International Journal of Biological Macromolecules 164 (2020) 818–825

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Removal of Brilliant Red dye (Brilliant Red E-4BA) from wastewater using
novel Chitosan/SBA-15 nanofiber
Farhad Bahalkeh, Mohammad Habibi juybari ⁎, Ramin Zafar Mehrabian, Mehdi Ebadi
Department of Chemistry, Gorgan Branch, Islamic Azad University, Gorgan postal code: 39975-49147, Iran

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

Article history: An environmental-friendly adsorbent composed of chitosan nanofibers modified by mesoporous silica sieve
Received 6 May 2020 (CTS-SBA-15) was synthesized via an electrospinning technique and used to remove of brilliant Red dye from
Received in revised form 1 July 2020 a wastewater solution. Characterization of the synthesized nanofibers using Fourier transform infrared (FT-IR),
Accepted 4 July 2020
X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses revealed that the chitosan
Available online 13 July 2020
nanofibers were effectively modified with mesoporous silica sieve (SBA-15). The effects of some adsorption
Keywords:
parameters such as pH, adsorbent dosage, and the time of adsorption process on the dye removal percentage
Nanocomposite were investigated in detail. Based on the kinetic and thermodynamic studies, the adsorption process obeyed
Chitosan/SBA-15 the pseudo-second order and Langmuir models, respectively. The obtained results revealed that the dye removal
Brilliant Red E-4BA efficiency of CTS-SBA-15 was about 98% in the presence of 0.03 g of the adsorbent and pH = 7 after 80 min. So, it
Adsorption isotherm was found that CTS-SBA-15 can act as inexpensive and efficient adsorbent for the brilliant Red E-4BA elimination
Kinetic study from the contaminated water.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction advantages, including lower prices, easier design, and availability

Nowadays٫ main water pollution arises from metal ions [1] and
organic dyes [2], which are originated from some industries including
textile [3], electroplating [4], printing [5], pharmaceutical units [6],
membrane separation [7] and the same. Therefore, the investigations
on the removal of contaminants from industrial wastewater have
attracted more and more attentions [8]. Brilliant Red E-4BA is an
odorless cationic dye in the triphenylmethane family, which are soluble
in water and alcohol. The complex aromatic structure of the brilliant red
dye (Fig. 1) makes it stable and difficult to biodegrade. It has anti-
microbial, anti-parasitic, and anti-fungal properties [9].
Different chemical methods such as electrochemical methods [10],
chlorination [11], ozonation [12], ion exchange [13], oxidation [14],
and flocculation [15] have been introduced for water purification
processes. Some biological methods have also been used for the
contaminant removal from wastewater, including the use of
microorganisms [16], fungi [17], algae [18], and enzymes [19]. In
addition, several physical methods have been applied for water
purification such as membrane [20], air conditioning [21], radiation
[22], and adsorption [23].
Among different kinds of technologies that have been used for the
elimination of dye compounds and heavy metals from the industrial
wastewater, the adsorption process possesses some remarkable
⁎ Corresponding author.
E-mail address: m.habibi@gorganiau.ac.ir (M. Habibi juybari).
[24–28]. A large number of adsorbents have been demonstrated for
this purpose, such as silica [29], alumina [30], carbon materials from
bioresources [31,32], metal oxides, [33] and polymer resins [34]. In
this way, Ghaedi et al. [35] founded that multi-walled carbon nanotubes
(MWCNTs) can act as a potent adsorbent for malachite green (MG) dye
in the optimum conditions (pH of 8, 0.018 g MWCNT, 8 mg/L dye
processing time of 10 min). Lv et al. [36] prepared nanofibrous
membranes based on Polyvinyl alcohol (PVA) and konjac glucomannan
(KGM) nanofiber membranes loaded with active ZnO nanoparticles
using the electrospinning technique and founded that the
nanocomposite adsorbed the Methyl orange dye with a high removal
efficiency (98%). Tu et al. [37] observed that the addition of rectorite
(REC) into porous polycaprolactone/TiO2 nanofibrous mats could
enhance organic dye decolorization properties of the nanocomposite.
In another study, Ghaedi et al. [38] investigated the applicability of
activated carbon prepared from orange tree wood for removal of sunset
yellow dye from aqueous solution. Their results revealed that 0.5 g of
the adsorbent removed more than 98% of the dye compound from an
aqueous solution after 10 min. They also Some of the adsorbents suffer
from a series of disadvantages such as high costing, low efficiency,
thermal instability, acid and base sensitivity, low adsorption capacity,
low durability, and small pores diameter [39].
In recent years, siliceous mesoporous adsorbents have attracted
considerable attention because of their high surface area and large
pore diameter [40]. Among this category of materials, mesoporous silica
sieve with a tunable pore diameter of between 5 and 15 nm (SBA-15)

https://doi.org/10.1016/j.ijbiomac.2020.07.035
0141-8130/© 2020 Elsevier B.V. All rights reserved.
 F. Bahalkeh et al. / International Journal of Biological Macromolecules 164 (2020) 818–825
Fig. 1. Chemical structure of Brilliant Red E-4BA.
possesses higher stability in aqueous solutions due to its thicker pore
walls compared to other siliceous mesoporous adsorbents [41].
However, Gao et al. [40] demonstrated that the adsorption capacity of
the pure SBA-15 adsorbent is negligible. They showed that
functionalization of the SBA-15-based composite by natural polymer
chitosan (20 wt%) could increase the nanocomposite adsorption
capacity up to 232.6 mg/g, which is more than most of the conventional
adsorbents such as multi-walled carbon nanotubes and bentonite-
based composite.
Chitosan is an affordable, ecofriendly, and abundant natural polymer
with a high absorption capacity due to the presence of several amino
groups in its molecular structure [42]. Silva et al. [43] found that the
amine groups in the chitosan chemical structure can covalently bond
with organosilane structures via a hydrolysis/condensation process.
Thus, in the present paper, natural chitosan nanofibers modified by
SBA-15 composite was synthesized and used for Brilliant Red dye
elimination from an aqueous solution. In this way, chitosan modified
SBA-15 (CTS-SBA-15) was synthesized by electrospinning technique
and characterized by Fourier-transform infrared spectroscopy (FT-IR),
X-ray diffractometer (XRD), and transmission electron microscopy
(TEM). In addition, the kinetic and thermodynamic parameters of the
adsorption process were investigated by the related models.
Fig. 2. Schematic illustration of the SBA/chitosan synthesizing procedure.
819
2. Experimental
2.1. Materials
Chitosan powder (Chitosan Low) and Brilliant Red dye were
prepared from Merck Co. (Germany) and Dystar Co. (Singapore),
respectively, and used without any purification. Acetic acid (%96),
hydrochloric acid, ethanol, and pluronic “P123” tetraethylorthosilicate
(TEOS, 98%) were purchased from Merck Co.
2.2. Preparation of pure and chitosan functionalized SBA-15
At first, 2 g of P123 surfactant and 6.25 g of HCl (1.9 M) were added
to a gradual beaker. The content of the beaker was mixed for 45 min at
45 °C. Then, 3.4 g of TEOS was added to the solution and mixed for 24 h
at 45 °C. Afterwards, the temperature of the mixture was increased to
100 °C, and after 24 h, 50 mL of ethanol was added to the mixture to
leave a white sediment in the gradual beaker. The reflux was performed
for 24 h at 78 to 85 °C on a magnetic stirrer. After the desired time, the
precipitate was dried in an oven until a soft and white powder (SBA-15
silica porous material) was obtained.
To prepare 0.5% SBA-15/3% chitosan mixture, 0.2 g of the
synthesized SBA-15 powder was added to 39.8 g of deionized water
and homogenized by an ultrasonic probe device (model TOPSONIC).
Also, 3 g chitosan powder was added to 97 g acetic acid (%96), and
after 2 min of stirring with a glass stirrer, the mixture was homogenized
by the ultrasonic probe for 15 min. Finally, 16 mL of the SBA-15
containing solution and 64 mL of the chitosan containing solution
were mixed and homogenized by the ultrasonic probe device for
20 min. Then the prepared solution was transferred into a lab-scale
electrospinning apparatus (made by Fanavaran Nano Meghyas Co.
(Iran)). Electrospinning was carried out at an applied voltage of 20 kV,
tip-to-collector distance of 6 cm, and a flow rate of 0.5 mL/h at room
temperature. After 18 h, the nanofibrous mats were separated from
the collector surface and dried for 12 h at ambient temperature. The
synthesizing procedure was schematically shown in Fig. 2.
820 F. Bahalkeh et al. / International Journal of Biological Macromolecules 164 (2020) 818–825
2.3. Adsorption process
20 mL Brilliant Red dye aqueous solution (20 ppm, pH = 7) was
prepared, and its initial adsorption intensity was read in UV–Vis
spectrum (519 nm) as an indicator peak. 0.03 g of the synthesized
nano-adsorbent was added to the dye solution, and the dye elimination
was investigated by measurement of the intensity of the indicator peak.
For this purpose, the mixture was mixed with a magnetic stirrer for
40 min, and then the solution was centrifuged at 3500 rpm for
15 min. By comparing the initial and ultimate adsorption intensity of
the indicator peak, the percentage of dye removal was determined. All
of the above steps were repeated with pure chitosan (as adsorbent),
and the dye removal percentage was compared with both adsorbents
(nanocomposite and pure chitosan).
2.4. Characterization
Fourier-transform infrared spectroscopy (FT-IR) and X-ray
diffractometer (XRD) analyses were done by THERMO spectrophotometer
model AVATAR, and Philips, PW 1800 (with angles of 2 h = 0.6–3°),
respectively. The determination of the Red E-4BA concentration
in the aqueous phase was performed by a double beam UV–Vis
spectrophotometer (Perkin Elmer, Lambda 25, USA) at 519 nm as λMax.
Surface morphology of the synthesized nanofibers was characterized by
transmission electron microscopy (TEM) model Philips EM208S 100KV.
3. Results and discussion
3.1. Identification and characterization of CTS-SBA-15 nanocomposite
The FT-IR spectra of the pure SBA-15, pure chitosan (CTS) and CTS-
SBA-15 nanocomposites are shown in Fig. 3.
In the FT-IR spectrum of SBA-15, the stretching vibration peak of the
silanolic and other hydroxyl groups appeared at 3425 cm−1 [44,45]. In
addition, the peaks located at 1083 cm−1 and 803 cm−1 are assigned
to the symmetrical and asymmetrical stretching vibration of Si-O-Si
bonds [46]. Furthermore, the peak at 961 cm−1 is attributed to the
bending vibration of the Si-OH bond [47]. In the chitosan FT-IR
spectrum, the broad band at about 3364 cm−1 is related to the
stretching vibration of O\\H and N\\H bonds [48]. The peaks of
symmetrical and asymmetrical stretching vibration of C\\H bonds
appeared at 2877 cm−1 and 2927 cm−1, respectively [32,49]. The peak
and the shoulder at 1561 cm−1 and 1641 cm−1 are attributed to
Fig. 3. FT-IR spectra of SBA-15, CTS, and CTS-SBA-15.
CONH2 and NH2 vibration in amine groups, respectively [50,51]. The
characteristic absorption bands of epoxide (C-O-C) and aromatic rings
appeared at 1090 cm−1 and 656 cm−1, respectively [52]. As can be
seen in the CTS-SBA-15 spectrum, the O-H/N-H peak at about
3347 cm−1 was broader due to the formation of hydrogen bonding
between hydroxyl and amine groups in chitosan and SBA-15
compounds. In this sample, the presence of CONH2, NH2, C-O-C, Si-O-
Si, and aromatic ring vibrations in the related spectrum indicated that
the CTS-SBA-15 compound was synthesized successfully.
Fig. 4 shows the low angle XRD patterns of SBA-15, CTS, and the CTS-
SBA-15 nanocomposite.
As shown in Fig. 4, the diffraction peaks appearing at 2θ = 0.5°, and
1.2°, which are attributed to (100) and (110) planes, are consistent with
the SBA-15 compound as was reported by Gao et al. [40]. The polymeric
nature of the chitosan nanofibers led to the formation a non-diffracted
pattern in the related XRD result. The presence of the broad and low-
intense peak at 2θ = 0.5° in the XRD pattern of CTS-SBA-15 proved
that the chitosan nanofibers were successfully covered by a layer of
the mesoporous silica compound.
TEM micrographs of CTS and CTS-SBA-15 nanofibers after the
electrospinning process are shown in Fig. 5.
As is shown in Fig. 5(a), the surface of the pure chitosan nanofibers
was smooth and clean, with an average diameter size of about 25 nm.
After surface treatment of the chitosan nanofibers by SBA-15, the
roughness, as well as the average diameter size of the modified
nanofibers, were increased significantly. According to Fig. 5(b), the
average diameter size of CTS-SBA-15 nanofibers was equal to 60.8 nm,
which is about 2.4 times higher than the average diameter size of the
unmodified nanofibers. These variations in the diameter size and
surface morphology may indicate that a layer of the silica-based
compound was covered on the surface of the nanofibers.
3.2. Dye removal process and optimization of adsorption parameters
In this research, industrial wastewater polluted by Brilliant Red E-
4BA (20 ppm) was used as an initial solution, and then some parameters
such as adsorbent dosage, solution pH, and adsorption time were
optimized.
To investigate the effect of pH on the adsorption process, 7 solutions
containing 20 ppm of the bright red dye were injected into 100 mL of
the mixture containing 0.02 g nano-adsorbent. Using a pH meter, the
pH of these solutions was adjusted at 2, 3, 4, 5, 7, 9, and 11. To determine
the final dye concentration in the prepared solution before and after the
adsorption process, the absorbance intensity for the indicator peak
(519 nm) in the related UV–Vis spectrum of each solution was
considered, as was explained in the experimental section. The variations
of dye removal percentage versus pH after the adsorption process by
CTS and CTS-SBA-15 is presented in Fig. 6.
As can be seen in Fig. 6, pH = 7 was the optimum value to obtain the
highest dye removal from the polluted solution. In this pH, about 54%
3000
CTS
2500 SBA-15
CTS-SBA-15
Intensity (a.u.)
2000
1500
1000
500
0
0 0.5 1 1.5 2 2.5 3
2θ (degree)
Fig. 4. The low angle XRD patterns of SBA-15, CTS, and the CTS-SBA-15 nanocomposite.
 F. Bahalkeh et al. / International Journal of Biological Macromolecules 164 (2020) 818–825 821

Fig. 5. TEM micrographs of (a) CTS and (b) CTS-SBA-15 nanofibers after the electrospinning process.

and 72% of the dye compound was removed from the solution by using
the unmodified and silica modified chitosan nanofibers, respectively. In
fact, in pHs more or less than 7 (acidic or basic media), the protonation
or deprotonation of the dye compound may cause the formation of
repulsion force between the adsorbate molecules. Therefore, the
absence of electrostatic repulsion between the organic compound
molecules led to the achievement of the highest adsorption efficiency
at pH = 7.
In order to investigate the effect of the nano-adsorbent dosage on
the adsorption process, 5 solutions containing 0.01, 0.02, 0.03, 0.05,
and 0.07 g of the chitosan and CTS-SBA-15 nanofibers were prepared
90
80 CTS-SBA-15
70 CTS
Dye removal percentage (%)
and 20 ppm of the bright red dye at the optimal pH, was added to the
mixtures. The variations of dye removal percentage versus the amount
of the adsorbents are depicted in Fig. 7.
According to Fig. 7, in both mixtures containing the modified and
unmodified adsorbents, by increasing the amount of the adsorbent up
to 0.03 g, the dye removal percentage was increased. However, the
dye removal percentage remained almost constant by more increasing
the adsorbent dosage in both mixtures. It may be due to the
agglomeration of the nanofibers in the more adsorbent dosages. In
addition, in all of the adsorbent dosages, the dye removal percentage
of the mixtures containing modified nanofibers was more than the
dye removal percentage of the mixtures containing the pure chitosan
nanofibers.
In order to study the adsorption process time on the percentage of
dye removal from the polluted solution, 7 solutions containing 0.03 g
of the chitosan and CTS-SBA-15 nanofibers were prepared and
20 ppm of the bright red dye at the optimal pH, was added to the

110
60
100
50
90
Dye removal percentage (%)

40
80

30 70

20 60
CTS-SBA-15
10 50
CTS
40
0
2 4 6 8 10 30
pH 0.01 0.02 0.03 0.04 0.05 0.06 0.07
Amount of adsorbent (g)
Fig. 6. The variations of dye removal percentage versus pH after the adsorption process by
CTS and CTS-SBA-15. Fig. 7. The variations of dye removal percentage versus the amount of the adsorbents.
822 F. Bahalkeh et al. / International Journal of Biological Macromolecules 164 (2020) 818–825

mixtures and stirred for 5, 15, 30, 40, 60, 80, and 90 min. The variations
of dye removal percentage versus the contact time are depicted in Fig. 8.
As can be observed in Fig. 8, in the mixtures containing the modified
and unmodified adsorbents, the dye removal percentage was reached to
about 98% and 94% after 80 min, respectively. According to these plots,
the variation of dye removal percentage versus the processing time for
both adsorbents showed two stages. In stage (I) the variation rate of
dye removal percentage is high and after a certain time, in stage (II),
the variations of the percentage reaches to a steady state value. In fact,
in the stage (II), the most of adsorption sites on the adsorbent surface
were occupied with the dye molecules and so the variation rate of the
dye removal percentage decreased in this stage. In addition, as can be
seen in Fig. 8, the steady state condition was achieved after 45 min for
the CTS-SBA-15 sample while for the CTS adsorbent this condition was
obtained after about 80 min. This means that the kinetic of adsorption
process on the surface of the modified adsorbent is significantly more
than the adsorption rate on the unmodified nanofibers. Furthermore,
the removal percentage of the modified sample is more than the value
obtained for the pure CTS in both stages, especially at initial times. The
kinetic and thermodynamic aspects of the adsorption process are
investigated in the next sections.
one. The linear relationships of the models of pseudo-first-order
and pseudo-second-order have been drawn using the data in
supplementary information (Fig. S1). The kinetic parameters of the
two models are given in Table 1.
According to the obtained results, which are reported in Table 1, the
pseudo-second-order model (R2 = 0.99) fitted the adsorption kinetics
better than the pseudo-first-order model (R2 = 0.89). Therefore, it
can be concluded that the adsorption process is a chemisorption process
involving the exchange or sharing of electrons between the dyes and
functional groups of CTS-SBA-15 nanofibers.
3.4. Thermodynamic aspects of the absorption process
Adsorption isotherms are useful quantitative tools for
demonstrating the capacity and behavior of the synthesized adsorbent
[23]. In this way, Langmuir and Freundlich isotherm models were
used to obtain equilibrium adsorption parameters. Eq. (3) is the main
form of the Langmuir adsorption isotherm.
1=K L qm þ C e =qm ¼ C e =qe ð3Þ

3.3. Kinetic aspects of the absorption process
The adsorption kinetic data are analyzed for the understanding
dynamic and adsorption rate of the adsorption reaction. The kinetic
aspects of the dye adsorption process on the modified and unmodified
adsorbents can be studied by pseudo-first order (Eq. (1)) and pseudo-
second (Eq. (2)) order models [53].
ln ðqe −qt Þ ¼ lnqe −K 1 t
t=qt ¼ 1=K 2 qe 2 þ 1=qe  t
were KL (L/mg) is the Langmuir affinity constant, which is related to the
energy of adsorption. qe (mg/g) and qm (mg/g) are the adsorption
capacity of the adsorbents at equilibrium and the maximum adsorption
capacity, respectively. Ce (mg/L) is the equilibrium concentration of the
used dye in the aqueous solution. The Freundlich isotherm is a purely
empirical relationship based on adsorption onto a heterogeneous
surface. The linear form of the Freundlich model could be expressed as
Eq. (4).
ð1Þ
log qe ¼ 1=n log C e þ log K F ð4Þ
ð2Þ

where qe (mg/g) and qt (mg/g) are the adsorption capacity of the
adsorbents at equilibrium and at time t (min), respectively. K1 and K2
are the pseudo-first order and pseudo-second order rate constants,
respectively. When log (qe–qt) was plotted against time, a straight line
should be obtained with a slope of K1, if the pseudo-first order model
is valid. In the pseudo-second order model, a plot of t/q versus time (t)
would yield a line with a slope of 1/qe and an intercept of 1/(K2q2e ).
Therefore, the plot between log (qe–qt) versus time (t) shows the
pseudo-first order model, and the plot of t/q versus time t shows the
pseudo-second order model, respectively. The kinetic model with a
higher correlation coefficient (R2) was considered as the most suitable
120
were KF is the Freundlich constant and 1/n is a characteristic of the
system under study, which depends on the type of adsorbent. Plotting
log qe against log Ce gives a straight line with intercept and slope equal
to log KF and 1/n, respectively. The slope of 1/n ranging between 0 and
1 is a measure of adsorption intensity or surface heterogeneity,
becoming more heterogeneous as its value gets closer to zero. The linear
relationships of the isotherm models are shown in Fig. S2 in
supplementary information. The thermodynamic parameters obtained
from the used isotherm models are given in Table 2.
According to Table 2, The Langmuir isotherm model with R2 = 0.99
matches experimental data better than the Freundlich isotherm model,
indicating that a monolayer of the dye compound was formed on the
CTS-SBA-15 nanofibers.

Table 1
100 The kinetic parameters of the pseudo-first order and pseudo-second order models for the
adsorption of bright red dye by on the CTS-SBA-15 nano-adsorbent.
Dye removal percentage(%)

80 Kinetic models R2 K qe (mg/g)

Pseudo-first order 0.89 −0.038 9.39

Pseudo-second order 0.99 0.0049 15.15
60

40
Table 2
CTS-SBA-15
Isotherm data for the dye adsorption process on the surface of CTS-SBA-15 nanofibers.
20 CTS Isotherm Parameters Values

Langmuir KL −0.4
0 qm (mg/g) 19.23
0 20 40 60 80 100 R2 0.99
Time (min) Freundlich KF 22.64
1/n −90
R2 0.012
Fig. 8. The variations of dye removal percentage versus the adsorption process time.
 F. Bahalkeh et al. / International Journal of Biological Macromolecules 164 (2020) 818–825 823

Table 3
Comparison of CTS-SBA-15 adsorption results with other chitosan-based adsorbents.

Adsorbent Dye compound Highest removal percentage Isotherm model Kinetic model Ref.

CTS-SBA-15 Brilliant Red dye 98.2% Langmuir Pseudo-second order Present

Chitosan/acrylamide-co-sodium methacrylate Fuchsin dye 97.2% Freundlich Pseudo-second order [54]
Chitosan/poly(hydroxyalkanoate) Congo red dye 75.8% Langmuir Pseudo-second order [55]
Chitosan/polyacrylamide hydrogel/TiO2 Sirius yellow K-CF dye 96.8% Langmuir Pseudo-second order [56]
Chitosan/ZnO Methylene blue 96.7% Langmuir Pseudo-second order [57]
Cross-linked chitosan beads Reactive red 189 63% Langmuir Pseudo-second order [58]
Chitosan-zinc sulfide Acid Black 234 azo dye 96.7% Langmuir – [59]
Chitosan-MgO Reactive blue 19 77.6% Langmuir Pseudo-second order [60]

3.5. Comparison with other studies
The presence of modifiable sites in the molecular structure chitosan
is the major advantage of the component to use as a potent adsorbent
for dye compounds. In this way, the modification of chitosan-based
adsorbents to improve the adsorption capacitance of the compound
has been gained an immense interest by researchers in the recent
years. In Table 3, the results of some studies in this field were reported
and compared with the results obtained in the present research.
According to Table 3, most of the experimental data of adsorbents
were fitted best with the Langmuir and Pseudo-second order among
other thermodynamic and kinetic models. In addition, it can be found
from the table that the dye removal percentage of CTS-SBA-15 is higher
than other adsorbent indicating that the composite can be considered as
a potent adsorbent for dye compounds in aqueous solutions.
3.6. Adsorption mechanism
Generally, there are different mechanisms behind the adsorption
process of dye compounds on the adsorbents such as electrostatic
interaction, hydrogen bond, ion exchange, and π–π interaction [61]. A
schematic of brilliant red E-4BA removal mechanisms is shown in Fig. 9.
It is well known that the pKa value of the chitosan is about 6.7 [62]
and so, the amino groups from chitosan can be easily protonated even
in neutral solutions. Therefore, as is shown in Fig. 9, strong electrostatic
attractions could be formed between the protonated chitosan and
sulfonic acid group from brilliant red E-4BA dye. In addition, hydrogen
bonds between hydroxyl and amine groups from chitosan, SBA-15,
and brilliant red E-4BA can be considered as a general force in the
adsorption process. Furthermore, the physical capture of the dye
molecules in the mesoporous structure of SBA-15 may enhance the
dye removal capacitance of the synthesized adsorbent.
4. Conclusion
The results of this study showed that CTS-SBA-15 nanofibrous
composite is an effective adsorbent for removing Brilliant Red dye
from aqueous solutions. This can be attributed to the high aspect ratio
of the mesoporous silica sieve (SBA-15). FT-IR, XRD, and TEM results
indicated that the surface of the chitosan nanofibers was successfully
modified by the mesoporous silica sieve. Based on the obtained results,
the optimum values of pH, adsorbent dosage, and contact time were 7,
0.03 g, and 40 min, respectively. In addition, it was found that the
processes of the dye adsorption followed the Langmuir isotherm
model. It was also found that the kinetic of the adsorption process
obeyed the pseudo-second order model.
CRediT author statement
Mohammad habibi Joybari: Conceptualization, Methodology,
Validation, Supervision, Project administration, Writing - Review &
Editing, Visualization.

Fig. 9. A schematic of brilliant red E-4BA removal mechanisms by chitosan molecules.

824 F. Bahalkeh et al. / International Journal of Biological Macromolecules 164 (2020) 818–825
Farhad Bahalkeh: Conceptualization, Formal analysis, Investigation,
Data Curation, Writing - Original Draft, Writing - Review & Editing,
Visualization.
Ramin Zafar Mehrabian: Supervision.
Mehdi Ebadi: Supervision.
Declaration of competing interest
The authors declare that the research was conducted in the absence
of any commercial or financial relationships that could be construed as a
potential conflict of interest.
Acknowledgment
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ijbiomac.2020.07.035.
References
[1] G. Abdi, A. Alizadeh, S. Zinadini, G. Moradi, Removal of dye and heavy metal ion
using a novel synthetic polyethersulfone nanofiltration membrane modified by
magnetic graphene oxide/metformin hybrid, J. Membr. Sci. 552 (2018) 326–335,
https://doi.org/10.1016/J.MEMSCI.2018.02.018.
[2] L. Fan, C. Luo, M. Sun, H. Qiu, X. Li, Synthesis of magnetic B-cyclodextrin-chitosan/
graphene oxide as nanoadsorbent and its application in dye adsorption and
removal, Colloids Surf. B: Biointerfaces 103 (2013) 601–607, https://doi.org/10.
1016/j.colsurfb.2012.11.023.
[3] W. Konicki, M. Aleksandrzak, D. Moszyński, E. Mijowska, Adsorption of anionic azo-
dyes from aqueous solutions onto graphene oxide: equilibrium, kinetic and
thermodynamic studies, J. Colloid Interface Sci. 496 (2017) 188–200, https://doi.
org/10.1016/J.JCIS.2017.02.031.
[4] M.A.H. Badsha, I.M.C. Lo, An innovative pH-independent magnetically separable
hydrogel for the removal of Cu(II) and Ni(II) ions from electroplating wastewater,
J. Hazard. Mater. 381 (2020), 121000. https://doi.org/10.1016/J.JHAZMAT.2019.
121000.
[5] T.M. Valentin, A.K. Landauer, L.C. Morales, E.M. DuBois, S. Shukla, M. Liu, et al.,
Alginate-graphene oxide hydrogels with enhanced ionic tunability and
chemomechanical stability for light-directed 3D printing, Carbon 143 (2019)
447–456, https://doi.org/10.1016/J.CARBON.2018.11.006.
[6] C.S. Patil, D.B. Gunjal, V.M. Naik, N.S. Harale, S.D. Jagadale, A.N. Kadam, et al., Waste
tea residue as a low cost adsorbent for removal of hydralazine hydrochloride
pharmaceutical pollutant from aqueous media: an environmental remediation, J.
Clean. Prod. 206 (2019) 407–418, https://doi.org/10.1016/J.JCLEPRO.2018.09.140.
[7] L. Huang, M. Zhang, C. Li, G. Shi, Graphene-based membranes for molecular
separation, J. Phys. Chem. Lett. 6 (2015) 2806–2815, https://doi.org/10.1021/acs.
jpclett.5b00914.
[8] N. Abdullah, N. Yusof, W.J. Lau, J. Jaafar, A.F. Ismail, Recent trends of heavy metal
removal from water/wastewater by membrane technologies, J. Ind. Eng. Chem. 76
(2019) 17–38, https://doi.org/10.1016/J.JIEC.2019.03.029.
[9] M.I. El-Barghouthi, A.H. El-Sheikh, Y.S. Al-Degs, G.M. Walker, Adsorption behavior of
anionic reactive dyes on H-type activated carbon: competitive adsorption and
desorption studies, Sep. Sci. Technol. 42 (2007) 2195–2220, https://doi.org/10.
1080/01496390701444030.
[10] S.L., X. Yu, Electrochemical Alkaline Fe(VI) Water Purification and Remediation,
2005https://doi.org/10.1021/ES051084K.
[11] K. Kosaka, K. Ohkubo, M. Akiba, Occurrence and formation of haloacetamides from
chlorination at water purification plants across Japan, Water Res. 106 (2016)
470–476, https://doi.org/10.1016/J.WATRES.2016.10.029.
[12] Combined ozonation and electrolytic chlorination water purification method,
https://patents.google.com/patent/US6551518B2/en 2001. (Accessed 28 February
2020).
[13] M.S. Mohy Eldin, M.A. Abu-Saied, T.M. Tamer, M.E. Youssef, A.I. Hashem, M.M. Sabet,
Development of polystyrene based nanoparticles ions exchange resin for water
purification applications, Desalin. Water Treat. 57 (2016) 14810–14823, https://
doi.org/10.1080/19443994.2015.1080192.
[14] C. Wang, J. Kim, V. Malgras, J. Na, J. Lin, J. You, et al., Metal–organic frameworks and
their derived materials: emerging catalysts for a sulfate radicals-based advanced
oxidation process in water purification, Small 15 (2019), 1900744. https://doi.
org/10.1002/smll.201900744.
[15] J. Ma, K. Fu, X. Fu, Q. Guan, L. Ding, J. Shi, et al., Flocculation properties and kinetic
investigation of polyacrylamide with different cationic monomer content for high
turbid water purification, Sep. Purif. Technol. 182 (2017) 134–143, https://doi.org/
10.1016/J.SEPPUR.2017.03.048.
[16] M.O.M. Fufă, R.C. Popescu, A.M. Holban, Microorganisms: new trends in
environment-friendly and energy-saving water purification, Water Purif. (2017)
263–288, https://doi.org/10.1016/B978-0-12-804300-4.00007-1.
[17] Y. Park, S. Liu, T. Gardner, D. Johnson, A. Keeler, N. Ortiz, et al., Biohybrid nanofibers
containing manganese oxide–forming fungi for heavy metal removal from water, J.
Eng. Fibers Fabr. 15 (2020), 155892501989895. https://doi.org/10.1177/
1558925019898954.
[18] J. Zhan, Q. Zhang, M. Qin, Y. Hong, Selection and characterization of eight freshwater
green algae strains for synchronous water purification and lipid production, Front.
Environ. Sci. Eng. 10 (2016) 548–558, https://doi.org/10.1007/s11783-016-0831-4.
[19] M. Wang, S.K. Mohanty, S. Mahendra, Nanomaterial-supported enzymes for water
purification and monitoring in point-of-use water supply systems, Acc. Chem. Res.
52 (2019) 876–885, https://doi.org/10.1021/acs.accounts.8b00613.
[20] A. Lee, J.W. Elam, S.B. Darling, Membrane materials for water purification: design,
development, and application, Environ. Sci. Water Res. Technol. 2 (2016) 17–42,
https://doi.org/10.1039/C5EW00159E.
[21] D.B. Boman, S. Garimella, Absorption heat pump cycles for simultaneous space
conditioning and graywater purification, Appl. Therm. Eng. 167 (2020), 114587.
https://doi.org/10.1016/J.APPLTHERMALENG.2019.114587.
[22] M. Coto, S.C. Troughton, J. Duan, R.V. Kumar, T.W. Clyne, Development and
assessment of photo-catalytic membranes for water purification using solar
radiation, Appl. Surf. Sci. 433 (2018) 101–107, https://doi.org/10.1016/J.APSUSC.
2017.10.027.
[23] A.A. Javidparvar, R. Naderi, B. Ramezanzadeh, L-cysteine reduced/functionalized
graphene oxide application as a smart/control release nanocarrier of sustainable
cerium ions for epoxy coating anti-corrosion properties improvement, J. Hazard.
Mater. 389 (2020), 122135. https://doi.org/10.1016/J.JHAZMAT.2020.122135.
[24] A.A. Javidparvar, R. Naderi, B. Ramezanzadeh, Manipulating graphene oxide
nanocontainer with benzimidazole and cerium ions: application in epoxy-based
nanocomposite for active corrosion protection, Corros. Sci. (2019) 108379, https://
doi.org/10.1016/J.CORSCI.2019.108379.
[25] Ihsanullah, A. Abbas, A.M. Al-Amer, T. Laoui, M.J. Al-Marri, M.S. Nasser, et al., Heavy
metal removal from aqueous solution by advanced carbon nanotubes: critical
review of adsorption applications, Sep. Purif. Technol. 157 (2016) 141–161,
https://doi.org/10.1016/J.SEPPUR.2015.11.039.
[26] N.B. Singh, G. Nagpal, S. Agrawal, Rachna, water purification by using adsorbents: a
review, Environ. Technol. Innov. 11 (2018) 187–240, https://doi.org/10.1016/J.ETI.
2018.05.006.
[27] A.M. Ghaedi, M. Panahimehr, A.R.S. Nejad, S.J. Hosseini, A. Vafaei, M.M. Baneshi,
Factorial experimental design for the optimization of highly selective adsorption
removal of lead and copper ions using metal organic framework MOF-2 (Cd), J.
Mol. Liq. 272 (2018) 15–26, https://doi.org/10.1016/J.MOLLIQ.2018.09.051.
[28] E.A. Dil, M. Ghaedi, G.R. Ghezelbash, A. Asfaram, A.M. Ghaedi, F. Mehrabi, Modeling
and optimization of Hg2+ ion biosorption by live yeast Yarrowia lipolytica 70562
from aqueous solutions under artificial neural network-genetic algorithm and
response surface methodology: kinetic and equilibrium study, RSC Adv. 6 (2016)
54149–54161, https://doi.org/10.1039/C6RA11292G.
[29] F. Javaheri, Z. Kheshti, S. Ghasemi, A. Altaee, Enhancement of Cd2+ removal from
aqueous solution by multifunctional mesoporous silica: equilibrium isotherms and
kinetics study, Sep. Purif. Technol. 224 (2019) 199–208, https://doi.org/10.1016/J.
SEPPUR.2019.05.017.
[30] F. Lu, D. Astruc, Nanomaterials for removal of toxic elements from water, Coord.
Chem. Rev. 356 (2018) 147–164, https://doi.org/10.1016/J.CCR.2017.11.003.
[31] M.A. Yahya, Z. Al-Qodah, C.W.Z. Ngah, Agricultural bio-waste materials as potential
sustainable precursors used for activated carbon production: a review, Renew. Sust.
Energ. Rev. 46 (2015) 218–235, https://doi.org/10.1016/J.RSER.2015.02.051.
[32] A.R. Shahmoradi, N. Talebibahmanbigloo, A.A. Javidparvar, G. Bahlakeh, B.
Ramezanzadeh, Studying the adsorption/inhibition impact of the cellulose and
lignin compounds extracted from agricultural waste on the mild steel corrosion in
HCl solution, J. Mol. Liq. 304 (2020), 112751. https://doi.org/10.1016/J.MOLLIQ.
2020.112751.
[33] Y. Zou, X. Wang, A. Khan, P. Wang, Y. Liu, A. Alsaedi, et al., Environmental
remediation and application of nanoscale zero-valent iron and its composites for
the removal of heavy metal ions: a review, Environ. Sci. Technol. 50 (2016)
7290–7304, https://doi.org/10.1021/acs.est.6b01897.
[34] A. Azimi, A. Azari, M. Rezakazemi, M. Ansarpour, Removal of heavy metals from
industrial wastewaters: a review, ChemBioEng Rev. 4 (2017) 37–59, https://doi.
org/10.1002/cben.201600010.
[35] M. Ghaedi, K. Dashtian, A.M. Ghaedi, N. Dehghanian, A hybrid model of support
vector regression with genetic algorithm for forecasting adsorption of malachite
green onto multi-walled carbon nanotubes: central composite design optimization,
Phys. Chem. Chem. Phys. 18 (2016) 13310–13321, https://doi.org/10.1039/
c6cp01531j.
[36] J. Han, S.C. De Smedt, R. Xiong, C. Huang, Eco-friendly electrospun membranes
loaded with visible-light response nano-particles for multifunctional usages :
high-efficient air filtration, dye scavenger and bactericide, Appl. Mater. Interfaces
11 (2019) 12880–12889, https://doi.org/10.1021/acsami.9b01508.
[37] H. Tu, D. Li, Y. Yi, R. Liu, Y. Wu, X. Dong, et al., Incorporation of rectorite into porous
polycaprolactone/TiO2 nanofibrous mats for enhancing photocatalysis properties
towards organic dye pollution, Compos. Commun. 15 (2019) 58–63, https://doi.
org/10.1016/j.coco.2019.06.006.
[38] A.M. Ghaedi, M. Ghaedi, P. Karami, Comparison of ultrasonic with stirrer
performance for removal of sunset yellow (SY) by activated carbon prepared from
wood of orange tree: artificial neural network modeling, Spectrochim. Acta A Mol.
Biomol. Spectrosc. 138 (2015) 789–799, https://doi.org/10.1016/j.saa.2014.11.019.
 F. Bahalkeh et al. / International Journal of Biological Macromolecules 164 (2020) 818–825
[39] L. Duru, D. Ege, A.R. Kamali, Graphene oxides for removal of heavy and precious
metals from wastewater, J. Mater. Sci. 51 (2016) 6097–6116, https://doi.org/10.
1007/s10853-016-9913-8.
[40] Q. Gao, H. Zhu, W. Luo, S. Wang, C. Zhou, Preparation, characterization, and
adsorption evaluation of chitosan-functionalized mesoporous composites,
Microporous Mesoporous Mater. 193 (2014) 15–26, https://doi.org/10.1016/j.
micromeso.2014.02.025.
[41] H. Aghayan, A.R. Mahjoub, A.R. Khanchi, Samarium and dysprosium removal using 11-
molybdo-vanadophosphoric acid supported on Zr modified mesoporous silica SBA-15,
Chem. Eng. J. 225 (2013) 509–519, https://doi.org/10.1016/J.CEJ.2013.03.092.
[42] S.F. Hosseini, M. Rezaei, M. Zandi, F. Farahmandghavi, Bio-based composite edible
films containing Origanum vulgare L. essential oil, Ind. Crop. Prod. 67 (2015)
403–413, https://doi.org/10.1016/j.indcrop.2015.01.062.
[43] S.S. Silva, R.A.S. Ferreira, L. Fu, L.D. Carlos, J.F. Mano, R.L. Reis, et al., Functional
nanostructured chitosan–siloxane hybrids, J. Mater. Chem. 15 (2005) 3952,
https://doi.org/10.1039/b505875a.
[44] L.W.O. Soares, R.M. Braga, J.C.O. Freitas, R.A. Ventura, D.S.S. Pereira, D.M.A. Melo, The
effect of rice husk ash as pozzolan in addition to cement Portland class G for oil well
cementing, J. Pet. Sci. Eng. 131 (2015) 80–85, https://doi.org/10.1016/j.petrol.2015.
04.009.
[45] A.A. Javidparvar, R. Naderi, B. Ramezanzade, Incorporation of graphene oxide
nanoparticles modified with benzimidazole into an epoxy polyamide coating to
enhance the physical-mechanical properties, J. Color Sci. Technol. 13 (2020)
341–352, https://doi.org/10.1039/C6CP01531J.
[46] A.A. Javidparvar, B. Ramezanzadeh, E. Ghasemi, Effect of various spinel ferrite
nanopigments modified by amino propyl trimethoxy silane on the corrosion
inhibition properties of the epoxy nanocomposites, Corrosion 72 (2016) 761–774,
https://doi.org/10.5006/2021.
[47] A.A. Javidparvar, B. Ramezanzadeh, E. Ghasemi, The effect of surface morphology
and treatment of Fe3O4 nanoparticles on the corrosion resistance of epoxy coating,
J. Taiwan Inst. Chem. Eng. 61 (2015) 356–366, https://doi.org/10.1016/j.jtice.2016.
01.001.
[48] A.A. Javidparvar, B. Ramezanzadeh, E. Ghasemi, Effects of surface morphology and
treatment of iron oxide nanoparticles on the mechanical properties of an epoxy
coating, Prog. Org. Coat. 90 (2016)https://doi.org/10.1016/j.porgcoat.2015.09.018.
[49] A.A. Javidparvar, R. Naderi, B. Ramezanzadeh, Non-covalently surface modification
of graphene oxide nanosheets and its role in the enhancement of the epoxy-based
coatings` physical properties, Colloids Surf. A Physicochem. Eng. Asp. 602 (2020),
125061. https://doi.org/10.1016/J.COLSURFA.2020.125061.
[50] A.A. Javidparvar, B. Ramezanzade, E. Ghasemi, The effect of oleic acid/silane
treatments of Fe3O4 nanoparticles on the mechanical properties of an epoxy
coating, The 6th International Color & Coating Congress, Institute for Color
Science and Technology, Tehran, 2015https://www.researchgate.net/publication/
286722324. (Accessed 18 June 2019).
[51] P. Nie, C. Min, H.J. Song, X. Chen, Z. Zhang, K. Zhao, Preparation and tribological
properties of polyimide/carboxyl-functionalized multi-walled carbon nanotube
825
nanocomposite films under seawater lubrication, Tribol. Lett. 58 (2015) 1–12,
https://doi.org/10.1007/s11249-015-0476-7.
[52] A.A. Javidparvar, R. Naderi, B. Ramezanzadeh, G. Bahlakeh, Graphene oxide as a pH-
sensitive carrier for targeted delivery of eco-friendly corrosion inhibitors in chloride
solution: experimental and theroretical investigations, J. Ind. Eng. Chem. (2018)
https://doi.org/10.1016/J.JIEC.2018.12.019.
[53] Z. Geng, Y. Lin, X. Yu, Q. Shen, L. Ma, Z. Li, et al., Highly efficient dye adsorption and
removal: a functional hybrid of reduced graphene oxide–Fe3O4 nanoparticles as an
easily regenerative adsorbent, J. Mater. Chem. 22 (2012) 3527, https://doi.org/10.
1039/c2jm15544c.
[54] A.G. Ibrahim, A.Z. Sayed, H. Abd El-Wahab, M.M. Sayah, Synthesis of a hydrogel by
grafting of acrylamide-co-sodium methacrylate onto chitosan for effective
adsorption of Fuchsin basic dye, Int. J. Biol. Macromol. 159 (2020) 422–432,
https://doi.org/10.1016/J.IJBIOMAC.2020.05.039.
[55] C.Y. Soon, N.A. Rahman, Y.B. Tee, R.A. Talib, C.H. Tan, K. Abdan, et al., Electrospun
biocomposite: nanocellulose and chitosan entrapped within a poly
(hydroxyalkanoate) matrix for Congo red removal, J. Mater. Res. Technol. 8
(2019) 5091–5102, https://doi.org/10.1016/J.JMRT.2019.08.030.
[56] E. Binaeian, S. Babaee Zadvarzi, D. Yuan, Anionic dye uptake via composite using
chitosan-polyacrylamide hydrogel as matrix containing TiO2 nanoparticles;
comprehensive adsorption studies, Int. J. Biol. Macromol. 162 (2020) 150–162,
https://doi.org/10.1016/J.IJBIOMAC.2020.06.158.
[57] M.H. Mostafa, M.A. Elsawy, M.S.A. Darwish, L.I. Hussein, A.H. Abdaleem, Microwave-
assisted preparation of chitosan/ZnO nanocomposite and its application in dye
removal, Mater. Chem. Phys. 248 (2020), 122914. https://doi.org/10.1016/J.
MATCHEMPHYS.2020.122914.
[58] Ş.A. Çetinus, E. Şahin, D. Saraydin, Preparation of Cu(II) adsorbed chitosan beads for
catalase immobilization, Food Chem. 114 (2009) 962–969, https://doi.org/10.1016/
j.foodchem.2008.10.049.
[59] A. Aziz, N. Ali, A. Khan, M. Bilal, S. Malik, N. Ali, et al., Chitosan-zinc sulfide
nanoparticles, characterization and their photocatalytic degradation efficiency for
azo dyes, Int. J. Biol. Macromol. 153 (2020) 502–512, https://doi.org/10.1016/J.
IJBIOMAC.2020.02.310.
[60] P.H.V. Nguyen Kim Nga, Nguyen Thi Thuy Chau, Preparation and characterization of a
chitosan/MgO composite for the effective removal of reactive blue 19 dye from aqueous
solution, J. Sci. Adv. Mater. Devices 5 (2020) 65–72https://pdf.sciencedirectassets.com/
314568/1-s2.0-S2468217920X00025/1-s2.0-S2468217920300095/main.pdf?X-Amz-
Security-Token=IQoJb3JpZ2luX2VjEHkaCXVzLWVhc3QtMSJGMEQCIQDzv8vvXZ%
2FZslqCcXQ5pxKZ13x9FMfu86xrx8bUN79wyQIfWZHMFYUov4w76mkcTm0xIFV7iIGO-
snQlUccQCt956S. (Accessed 29 June 2020).
[61] F. Zhang, C. Yang, Y. Li, M. Chen, S. Hu, H. Cheng, The preparation of
organophosphorus ligand-modified SBA-15 for effective adsorption of Congo red
and Reactive red 2, RSC Adv. 9 (2019) 13476–13485, https://doi.org/10.1039/
c9ra02287b.
[62] J. Xing, X. Wang, J. Xun, J. Peng, Q. Xu, W. Zhang, et al., Preparation of micro-
nanofibrous chitosan sponges with ternary solvents for dye adsorption, Carbohydr.
Polym. 198 (2018) 69–75, https://doi.org/10.1016/j.carbpol.2018.06.064.