Reactive and Functional Polymers 160 (2021) 104840

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Reactive and Functional Polymers

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Perspective Article

Xanthated chitosan/cellulose sponges for the efficient removal of anionic

and cationic dyes
Xianlin Xu a, b, Jiajing Yu a, b, Chang Liu a, b, Guang Yang a, b, Lei Shi a, b, *, Xupin Zhuang a, b, *
a
State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin 300387, China
b
School of Textile Science and Engineering, Tiangong University, Tianjin 300387, China

A R T I C L E I N F O A B S T R A C T

Keywords: Biomass can adsorb dyes and then degrade. Although this material has remarkable prospects, its application is
Chitosan xanthate limited by its adsorption capacity and the simultaneous adsorption of cations/anions. Herein, a pore-forming
Dye removal agent in a solvent exchange phase transformation was used to fabricate chitosan xanthate and cellulose
Anionic and cationic dye
xanthate (xanthated chitosan/cellulose) sponges. Owing to the hierarchical pores and the presence of xanthic
Adsorption capacity
acid and amino groups, the sponges show efficient removal ability for anionic (congo red) and cationic (meth­
ylene blue) dyes. The adsorption mechanism, isotherm, kinetics, and thermodynamics were comprehensively
studied. The xanthated chitosan/cellulose sponges exhibited the maximum adsorption capacities of 213.220 and
289.855 mg g− 1 toward methylene blue and Congo red, respectively. The mechanism is a spontaneous physic-
sorption process that fitted well with the pseudo-second-order and Langmuir isotherm models. These results
revealed that xanthated chitosan/cellulose sponges are effective adsorbents for the removal of methylene blue
and Congo red dyes and provide a new platform for dye decontamination.

1. Introduction [29–32]. As a kind of natural cationic polysaccharide containing abun­

With the rapid economic and industrial development, dye pollutants
have received extensive global attention as the primary source of water
contamination [1,2]. Different types of dyes coexisting in industrial
wastewater cannot be thoroughly degraded through conventional
wastewater treatment processes because of their complex molecular
structures [3,4]. A wide scope of wastewater treatment strategies have
been proposed, such as membrane filtration [5–7], chemical reduction
[8], electrochemical treatment [9], photocatalysis, ion exchange, and
biological treatment [10–14]; however, most of these methods are
associated with sophisticated process, complex operation, or high cost,
thereby limiting their practical applications [15–17].
Adsorption is one of the most promising appropriate and convenient
techniques due to its advantages of economical, high efficiency, simple
operation, and lack of secondary pollution [18,19]. Numerous kinds of
adsorbents, including carbon-based materials [20,21], nanocomposites
[22], porous polymers [23], natural clay [24], fibers [25], functional­
ized membranes [5,6] and gels [26–28], have been developed to remove
dyes. An ideal adsorbent should have excellent adsorption ability, sim­
ple formability, eco-friendliness, abundant resources, and low cost
dant amine groups, chitosan (CS) shows good adsorption efficiency for
eliminating anionic contaminants through electrostatic attraction
[33–39]. Various derivatives possess enhanced properties. According to
the hard and soft acid and base classification system, adsorbents with
introduced sulfur atoms in their functional groups exhibit strong affinity
[40]; for example, xanthate groups have been applied to remove metal
ions by forming a stable metal complex with the cations and anions
through chelation [41–43]. CS xanthate (ChX), a sulfur-bearing com­
pound obtained from the esterification between hydroxyl group and
carbon disulfide [44], is expected to show good adsorption for anionic
and cationic dyes and improved application range due to its xanthate
and amino components.
In our previous work, a new cellulose sponge was prepared by mixing
sodium sulfate crystals as a pore-forming agent in cellulose xanthate
(CeX) to achieve high specific surface area (SSA) for adsorption. How­
ever, xanthate groups are removed in that reaction, and a high SSA is
achieved by controlling the pore size. Herein, the composite sponges of
ChX and CeX were prepared through phase inversion with sodium
dodecyl sulfate (SDS) as the pore-forming agent. The structure of ChX/
CeX sponges was characterized by FT-IR, SEM, and XRD analyses.

* Corresponding authors at: State Key Laboratory of Separation Membranes and Membrane Processes, TianGong University, Tianjin 300387, China.
E-mail addresses: shilei@tiangong.edu.cn (L. Shi), zhxupin@tiangong.edu.cn (X. Zhuang).

https://doi.org/10.1016/j.reactfunctpolym.2021.104840
Received 17 November 2020; Received in revised form 24 January 2021; Accepted 28 January 2021
Available online 4 February 2021
1381-5148/© 2021 Published by Elsevier B.V.
X. Xu et al. Reactive and Functional Polymers 160 (2021) 104840

Furthermore, the dye absorption behavior was studied using congo red
(CR, anionic dye) and methylene blue (MB, cationic dye) as anionic- and
cationic-simulated dyeing effluents, respectively.
2. Materials and methods
2.1. Chemicals and reagents
Cellulose (670 degree of polymerization) was supplied by Chengdu
Grace Co., Ltd. (Sichuan Province, P.R. China). Chitosan (deacetylation
≥99%) was provided by Shandong Aokang Biotechnology Co., Ltd.
(Shandong Province, China). Other materials such as carbon disulfide
(CS2, anhydrous, ≥99%), sodium hydroxide (NaOH), SDS, anhydrous
ethanol, MB, and CR were purchased from Shanghai Aladdin Co., Ltd.
(Shanghai, China).
2.2. Preparation of ChX and CeX
ChX was prepared as follows: chitosan powder was mixed with 7.6
wt% NaOH solution in the ratio of 1:11 (w/v) at room temperature and
stirred for 180 min. The alkaline chitosan was added into the flask, and
6.67 wt% CS2 was added at room temperature under stirring. The re­
action was maintained for approximately 240 min to obtain a dark
orange-like stable solution of ChX. ChX was synthesized following the
same procedure for CeX but at a low reaction temperature of 35 ◦ C [45].
Cellulose pulp was mixed with 23.76 wt% NaOH in the ratio of 1:12 (w/
v) at room temperature, stirred for 30 min, and added with 3.51 wt% CS2
under stirring. The reaction was maintained for approximately 120 min
to obtain an orange-like CeX solution.
2.3. Fabrication of ChX/CeX sponge
ChX was blended initially with CeX of different mass ratios (4:6, 5:5,
and 6:4), added with some pore-forming agents of SDS, and blended
uniformly. After vacuum degassing, the mixture was transferred into a
Petri dish and placed in an ethanol bath for 5 h, followed by washing
with water several times to form ChX/CeX sponges. The composite
sponges were coded as ChX/CeX-40, ChX/CeX-50, and ChX/CeX-60
according to ChX percentage.
2.4. Instrumentation
concentrations (6.25–200 mg g− 1). The effects of pH and temperature on
the adsorption efficiency of dyes were examined by adding a certain
mass of sponge into 100 mL of dye solution (100 mg g− 1) at different pH
levels (3–9) and temperatures (303, 313, and 323 K). The supernatant
liquid (2 mL) was obtained, and the dye concentration in the diluted
filtrate was determined every hour using a UV–vis spectrophotometer.
The difference in the dye concentration in aqueous solution before and
after adsorption was used to calculate the adsorption amount [46] as
follows:
(C0 − Ce )V
qe = (1)
W
(C0 − Ct )V
qt = (2)
W
where C0 is the initial concentrations (mg g− 1) of dye solutions; Ct and Ce
(mg g− 1) are the dye concentrations at t time and equilibrium (or at fixed
time) concentrations respectively; V(L) is the volume of dye solution;
and m(g) is the sorbent dosage.
The adsorption recyclability of the ChX/CeX sponges was investi­
gated. First, the saturated adsorbed sponges with 100 mL of 50 mg L− 1
MB/CR solution were immersed in ethanol solution for a certain period
of time at 30 ◦ C to completely elute the adsorbed MB/CR. The sponges
were then washed to neutral with deionized water. The regenerated
sponges were used for the next adsorption test. The procedure was
repeated six times.
2.6. Adsorption kinetics model
The adsorption kinetics model interprets the absorption data to gain
an insight into the absorption efficiency and rate-controlling steps.
Pseudo-first-order (PFO) and pseudo-second-order (PSO) kinetic models
were used to elucidate the MB and CR adsorption mechanism of the
viscose cellulose/chitosan composite sponges [47,48].
The PFO model can be formulated as shown in Eq. (5),
log(qe − qt ) = lnqe − k1 t (3)
The PSO model can be formulated using Eq. (6),
t 1 t
= + (4)
qt k2 q2e qe

Intra-particle diffusion model is shown using Eq. (7),

An ultraviolet spectrophotometer (model UV1700, Shimadzu,
Japan) was used to analyze the dye concentrations by measuring the qt = kid t0.5 + C (5)
maximum absorbance at wavelengths of 664 and 497 nm for MB and CR,
respectively. The surface morphologies of sponges were characterized where qt (mg g− 1) and qe (mg g− 1) represent the adsorption capacity of
via scanning electron microscopy (SEM, Hitachi S-4800). Energy chitosan sample at equilibrium and time t(min), respectively; k1 (mg g− 1
dispersive spectrometry (EDS) was applied to investigate the atomic h− 1) is the pseudo-first-order rate constant; k2 (mg g− 1 h− 1) is the
percentage of the main elements in the samples. Fourier transform adsorption rate constant of the PSO; and kid (mg g− 1 min 0.5) is the rate
infrared spectroscopy (FT-IR, model Nicolet 6700, MA, USA) was used to constant of the intra-particle diffusion models.
study the functional groups of the sponges before and after adsorption.
All sponges were characterized by X-ray photoelectron spectroscopy 2.7. Adsorption isotherm model
(XPS; Thermo-VG Scientific Ltd., West Sussex, UK). XRD was performed
using an XRD spectrometer (D8 Discover with GADDS, 40 kV, 40 mA) at The adsorption isotherm describes the ratio of the adsorbed dye to
10–80 with Cu Kα radiation (λ = 1.541 Å). the remaining dye in the solution. The three mathematical expressions
of Langmuir model, Freundlich model, and Temkin model were as
2.5. Adsorption experiments follows:
Langmuir isotherm model:
The adsorption behavior of MB and CR by ChX/CeX adsorbent was
investigated through batch adsorption experiments in each dye solution Ce 1 Ce
= + (6)
performed in a vapor-bathing constant temperature vibrator with a qe KL qm qm
shaking speed of 160 rpm. A certain mass of the sponge sample was Freundlich isotherm model:
mixed with 50 mg g− 1 dyes (100 mL, initial pH) at 30 ◦ C for pre­
determined time intervals to evaluate the kinetics of dyes. Adsorption 1
logqe = logCe + logKF (7)
isotherm studies were conducted by adding a certain mass of the sponge n
into 100 mL of dye solution under the initial pH at different dye initial Temkin isotherm model:

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X. Xu et al. Reactive and Functional Polymers 160 (2021) 104840

qe = B1 lnKT + B1 lnCe (8) binding energy. Constant B1 is related to the heat of adsorption.

where qm (mg g− 1) is the maximum adsorption capacity of the adsor­

2.8. Adsorption thermodynamic model
bent, and KL (L mg-1) is the Langmuir constant. The KF (L g− 1) of
Freundlich isotherm model is the unit capacity coefficient showing the
Enthalpy (ΔH◦ ) and entropy (ΔS◦ ) values were deduced by plotting
adsorptive bond strength, and n is the constant related to the system
Ln (qe C−e 1) as a function of the inverse of the temperature (1/T)
heterogeneity degree [49,50]. KT (L mg− 1) is the equilibrium binding
(Fig. 4bc). Ln was calculated by determining thermodynamic parame­
constant of Temkin isotherm model corresponding to the maximum
ters during MB and CR adsorption as follows [5,45,51]:

Fig. 1. SEM images (a), EDS mapping (b), FT-IR spectra (c), and XRD patterns (d) of ChX/CeX sponges.

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X. Xu et al.
qe ΔS0 ΔH0
ln = − (9)
Ce R RT
ΔG0 = ΔH0 + TΔS0 (10)
where T (K) is the temperature, R (J mol− 1⋅K− 1) is the universal gas
constant equal to 8.314, and KL (L mol− 1) is the Langmuir constant. ΔH
and ΔS can be calculated from the slopes and intercepts of the Ln (qe C−e 1)
versus 1/T, respectively.
3. Results and discussion
3.1. Formation and structure of ChX/CeX composite sponges
The SEM images of ChX/CeX sponges with different ChX proportions
were taken to examine the structure. As shown in Fig. 1, the ChX/CeX
sponges prepared by phase inversion present a typical porous structure,
including pores (10–20 nm) from SDS pore-forming agent and phase
separation, when precipitated in an ethanol-coagulating bath [52]. The
effect of SDS loading on sponge toward porosity is shown in Table 1.
When the SDS content is high, the porosity is slightly increased. With
ChX/CeX-60 as the example, the porosities are 93.56%, 94.77%,
98.87%, and 99.50% when the SDS content is 0 wt%, 0.5 wt%, 2.0 wt%,
and 4.0 wt%, respectively. For same category of SDS-4.0 wt%, the po­
rosities of ChX/CeX-60, ChX/CeX-50, and ChX/CeX-40 are almost
similar at 95.50%, 95.84%, and 96.9%, respectively. The SEM image in
Fig. 1a indicates that for a specific ChX/CeX proportion, the porous
structure becomes evident when the concentration of SDS is increased.
For ChX/CeX with the same SDS content, a good foam porous
morphology can be achieved when the cellulose content is high. The wet
phase inversion method can be adopted to obtain a composite sponge
with rich pore structure, fast dye absorption rate, and shape recovery
ability, resulting in the intra-particle diffusion of dye molecules into the
adsorbent particles. EDS mapping analysis revealed that the elements
are evenly distributed, especially N (Fig. 1b). This finding is attributed to
the compatibility of the two polymers from their similar chemical
structure and the high fluidity of the solutions.
FT-IR spectroscopy was performed to further study the structure of
the sponge. The FT-IR spectra of sponges were analyzed in the
500–4500 cm− 1 region as shown in Fig. 1c. The peaks and associated
chemical groups are listed in Table S2. After solvent exchange, the
sponge possessed xanthate and amino groups. The three crucial absor­
bance peaks appeared at wavenumbers of 3351 (broad), 2879, 1640,
and 897–1151 cm− 1, which were attributed to the hydroxyl (O–H),
methyl (C–H), and carbonyl (C– – O) in the acylamino group and
methoxy (–C–O–) groups, respectively [53–58]. The N-containing
functional groups corresponding to the stretching vibration of C–N
amine I, bending vibration of N–H amide, and stretching vibration of
N–H amide were observed at 1313, 1545, and 3351 cm− 1, respectively
[37,59]. Fig. 1d shows the XRD patterns of each ChX/CeX sponge. The
sponge exhibits two intense peaks of regenerated cellulose at 14.6◦ and
21.8◦ ascribed to (101) and (002) of cellulose II, respectively. The 2θ
peaks for chitosan also occurred at approximately 10.1◦ , 19.8◦ , and
21.8◦ [60,61]. This result is attributed to the uniform mixing of CeX and
ChX in NaOH solution, thereby reflecting the good compatibility of these
materials.
Table 1
Porosity of Chitosan/cellulose xanthate (ChX/CeX) sponge.
SDS Proportion 0 wt% 0.5 wt% 2.0 wt% 4.0 wt%
ChX/CeX-60 85.56% 89.77% 93.87% 95.50%
ChX/CeX-50 87.25% 91.24% 94.74% 95.84%
ChX/CeX-40 88.96% 93.69% 94.92% 96.9%
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Reactive and Functional Polymers 160 (2021) 104840
3.2. Dye adsorption performances of ChX/CeX
3.2.1. FT-IR and XPS analysis
Comparison of the color change of the dye solution before and after
adsorption revealed that the solution had almost no color after adsorp­
tion(Fig. 2). Meanwhile, the sponge turned blue or red. The adsorption
mechanism of dyes was examined using FT-IR and XPS (Fig. 2b-c).
Comparison of the spectra of the MB-adsorbed ChX/CeX-50 sponge,
ChX/CeX-50 sponge, and MB powders indicated that aside from the
peaks existing in chitosan and cellulose or MB, no new peak appeared for
the dye-adsorbing sponge. CR adsorption showed a similar phenome­
non, indicating that adsorption is a physical process ascribed to the
electrostatic interaction between anionic and cationic molecules.
The XPS spectra of high resolution scans for the key elements on
ChX/CeX surface before and after MB and CR adsorption are shown in
Fig. 2c–k. The results revealed the changes in element content. Fig. 3(c)
shows the peaks corresponding to C1s (binding energy of 168.5 eV) and
Na1s (binding energy of 1072 eV), indicating the presence of the
xanthate group [62]. After MB/CR adsorption C1s, the N1s bonds were
slightly changed (Fig. 3f, i). As shown in Fig. 3(d, g, j), the fitted XPS
spectra of the C1s region presented four components at 283.8, 285.5,
287.1, and 288.5 eV corresponding to C–C bonds, C–N bonds, C–O,
and C–– O, respectively [41]. Compared with that of the pristine sponge,
the N1s signal increased after MB/CR adsorption (Fig. 2e, h, and k). The
N1s spectra of original samples displayed peaks at 397.8 and 399.2 eV
corresponding to –NH2 and N–C bonds, respectively (Fig. 2e). The N1s
spectra of after MB absorption displayed peaks at 397.9, 399.1, 400.8,
and 401.8 eV attributed to –NH2, N–C, –NH–, and –N– – bonds,
respectively (Fig. 2h). The N1s spectra of post-CR absorption displayed
peaks at 399.3, 400.4, and 401.5 eV corresponding to N–C, –NH–, and
–N– – bonds, respectively (Fig. 2k). The increase in nitrogen content and
different bonds further indicated that the sponge adsorbed the dyes
mainly due to electrostatic interaction [63].
3.2.2. Effect of pH on adsorption
The pH of a dye solution is an important factor in determining solute
adsorption [6]. The effect of pH on the removal of MB and CR from
sponges was investigated to gain further insights into the adsorption
process. MB and CR adsorption was conducted with initial pH range of
3.0 to 9.0, and the highest adsorption capacities are shown in Fig. 3.
With the increase in the initial pH, the adsorption capacity and removal
rate of MB/CR onto the ChX/CeX sponge adsorbent increased first and
then decreased. The highest adsorption capacity for MB and CR was
obtained at pH of 7.0 and 6.0, respectively. These trends are attributed
to the available H+ ion groups on the surface of the adsorbent at low pH,
resulting in the electrostatic repulsion between the positively charged
dye and the adsorbed H+ ions. The absorption capacities of ChX/CeX-50
and ChX/CeX-60 were higher for MB and CR than for other substances.
This finding implied that xanthate and the amino group in the sponge
could promote the adsorption of MB and CR, respectively. Their elec­
trostatic attraction leads to high qe values. Similar results have been
reported for other adsorbents [64,65].
3.2.3. Effect of temperature on adsorption
The effect of 30 ◦ C, 40 ◦ C, and 50 ◦ C temperature on the adsorption of
MB and CR is shown in Table 2 and Fig. 4. These results confirmed that
the adsorption capacity of sponges decreased with the increase in tem­
perature, suggesting the exothermic nature of this process. This
exothermic nature is beneficial for practical application without the
need for additional energy.
The computed thermodynamic parameters are shown in Table 2. The
Gibbs values for all dyes were negative at various temperatures, indi­
cating that the adsorption of MB and CR on the sponge samples was
spontaneous (Table 2) [66]. The values of ΔH and ΔS0 of ChX/CeX-40
after CR absorption were equal to − 6313.614 and − 16.001 J mol− 1
K− 1, respectively, according to the plot of ln(qe/Ce) versus 1/T. The
X. Xu et al. Reactive and Functional Polymers 160 (2021) 104840

Fig. 2. Solution color before and after adsorption (a); FT-IR spectra of the sponges and dyes (b); XPS spectra for the ChX/CeX sponge (c–e); and ChX/CeX sponge
after MB adsorption (f–h) and CR adsorption (i–k).

Fig. 3. Influence of pH on the removal of MB(a) and CR(b).

negative values of ΔH suggest that the adsorption is an exothermic [51].

process, and the negative values of ΔS0 are attributed to the decrease in
the freedom degree of adsorbed species at the solid/solution interface

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X. Xu et al. Reactive and Functional Polymers 160 (2021) 104840

Table 2
Thermodynamic parameters (Gibbs free energy, enthalpy, and entropy changes) during MB and CR adsorption for sponges at 30 ◦ C, 40 ◦ C, and 50 ◦ C.
ChX/CeX-60 ChX/CeX-50 ChX/CeX-40

MB CR MB CR MB CR

△H (kJ/mol) − 28,809. 314 − 20,060.120 − 35,574.435 − 20,743.864 − 26,139.884 − 6313.614

△S (J/mol K) − 89.520 − 59.039 − 110.421 − 62.484 − 81.250 − 16.001
△G-30 (kJ/mol) − 55,933.840 − 37,949.058 − 69,031.876 − 39,676.455 − 50,758.695 − 11,161.947
△G-40 (kJ/mol) − 56,828.043 − 38,539.452 − 70,136.082 − 40,301.293 − 51,571.197 − 11,321.983
△G-50 (kJ/mol) − 57,724.242 − 39,129.846 − 71,240.288 − 40,926.131 − 52,383.699 − 11,481.969

Fig. 4. (a) Effects of temperature on adsorption of MB and CR; (b) plots of 1/T versus ln(qe/Ce) for MB absorption; and (c) plots of 1/T versus ln(qe/Ce) for
CR absorption.

3.2.4. Thermal analysis
The thermal stability of dye-free and dye-loaded sponge was studied
via TGA and DTG (Fig. 5). The three dye-free sponge samples showed
similar results with three main degradation stages, whereas the two
other dye-loaded sponges exhibited differences. The first mass loss of the
curve changes below 40 ◦ C–99 ◦ C was attributed to the moisture evap­
oration in the sponge. The second decomposition temperatures of ChX/
CeX before and after adsorption were 303.3 ◦ C, 301.9 ◦ C, 300.1 ◦ C,
314.0 ◦ C, and 337.8 ◦ C, indicating the degradation of the side chain
groups of the cellulose/chitosan molecule and the breaking of the main
cellulose/chitosan molecule to small chain. Moreover, the decomposi­
tion temperature of ChX/CeX after adsorption was higher than before. A
third mass loss was observed between 347 ◦ C/361 ◦ C and 500 ◦ C due to
complete cellulose/chitosan chain oxidation and dye decomposition.
These results suggested that the decomposition temperature was slightly
reduced, and the decomposition rate was slowed down with the increase
in ChX content in the sponges. The decomposition temperature and
amount of dye in the sponge increased after adsorption. This result is in
accordance with the findings from FT-IR, XPS, and XRD analyses.
3.3. Adsorption kinetics
ChX/CeX sponges were used to remove anionic and cationic dyes (CR
and MB, respectively) from aqueous solution in a range of sorbent
dosage to further understand the mechanism of adsorption. The effects
of contact of time on MB and CR adsorption are shown in Fig. 6. When
the ChX/CeX sample adsorbed MB or CR, the process was rapidly
completed before 2 and 10 h, respectively, due to the specific adsorption
among xanthate, amino groups, and dye molecules. Therefore, the
adsorption sites are the nitrogen atoms of the amino group in chitosan
and the sulfur atoms of attached xanthate group [67]. This initial rapid
increase in the adsorption of MB/CR was attributed to the abundant

Fig. 5. TGA(a) and DTG(b) analysis of ChX/CeX sponge.

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X. Xu et al. Reactive and Functional Polymers 160 (2021) 104840

Fig. 6. Effect of time on adsorption of MB (a) and CR(b); (c) Pseudo-first-order model of adsorption MB; (d) Pseudo second-order models of adsorption MB; (e)
Pseudo-first-order model of adsorption CR; (f) Pseudo-second-order model of adsorption CR; (g) Intra-particle diffusion model of adsorption MB; and (h) Intra-particle
diffusion model of adsorption CR.

7
X. Xu et al.
accessible sites and the adsorption driving force originating from the
large difference between the concentration of dye molecules in the so­
lution and the surface of ChX/CeX [43,68,69]. Adsorption proceeds at a
slow rate until it reaches equilibrium. Equilibrium was achieved within
3 h for MB and within 15 h for CR. This result implies that in the initial
stage of adsorption, the diffusion of dyes from the bulk to the surface has
reached the limiting adsorption step. The remaining vacant sites become
sterically hindered by the already bound dye molecules [70].
The adsorption capacities (qe) for MB and CR at equilibrium are
approximately 120 mg g− 1, indicating the potential for ChX/CeX dye
removal. These results are attributed to the high amino and xanthate
group content and the porous structure of the sponge that improves the
interaction between the dyes and ChX/CeX.
Fig. 6(c–f) show the linear plots of the PFO and PSO models of ChX/
CeX-50 and ChX/CeX-60. Kinetic parameters are listed in Table 3. On
the basis of the low correlation coefficient for PFO and the high value for
PSO, the adsorption abilities of ChX/CeX-50 and ChX/CeX-60 follow the
PSO rather than PFO kinetic mechanism. This finding suggested that the
PSO kinetic equation can best predict the kinetic process. The values of
qe calculated by PSO were more similar to practical qe adsorption than
PFO. The applicability of PSO models indicated the interaction between
BSA molecule and the amino groups of ChX/CeX. Hence, the adsorption
system is a chemical process involving electron sharing or electron
transfer [71].
Fig. 6(g, h) show the fitting plots divided into three linear portions,
implying that three steps occurred during adsorption [72]. The intra-
particle diffusion rate constants in Table 3 follow the order kid.1 >
kid.2 > kid.3. The first linear portion with the highest kid value represents
the external surface adsorption or instantaneous diffusion stage (kid.1);
at this stage, large amounts of MB and CR are rapidly adsorbed by the
exterior surface of sponge groups [46]. The dye molecules then gradu­
ally diffuse into the inside of the adsorbent, and the diffusion resistance
increases, which is the speed limit step [46]. Finally, adsorption is close
to equilibrium in the lowest kid.3 stage. The plots of the intra-particle
diffusion model for MB show linearity with lower kid and R2 values
than those for CR. This finding indicated that adsorption on the external
surface of the sponge for MB is slower than that for CR. Fig. 6(g, h) shows
that the plots deviated from the origin, indicating that adsorption is not
only controlled by intra-particle diffusion but also involves complex
mechanisms, including chemical and physical adsorption [46].
3.4. Adsorption isotherm
Langmuir, Freundlich, and Temkin models were used to model the
adsorption isotherm data of MB and CR on ChX/CeX. As an empirical
model, the Langmuir isotherm is mainly applied to describe the mono­
layer adsorption on the homogeneous surface of an adsorbent [73,74].
The Freundlich model describes heterogeneous surface adsorption and
multilayer adsorption under various non-ideal conditions [74,75].
Temkin isotherm assumes that the heat of adsorption of all molecules in
the layer decreases linearly with coverage [46].
The relationship between the adsorption capacities and the
Table 3
PFO and PSO kinetic model parameters for MB and CR adsorption by ChX/CeX-50 and ChX/CeX-60 in their single and mixed dye solutions at 303 K.
Absorbate C0 (mg g− 1) qe (mg g− 1) PFO kinetics model
qcal (mg g− 1)
MB 50 120.363 12.828
CR 50 120.675 15.242
Absorbate C0 (mg g− 1) First stage
R21 C1 Kid1
MB 50 0.911 44.357 48.089
CR 50 0.997 − 31.294 44.611
Reactive and Functional Polymers 160 (2021) 104840
equilibrium concentration in the solution for MB and CR is plotted in
Fig. 7. The fitting parameters are tabulated in Table 4. With the increase
in equilibrium concentration, the adsorption capacity increased signif­
icantly until the adsorption reached saturation. This phenomenon can be
attributed to the high initial concentration of the dye, which facilitated
its accelerated diffusion onto the adsorbent surface [76]. The experi­
mental data were well correlated with Langmuir (R2>0.983/0.99) and
very well correlated with Freundlich (R2>0.953/0.978) and Temkin
models (R2>0.9614 / 0.9657). The n value reflects whether the ab­
sorption characteristic is good (2 < n 〈10), difficult (1 < n < 2), or poor
(n < 1) [54]. Table 4 shows that MB and CR adsorption was favorable
because n>2 [50]. The monolayer adsorption capacities on the homo­
geneous surface [77] were 213.22 and 289.86 mg g− 1 for MB and CR,
respectively, as calculated using the Langmuir model. These values
agree well with the adsorption capacity obtained in the experiments. In
addition, the adsorption performance of the ChX/CeX sponge is better
than that of other reported adsorbents (Table 5). Therefore, the ChX/
CeX sponges exhibit the advantages of biodegradability, mature pro­
cessing, low cost, and wide availability.
3.5. Recyclability study
The reusability of adsorbents is an important factor to evaluate their
industrial suitability. Six cycles of adsorption and elution were con­
ducted on the optimum sample, and the capacity was measured at the
end of each cycle to study the recyclability of the ChX/CeX adsorbents.
Fig. 8 shows that after six cycles, ChX/CeX performance was slightly
reduced in the subsequent cycles and recovered over 86% of its original
capacity, implying its reliable desorption and recyclability. In conclu­
sion, the hierarchal porous sponge adsorbents offer grand superiority in
terms of recyclability and reliable capability.
4. Conclusions
A novel xanthated chitosan/cellulose sponge containing xanthates
and amino groups was applied for the adsorption of MB (cations) and CR
(anions) with excellent performance. The kinetic results were well-fitted
by the PSO kinetic model, indicating that the adsorption process is
controlled by intra-particle diffusion and involves complex mechanisms,
including chemical and physical adsorption. Adsorption studies were
modeled using Langmuir, Freundlich, and Temkin isotherms. The
maximum adsorption capacities of ChX/CeX obtained for MB and CR
were 213.220 and 289.855 mg g− 1, respectively. Therefore, ChX/CeX
can be a highly efficient sorbent for removing cationic contaminants and
metal ions from aqueous solutions. Its aforementioned excellent per­
formance renders ChX/CeX as a promising dye adsorbent for wastewater
purification.
CRediT authorship contribution statement
Xianlin Xu: Conceptualization, Methodology, Supervision. Jiajing
Yu: Conceptualization, Methodology, Investigation, Writing - original
PSO kinetics model
K1 (min− 1) R2 qcal (mg g− 1) K2 (mg g− 1
min− 1) R2
0.232 0.657 122.699 0.050 0.999
3
0.052 0.938 128.041 3.456 × 10^− 0.998
Second stage Third stage
R22 C2 Kid2 R23 C3 Kid3
0.989 97.420 8.783 0.830 119.071 0.115
0.976 69.566 11.379 0.952 109.384 1.634
8
X. Xu et al. Reactive and Functional Polymers 160 (2021) 104840

Fig. 7. (a) Adsorption isotherm of dyes adsorptions at 30 ◦ C; (b) Fit of the equilibrium data with the Langmuir isotherm model; (c) Fit of the equilibrium data with
the Freundlich isotherm model; and (d) Fit of the equilibrium data with the Temkin isotherm model.

Table 4
Langmuir, Freundlich, and Temkin constants and correlation coefficients for MB and CR adsorption.
Absorbate Langmuir isotherm model Freundlich isotherm model Temkin isotherm model

KL(L mg− 1) qm (mg g− 1) R2 n KF(mg⋅g− 1) R2 KT(L mg g− 1) B1 R2

MB 0.020 213.220 0.983 2.049 511.105 0.953 0.062 42.221 0.966

CR 0.014 289.855 0.990 2.011 575.387 0.978 0.044 49.169 0.961

Table 5
Comparison of ChX/CeX sponge with other reported adsorbents.
Adsorbents Dyes Adsorption Reference
capacity (mg g− 1)

Polyurethane/chitosan Acid Violet 30 [78]

composite foams 48
Cross-linked chitosan/sepiolite Methylene 40.986 [79]
blue
Chitosan-crosslinked Methylene 130.4 [80]
ĸ-carrageenan blue
Cellulose nanocrystal/alginate Methylene 256.4 [81]
blue
Hyperbranched polyglycerol- Methylene 179.01 [82]
based multi-carboxylic blue
magnetic gel Methyl 148.33
violet
Chitosan and Alginate Sponge Congo red 117.64 [83]
Cellulose/chitosan composite Congo red 382 [84]
CTAB impregnated chitosan Congo red 272 [85]
hydrogel
Xanthated chitosan/cellulose Congo red 289.855 This
sponges study
Methylene 213.220 This
blue study
Fig. 8. Recyclability test of ChX/CeX sponge (MB/CR concentration: 50
mg L− 1).

9
X. Xu et al.
draft. Chang Liu: Methodology. Guang Yang: Conceptualization, Su­
pervision. Lei Shi: Conceptualization, Supervision. Xupin Zhuang:
Conceptualization, Methodology, Supervision, Writing - review &
editing.
Declaration of Competing Interest
The authors declare no conflict of interest.
Acknowledgments
The author would like to thank National Key R&D Program of China
(2017YFB0309303), National Natural Science Foundation of China
(51603148) and the Science and Technology Plans of Tianjin
(20JCQNJC00250) for their financial supports.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.reactfunctpolym.2021.104840.
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