorption isotherm parameters of the Langmuir and Freundlich for Cu(II) and
Pb(II) on hybrid aerogel.
Adsorbates Langmuir Freundlich
Qmax (mg g−1) KL (L mg−1) R2 KF (mg−1) 1/n
Cu(II) 318.471 0.013 0.995 13.678 0.539
Pb(II) 350.877 0.021 0.996 22.113 0.497
indicating that the hybrid aerogel retained some oxygen containing
functional groups. Meanwhile, the vibration of C]N band appeared at
1630 cm−1. Besides, the strong band at 1517 cm−1 was assigned to
NeH stretching vibration on the surface of hybrid aerogel, and it im-
plied some nitrogen-containing functional groups of MWCNT-PDA were
introduced into the hybrid aerogel. These O and N functional groups
can serve as the active adsorption sites for binding to heavy metal ions.
Raman spectrum is an efficient technique to characterize the
structure of carbon-based materials without causing damage. As shown
in Fig. 3b, the Raman spectra of GO, MWCNT-PDA and hybrid aerogel
exhibited two prominent bands at 1355 and 1589 cm−1, corresponding
to D and G bands, respectively. The G-band was related to the vibration
of sp2 carbon atoms in the hexagonal carbon framework, while the D
band was ascribed to the vibration of sp3-hybridized carbon atoms at
the edges or defects within the hexagonal graphitic structure. Herein,
we used the intensity ratio of ID/IG to evaluate the degree of graphite
structure defect. The ID/IG increased slightly from 1.01 for GO to 1.04
for hybrid aerogel due to the incorporation of MWCNT-PDA, which il-
lustrated a relative higher degree of disorder and structural defects.
Fig. 3c shows the XRD spectra of MWCNT-PDA, GO and hybrid
aerogel. A peak can be seen at 2θ = 25.76° (d-spacing of 0.35 nm),
corresponding to the distance between walls in MWCNT-PDA. The GO
exhibited a prominent peak at 2θ = 11.85° (d-spacing of 0.74 nm),
which was due to oxygen functional groups on GO nanosheets. How-
ever, this peak in the pattern of hybrid aerogel had been greatly wea-
kened, implying that the partial reduction of GO, and a new diffraction
peak presented at 2θ = 21.82° and an interlayer spacing of 0.41 nm.
The broad peak in XRD pattern of the hybrid aerogel indicated the GO
sheets formed less ordered self-assembly along their stacking direction,
reflecting that the cellular structure of the hybrid aerogel consists of
few-layer graphene nanosheets, which was consistent with the SEM
observation.
The specific surface area and porous structure of hybrid aerogel
were further studied by the nitrogen adsorption/desorption experi-
ments. The good adsorption capacities for heavy metal ions could be
Fig. 8. Fitting results for the Pseudo-first-order (a) and Pseudo-second-order (b) kinetic models for Cu(II) and Pb(II) adsorption on hybrid aerogel.
Applied Surface Science 467–468 (2019) 1122–1133
accomplished using a high specific surface of the adsorption materials,
which provided a large number of available active sites and contact
areas. By fitting the isotherm curves with the Langmuir model and the
BET model, the specific surface area of hybrid aerogel was calculated to
be 356.1 and 117.3 m2 g−1, respectively (Fig. 3d), suggesting a multi-
R2 porous feature in the hybrid aerogel structure. The pore size distribu-
tion analysis determined by the BJH method showed the size of me-
0.961
0.942 sopores in hybrid aerogel was mainly within the range of 10–20 nm,
which was derived from the tubular structure of multi-walled carbon
nanotubes. The total pore volume of the hybrid aerogel was up to
0.271 cm3 g−1.
In this study, the chemical composition and atomic ratio of each
element in the different aerogels has been investigated by XPS. From
XPS survey scan in Fig. 4a, the peaks of C 1s at 285 eV and O 1s at
532 eV emerged in GO, while a new peak of N 1s emerged at 399 eV in
the hybrid aerogel, which should arise from MWCNT-PDA in the hybrid
aerogel. The oxygen contents decreased from 29.92 atom % for GO to
19.47 atom % for the hybrid aerogel. The atomic ratio of carbon to
oxygen (RC/O) of GO was 2.34, but that of hybrid aerogel increased to
3.98 (see Table S1). These above results indicated that even though the
process of self-assembly accompanied with the reduction of GO, there
were still abundant oxygen-containing groups on the partially reduced
GO surface. The increase in the content of nitrogen element showed
that the MWCNT-PDA was successfully introduced into the aerogel. In
Fig. 4b, the C 1s spectrum of hybrid aerogel sample can be deconvolved
into four peak components at about 284.8, 286.5, 288.3 and 290.3 eV,
attributable to the C]C/CeC (aromatic rings), CeO (hydroxyl and
epoxy), C]O (carbonyl) and OeC]O (carboxyl groups), respectively.
After hydrothermal reduction, the peak associated with C]C/CeC in
aromatic rings became dominant, and the intensities of peaks asso-
ciated with oxygen-containing groups decreased significantly. In
Fig. 4c, the O 1s spectrum of hybrid aerogel peaks can be deconvoluted
into three different peaks with binding energies of 530.9, 532.1 and
533.7 eV, corresponding to C]O, OeC]O and CeO, which were in
accordance with those of C 1s. The N 1s peaks at 401.1, 399.8 and
398.5 eV were attributed to R-NH2 (amine groups), R-NH-R (substituted
amines) and ]NeR (imino groups), respectively (Fig. 4d). The relative
amount of N 1s components further illustrated the presence of PDA in
the hybrid aerogel. The results of XPS spectrum of hybrid aerogel were
in consistent with those of FT-IR spectra and XRD results.
In Fig. 5a, the TEM images of the MWCNT-PDA proved that the PDA
coating fully covered the surface of MWCNT. PDA improve the dis-
persity of MWCNT-PDA in GO dispersion, which resulted in the uniform
distribution of MWCNT-PDA in the resulting hybrid aerogels, as shown
in Fig. 5b. It can be seen that the MWCNT-PDA in hybrid aerogel played
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Table 2
Parameters for the Pseudo-first-order Model and Pseudo-second-order kinetic model of Cu(II) and Pb(II) ions adsorption on hybrid aerogel.
Adsorbates Qexp (mg g−1) Pseudo-first-order model Pseudo-second-order model

−1
Q1e (mg g ) K1 R 2
Q2e (mg g−1) K2 × 10−4 R2

Cu(II) 243.1 163.3 0.0038 0.928 245.7 1.394 0.994

Pb(II) 290.8 151.8 0.0045 0.917 280.9 0.482 0.997

Fig. 9. (a) XPS survey of the hybrid aerogel after adsorption of Pb and (b) High-resolution Pb 4f spectra of hybrid aerogels after adsorption; (c) XPS survey of the
hybrid aerogel after adsorption of Cu and (d) High-resolution Cu 2p spectra of hybrid aerogels after adsorption.

a role as the skeleton to enhance the stability of aerogel and prevented
GO agglomeration, and increased the accessible area of the aerogel for
heavy metal ions. The hybrid aerogel can be restored to the original
state under compression deformation without collapse, indicating the
good compressibility and structural stability of the hybrid aerogel. The
cyclic compression tests of the hybrid aerogel with a maximum strain
up to 50% were shown in Fig. S3†. In Fig. 5c, d, the SEM images re-
vealed that the hybrid aerogel had a well-defined and interconnected
3D porous framework with the pore sizes ranging from 50 to 90 μm. The
unique structure composed of interconnected micropores facilitated the
free diffusion of heavy metal ions and mass transfer in the 3D porous
framework, and the fully exposed active adsorption sites would increase
the contact opportunity with heavy metal ions. Therefore, the unique
hierarchical porous structure consisting of GO sheets and MWCNT-PDA
in hybrid aerogel was expected to provide highly efficient adsorption
for heavy metal ions.
3.2. Removal performance of MWCNT-PDA/GO hybrid aerogel towards
heavy metal ions
3.2.1. Effect of MWCNT-PDA content
The incorporation of different amounts of MWCNT-PDA can not
only regulate the pore size and the morphology of the hybrid aerogels,
but can also affect the adsorption capacity to heavy metal ions. The
adsorption capacity could be affected by changing the mass ratio of GO
and MWCNT-PDA (Fig. S4†). With the decrease of MWCNT-PDA con-
tent, the adsorption capacity of heavy metal ions increased. This is
because polydopamine acted as a reducing agent during the assembly
process of GO sheets, and the lower the dopamine content would lead to
more reservation of oxygen-containing functional groups in the hybrid
aerogel. XPS analysis gave a further proof, as shown in Fig. S5†. With
the decrease of MWCNT-PDA content, the atomic percentages of O 1s
increased, and the C/O ratio decreased from 4.76 to 3.58, which was in
accordance with the aforementioned adsorption capacity to heavy
metal ions.

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Fig. 10. High resolution spectra of C 1s (a–c), O 1s (d–f) and N 1s (g–i) for hybrid aerogels before and after adsorption with Pb(II) and Cu(II).

Fig. 11. The complexation (red) and chelation (blue) interaction of Pb(II) and Cu(II) adsorption on MWCNT-PDA/GO hybrid aerogel.

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3.2.2. Effect of solution pH value, adsorption time and initial heavy metal
ion concentration
The adsorption capacity of heavy metal ions is related to several
adsorption factors such as pH value, initial heavy metal ions con-
centration, and adsorption time, etc. The pH value of solution is a
significant parameter that greatly influence adsorption characteristics
and the surface charges of the adsorbents. As presented in Fig. 6a, the
adsorption capacity increased remarkably with the increase of pH value
from 2 to 5, and then changed slowly. With the increased of pH value
ranging from 2 to 7, the Cu(II) and Pb(II) adsorption capacity of hybrid
aerogel increased obviously from 67 and 95 mg g−1 to 224 and
271 mg g−1, respectively.
The zeta potentials at different pH values were measured to further
study the effect of pH value on heavy metal ions adsorption. The zeta-
potentials of MWCNT-PDA and GO decreased with the increase of pH
value from 2 to 7, as shown in Fig. 6b. The GO surface exhibited a
negative charged because of the effects of hydroxyl, carboxyl and epoxy
functional groups. At lower pH value, the relatively high concentration
of hydrogen ions would be fiercely competitive with Cu(II) and Pb(II)
for the adsorption sites on the surface of hybrid aerogel, and resulted in
virtual repulsion of heavy metal ions. As the pH value increased, there
was less competition between heavy metal ions and hydrogen ions for
the adsorption sites on the surface of hybrid aerogels, leading to a better
adsorption capacity. In addition, the GO surface charge became more
negative when pH value of solution increased, which could enhance the
electrostatic attraction with heavy metal ions to promote the adsorption
process. The isoelectric points (IEPs) of MWCNT-PDA occurred at pH
value of 4.2. When the pH value of solution was below 4.2, the surface
charge of MWCNT-PDA was positive because of the protonation of the
amine groups, so the electrostatic exclusion between the positively
charged adsorption sites and heavy metal ions resulted in lower ad-
sorption capacity. The MWCNT-PDA surface started to show negative
charge when the pH value exceeded the isoelectric points of MWCNT-
PDA. The more negative charge naturally enhanced the electrostatic
interactions with heavy metal ions, resulting in increased metal ion
adsorption.
In this study, the Cu(II) and Pb(II) adsorption capacities increased
rapidly with increasing concentrations of Cu(II) and Pb(II) in the low
initial concentration, and finally reached the saturated value at a high
initial concentration (Fig. 6c). The adsorption capacity of hybrid
aerogel to two kinds of heavy metal ions increased from 56.7 and 61.9
to 243.2 and 290.8 mg g−1, respectively, with increase at the initial
concentration of Cu(II) and Pb(II) from 50 to 400 mg L−1. Because the
higher initial heavy metal ions concentrations, the greater the possi-
bility of collision between heavy metal ions and the adsorption sites in
hybrid aerogel, and the adsorption capacity was higher correspond-
ingly. The difference in affinity of Cu(II) and Pb(II) for the hybrid
aerogel was demonstrated by the competitive adsorption using a mix-
ture of equal concentrations of metal ions (Fig. S6†). The results in-
dicated that the hybrid aerogel showed stronger interaction and higher
affinity with Pb(II).
As shown in Fig. 6d, the adsorption capacity of the hybrid aerogel to
Cu(II) and Pb(II) increased rapidly in the first 100 min and reached
equilibrium at about 600 min. The results can be ascribed to that the
available adsorption sites on the hybrid aerogel surface for binding
heavy metal ions were sufficient in the early stage, and then the binding
efficiency gradually declined with the reduction of active sites.
3.2.3. Adsorption isotherms
Adsorption isotherms models were commonly employed to under-
stand the adsorption behaviors and mechanisms of heavy metal ions. In
this study, Langmuir and Freundlich isotherm models were applied to
analyze the above equilibrium data of the Cu(II) and Pb(II) on hybrid
aerogel at different initial metal ions concentrations.
The Langmuir isotherm model could be given by the following
equation [53]:
1131
Applied Surface Science 467–468 (2019) 1122–1133
Ce C 1
= e +
Qe Qm KL Qm (2)
where Ce is the equilibrium concentration of heavy metal ions in the
solution (mg L−1). Qe is the amount of metal ions adsorbed at equili-
brium (mg g−1). Qm is the maximum amount of metal ions during the
whole adsorption process (mg g−1). KL is the constant correlated with
the affinity of binding sites and energy of adsorption (L mg−1). The
values of KL and Qm can be obtained from the intercept and slope of Ce/
Qe and Ce (Fig. 7a).
The Freundlich isotherm model equations could be written as fol-
lows [54]:
1
logQe = logKF + logCe
n (3)
where Ce is the equilibrium concentration of metal ions (mg L−1), Qe is
the adsorption capacity at equilibrium (mg g−1). The slope 1/n in-
dicates the adsorption intensity or surface heterogeneity. KF is the index
of correlation reflecting the adsorption performance. The value of n and
KF can be derived from the intercept and slope of log Qe and log Ce
(Fig. 7b).
The fitting results of the adsorption isotherm models are listed in the
Table 1. The higher correlation coefficient (R2 = 0.995 and 0.996 for
Cu(II) and Pb(II), respectively) was revealed in the Langmuir isotherm
model than that in the Freundlich isotherm model (R2 = 0.961 and
0.942 for Cu(II) and Pb(II), respectively). It demonstrated that the
Langmuir isotherm model was more appropriate to study the adsorp-
tion behavior of aerogel material, which was applied equally to other
heavy metal ions (such as Sr(II), Eu(III), Co(II), Cd(II) and Zn(II)) ad-
sorption process in previous literatures[19,47,55]. The experimental
data and fitted results presented that the adsorption behavior of Cu(II)
and Pb(II) mainly occurred on the uniform surface of the hybrid aerogel
through monolayer adsorption. The Langmuir fitting results showed
that the maximum Cu(II) and Pb(II) adsorption capacity of the hybrid
aerogel was 318.47 and 350.87 mg g−1, respectively, which was rela-
tively higher than that of most carbon-based adsorbents reported in the
literatures (Table S2).
3.2.4. Adsorption kinetics
To further elucidate the adsorption process, the adsorption experi-
mental data was fitted by the pseudo-first-order kinetic model and
pseudo-second-order kinetic model. The linear equations of two models
were expressed as follows [56]:
log(Qe − Qt ) = logQ e − k1 t (4)
t 1 t
= +
Qt k2 Qe2 Qe (5)
where Qe and Qt (mg g−1) are the amount of adsorption at equilibrium
state and at contact time t (min), respectively. k1 (min−1) is the rate
constant of pseudo-first-order kinetic, and k2 (g mg−1 min−1) is the
pseudo-second-order kinetic rate constant. The fitting plots of the above
kinetic models for Cu(II) and Pb(II) adsorption are illustrated in Fig. 8,
and the kinetic parameters calculated from linear fitting equation are
exhibited in Table 2. It can be seen that the correlation coefficient of the
pseudo-second-order kinetic model (R2 = 0.994 and 0.997) is higher
than that of the pseudo-first-order kinetic model (R2 = 0.928 and
0.917) for the adsorption of Cu(II) and Pb(II) in the hybrid aerogel.
Furthermore, the Qe values calculated from the pseudo-second-order
model were 245.7 and 280.9 mg g−1 for Cu(II) and Pb(II), which were
close to the experimental values. The fitting results of the pseudo-
second-order kinetic model indicated that the adsorption process of Cu
(II) and Pb(II) on hybrid aerogel was dominated by chemical adsorption
involving the strong surface complexation and chelation interaction of
metal ions with the functional groups in the hybrid aerogel.
W. Zhan et al.
3.3. Adsorption mechanism of hybrid aerogel
In this study, the electrostatic interaction between heavy metal ions
and negatively charged hybrid aerogel became stronger with the in-
creased pH value of solution, and provided an enhanced driving force
for the adsorption behavior. The adsorption capacity of hybrid aerogel
to Pb(II) and Cu(II) followed the order of Pb(II) > Cu(II). This order
agreed well with the metal electronegativity. The higher electro-
negativity of heavy metal ions, the stronger attraction of the heavy
metal ions on the negatively charged hybrid aerogel surface. It in-
dicated that the adsorption order of heavy metal ions in water onto
hybrid aerogel closely related with the metal electronegativity. In ad-
dition, the coordination of heavy metal ions with the surface functional
groups including oxygen and nitrogen was also one possible adsorption
mode.
XPS was further utilized to explore the adsorption mechanism and
the elemental composition of the hybrid aerogel after Pb(II) and Cu(II)
adsorption. As expected, the strong and clear Pb peaks appeared in the
XPS spectrum of hybrid aerogel. As shown in Fig. 9b, the high-resolu-
tion Pb 4f spectrum can be deconvolved into two peaks located at
143.9 eV (assigned to Pb 4f5/2) and at 139.1 eV (assigned to Pb 4f7/2),
which demonstrated that the valency of Pb was unchanged during the
adsorption [57]. The peak of Pb 4f5/2 was attributed to the reaction
between Pb(II) and eCOOH group bonded on the hybrid aerogel sur-
face, and the peak of Pb 4f7/2 was formed by the reaction of Pb(II) and
eOH group. Similarly, the adsorption of Cu(II) in the hybrid aerogel
sample can be demonstrated considering of the presence of peak at
932.6 eV (assigned to Cu 2p3) in Fig. 9d.
In order to analyze the combination of metal ions with the oxygen-
containing groups and amino groups, the C 1s, O 1s and N 1s peaks of
the hybrid aerogel were studied in detail to understand the chemical
state and structural characteristics of hybrid aerogel. As shown in
Fig. 10a–c, the high-resolution C 1s spectra indicated that there were
some differences between the C 1s peaks for hybrid aerogel before and
after adsorption of Pb(II) and Cu(II). The significant difference in peak
position can be seen for peaks related to oxygen functional such as C]
O bonds in carbonyl (287.9 and 287.1 eV for Pb(II) and Cu(II)), OeC]
O in carboxylic groups (289.0 and 288.5 eV for Pb(II) and Cu(II)) and
CeO in hydroxyl and epoxy group (286.8 and 287.1 eV for Pb(II) and
Cu(II)). The peaks of both the OeC]O (532.1 eV) and C]O (530.9 eV)
groups shifted to higher binding energies, and the peak of CeO
(533.7 eV) groups shifted to lower binding energies after the adsorption
of Pb(II) and Cu(II) (Fig. 10d–f). The significant difference between C 1s
and O 1s peaks demonstrated that the oxygen-containing groups (such
as hydroxyl and carboxyl groups) in the hybrid aerogel took place
strong complexing reactions with Pb(II) and Cu(II) [58,59]. The
abundant hydroxyl and carboxyl groups locating at the edges of GO
sheets can make the 2 or 3 adjacent oxygen atoms available to bind Pb
(II) and Cu(II). Fig. 10g reveals that the N 1s peaks of the hybrid aerogel
could be decomposed into three peaks at 398.5, 399.8 and 401.1 eV
corresponding to eN], eNHe and eNH2 groups. After adsorption of
heavy metal ions, the binding energy of eNHe and eNH2 group was
slightly shifted (about 0.4 eV) to higher energy than that of the original
hybrid aerogel, which implied that there was a strong chelating inter-
action between eNHe and eNH2 groups and metal ions, while the peak
of eN] remained unchanged [57,60]. These results indicated that the
N atoms of the eNHe and eNH2 groups shared their lone pair of
electrons with the heavy metal ions, resulting in the increase of the
binding energies.
These findings from XPS analysis were in accordance with the re-
sults of adsorption isotherm and kinetic studies. Consequently, the
complexation and chelation interactions between N, O and the metal
ions were regarded as the main adsorption mechanism of Pb(II) and Cu
(II) into the hybrid aerogel. Considering that carboxyl and hydroxyl
groups locating presumably at the edges of GO nanosheets and catechol
and amino groups existing on the surface of MWCNT-PDA, the
1132
Applied Surface Science 467–468 (2019) 1122–1133
speculated adsorption mechanism of hybrid aerogel for Pb(II) and Cu
(II) was schematically illustrated in Fig. 11.
4. Conclusion
A green synthesis of three-dimensional hybrid aerogel was pre-
sented, which needed no additional reducing agents during the forming
process. After combining with MWCNT-PDA, the hybrid aerogels ex-
hibited excellent structural stability and compressibility, as well as high
specific surface area, which ensured the availability of active adsorp-
tion sites in wastewater and overcame the defect of tending to pile up
and fragile nature for neat GO aerogels. The hybrid aerogel showed
high adsorption capacity of 318.47 and 350.87 mg g−1 for Cu(II) and
Pb(II), respectively, due to the synergistic effect of its sufficient active
adsorption sites and interconnect porous structure. Langmuir isotherms
fitted well for the Cu(II) and Pb(II) adsorption behavior of the hybrid
aerogel, implying a general monolayer adsorption manner. Meanwhile,
the pseudo-second-order kinetic model gave a better correlation with
the adsorptions of Cu(II) and Pb(II) than the pseudo-first-order one,
which revealed that the adsorption process involved typical chemical
adsorption and intraparticle diffusion. The prepared hybrid aerogel will
be a promising candidate and play an important application value in
wastewater treatment.
Notes
The authors declare no competing financial interest.
Acknowledgements
The authors acknowledge the financial support from the National
Natural Science Foundation of China (No. U1362205 and No.
U1664251).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apsusc.2018.10.248.
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