J Mater Sci (2020) 55:4656–4670

Composites
C O M P O S I T E S & N&
A Nnanocomposites
OC O M P O S I T E S

Acrylic acid grafted-multi-walled carbon nanotubes

and their high-efficiency adsorption of methylene blue
Yangyang Huan1 , Guanglin Wang1 , Chunqing Li1 , and Guangfen Li1,*

1
State Key Laboratory of Separation Membranes and Membrane Processes, School of Materials Science and Engineering, Tianjin
Polytechnic University, Tianjin 300387, China

Received: 7 August 2019 ABSTRACT

Accepted: 30 October 2019
Published online:
3 January 2020
Ó Springer Science+Business
Media, LLC, part of Springer
Nature 2020
A novel and simple method was explored to obtain (polyacrylic acid) PAA-g-
MWCNTs by grafting acrylic acid (AA) onto the surface of the multi-walled
carbon nanotubes (MWCNTs) using azobisisobutyronitrile (AIBN) as an initia-
tor. The results of TEM, FTIR, XPS, Raman spectra and TG proved that AA is
successfully grafted onto the surface of MWCNTs. Contact angle measurement
and dispersion tests revealed that the hydrophilicity of PAA-g-MWCNTs is
significantly higher than that of pretreated MWCNTs. The adsorption experi-
ments of methylene blue (MB) showed that the adsorption capacity is propor-
tional to the degree of functionalization and increases with initial concentration,
pH and temperature. The maximum adsorption capacity is about 329.8 mg g-1.
The kinetic and isothermal studies also showed that the adsorption data are
consistent with pseudo-first-order and pseudo-second-order kinetic and Lang-
muir isothermal models. The remarkable adsorption capacity of PAA-g-
MWCNTs can be attributed to the interaction of various adsorption mecha-
nisms, and further analysis indicated that hydrogen bonding and electrostatic
attraction play a decisive role in the adsorption process. In addition, the rela-
tionship between oxygen-containing groups content (OC) and MB adsorption
capacity was revealed by a simulation using a mathematical model.

Introduction Moreover, the cyclic aromatic structure of most dyes

In recent years, the rapid development of textile,
printing and other industries has resulted in a large
amount of organic dye wastewater. Since organic
dyes have great solubility and are biologically non-
degradable, they can easily accumulate in the envi-
ronment and become difficult to remove [1–3].
is carcinogenic, which will do great harm to the
human body [4, 5].Therefore, efficient removal of
dyes from wastewater has become a hot research
topic. Compared with photocatalytic degradation
[6, 7], membrane separation [8], extraction [9] and
chemical oxidation [10], adsorption is considered to

Address correspondence to E-mail: liguangfen@tjpu.edu.cn

https://doi.org/10.1007/s10853-019-04167-3
J Mater Sci (2020) 55:4656–4670
be the most attractive method [11] due to its sim-
plicity, high efficiency, low cost and reusability [5].
Since the discovery, carbon nanotubes (CNTs) have
been widely used in batteries, sensors and superca-
pacitors because of excellent electrical, mechanical
and thermal properties [12, 13]. To date, CNTs are
also regarded as one of the most desirable adsorbents
in adsorption field owing to large specific surface
area, small size, high porosity and easily functional-
ized surface [14–16]. Yao et al. [3, 11] described the
highly effective adsorption of methyl orange (MO)
and methylene blue (MB) from aqueous solution by
pristine multi-walled carbon nanotubes (MWCNTs).
Wu [2, 17] reported the equilibrium, kinetics and
thermodynamics of adsorbed reactive dyes and cop-
per ions (Cu2?) by MWCNTs. These studies declared
that CNTs have great application prospects in dye
wastewater treatment. However, the hydrophobicity
of CNTs and the strong van der Waals forces between
them lead to entanglement and agglomeration in
aqueous solution, which makes them difficult to
disperse uniformly [12]. The adsorption efficiency of
CNTs is thus limited by the inadequate contact
between CNTs and dye molecules in dye wastewater.
To solve this problem, many researchers have adop-
ted either physical or chemical methods to modify
CNTs [4, 18]. Physical methods such as ball milling
and high-speed agitation can improve the dispersion
by shortening the length of MWCNTs, but this will
cause serious damage to its structure [19, 20].
Therefore, modifying carbon nanotubes through
physical methods is not an ideal method. Chiang
et al. [21] treated MWCNTs with sulfuric acid and
nitric acid (H2SO4/HNO3) to introduce oxygen-con-
taining groups on MWCNTs surface, which signifi-
cantly improved their hydrophilicity. Cheng et al.
[22] prepared magnetic carbon nanotube–cyclodex-
trin for an improvement of their dye adsorption
properties. Zheng et al. [14] modified MWCNTs with
gallic amine and found that gallic–MWCNTs possess
excellent adsorption performance for organic dyes
through adsorption experiments. Compared with
physical modification, mild chemical modification
can ameliorate the hydrophilicity of CNTs by intro-
ducing functional groups and creating a large num-
ber of adsorption sites for dye molecules without
damaging their main structure. The adsorption
capacity of dye molecules on functionalized CNTs
was usually determined by a variety of interaction
forces. Earlier studies have disclosed the adsorption
4657
kinetics and isotherm for dyes of modified MWCNTs
based on the adsorption equilibrium data [2, 11, 23].
However, a detail explanation on interaction forces
and adsorption mechanism in these studies is insuf-
ficient for the researchers to understand the adsorp-
tion performance of the adsorbent. To this goal, this
paper focuses on the studying of the adsorption
properties of adsorbents to dyes, and the adsorption
mechanism is described in more detail.
In this study, PAA-g-MWCNTs were obtained by
an innovative modification of MWCNTs with acrylic
acid (AA) monomer. The advantage of this method is
that the use of monomer modification avoids the
steric hindrance effect of the polymer chain, which
improves the grafting rate of AA on MWCNTs. Sur-
face morphology, chemical compositions, element
content, structural defects, component content and
hydrophilicity of PAA-g-MWCNTs are characterized
by transmission electron microscope (TEM), Fourier-
transform infrared spectroscopy (FTIR), X-ray pho-
toelectron spectroscopy (XPS), Raman spectrometer
(Raman), thermogravimetric analyzer (TG) and con-
tact angle analyzer, respectively. PAA-g-MWCNTs
are used as an adsorbent to remove MB from aqueous
solution. The effects of pH, adsorption time, solution
concentration and temperature on the adsorption
properties of the adsorbent have been studied. In
addition, the adsorption equilibrium and kinetic
adsorption models of adsorbent to dye were investi-
gated and an adsorption mechanism is proposed. A
nonlinear correlation between the adsorption capac-
ity of MB by PAA-g-MWCNTs and oxygen-contain-
ing groups content (abbreviated as OC) was fitted by
Gaussian mathematical model.
Experimental
Materials
Toluene, H2SO4 (95–98%) and HNO3 (65–68%) were
purchased from Tianjin Sailboat Chemical Reagent
Technology Co., Ltd., China. AA and azobisisobuty-
ronitrile (AIBN) were provided by Shanghai Energy
Chemical Technology Co., Ltd., China. MWCNTs
(purity [ 98 wt%) were obtained from Chengdu
organic chemistry Co., Ltd., China. The adsorbate
used in the adsorption experiment is MB (Mw =
373.9, Tianjin Guangfu Chemical Research Institute
4658
Co., Ltd., China), and its chemical structural formula
is shown in Fig. 1.
Preparation of PAA-g-MWCNTs
The modification of MWCNTs includes two pro-
cesses of pretreatment and AA grafting modification,
as shown in Fig. 2. In the first step, in order to remove
surface impurities (amorphous carbon and metal
catalyst particles) of MWCNTs, 0.5 g of pristine
MWCNTs was ultrasonically stirred (150 W,
100 kHz) in 200 ml of the mixed solution of H2SO4
and HNO3 (3:1) for 1 h. The mixed solution was
washed with deionized water to neutrality (pH = 7)
in a suction filtration apparatus. Then, it was dried in
a vacuum oven at 60 °C for 12 h, and the dried pro-
duct was ground to obtain pretreated MWCNTs (C0).
In the second step, C0 was modified with AA. 0.05 g
of C0 was dispersed in 40 ml of toluene and ultra-
sonicated for 1 h until achieving a uniform disper-
sion. As the temperature of the water bath was raised
to 60 °C, AA and AIBN initiator (100:1) were slowly
added dropwise in sequential order, and the reaction
mixture was stirred continuously for 6 h. Afterward,
the products were rinsed with deionized water to
remove residual of AA monomer, initiator and sol-
vent. Finally, it was dried in a vacuum oven at 60 °C
for 12 h, and the final product was ground for sub-
sequent use. Modified MWCNTs prepared by adding
0.5, 1, 2 and 3 ml of different AA doses are abbrevi-
ated as C1, C2, C3 and C4, respectively.
Figure 1 Chemical structure formula of methylene blue. (The
symbol ‘‘?’’ represents positive charge, whereas the blue, white
and yellow spheres represent nitrogen atom, hydrogen atom and
sulfur atom, respectively).
J Mater Sci (2020) 55:4656–4670
Characterizations of PAA-g-MWCNTs
C0–C4 were dispersed in ethanol and evenly dripped
on the surface of micromesh support film (300 mesh).
Then, the surface morphology of the sample was
observed by TEM (Hitachi H7650, Japan). FTIR (Nicolet,
Thermo Fisher Science, USA) was used for the analysis
of chemical compositions of samples in the range of
500–4000 cm-1. The element content and OC on the
carbon nanotubes surface were further analyzed by XPS
(Thermo Fisher Science, K-Alpha). A Raman spectrom-
eter (XploRa Plus, Horiba, Japan) with 532 nm laser
wavelength was used to qualitatively analyze the
structure and surface defects of samples in the range of
500–3000 cm-1. The degradability of C0–C4 was quan-
titatively analyzed by TG (STA409F3, Hitachi, Japan) at
a heating rate of 10 °C/min in nitrogen atmosphere. The
test temperature range is set from 25 to 1000 °C. The
charges of carbon nanotubes surface were tested by the
solid surface zeta potentiometer (SurPASS 3, Anton
Paar, Austria) at room temperature. The pH (2–10) of
the solution used in the experiment was adjusted by
dilute hydrochloric acid and sodium hydroxide. Each
pH point was measured three times and averaged. The
contact angle analyzer (DSA100, Kruss, Germany) was
used to measure the contact angle of all samples to
determine the surface hydrophilicity.
Adsorption experiment
To perform adsorption experiment, 5 mg of each sam-
ple was placed in 30 ml of 50 mg l-1 MB solution, and
the carbon nanotubes were ultrasonicated for 10 min to
uniformly disperse in the dye solution and then
remained at room temperature for 6 h until reaching
adsorption equilibrium. The dye and PAA-g-MWCNTs
samples were then separated by 0.45 lm syringe filter.
The absorbance of the filtered dye solution was deter-
mined at kmax = 663 nm using a UV–Vis spectropho-
tometer (UV–Vis, Lambda 35, PerkinElmer, USA). The
adsorption capacity Qt (mg g-1) of samples for MB was
calculated by Eq. (1) [15].
ðC0  Ct Þ  V
Qt ¼ ð1Þ
m
where C0 and Ct (mg l-1) are the initial and t time
concentrations of MB. V (l) and m (g) are the dye
volume and adsorbent mass, respectively.
The sample with the highest adsorption capacity of
MB was selected to study the influences of
J Mater Sci (2020) 55:4656–4670
Figure 2 Route of synthesizing PAA-g-MWCNTs by grafting acrylic acid onto MWCNTs. (The gray, green and red spheres represent the
carbon atom, hydroxyl and carbonyl groups, respectively. Hydrogen atoms are not displayed).
experimental factors on adsorption capacity. The
influences of initial concentration of MB solution
ranging from 30 to 60 mg l-1 and adsorption time
from 0 to 4 h on adsorption capacity were performed
by testing the absorbance of supernatant at intervals
of time. And the results were fitted with kinetics and
isotherm adsorption models to analyze the adsorp-
tion process. Additionally, the impacts of environ-
mental temperature varying from 298 to 328 K and
solution pH from 2 to 10 on the adsorption perfor-
mance were carried out for revealing the adsorption
mechanism.
Results and discussion
Characterizations of PAA-g-MWCNTs
TEM analysis
Figure 3 displays the TEM images of the original and
modified carbon nanotubes. It can be found that the
Figure 3 TEM images of five
samples prepared by the
addition of different dosages
of AA varying from 0 (C0),
0.5 (C1), 1.0 (C2), 2.0 (C3)
and 3.0 ml (C4), respectively.
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average external diameter of C0 is approximately
10–20 nm, while those of C1–C4 are larger than
30 nm. Among them, C2 has the highest value and its
average external diameter is about 40 nm. With the
increase in AA monomer dosage, the surface struc-
ture of modified carbon nanotubes changed remark-
ably, indicating a successful attachment of AA
monomers on CNTs and subsequent polymerization
of AA. However, when the dosage of AA monomer
further increases, AA monomers are prone to self-
polymerization to form PAA under the combined
action of heating and initiator. Compared with AA
monomers, long-chain PAA molecules have greater
steric hindrance, which makes it difficult to reach the
active groups on the surface of carbon nanotubes and
therefore restricts the occurrence of functionalization.
FTIR and Raman analyses
Figure 4a shows FTIR spectra of samples C0–C4 for
identifying the presence of function groups. A similar
4660
Figure 4 a FTIR and b Raman spectra of pretreated MWCNTs (C0, 0 ml AA) and four PAA-g-MWCNTs (C1, 0.5 ml AA; C2, 1 ml AA;
C3, 2 ml AA; and C4, 3 ml AA) samples.
height of the peak at 3454 cm-1 was observed, which
corresponds to the tensile vibration of -OH existing in
acrylic acid, MWCNTs and moisture in the samples.
The peak strength of three characteristic peaks of AA
at 1735, 1586 and 1195 cm-1 increases significantly
[24]. The peak at 1735 cm-1 is attributed to the
stretching vibration of –C=O, whereas the peaks at
1586 and 1195 cm-1 are assigned to the stretching
vibration of –C = C and the asymmetric stretching
vibration of –COC–. The increase in the above char-
acteristic peak strength indicates the successful
modification of MWCNTs by AA.
The Raman spectra of C0–C4 in the range of
500–3000 cm-1 are presented in Fig. 4b. Three char-
acteristic peaks of the D band (representing the lattice
defect of the carbon atom), the G band (graphite band
of sp2-hybridized carbon atoms) and the G0 band
(second overtone of the defect-induced D band)
appeared at 1343.9, 1584.9 and 2681.2 cm-1, respec-
tively [25]. The degree of disorder in the structures of
the MWCNTs and the defects of the crystal of the
carbon atom can be represented by the intensity ratio
of the D band to the G band (ID/IG) [26]. The ID/IG
ratio increases from 0.79 (C0) to 1.12 (C1), 1.21 (C2),
1.08 (C3) and 1.07 (C4). A largest ID/IG ratio was
found in sample C2 in this case. This complies that
the larger intensity ratio represents the more defects
of carbon atom crystals [27]. The number of defect
sites determines that only an appropriate dosage of
AA monomers can maximally graft on MWCNTs. An
excess of AA may lead to the formation of active
J Mater Sci (2020) 55:4656–4670
oligomer and PAA, which eventually prevent them in
contacting with MWCNTs surfaces.
XPS and TG analyses
To estimate the content of functional groups on the
surfaces of MWCNTs, XPS analysis was carried out
and its corresponding spectra are present in Fig. 5a,
b. The binding energies of C1s and O1s characteristic
peaks of samples are 284.5 and 532.0 eV, respectively.
Obviously, the C1s peak intensity of C1–C4 is lower
than that of C0 (Fig. 5a), while the O1s peak intensity
is significantly higher than that of C0 (Fig. 5b). The
oxygen content in sample C0 is about 2.36 at.%,
which is due to the strong oxidizability of H2SO4 and
HNO3 in the pretreatment stage, as shown in Fig. 2.
C2 has the highest oxygen content of 8.11 at.%, which
is 3.5 times that of C0.
The C1s peaks of C0–C4 are subjected to decon-
volution for obtaining quantitatively content of
functional groups, and the data of deconvolution are
listed in Table 1. The surface structure of carbon
nanotubes was to some extent destroyed during the
modification process, resulting in a decrease in C=C
content. This, in turn, results in a decrease in content
of p–p bonds in the structure of carbon nanotubes. An
increase in C–C structure and OC (–OH, –C=O and –
COOH) content can be attributed to pretreatment by
the mixture of acid and AA grafting onto the surface
of carbon nanotubes. The OC content of C0 is
7.12 at.%, while the OC content of C1–C4 is 2–3 times
J Mater Sci (2020) 55:4656–4670 4661

Figure 5 XPS spectra corresponding to the carbon (C1s) (a) and oxygen (O1s) (b) of all samples; TG (c) and weight loss rate (d) curves
of all samples (C0, 0 ml AA; C1, 0.5 ml AA; C2, 1 ml AA; C3, 2 ml AA; and C4, 3 ml AA).

Table 1 Contents of functional groups in C0–C4 after deconvolution of C1s peak (C0, 0 ml AA; C1, 0.5 ml AA; C2, 1 ml AA; C3, 2 ml
AA; C4, 3 ml AA)

Sample (at.%) Binding energy (eV)

284.5 (C=C) 285.2 (C–C) 286.3 (–OH) 287.6 (–C=O) 289.3 (–COOH) 291.6 (p–p)

C0 65.97 14.72 2.76 3.85 0.51 12.19

C1 58.41 17.57 4.51 6.01 6.12 7.38
C2 56.54 17.47 6.06 8.16 8.03 3.74
C3 59.11 16.96 4.82 7.39 5.26 6.46
C4 59.98 16.64 3.53 8.70 3.57 7.58

higher than that of C0. The highest OC content of
22.25 at.% is especially found in sample C2, which
also owns the highest content of carboxyl and
hydroxyl groups. This further proves that the suc-
cessfully grafting of AA onto MWCNTs surfaces is
extremely in dependence of appropriate usage of AA.
The composition and its degradability behavior of
C0–C4 were quantitatively analyzed by TG in the
range of 25–1000 °C, and the corresponding curves
are displayed in Fig. 5c. And the whole process was
divided into four stages according to the weight loss
rate curves (Fig. 5d). The weight of all the samples
4662
attenuates in the first stage, with a maximum weight
loss about 1.3 wt%, indicating higher moisture con-
tent present in the sample. The weight loss between
108.1 °C and 332.2 °C is caused by decarboxylation of
carboxyl groups grafted on the surface of carbon
nanotubes when heated [28, 29]. From Fig. 5d, it is
found that C2 has the highest weight loss rate at this
stage, which indicates that C2 has more carboxylic
groups on its surface. This is consistent with XPS data
of C1s deconvolution. In the third stage
(332.2–692.3 °C), the weight decay of C0 slows down,
while C1–C4 remain rapidly decreasing as the
hydroxyl on the surface of the carbon nanotubes
dehydrolyzed and the PAA macromolecular chains
began thermal degradation [28]. The weight loss at
the last stage (692.3–1000 °C) was attributed to the
combustion of amorphous carbon in the samples.
From Table 2, C0 weight decreases by about
6.3 wt% in the first three stages (25–692.3 °C), while
C1–C4 decrease by 10.2–14.8 wt%. The elimination of
functional groups can easily cause the collapse of
carbon nanotube structure, which promotes the
combustion of amorphous carbon [30]. Therefore, in
the last stage, C0 weight decreases by only 1.5 wt%,
while C1, C3 and C4 drop by approximately 2.1 wt%
and C2 by about 2.5 wt%.
Hydrophilicity
The grafting of AA on MWCNTs surface can actually
give rise to the changes in surface hydrophilicity.
Here, the surface hydrophilicity of all samples was
evaluated by measuring water contact angle (Fig. 6a)
and dispersibility (Fig. 6b) of pretreated and modi-
fied MWCNTs, as shown in Fig. 6. The water contact
angle on the sample C0 is about 122.1°, demonstrat-
ing that it has hydrophobic surface. For the sample of
C1–C4, the water contact angles are below 41.3° (C3),
a maximum value in all modified samples, while a
minimum value of 31.2° was found for C2. The
Table 2 Weight loss of
samples C0–C4 at different Samples Final weight (wt%)
stages (C0, 0 ml AA; C1,
0.5 ml AA; C2, 1 ml AA; C3,
2 ml AA; C4, 3 ml AA) C0 92.2
C1 86.5
C2 82.7
C3 87.6
C4 87.5
J Mater Sci (2020) 55:4656–4670
lowered water contact angles indicate that C1–C4
samples contain more hydrophilic groups than that
of C0, further verifying that AA was successfully
grafted onto the surface of carbon nanotubes.
Figure 6b shows the photographs of sample dis-
persibility in water at different times from 1 h, 1 day
to 7 days. A certain amount of samples is placed in
20 ml water and dispersed uniformly by ultrasound
for 10 min. It can be found that all the samples
remain evenly dispersed in water after 1 h. A day
later, C1–C4 samples were still uniformly dispersed
in the water, while C0 settled to the bottom of the
bottle except for a small amount of carbon nanotubes
adhered on the wall. Amazingly, after 7 days, C0 had
all sunk to the bottom of the bottle, while C1–C4
showed no sign of precipitation. This is due to the
existence of van der Waals force between C0, which
leads to the entanglement and agglomeration of car-
bon nanotubes. However, a large number of OC on
the modified C1–C4 surface increase the surface
charge of carbon nanotubes and the electrostatic
repulsive force between them. Therefore, C1–C4 can
be dispersed in water for a long time.
Adsorption experiment
Effect of AA dosage on adsorption capacity
Figure 7 shows the adsorption capacity of C0–C4 in
MB solution of 50 mg l-1 at 298 K and the pho-
tographs for the supernatant of MB solution after
reaching adsorption equilibrium. Apparently, the
adsorption capacity of PAA-g-MWCNTs is compa-
rably higher than that of pretreated MWCNTs. The
adsorption capacity of C0 to MB is only 63.3 mg g-1.
The mazarine color of MB solution in the photograph
hints a poor removal of MB by adsorbent from
solution and proves that C0 have poor adsorption
performance. This is because of the strong
hydrophobicity of C0 surface, which makes it
Weight loss at different stages (wt%)
25–108.1 °C 108.1–692.3 °C 692.3–1000 °C
0.5 5.8 1.5
0.8 10.6 2.1
1.3 13.5 2.5
1.0 9.2 2.2
0.8 9.6 2.1
J Mater Sci (2020) 55:4656–4670
Figure 6 a Water contact angle and b dispersibility in water of all
samples prepared by the addition of different dosages of AA
ranging from 0 (C0), 0.5 (C1), 1.0 (C2), 2.0 (C3) and 3.0 ml (C4),
respectively.
difficult for MB molecules to transfer to the surface of
carbon nanotubes. Moreover, the limited contents of
functional groups on C0 surface can hardly provide
enough adsorption sites for the attachment of dye
molecules. The above problems were successfully
solved by AA grafting modification on MWCNTs
surface. The introductions of OC from AA monomers
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Figure 7 Adsorption capacity of C0–C4 in 50 mg l-1MB
solution (pH = 7, adsorption time: 4 h, 298 K) and photographs
of MB solution after reaching adsorption equilibrium.
are in favor to improve the hydrophilicity of carbon
nanotubes, and the long chains subsequently formed
by AA polymerization also provide more adsorption
sites. Therefore, the mazarine color of MB solution in
C1–C4 photographs becomes pale blue, and the
adsorption capacity increases up to the highest value
of 292.9 mg g-1 in sample C2, which is about 4.5
times that of C0. This result is consistent with the
former characterization of carbon nanotubes and
indicates that the adsorption capacity of carbon
nanotubes to MB is proportional to the degree of
functionalization.
Effects of pH, initial concentration, adsorption time
and temperature
The adsorption curves of C2 to MB at different pH
value can be viewed from Fig. 8a. With the increase
in pH, the adsorption capacity increased gradually.
The adsorption capacity of C2 increases from 161.4 to
329.8 mg g-1 when pH varies from 2 to 10, implying
a pronounced effect of solution pH on the adsorption
properties of PAA-g-MWCNTs. It is speculated that
the impact of pH on the adsorption capacity is caused
by the amount of charges on the surface functional
groups of the carbon nanotubes. To verify this spec-
ulation, the zeta potential of C2 at different pH was
measured (Fig. 8a). From the surface zeta curve (blue
line), the surface charges turn from positive into
negative as the solution changes from acidic into
alkaline. The charge value drops from 1.5 mV
(pH = 2) to - 58.7 mV (pH = 10). Since MB is a
cationic dye, when the pH value is 2, the surface of
4664
Figure 8 a Curves of C2 equilibrium adsorption capacity (MB
50 mg l-1, adsorption time 4 h, 298 K) and surface zeta potential
with pH value; b the effects of initial concentration and adsorption
time on C2 adsorption capacity (pH = 7, 328 K); c the effects of
temperature and initial concentration on C2 adsorption capacity
(pH = 7, adsorption time 4 h).
the carbon nanotubes is positively charged, and the
electrostatic repulsion between them hinders the
movement of the MB molecules toward the adsor-
bent. Simultaneously, a large amount of H? in acidic
J Mater Sci (2020) 55:4656–4670
solution will compete with MB molecules, resulting
in low adsorption capacity. However, when the
solution is alkaline, the OH- in the solution causes
massive negative charges on the carbon nanotubes’
surface, which enhance electrostatic interaction
between the carbon nanotubes and MB and promote
the adsorption capacity [31].
Apart from the effect of pH on the adsorption
properties, it is well known that the adsorption pro-
cess can be also positively affected by initial con-
centration, adsorption time and temperature.
Figure 8b displays that the adsorption capacity of C2
varies with adsorption time in different initial con-
centration solutions. Firstly, the adsorption capacity
increases with the increase in the concentration. As
the concentration changes from 30 to 60 mg l-1, the
corresponding adsorption capacity varies from 213.2
to 323.4 mg g-1. This is because the higher the dye
concentration, the greater the driving forces to over-
come the mass transfer resistance between the solu-
tion and the adsorbent, which is more conducive to
the contact between MB molecules and carbon nan-
otubes [18]. Secondly, with prolonging adsorption
time, all curves have similar trends. An initial sharp
increase in adsorption capacity was observed right
within adsorption time of 0.5 h. After 2 h, the
adsorption capacity almost reaches the adsorption
equilibrium. This phenomenon can be explained by
the existence of abundant adsorption sites on the
surface of carbon nanotubes at the initial stage, and
the free-moving MB molecules can rapidly bind to
the adsorption sites. In the later stage, the adsorption
rate slows down because of the decrease in the
number of adsorption sites and MB molecules, and
the lower of driving force provided by the solution
[32].
Figure 8c displays that the adsorption capacity
simultaneously increases with initial concentration of
MB and temperature. The adsorption capacity chan-
ges from 302.3 to 310.5, 315.4 and 323.4 mg g-1 as the
temperature increases from 298 to 308, 318 and 328 K.
An increase in temperature can accelerate the free
movement rate of MB molecules, which boosts the
probability of MB contacting with the adsorption site.
Moreover, the effect of temperature is more obvious
at high concentration, which is mainly related to the
number of MB molecules and adsorption sites in the
system.
Table 3 lists the monolayer maximum adsorption
capacity of modified carbon nanotubes obtained from
J Mater Sci (2020) 55:4656–4670 4665

Table 3 Monolayer maximum adsorption capacity of various adsorbents for MB dye

Adsorbents Qm (mg g-1) Experimental condition References

Oxidized CNTs 35.4–64.7 23 mg l-1, 333 K, pH = 7 [3]

Magnetic graphene–carbon nanotube composite 65.8 35 mg l-1, 313 K, pH = 7 [33]
MWCNTs functionalized thiol 28 40 mg l-1, 298 K, pH = 6 [34]
Acid-treated CNTs 188.7 40 mg l-1, 298 K, pH = 6 [35]
NH2-MWCNTs@Fe3O4 178.6 100 mg l-1, 298 K, pH = 7 [36]
Magnetic RCNT–cyclodextrin 196 166 mg l-1, 298 K, pH = 7 [22]
Alkali-activated MWCNTs 400 270 mg l-1, 298 K, pH = 7 [1]
Gallic-MWCNTs 310 320 mg l-1, 298 K, pH = 7.5 [14]
PAA-g-MWCNTs 323.4 60 mg l-1, 328 K, pH = 7 This work
The experimental conditions as initial concentration, temperature and pH were given in details

recent studies and PAA-g-MWCNTs prepared in this
paper to MB dye. Apparently, PAA-g-MWCNTs
exhibit the highest adsorption performance under
similar experimental conditions, indicating that their
potential application prospects in the field of dye
wastewater treatment.
Kinetics and isothermal studies
The obtained results were further used for simulation
with both kinetic and isotherm adsorption models for
exploring the adsorption mechanism between
adsorbent and adsorbate, as shown in Fig. 9. The
derived parameters from simulation results are
compared in Tables 4 and 5. For kinetic studies, two
commonly used kinetic models as pseudo-first order
and pseudo-second order are applied for the analysis
of experimental results. The former is suitable for the
adsorption process with only one factor determining
the rate, while the latter applies to the adsorption
process with saturated sites and multiple adsorption
mechanisms. These two models can be represented
by the following Eqs. (2) and (3) [2]:
lnðQe  Qt Þ ¼ lnðQe Þ  k1 t ð2Þ
t 1 t
¼ 2
þ ð3Þ
Qt k2 Qe Qe
where t (min) is time, and Qe (mg g-1) refers to the
adsorption capacity at equilibrium. k1 (min-1) and k2
(g mg-1 h-1) are the rate constants for adsorption
kinetics.
Figure 9a displays that both the simulated curves
by two models coincide very well with the experi-
mental data. The values of correlation coefficients
(R2) are near to 1 (Table 4), implying that the
adsorption process may involve both physical
adsorption and chemical adsorption.
Langmuir and Freundlich isotherm adsorption
models are utilized to further study the equilibrium
adsorption mechanism, as shown in Fig. 9b. The
former assumes that adsorption is based on mono-
layer adsorption on homogeneous surface, and there
is no interaction between adsorbate molecules. The
latter can be used for adsorption on non-uniform
surfaces, typically for multilayer adsorption [17]. The
following Eqs. (4) and (5) can describe the above two
isotherm models [11]:
Ce 1 Ce
¼ þ ð4Þ
Qe Qm KL Qm
lnCe
lnQe ¼ lnKF þ ð5Þ
n
where Ce (mg l-1) is the concentration of MB at
equilibrium; Qm (mg g-1) is the theoretical saturation
capacity of the monolayer (mg g-1); KL (l mg-1) and
KF [(mg g-1) (l mg-1)1/n] are the correlation indices
of two models; n is the model reaction constant.
Table 5 lists the derived relevant parameters of two
isotherm models. As the R2 of the Langmuir isotherm
is higher than that of Freundlich isotherm, the
adsorption process of C2 to MB is more consistent
with the former. As we can see from Fig. 3, the sur-
face of PAA-g-MWCNTs is quite smooth, suggesting
that MWCNTs are homogenously grafted by AA, and
the adsorbent sites are distributed with equal size
and shape on the PAA-g-MWCNTs surface; thus, the
process is in favor of monolayer adsorption. Other
studies also confirmed a preferential Langmuir
adsorption isotherm of GO when GO has higher OC
content [37]. This is due to the force field effect on the
4666 J Mater Sci (2020) 55:4656–4670

Figure 9 Adsorption a kinetic models (pH = 7, MB 60 mg l-1, 298 K) and b isotherm models (pH = 7, adsorption time 4 h, 328 K) of
C2.

Table 4 Parameters of
pseudo-first-order and pseudo- C (mg l-1) Pseudo-first-order model Pseudo-second-order model
second-order adsorption R2 Qe (mg g-1) k1 (min-1) R2 Qe (mg g-1) k2 (g mg-1 h-1)
kinetic models
30 0.991 208.1 4.34 0.998 215.3 0.059
40 0.989 264.8 4.18 0.999 274.4 0.043
50 0.988 297.1 4.29 0.999 307.8 0.040
60 0.986 319.7 4.34 0.999 331.1 0.038

Table 5 Parameters of the Langmuir and Freundlich isotherm models at different temperatures

T (K) Langmuir isotherm Freundlich isotherm

2
R -1
KL (l mg ) Qm (mg g )-1
R2 KF [(mg g-1) (l mg-1)1/n] n

298 0.978 0.0169 612.4 0.960 28.07 1.704

308 0.980 0.0175 620.5 0.963 30.31 1.735
318 0.972 0.0177 626.5 0.953 31.98 1.769
328 0.975 0.0181 631.8 0.956 34.62 1.819

surface of carbon nanotubes, which can promote MB
molecules to approach and combine with adsorption
sites. Once the surface sites of carbon nanotubes are
occupied, the force field is reduced to be insufficient
to attract the MB molecules to cover again. Thus,
monolayer adsorption occurs.
Adsorption mechanism
Figure 10a shows photographs of C2 before and after
adsorption in MB solution. Before adsorption, C2 was
evenly dispersed in the solution, but as the
adsorption progresses, C2 settled to the bottom. To
explain this phenomenon, TEM images of C2 before
and after adsorption were compared. As shown in
Fig. 10b, MB molecules were attached to the surface
of C2 after adsorption, and serious entanglement was
found between the carbon nanotubes. By comparison,
it can be concluded that the phenomenon in Fig. 10a
is due to the force field interaction between C2 and
MB molecules, which leads to the accumulation of
MB on C2 surface. And MB molecules as the con-
nection points make carbon nanotubes entangle and
cause them to sink. When it comes to the force field,
J Mater Sci (2020) 55:4656–4670
Figure 10 a Photographs of
C2 before and after adsorption
in MB solution; b TEM
images of C2 before and after
adsorption; c schematic
diagrams of adsorption
mechanism: (I) electrostatic
interaction, (II) hydrogen
bonding and (III) p–p electron
coupling. (The gray, green,
red, blue, white and yellow
spheres represent carbon atom,
hydroxyl, carbonyl groups,
nitrogen atom, hydrogen atom
and sulfur atom, respectively.
The dotted lines represent
various applied forces).
the van der Waals force that is ubiquitous between
molecules is the first to be considered. However,
there are other major interactions present in the
adsorption process of organic chemicals [38], for
instance, electrostatic interaction, hydrogen bonding
and p–p electron coupling [39].
From the analysis of influencing factors of
adsorption capacity, it can be found that pH has a
pronounce effect on adsorption capacity, which is
due to the key role played by electrostatic attraction
[40, 41]. With the increase in pH, carbon nanotubes
have more negative charges, while methylene blue is
a cationic dye, which will enhance the electrostatic
attraction between carbon nanotubes and the dye.
This can be verified by the results that adsorption
capacity increases with pH in Fig. 8a. Hydrogen
bonding also needs to be considered in the adsorp-
tion of organic chemicals. A large number of func-
tional groups attached on the surface of carbon
nanotubes, such as hydroxyl and carboxyl, and
nitrogen atoms in methylene blue molecules are
hydrogen bonding donors, and hydrogen atoms
between them can act as hydrogen bonding receptors
[40, 42]. In this way, various forms of hydrogen
bonding can be formed between carbon nanotubes
and MB molecules. In addition, p–p electron coupling
is also often used to explain the adsorption of carbon
nanotubes to organic compounds containing
4667
aromatic ring structures [40, 43]. It is well known that
carbon atoms in carbon nanotubes are mainly sp2
hybrid, and large p bonds are formed between
unpaired p orbital electrons to generate free-moving
p electrons. The complex aromatic ring structure of
MB molecule also contains p electron, which is easily
combined with the adsorbent in solution by p–p
electron coupling [44]. The schematic diagram of
adsorption mechanism based on the above detailed
description is shown in Fig. 10c.
According to the deconvolution data of C0–C4
C1s peak in Table 1, the OC content in samples C1–
C4 is significantly higher than that of C0, which is
consistent with the trend of adsorption capacity.
However, the adsorption capacity shows a reverse
trend to the content of p–p, which indicates that the
effect of p–p electron conjugation is not significant in
this case. Therefore, hydrogen bonding and electro-
static attraction are assumed to be the main forces in
the adsorption process. As the content of OC plays a
decisive role in hydrogen bonding and electrostatic
attraction, a mathematical model can be established
to quantitatively analyze the relationship between
OC content and adsorption capacity. The experi-
mental data were best fitted with Gauss mathematical
model, and the fitting coefficient is as high as 0.994, as
shown in Fig. 11. Because the OC is responsible for
establishing hydrophilic interaction, which again
4668
Figure 11 Experimental data of adsorption capacity (50 mg l-1,
adsorption time 4 h, pH = 7, 298 K) versus OC content of C0–C4
were fitted with a Gauss mathematical model.
demonstrates that the electrostatic attraction and
hydrogen bonding are the causes for the higher
adsorption capacity of MB by PAA-g-MWCNTs.
Conclusions
PAA-g-MWCNTs are successfully prepared by
in situ polymerization. A series of characterization
show that the diameter and OC of PAA-g-MWCNTs
are significantly increased. Meanwhile, the contact
angle reduces from 122.1° to 31.2° resulting in a better
aqueous dispersibility. Appropriate dosage of AA
can provide desirable adsorption performance of dye
on PAA-g-MWCNTs, as the excess of AA may induce
self-polymerization and thus prevent the MWCNTs
functionalization.
The studies on adsorption process further show
that the adsorption capacity of C1–C4 is much higher
than that of C0 owing to the addition of a large
number of adsorption sites on the surface of
MWCNTs by AA grafting. The adsorption capacity
increases with the increase in dye initial concentra-
tion, pH and temperature. In this paper, the most
efficient adsorption time is 2 h and the maximum
adsorption capacity of 329.8 mg g-1. The adsorption
data are found to be more consistent with both
pseudo-first-order and pseudo-second-order kinetic
models and Langmuir isotherm models. Further
analysis indicates that the high adsorption efficiency
of PAA-g-MWCNTs for MB depends on the
J Mater Sci (2020) 55:4656–4670
cooperation of electrostatic adsorption and hydrogen
bonding. An adsorption mechanism was proposed
for the adsorption process. Finally, the correlation
between adsorption capacity and oxygen-containing
group content was simulated by a mathematical
Gaussian function. The results of this study are of
great significance for exploring the potential appli-
cations of functionalized MWCNTs in dye wastewa-
ter treatment.
Acknowledgements
The work was supported by the National Natural
Science Foundation of China (No. 51378350) and the
Nature Science Foundation of Tianjin City (No.
17JCTPJC47000).
Compliance with ethical standards
Conflict of interest The authors declare that they
have no conflict of interests.
References
[1] Ma J, Yu F, Zhou L, Jin L, Yang M, Luan J, Tang Y, Fan H,
Yuan Z, Chen J (2012) Enhanced adsorptive removal of
methyl orange and methylene blue from aqueous solution by
alkali-activated multiwalled carbon nanotubes. ACS Appl
Mater Interfaces 4(11):5749–5760
[2] Wu CH (2007) Adsorption of reactive dye onto carbon
nanotubes: equilibrium, kinetics and thermodynamics.
J Hazard Mater 144(1–2):93–100
[3] Yao Y, Xu F, Chen M, Xu Z, Zhu Z (2010) Adsorption
behavior of methylene blue on carbon nanotubes. Bioresour
Technol 101(9):3040–3046
[4] Mishra AK, Arockiadoss T, Ramaprabhu S (2010) Study of
removal of azo dye by functionalized multi walled carbon
nanotubes. Chem Eng J 162(3):1026–1034
[5] Cheng S, Zhang L, Ma A, Xia H, Peng J, Li C, Shu J (2018)
Comparison of activated carbon and iron/cerium modified
activated carbon to remove methylene blue from wastewater.
J Environ Sci (China) 65:92–102
[6] El Hassani K, Kalnina D, Turks M, Beakou BH, Anouar A
(2019) Enhanced degradation of an azo dye by catalytic
ozonation over Ni-containing layered double hydroxide
nanocatalyst. Sep Purif Technol 210:764–774
[7] Mohamed A, Ghobara MM, Abdelmaksoud MK, Mohamed
GG (2019) A novel and highly efficient photocatalytic
degradation of malachite green dye via surface modified
J Mater Sci (2020) 55:4656–4670
polyacrylonitrile nanofibers/biogenic silica composite nano-
fibers. Sep Purif Technol 210:935–942
[8] Shi P, Hu X, Wang Y, Duan M, Fang S, Chen W (2018) A
PEG-tannic acid decorated microfiltration membrane for the
fast removal of Rhodamine B from water. Sep Purif Technol
207:443–450
[9] Othman N, Raja Sulaiman RN, Rahman HA, Noah NFM,
Jusoh N, Idroas M (2019) Simultaneous extraction and
enrichment of reactive dye using green emulsion liquid
membrane system. Environ Technol 40(11):1476–1484
[10] Tehrani-Bagha AR, Mahmoodi NM, Menger FM (2010)
Degradation of a persistent organic dye from colored textile
wastewater by ozonation. Desalination 260(1–3):34–38
[11] Yao Y, Bing H, Feifei X, Xiaofeng C (2011) Equilibrium and
kinetic studies of methyl orange adsorption on multiwalled
carbon nanotubes. Chem Eng J 170(1):82–89
[12] Chang PR, Zheng P, Liu B, Anderson DP, Yu J, Ma X (2011)
Characterization of magnetic soluble starch-functionalized
carbon nanotubes and its application for the adsorption of the
dyes. J Hazard Mater 186(2–3):2144–2150
[13] Eskandarian L, Arami M, Pajootan E (2014) Evaluation of
adsorption characteristics of multiwalled carbon nanotubes
modified by a poly(propylene imine) dendrimer in single and
multiple dye solutions: isotherms, kinetics, and thermody-
namics. J Chem Eng Data 59(2):444–454
[14] Zheng S, Guo H, Yang F, Hong B (2015) Novel organic dye
sorbent: synthesis and adsorption properties of multi-walled
carbon nanotubes modified with gallic amide units. Desalin
Water Treat 57(26):12264–12273
[15] Ghobadi J, Arami M, Bahrami H, Mahmoodi NM (2013)
Modification of carbon nanotubes with cationic surfactant
and its application for removal of direct dyes. Desalin Water
Treat 52(22–24):4356–4368
[16] Wang S, Ng CW, Wang W, Li Q, Li L (2012) A comparative
study on the adsorption of acid and reactive dyes on multi-
wall carbon nanotubes in single and binary dye systems.
J Chem Eng Data 57(5):1563–1569
[17] Wu CH (2007) Studies of the equilibrium and thermody-
namics of the adsorption of Cu2? onto as-produced and
modified carbon nanotubes. J Colloids Interface Sci
311(2):338–346
[18] Gong JL, Wang B, Zeng GM, Yang CP, Niu CG, Niu QY,
Zhou WJ, Liang Y (2009) Removal of cationic dyes from
aqueous solution using magnetic multi-wall carbon nanotube
nanocomposite as adsorbent. J Hazard Mater
164(2–3):1517–1522
[19] Kierkowicz M, Pach E, Santidrián A, Sandoval S, Gonçalves
G, Tobı́as-Rossell E, Kalbáč M, Ballesteros B, Tobias G
(2018) Comparative study of shortening and cutting strate-
gies of single-walled and multi-walled carbon nanotubes
4669
assessed by scanning electron microscopy. Carbon
139:922–932
[20] Park KC, Fujishige M, Takeuchi K, Arai S, Morimoto S,
Endo M (2008) Inter-collisional cutting of multi-walled
carbon nanotubes by high-speed agitation. J Phys Chem
Solids 69(10):2481–2486
[21] Chiang Y-C, Lin W-H, Chang Y-C (2011) The influence of
treatment duration on multi-walled carbon nanotubes func-
tionalized by H2SO4/HNO3 oxidation. Appl Surf Sci
257(6):2401–2410
[22] Cheng J, Chang PR, Zheng P, Ma X (2014) Characterization
of magnetic carbon nanotube–cyclodextrin composite and its
adsorption of dye. Ind Eng Chem Res 53(4):1415–1421
[23] Hosseinzadeh S, Hosseinzadeh H, Pashaei S, Khodaparast Z
(2018) Synthesis of magnetic functionalized MWCNT
nanocomposite through surface RAFT co-polymerization of
acrylic acid and N-isopropyl acrylamide for removal of
cationic dyes from aqueous solutions. Ecotoxicol Environ
Saf 161:34–44
[24] Gumus H (2018) Determination of progress in acrylic acid
modification on polyvinylidene fluoride membrane by
infrared spectroscopy. J Mol Struct 1174:122–126
[25] Liang S, Li G, Tian R (2015) Multi-walled carbon nanotubes
functionalized with a ultrahigh fraction of carboxyl and
hydroxyl groups by ultrasound-assisted oxidation. J Mater
Sci 51(7):3513–3524. https://doi.org/10.1007/s10853-015-9
671-z
[26] Zhao Z, Yang Z, Hu Y, Li J, Fan X (2013) Multiple func-
tionalization of multi-walled carbon nanotubes with carboxyl
and amino groups. Appl Surf Sci 276:476–481
[27] Shao D, Sheng G, Chen C, Wang X, Nagatsu M (2010)
Removal of polychlorinated biphenyls from aqueous solu-
tions using beta-cyclodextrin grafted multiwalled carbon
nanotubes. Chemosphere 79(7):679–685
[28] Datsyuk V, Kalyva M, Papagelis K, Parthenios J, Tasis D,
Siokou A, Kallitsis I, Galiotis C (2008) Chemical oxidation
of multiwalled carbon nanotubes. Carbon 46(6):833–840
[29] He J, Shang H, Zhang X, Sun X (2018) Synthesis and
application of ion imprinting polymer coated magnetic
multi-walled carbon nanotubes for selective adsorption of
nickel ion. Appl Surf Sci 428:110–117
[30] Martı́n O, Gutierrez HR, Maroto-Valiente A, Terrones M,
Blanco T, Baselga J (2013) An efficient method for the
carboxylation of few-wall carbon nanotubes with little
damage to their sidewalls. Mater Chem Phys
140(2–3):499–507
[31] Mittal A, Mittal J, Malviya A, Kaur D, Gupta VK (2010)
Adsorption of hazardous dye crystal violet from wastewater
by waste materials. J Colloids Interface Sci 343(2):463–473
4670
[32] Wu F-c, Tseng R-l, Juang R-s (2001) Kinetic modeling of
liquid-phase adsorption of reactive dyes and metal ions on
chitosan. Water Res 35(3):613–618
[33] Wang P, Cao M, Wang C, Ao Y, Hou J, Qian J (2014)
Kinetics and thermodynamics of adsorption of methylene
blue by a magnetic graphene–carbon nanotube composite.
Appl Surf Sci 290:116–124
[34] Robati D, Mirza B, Ghazisaeidi R, Rajabi M, Moradi O,
Tyagi I, Agarwal S, Gupta VK (2016) Adsorption behavior
of methylene blue dye on nanocomposite multi-walled car-
bon nanotube functionalized thiol (MWCNT-SH) as new
adsorbent. J Mol Liq 216:830–835
[35] Li Y, Du Q, Liu T, Peng X, Wang J, Sun J, Wang Y, Wu S,
Wang Z, Xia Y, Xia L (2013) Comparative study of
methylene blue dye adsorption onto activated carbon, gra-
phene oxide, and carbon nanotubes. Chem Eng Res Des
91(2):361–368
[36] Ahamad T, Naushad M, Eldesoky GE, Al-Saeedi SI, Nafady
A, Al-Kadhi NS, AaH Al-Muhtaseb, Khan AA, Khan A
(2019) Effective and fast adsorptive removal of toxic catio-
nic dye (MB) from aqueous medium using amino-function-
alized magnetic multiwall carbon nanotubes. J Mol Liq
282:154–161
[37] Yan H, Tao X, Yang Z, Li K, Yang H, Li A, Cheng R (2014)
Effects of the oxidation degree of graphene oxide on the
adsorption of methylene blue. J Hazard Mater 268:191–198
J Mater Sci (2020) 55:4656–4670
[38] Yang K, Xing B (2010) Adsorption of organic compounds
by carbon nanomaterials in aqueous phase: Polanyi theory
and its application. Chem Rev 110:5989–6008
[39] Ghaffar A, Younis MN (2015) Interaction and thermody-
namics of methylene blue adsorption on oxidized multi-
walled carbon nanotubes. Green Process Synth 4(3):209–217
[40] Yang K, Xing B (2009) Adsorption of fulvic acid by carbon
nanotubes from water. Environ Pollut 157(4):1095–1100
[41] Hyung H, Kim J-h (2008) Natural organic matter (NOM)
adsorption to multi-walled carbon nanotubes: effect of NOM
characteristics and water quality parameters. Environ Sci
Technol 42:4416–4421
[42] Franz M, Arafat HA, Pinto NG (2000) Effect of chemical
surface heterogeneity on the adsorption mechanism of dis-
solved aromatics on activated carbon. Carbon 38:1807–1819
[43] Wu T, Cai X, Tan S, Li H, Liu J, Yang W (2011) Adsorption
characteristics of acrylonitrile, p-toluenesulfonic acid,
1-naphthalenesulfonic acid and methyl blue on graphene in
aqueous solutions. Chem Eng J 173(1):144–149
[44] Pan B, Xing B (2008) Adsorption mechanisms of organic
chemicals on carbon nanotubes. Environ Sci Technol
42:9005–9012
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