828194

research-article2019
JEF0010.1177/1558925019828194Journal of Engineered Fibers and FabricsYue et al.

Original Article

Journal of Engineered Fibers and Fabrics

Synthesis and characterization of Volume 14: 1­–10

© The Author(s) 2019
https://doi.org/10.1177/1558925019828194
DOI: 10.1177/1558925019828194
cellulose-based adsorbent for removal journals.sagepub.com/home/jef

of anionic and cationic dyes

Xinxia Yue1,2,3, Jiwei Huang1,2, Fang Jiang2, Hong Lin1

and Yuyue Chen1

Abstract
Synthetic dyes are widely used in textile, paper, plastic, and other industries, which are toxic and harmful to environment
and human. Adsorption is an efficient method to control wastewater. Cellulose is an abundant, renewable, and eco-
friendly polymer produced by plants and trees. An adsorbent for removal of dyes was successfully prepared by grafting
amino-terminated hyperbranched polymer (NH2-HBP) and beta-cyclodextrin (β-CD) onto cotton fibers in this study.
The adsorbent were characterized using Fourier-transform infrared spectroscopy, scanning electron microscopy, and
X-ray photoelectron spectroscopy analysis. The influences of adsorption parameters in a batch mode including initial
solution pH, contact time, and dye initial concentration were evaluated in the experiments. The experiment results
showed that the adsorption equilibrium was reached within 6 h for Congo red and within 4 h for methylene blue. Both
the adsorption isotherms and kinetic studies showed that the behaviors of Congo red and methylene blue removal
by the adsorbent based on cotton fibers conformed with Freundlich model and fitted pseudo-second-order model,
respectively.

Keywords
Cotton fibers, adsorbent, adsorption, Congo red, methylene blue

Date received: 20 December 2016; accepted: 9 January 2019

Introduction
Synthetic dyes are widely used in textile, paper, plastic, 1College of Textile and Clothing Engineering, Soochow University,
rubber, cosmetics, and food industries, which are stable Suzhou, China
2College of Biological and Chemical Engineering, Guangxi University of
and difficult to degrade in the nature. A large of amount
Science and Technology, Liuzhou, China
dyes were discharged into the water systems with dye- 3Key Laboratory for Processing of Sugar Resources of Guangxi Higher
ing wastewater due to improper processing and dying Education Institutes, Guangxi University of Science and Technology,
methods.1 In the textile industry, it was estimated that Liuzhou, China
10%–15% of dyes has not been utilized during the dye-
Corresponding authors:
ing process and released with the effluents.2–4 Many Xinxia Yue, College of Textile and Clothing Engineering, Soochow
kinds of synthetic dyes are toxic, which pose a risk to University, Suzhou 215021, China.
water system, aquatic organisms, and human.5,6 These Email: xinxiayue@126.com
harmful dyes can break the ecological balance and cause Yuyue Chen, College of Textile and Clothing Engineering, Soochow
some risks to food safety and environment.7 There are University, Suzhou 215021, China.
several methods to remove dyes from wastewater, such Email: chenyy@suda.edu.cn

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2 Journal of Engineered Fibers and Fabrics 
as adsorption, membrane separation, flocculation, and
oxidation. Among these methods, adsorption is a versa-
tile and widely control method used for the removal of
different pollutants for its easy handling and efficiency.8–12
Activated carbon,13 graphene,14 bentonite,15 clay,16
composite fiber,17 and nanofiber membranes18 have
been utilized as adsorbents in some studies. However,
many of these materials are non-renewable or nonbiode-
gradable or difficult to recover and may cause second-
ary pollution.
Cellulose is a natural polymer produced by plants and
trees that is biodegradable and eco-friendly resource in
nature. Cellulose molecules have many active hydroxyl
groups, so it can easily be chemically modified according
to the introduction of various functional groups on
hydroxyl.11 Cotton fiber is a natural fiber made from cellu-
lose and it is renewable, degradable, cheap, and does not
cause secondary pollution. In addition, cotton fiber has hol-
low, flat-banded structure, and large specific surface area,
which is beneficial to adsorption. Hyperbranched poly-
mers, such as hyperbranched poly(ethylene imine), hyper-
branched polyamide amine, and hyperbranched polyester,
have shown efficiently to entrap heavy metal ions and
organic molecules in their interior.19–23 Amino-terminated
hyperbranched polymer (NH2-HBP) have abundant func-
tional groups to be used in the dyeing as an auxiliary.24
Beta-cyclodextrin (β-CD) is a torus-shaped cyclic oligo-
saccharide made up of seven α-1,4-linked-d-glucopyranose
units. This structure gives rise to a remarkable capacity to
form inclusion complexes with appropriate size organic
molecules through host–guest interactions.25–29 In this
study, an cellulose adsorbent based on cotton fiber was pre-
pared. Specifically, cotton fibers were activated by NaOH
aqueous solution, and then activated cotton was chemically
modified with β-CD and NH2-HBP, respectively. The mod-
ified cotton fibers were used to remove azo dyes from
aqueous solutions. Congo red (CR) and methylene blue
(MB) were chosen as the representatives of anionic and
cationic dyes in the experiments. The influences of solution
pH, adsorption time, and initial concentration of CR and
MB were investigated, which were critical to adsorption
property investigation of adsorbent.
Experimental
Materials
Cotton fibers were purchased in the local market. Nitric
acid (HNO3), sodium hydroxide (NaOH), sodium perio-
date (NaIO4), triethylene tetramine, methyl acrylate, dime-
thyl sulfoxide (DMSO), β-CD, epichlorohydrin (EPI),
ethanol, phenolphthalein, CR, and MB were purchased
from Sinopharm Chemical Reagent Co., Ltd (Shanghai,
China). NH2-HBP was synthesized in laboratory according
to our previous study.24 These reagents were used without
further purification.
Pretreatment of cotton fibers
Cotton fibers (10 g) were boiled in 300 mL of NaOH aque-
ous solution (2 wt%) for 60 min. Then the fibers were fil-
tered and transferred into 300 mL NaOH aqueous solution
(18 wt%) for 240 min at room temperature to break down
the strong hydrogen bonds between cellulose molecular
chains for the subsequent reactions. The fibers were then
washed and dried to obtain activated cotton fibers (named
as ACF). ACF were cut into segments about 5 mm.
Preparation of adsorbent
The grafting reaction between β-CD and ACF was adopted
using EPI as coupling agent through a one-step procedure.30
First, 5 g ACF were immersed into 150 mL NaIO4 solu-
tion(10 g/L) for 2 h under continuous stirring at 50°C. Then
the fibers were filtered, washed, and dried. ACF were oxi-
dized selectively to obtain dialdehyde-cotton fibers
(DA-cotton) in this process. Next, 10 g β-CD was dissolved
in 200 mL NaOH solution (30 wt%), and DA-cotton was
then dispersed into this alkaline β-CD solution. Thirty-five
milliliters of EPI and 0.2 g of cetyltrimethylammonium
bromide were added into above mixture system and kept
uniform mixing for 30 min, and the reaction was allowed to
proceed at 40°C for 6 h. The product (CD-cotton) was col-
lected and washed to remove ungrafted β-CD and residual
NaOH. At last, the CD-cotton was added to NH2-HBP solu-
tion (20 g/L) and stirred at 60°C for 2 h, and then the fibers
were collected, washed, and dried at 50°C. The product was
named as NC-cotton. The preparation of the adsorbent is
summarized in Figure 1.
Characterization of NC-cotton
The Fourier-transform infrared (FTIR) spectroscopy meas-
urements were used to identify NC-cotton fiber with a
Nicolet 5700. X-ray photoelectron spectroscopy (XPS)
measurements were conducted with an Axis Ultra HAS
system. The morphologies and surface structures of ACF,
CD-cotton, and NC-cotton were characterized with Hitachi
S-4800 scanning electron microscope (SEM). The grafting
rate of β-CD on cotton fibers was determined according to
spectrophotometric method.31 The absorbance of CR and
MB was estimated by ultraviolet (UV)/visible spectros-
copy (Hitachi, U3010) at 497 and 665 nm, respectively.
The standard curves were drawn about the corresponding
absorbance and the concentration of dye solution. The
concentration of CR and MB was calculated according to
the regression equation, respectively.
Adsorption experiments
In the static adsorption experiments, adsorbents at a dos-
age of 2.0 g/L were added to dye solutions (each for
100 mL) at desired concentrations. Initial pH values of the
Yue et al. 3

O
O
CH2OH CH2OH
* * O * * * O *
O * NaIO EPI *
4
O O O
β-CD
OH n-1 n-1 n-1
HO O O
O O

O
O
* * O *
NH2-HBP *
O
n-1
N N

H2N NH2

H2N NH2

Figure 1.  Preparation route of NC-cotton fibers.

Table 1.  Experimental design for batch adsorption study.

Investigation Control parameters Variable parameters

Effect of pH values Initial concentration: 500 mg/L Solution pH: 3, 4, 5, 6, 7, 8, 9, 10, 11, 12
Adsorption kinetics Contact time: 720 min Contact time (min): 10, 20, 30, 60, 90, 120, 180, 240, 300, 600, 720
Initial concentration: 500 mg/L
pH: CR, 7.3 and MB, 8.0
Adsorption isotherms pH: CR, 7.3 and MB, 8.0 Initial concentration (C0) (mg/L): 50, 100, 200, 300, 400, 500, 600, 800, 1000
Contact time: 720 min

solution were adjusted ranging from 3 to 12 using HNO3
and NaOH solutions. Adsorption was held during agitation
of mixture solutions at desired concentrations (50–
1000 mg/L) for a set time period at 30°C. Adsorption was
held for 5–720 min to study adsorption kinetics. The super-
natant dye was taken, centrifuged, and the absorbance was
measured with UV–visible spectrophotometer, and then
the concentration of dye solution was calculated from the
standard curve.
The experiment parameters are shown in Table 1. The
equilibrium adsorption capacities (qe) and removal effi-
ciency (R) are calculated according to equations (1) and
(2) as follows
V (C0 − Ce )
qe = (1)
m
( C0 − Ce )
R= × 100% (2)
C0
where C0 and Ce are the initial and equilibrium concen-
tration of adsorbate (mg/L), respectively. V is the vol-
ume (L) of adsorbate solution, and m is the mass of
adsorbent (g) used. Three sets of level experiments were
conducted and the average values were calculated for
accurate investigation.
Results and discussion
Characterization of NC-cotton
FTIR analysis, XPS characterization, and SEM study of
NC-cotton were conducted to describe the characteristics
of NC-cotton. The grafting rate of β-CD on cotton fibers
was determined to confirm whether β-CD was cross-linked
to cotton fibers.
FTIR analysis of NC-cotton.  The infrared spectra of ACF (a),
CD-cotton (b), and NC-cotton prepared (c) are shown in
Figure 2. In the spectrum of CD-cotton (b), a new peak
4 Journal of Engineered Fibers and Fabrics 
Figure 2.  FTIR spectra of ACF, CD-cotton, and NC-cotton.
appeared at 1729 cm−1, which showed the carbonyl (C=O)
stretching vibration of the aldehyde group and indicated
cotton fiber had been oxidized by NaIO4. The characteris-
tic peak of β-CD and cellulose roughly coincides due to
β-CD and cellulose being composed of cyclic glucose,32 so
the grafting rate of β-CD on cotton fibers was determined
according to spectrophotometric method30 to verify β-CD
being grafted onto cotton fibers in the article. In the spec-
trum of (c), the peak at 1729 cm−1 disappeared, and a new
peak at 1558 cm−1 appeared, which was attributed to N–H
bending vibration absorption peak of imine group in NC-
cotton. The weakening band at 1427 cm−1 revealed the
reduction in intermolecular or intramolecular hydrogen
bonding between the hydroxyl groups of cellulose from
cotton fibers to NC-cotton fibers. This indicated that the
crystallinity of the cotton fibers reduced after chemical
modification. The characteristic absorption bands of cel-
lulose at about 3420, 2900, 1640, 1060, and 896 cm−1 have
no significant change, which suggests that the main com-
position and structure of the cotton fibers did not change
after chemical modification.33
XPS characterization of NC-cotton. The chemical state of
the elements in NC-cotton was further investigated by
XPS (Figure 3). The wide scan XPS spectrum (Figure
3(a)) of ACF, CD-cotton, and NC-cotton displayed photo-
electron lines at binding energies of about 284, 399, and
530 eV, which can be attributed to C1s, N1s, and O1s,
respectively. The high resolution C1s peaks of ACF, CD-
cotton, and NC-cotton are shown in Figure 3(b) to (d). The
C1s peak of ACF can be divided into two components
(Figure 3(b)): the carbon in C–C (284.5 eV) and the carbon
in C–O (286.2 eV). The C1s peak of CD-cotton can be
divided into three components (Figure 3(c)): the C–C spe-
cies (284.6 eV), C–O species (286.2 eV), and C=O species
(288.2 eV). The C1s spectra of the NC-cotton contains
three peaks at 284.6, 285.5, and 286.4 eV, corresponding to
the C–C, C–N, C–O bonds, respectively (Figure 3(d)).
Obviously, the nitrogen element existed in the NC-cotton
due to the chemical interaction.
SEM study of NC-cotton.  The surface morphology of cotton
fibers after modification with β-CD and NH2-HBP, respec-
tively, is revealed by SEM. As shown in Figure 4, the sur-
face of ACF (a) was smooth and has no obvious feature.
There are many grooves and cracks on the surface of DA-
cotton (b) and CD-cotton (c), which could be attributed to
the oxidation and hydrolysis of the cellulose macromole-
cule chains, leading to part of the cellulose molecular
chain breaking, and the further decomposition of the crys-
tal zone. The CD-cotton had a somewhat smooth surface
compared to DA-cotton, while there was no clear evidence
that grafting reaction (β-CD and cellulose) had occurred
by SEM analysis. Some grooves on the surface of NC-
cotton (d) were filled up with NH2-HBP and appeared like
cross-linked layer, indicating NH2-HBP coated to the sur-
face of cotton fibers.
The grafting rate of β-CD on cotton fibers.  The grafting
rate of β-CD on cotton fibers was determined according
to spectrophotometric method.30 Phenolphthalein stand-
ard solution (250 mg/L) (volume ratio of ethanol to
water was 1:1), anhydrous sodium carbonate standard
solution (30 mg/L), and a series of β-CD standard solu-
tions of different concentration (10, 15, 20, 25, 30, 35,
40, 45, and 50 mg/L) were prepared. The maximum
absorption wavelength of the phenolphthalein solution
was determined to be 553 nm. Phenolphthalein (2 mL)
and anhydrous sodium carbonate standard solution
(2 mL) were added into the above β-CD standard solu-
tions (50 mL) and mixed evenly, respectively, and the
absorbance was measured at 553 nm. And the absorb-
ance drop value was obtained using the absorbance
value of the blank solution without β-CD subtracting
the absorbance value of mixture solutions with β-CD
and phenolphthalein. Then the standard curve could be
drawn (the concentration of β-CD as X-axis and the
absorbance drop value as Y-axis). A certain amount of
cotton fiber grafted β-CD was added to the solution
containing phenolphthalein and sodium carbonate, and
the absorbance of the solution at 553 nm was measured
after 30 min. The grafting rate of β-CD on cotton fibers
was calculated according to formula (3)
C ×V
R ( mg/g ) = (3)
m
where R (mg/g) is the grafting rate of β-CD on cotton fib-
ers, C is the concentration of β-CD, V is the volume of
solution, and m is the mass of fibers. The experimental
results showed that the grafting rate of β-CD on cotton fib-
ers was about 80.8 mg/g in CD-cotton.
Yue et al. 5

Figure 3.  XPS spectra of ACF, CD-cotton, and NC-cotton: (a) wide scan, (b) C1s spectra of ACF, (c) C1s spectra of CD-cotton,
and (d) C1s spectra of NC-cotton.

Figure 4.  SEM images: (a) ACF, (b) DA-cotton, (c) CD-cotton, and (d) NC-cotton.
6 Journal of Engineered Fibers and Fabrics 
Figure 5.  (a) UV–vis spectra of CR varying with pH, (b) effect
of pH values on the adsorption capacity of NC-cotton, and (c)
zeta potential curve of raw cotton, CD-cotton, and NC-cotton.
Effect of pH on adsorption
The effect of initial solution pH on the adsorption capacity
was studied at adsorption equilibrium conditions. The pH
value of the solution plays a significant role in the adsorp-
tion process, which can influence the surface charge of the
adsorbent, the degree of ionization, even the molecule
structure of the adsorbate in the solution.34,35 The effects of
pH on adsorption are displayed in Figure 5. Figure 5(a)
shows the variation of maximum absorption wavelength
and absorbance at the same concentration (10 mg/L) and
different pH values. It can be seen that the maximum
absorption wavelength and absorbance changed constantly
when pH value was smaller than 6.5, and the maximum
absorption wavelength and absorbance did not change
when pH value was greater than 6.5. It suggested that the
pH value could change the molecule structure of CR in
aqueous solution. In addition, CR has a pKa value at 4.5–
5.5, which can exist in both cationic form at acidic pH and
anionic form at basic pH.36 In addition, the adsorbent sur-
face charge is affected by pH values in the processing of
adsorption.37 The surface charge of raw cotton and
NC-cotton was studied by zeta potential measurement in
pH range 3–12, as shown in Figure 5(b), and the isoelectric
point of NC-cotton is 6.8. For NC-cotton, it is positive at
low pH due to the protonation of amino and imino groups
form NH2-HBP (−NH2 + H+ → NH3+). Particularly, owing
to the introduction of NH2-HBP onto cotton, zeta potential
value of NC-cotton is always higher than that of raw cotton
over the whole pH range. This phenomenon reveals the
excellent electrostatic adsorption capacity of NH2-HBP as
an adsorbent component in NC-cotton. With the increase in
the pH value, the zeta potentials decrease and become neg-
ative, resulting from the deprotonation of corresponding
groups under alkalic condition. As shown in Figure 5(c),
The adsorption capacity for CR is relatively large in acid
medium, and the most CR adsorption value was obtained at
pH 6. At lower pH, CR and NC-cotton both exhibit a posi-
tively charged surface due to the protonation of nitrogen
atoms and sulfonate groups for CR and amino groups for
NC-cotton,36,38 hindering the adsorption by electrostatic
repulsion. As pH increased to 6, the surface of NC-cotton is
positively charged, and an electrostatic attraction generated
with negatively charged CR, which led to a maximum
adsorption capacity of 243 mg/g at round pH 6. As pH
increases from 6 to 12, the negative charge on the surface of
NC-cotton prevents the adsorption of negatively charged
CR. Remarkably, the adsorption for CR decreases dramati-
cally at pH >10, which is ascribed to strong electrostatic
repulsion and the competitive adsorption of hydroxide ion.
It can be seen from Figure 5(c) that the adsorption capacity
for MB improved with the initial pH growth. MB is a typi-
cal cationic dye, and NC-cotton became deprotonated as
pH increased, which led to the electrostatic attraction was
enhanced between MB and the adsorbent with increasing
pH value. In addition, hydrophobicity of MB was enhanced
and the effect on electron-rich cavity of β-CD was weak-
ened with the increase in pH value, and promoting MB
molecule more easily enter the cavity of β-CD forming sta-
ble inclusion. CR is a typical anionic dye, so NC-cotton
containing amino groups showed larger adsorption capac-
ity for it. Notably, electrostatic attraction is not the only
mechanism of adsorption. Hydrogen bonding force and
inclusion complex formed by host-guest interaction also
promote the adsorption for dyes by NC-cotton.39 The dyes
Yue et al. 7
Figure 6.  Effect of adsorbent dosage on the removal efficiency
and adsorption capacity.
adsorption by β-CD in NC-cotton might be characterized
by hydrogen bonding and inclusion.
Effect of adsorbent dosage
The effect of adsorbent dosage on adsorption for CR and
MB was evaluated by the weight range from 0.05 to 0.4 g
and 100 mL solution of 500 mg/L. As shown in Figure 6,
highest efficiency is about 94% for CR and 42% for MB at
0.4 g, and highest adsorption is 300.8 mg/g for CR and
98.7 mg/g for MB. Higher removal of dyes with increasing
adsorbent dosage is attributed to the increase in total adsor-
bent surface area and adsorption sites.37 It showed no
apparent change in the removal efficiency for CR and MB
as adsorbent amount increased to more than 0.2 and 0.3,
respectively. This phenomenon might be ascribed to the
aggregation of adsorbent, decreasing the surface area and
less adsorption sites available.39 In addition, the amounts
of adsorbent might affect the physical properties of the
solid–liquid suspensions and inhibit dye molecules to dif-
fuse onto the adsorbent surface.40 Therefore, 2.0 g/L adsor-
bent dosage is considered as suitable for CR and MB
removal in this study.
Adsorption isotherms
The adsorption isotherm is used to describe how the adsor-
bent interacts with the adsorbate, which is critical for opti-
mizing the use of the adsorbent. In order to optimize the
design of an adsorption system to remove pollutants from
solutions, it is important to establish the most appropriate
correlation for the equilibrium curve. In this study, the
Freundlich and Langmuir adsorption isotherms were con-
structed using the adsorption equilibrium data of CR and
MB by NC-cotton. The Langmuir isotherm model pre-
sumes that adsorbate can cover on the surface of adsorbent
with monolayer and often valid for homogeneous surfaces
of adsorbent. The linearized Langmuir equation (4)41 is
expressed as follows
Ce C 1
= e + (4)
qe qmax K L qmax
where qe is the equilibrium adsorption capacity (mg/g), Ce
is the equilibrium concentration (mg/L) in solution, and qm
is the maximum amount of adsorption (mg/g). Langmuir
constants (KL) is the adsorption equilibrium constant
related to the energy of adsorption.
The Freundlich isotherm model is suitable for adsor-
bent of highly heterogeneous surfaces. The Freundlich
equation (5)42,43 is expressed by the following equation
1
lnqe = lnCe + lnK F (5)
n
where qe is the equilibrium adsorption amount (mg/g), KF
is the Freundlich constant related to the bonding energy,
and n is Freundlich constant. 1/n determines the energy
and intensity of the adsorption reaction, and the value of
n from 2 to 10 indicates beneficial adsorption.43 The
influence of initial concentrations on the adsorption
capacity of NC-cotton, the linear fitting of Langmuir iso-
therm, and Freundlich isotherm for CR and MB are
shown in Figure 7, respectively. The adsorption constants
for Freundlich and Langmuir adsorption isotherm models
and the correlation coefficients (R2) with the experimen-
tal data are listed in Table 2.
From the results of Figure 7 and Table 2, the adsorption
of CR and MB on NC-cotton conformed better to the
Freundlich isotherm model (R2 = 0.9984, 0.9952) than
the Langmuir isotherm model (R2 = 0.9381, 0.8255).
Apparently, the plots in Figure 7 and Table 2 demonstrate
that the Freundlich isotherm model provided a reasonable
description for the experimental data. It can be seen from
Figure 7 and Table 2 that the adsorption capacity for CR by
NC-cotton was more larger than MB. NC-cotton can show
polycation characteristics because it contains many amino
and imino groups,24 so it could aggregate more CR mole-
cules at certain pH value by electrostatic attraction. It can
be suggested that the adsorbent was more effective in
adsorbing anionic dyes than cationic dyes.
Adsorption kinetics
The study of adsorption dynamics is important in water
treatment. It describes the solute adsorption rate, which
commands the residence time of adsorbate adsorption at
the solid–solution interface.44,45 The adsorption kinetics
was evaluated using both the pseudo-first-order (6) and the
pseudo-second-order (7) equations44 to represent the con-
trolling adsorption mechanism of CR and MB onto the
NC-cotton in this study
ln ( qe − qt ) = lnqe − k1t (6)
8 Journal of Engineered Fibers and Fabrics 

Figure 7.  (a) Influence of initial concentrations on the adsorption capacity of NC-cotton, (b) Freundlich adsorption isotherm of
NC-cotton, and (c) Langmuir adsorption isotherm of NC-cotton.

Table 2.  Langmuir and Freundlich parameters for adsorption isotherms of NC-cotton.

Adsorbate Langmuir Freundlich

qmax KL R2 n Kf R2
CR 350.8 0.0047 0.9381 2.8217 4.5417 0.9984
MB 102.7 0.0014 0.8255 1.5469 3.0384 0.9952

CR: Congo red; MB: methylene blue.

Figure 8.  (a) Adsorption behavior for CR and MB, (b) pseudo-first-order kinetic plots of NC-cotton, and (c) pseudo-second-order
kinetic plots of NC-cotton.

t 1 1 be seen that pseudo-second order model shown better fit to

= + t (7) the experimental data, and R2 close to 1.0 compared to
qt K 2 qe qe
pseudo-first order model, and the theoretical adsorption
2

capacities (qe2) calculated from pseudo-second-order

where qt and qe are the amount adsorbed at time t and at
equilibrium (mg/g), k1 (min−1) and k2 (g/mg min) represent
the rate constants of the pseudo-second-order kinetic equa-
tions, respectively. The adsorption process for CR and MB
was completed within 12 h. Adsorption capacity for CR
and MB, the pseudo-first order, and pseudo-second order
adsorption kinetics for CR and MB are shown in Figure 8.
It can be seen that adsorption equilibrium was reached
within 4 h for MB, and within 6 h for CR. It took longer
time to achieve adsorption equilibrium for CR than MB,
which could be due to a more larger adsorption for CR by
NC-cotton, and needing longer time to establish equilib-
rium. The corresponding parameters calculated and exper-
imental adsorption capacities were shown in Table 3. It can
kinetic equation were closer to qe for CR and MB, which
demonstrated pseudo-second-order kinetics could reason-
ably describe the adsorption process.37
Conclusion
Cotton fibers were chemically modified with NH2-HBP
and β-CD, and its characteristics and application for
removal of CR and MB from aqueous solution were inves-
tigated in this work. It could reach adsorption equilibrium
within 4 h for MB and 6 h for CR. The Langmuir adsorp-
tion capacities were350.8 mg/g for CR and 102.7 mg/g for
MB, respectively. The adsorption processes for dyes were
more agreed with pseudo-second-order kinetic equation
Yue et al. 9

Table 3.  Kinetic parameters and experimental adsorption capacities.

Adsorbate qe (exp) (mg/g) Pseudo-first order Pseudo-second order

qe1 (mg/g) k1 (g/mg min) R2 qe2 (mg/g) k2 (g/mg min) R2

CR 227.7 156.7 0.0038 0.8278 229.8 0.0002 0.9984
MB 83.2 38.2 0.0053 0.7350 88.5 0.0007 0.9955

CR: Congo red; MB: methylene blue.

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Declaration of conflicting interests 12. Rafatullaha M, Sulaiman O, Hashim R, et al, Adsorption of
The author(s) declared no potential conflicts of interest with methylene blue on low-cost adsorbents: a review. J Hazard
respect to the research, authorship, and/or publication of this Mater 2010; 177: 70–80.
article. 13. Hameed BH, Din ATM and Ahmad AL. Adsorption of meth-
ylene blue onto bamboo-based activated carbon: kinetics and
Funding equilibrium studies. J Hazard Mater 2007; 141: 819–825.
14. Zhang W, Zhou C, Zhou W, et al. Fast and considerable
The author(s) disclosed receipt of the following financial support
adsorption of methylene blue dye onto graphene oxide. Bull
for the research, authorship, and/or publication of this article:
Environ Contam Toxicol 2011; 87: 86–90.
This research was funded in part through a grant by the National
15. Hong S, Wen C, He J, et al. Adsorption thermodynamics of
High Technology Research and Development Program of China
methylene blue onto bentonite. J Hazard Mater 2009; 167:
(No.2012AA030313), Key Laboratory for Processing of Sugar
630–633.
Resources of Guangxi Higher Education Institutes(2015TZYKF03),
16. Ozdes D, Duran C and Senturk HB. Adsorptive removal
and Basic capacity improvement project of young teachers in the
of Cd(II) and Pb(II) ions from aqueous solutions by using
Guangxi Zhuang Autonomous Region (2016).
Turkish illitic clay. Environ Manag 2011; 92: 3082–3090.
17. Ji F, Li C, Tang B, et al. Preparation of cellulose acetate/zeo-
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