Composites Part B 169 (2019) 45–54

Contents lists available at ScienceDirect

Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Adsorption performance of a polysaccharide composite hydrogel based on T

crosslinked glucan/chitosan for heavy metal ions
Chenglong Jiang, Xiaohong Wang∗, Ganghu Wang, Chen Hao∗∗, Xin Li, Tihai Li
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, Jiangsu, 212013, China

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

Keywords: Glucan/chitosan (GL/CS) hydrogels as adsorbents for heavy metal ions in wastewater treatment were synthe-
Hydrogel sized by ultrasound-assisted free radical polymerization. The samples were characterized by Fourier transform
Adsorption infrared spectroscopy (FT-IR), field emission scanning electron microscopy (SEM) and thermogravimetric ana-
Heavy metal ions lysis (TGA). In the study of adsorption process, the effects of temperature, acidity and alkalinity, dosage of
Chitosan
adsorbent, adsorption time and concentration of heavy metal ions on adsorption behavior of GL/CS adsorbent in
Glucan
simulated wastewater were discussed. On the basis of the above research, the adsorption thermodynamics,
adsorption kinetics and adsorption mechanism were also studied. When the temperature was 20 °C, the pH value
was 7.0 and the amount of adsorbent was 0.01 g, the results showed that the adsorption capacities of GL/CS
hydrogels for Cu2+, Co2+, Ni2+, Pb2+ and Cd2+ were 342 mg g−1, 232 mg g−1, 184 mg g−1, 395 mg g−1,
269 mg g−1, respectively. The fitting results of the isothermal models, the kinetic models and thermodynamics of
the experimental data of the ion adsorption process show that the adsorption of heavy metal ions by GL/CS is a
spontaneous process of single-layer chemisorption.

1. Introduction ions. The application principle of the method is to add a chemical re-
agents capable of forming a water-insoluble precipitate with heavy
The development of industry has brought convenience to people, metal ions in the wastewater, and then filter out the precipitates so as to
but it has also caused serious harm to the environment. Among them, achieve the purpose of removing heavy metal ions. The chemical floc-
the pollution of water is more serious. The pollution of heavy metal ions culation method has the advantages of large removal, simple im-
in the wastewater has brought great damage to the biosphere. In es- plementation, good removal efficiency, mature technology, low in-
sence, heavy metals mean that the density of the substance can be vestment, low cost, and the like, and is widely applied to the removal of
greater than 4.5 kg dm−3, and the metal in the periodic table is 21–83. heavy metal ions. However, the deficiency of this method is that the
It mainly includes about 40 species of lead (Pb), nickel (Ni), cobalt addition of precipitant will produce a large amount of flocculent sludge,
(Co), cadmium (Cd), copper (Cu) and so on [1–6]. There is no uniform which will cause a secondary contamination. The heavy metal ions
definition of heavy metals. Generally, metals that cause pollution to the involved in oxidation-reduction methods usually have multiple valence
environment and cause harm to human body are heavy metals [7–10]. states, and the ionic properties of different valence states are different.
Heavy metal ions in wastewater cover the whole biological world, and The method is to add a reducing agent or an oxidizing agent to the
they can do great damage to the natural water and the whole ecosystem wastewater, convert the refractory valence state into a manageable
through the cycle of biological action. Due to the enrichment in the valence state and form a precipitate, and the process generates a large
biological chain, the final heavy metal ions will threaten the safety of amount of waste residue, resulting in a limited treatment range. Elec-
human life. The removal of heavy metal ions is also a hot topic in the trolysis is the process of chemical changes in a substance caused by
scientific community today. electrical current. The positive ions in the solution move toward the
There are many measures to treat heavy metal ions in wastewater. cathode, and the negative ions move to the anode and undergo re-
The most commonly used ones are chemical flocculation, oxidation- duction and oxidation reactions, respectively. This process is well de-
reduction, adsorption, electrolysis and so on [11–18]. Chemical floc- veloped, but the sewage treatment capacity is not strong enough, the
culation is one of the most widely used methods to treat heavy metal cost of ion removal is relatively high and causes secondary pollution, so

∗
Corresponding author.
∗∗
Corresponding author.
E-mail addresses: [email protected] (X. Wang), [email protected] (C. Hao).

https://doi.org/10.1016/j.compositesb.2019.03.082
Received 30 October 2018; Received in revised form 16 March 2019; Accepted 31 March 2019
Available online 06 April 2019
1359-8368/ © 2019 Elsevier Ltd. All rights reserved.
C. Jiang, et al. Composites Part B 169 (2019) 45–54

its application is limited. The adsorption method is simple in operation, Table 1

excellent in treatment effect, low in adsorbent price, and no secondary The results and analysis of L16 (54) orthogonal experiment design.
pollution in the treatment process. Therefore, the method is widely Factors GL/g K2S2O8/g NMBA/g AA% CS/g Result(Cu2+ qe/mg g−1)
applied to the removal of heavy metal ions in wastewater, and is con-
sidered to be one of the greenest and most promising methods for 1 0.1 0.07 0.0085 65 0.01 249.69170
2 0.1 0.09 0.0115 70 0.06 253.80796
treating heavy metal ion wastewater [19–26]. Hydrogel is a kind of
3 0.1 0.11 0.0145 75 0.11 286.83799
polymer with three-dimensional network structure [27–30], which was 4 0.1 0.13 0.0175 80 0.16 295.83709
used in medical treatment when it was first discovered. Due to its high 5 0.2 0.07 0.0115 75 0.16 232.71007
water absorption, it is widely used in agriculture, health care and so on. 6 0.2 0.09 0.0085 80 0.11 239.19275
In recent years, it has been found that the hydrogel has a polyfunctional 7 0.2 0.11 0.0175 65 0.06 248.85845
8 0.2 0.13 0.0145 70 0.01 231.52685
structure so that it also exhibits excellent performance as an adsorbent
9 0.3 0.07 0.0145 80 0.06 268.27318
for heavy metal ion treatment. 10 0.3 0.09 0.0175 75 0.01 260.39063
Chitosan is produced by deacetylation of chitin, so chitosan is also 11 0.3 0.11 0.0085 70 0.16 239.54272
called deacetylated chitin [31–33]. Since the French Rouget first got 12 0.3 0.13 0.0115 65 0.11 257.05763
13 0.4 0.07 0.0175 70 0.11 287.20462
chitosan in 1895, the biocompatibility, blood compatibility, safety,
14 0.4 0.09 0.0145 65 0.16 180.63194
microbial degradation and other advantages of this natural polymer 15 0.4 0.11 0.0115 80 0.01 247.30861
have been widely concerned by all walks of life. Significant progress has 16 0.4 0.13 0.0085 75 0.06 244.59221
been made in the fields of medicine, food, chemical, cosmetic water
treatment, metal extraction and recovery, biochemistry and biomedical Analysis A(GL) B(K2S2O8) C(NMBA) D(AA) E(CS)
engineering [34–39]. Chethan et al. [40] prepared ethylenediamine-
k1 271.544 259.470 243.255 234.06 247.229
modified chitosan microspheres by chemical crosslinking method to k2 238.072 233.506 247.721 253.021 253.883
adsorb Cu2+,Zn2+,Pb2+,Cr4+. Glucan is a kind of homologous poly- k3 256.316 255.637 241.817 256.133 267.573
saccharide composed of glucose monosaccharide and glucan units are k4 239.934 257.253 273.818 262.653 237.18
linked by glycoside bonds. According to the type of glycosidic bond, Range 33.472 25.964 31.256 28.593 30.393
alpha-glucan and beta-glucan can be further divided into two groups.
Alpha-glucan, also known as glucan, is a polysaccharide found in the nitrate, nickel nitrate hexahydrate, and hexahydrate nitric acid. All
mucus secreted by certain microorganisms during their growth. Fabri- aqueous solutions used for reactant polymerization, water swelling and
cation and application of composite materials is the development di- adsorption studies of hydrogels were prepared using deionized water.
rection of modern functional materials research,.and the composite
materials can make up for the shortcomings of different components,
and give full play to the advantages of different components, so as to 2.2. Synthetic GL/CS hydrogel
achieve performance efficiency [41,42]. Adding glucan into the hy-
drogel not only improves the adsorption performance, but also greatly The GL/CS hydrogel was synthesized according to the following
reduces its biological toxicity. In recent years, many researchers have steps, a certain amount of NaOH was weighed and dissolved in water,
used the excellent adsorption properties of hydrogels to treat heavy and 5 mL of acrylic acid was added dropwise with a dropper to neu-
metal ions. Wang et al. [43] used the unique adsorption properties of tralize the above NaOH solution in an ice water bath, and a continuous
hydrogels to treat Co2+ in wastewater. Kankeu et al. [44] prepared stirring was accompanied. Then potassium persulfate, NMBA, CS and
hydrogels from graft copolymerization of ammonium acrylate and ge- GL were added, and then the system was placed in a KQ-100 ultrasonic
latin and used them to adsorb Cd2+ in mine wastewater. cleaner (bath, 250 W, 40 kHz) and the reaction was maintained at 80 °C
Ultrasound-assisted synthesis has been proved to be a simple and for 3 h. Finally, the synthesized hydrogel was washed with anhydrous
effective technology for polymer synthesis. Due to its high acoustic ethanol to remove unreacted monomer, and the sample was dried under
frequency and large energy, ultrasonic assisted synthesis can increase vacuum at 70 °C for 24 h. The amount of the above reagents is listed in
the chemical reaction rate, reduce the reaction conditions, shorten the the orthogonal list below (Table 1).(Detailed experiments see support
reaction induction time and improve the reaction selectivity. In ultra- information (SI) Fig. S1).
sonic polymerization, ultrasonic cavitation effects can increase the
chance of collision between molecules and generate free radicals in the
2.3. Experiment and reaction mechanism
liquid, thereby initiating and accelerating the polymerization between
the monomers [45,46].
Both GL and CS are polysaccharides with multiple hydroxyl groups,
In this paper, GL/CS hydrogel was synthesized by ultrasonic assisted
and the O-H bond is very easy to break under the action of heat and
method using glucan and chitosan as the main raw materials. The hy-
initiator. Firstly, persulfate radical dissociates the hydroxyl groups on
drogel belongs to acrylic hydrogel and is applied to the treatment of
GL and CS, and transforms them from stable molecules into active ra-
Cu2+, Co2+, Ni2+, Pb2+ and Cd2+ in wastewater. The hydrogel ex-
dical groups. The active sites will receive the attack of acrylonitrile and
hibits excellent adsorption properties, outstanding use value, and is
produce a large number of polymer branched chains. Then, all the
easy to promote.
grafted chains are cross-linked together to form reticulated macro-
molecules under the action of crosslinking agents. The intact monomer
2. Experiment
and branched chain were removed by anhydrous ethanol, and finally
the hydrogel samples were obtained by vacuum drying. The specific
2.1. Experimental materials
process of the reaction is shown in Fig. 1.

Acrylic acid (AA) came from Shanghai McLean Biochemical Co.,

Ltd. Chitosan (CS), glucan (GL) and N'N-methylenebisacrylamide 2.4. Hydrogel swelling capacity
(NMBA) were from Sinopharm Chemical Reagent Co., Ltd. (Shanghai,
China). Potassium persulfate (K2S2O8) was purchased from Shanghai At 25 °C, the dry GL/CS hydrogel was weighed as m1 g and put into
Suran Chemical Reagent Co., Ltd. Other experimental reagents were deionized water until the hydrogel reached adsorption equilibrium.
from Nanjing Chemical Reagents Co., Ltd., such as sodium hydroxide, Then the mass of the adsorbed hydrogel was weighed as m2 g. The
ethanol, cadmium tetrahydrate, copper nitrate pentahydrate, lead swelling rate of GL/CS was calculated by the following formula:

46
C. Jiang, et al. Composites Part B 169 (2019) 45–54

Fig. 1. Ultrasound-assisted synthesis reaction mechanism of GL/CS hydrogel.

m2 − m1 3. Experimental results and discussion

Qe =
m1 (1)
3.1. Orthogonal test results and analysis
Where,Qe (g g−1) is the quality of adsorbed water per unit mass of
hydrogel. The data obtained in this paper are averaged by multiple
In the experiment, ultrasonic synthesis was used to accelerate the
measurements.
collisions between liquid molecules and free radicals, and the synthesis
conditions were optimized by orthogonal experimental design. The
2.5. Adsorption properties of GL/CS hydrogels results of orthogonal experiment of hydrogel are shown in Table 1, and
each qe in the table is the average of multiple experimental data. The
A certain amount of dried hydrogel was added to the prepared results of orthogonal experiments of GL/CS hydrogels are shown in
50 mL 100 mg L−1 M2+ (M = Cu, Co, Ni, Pb, Cd) solution. It was then Table 1. The magnitude of the influence of these several influencing
placed in a thermostatic shaker until the adsorption equilibrium is factors is the amount of GL > the amount of NMBA > the amount of
absolutely reached. The residual M2+ concentration in the solution was CS > the degree of neutralization of AA > the amount of K2S2O8. The
determined using a TAS-986 atomic absorption spectrophotometer. The best level of each factor is A1B1C4D4E3. It can be seen that among the
hydrogel adsorption capacity is calculated by the following equation: several factors investigated, the amount of GL is the biggest factor af-
fecting the adsorption of heavy metal ions by hydrogels. This may be
(C0 − Ce ) V
qe = due to the fact that the dextran contains more hydroxyl groups capable
m (2)
of chelating with heavy metal ions, so it contributes greatly to the ad-
−1 −1 sorption of heavy metal ions on the hydrogel. The effect of crosslinking
When Co (mg L ) and Ce (mg L ) represent the initial concentration
and the equilibrium concentration of M2+ in the solution, respectively. agent was the second, which also confirmed that the crosslinking de-
qe (mg g−1) is the amount of M2+ adsorbed on the adsorbent, V (L) is gree of hydrogels had great influence on the overall structure of hy-
the volume of M2+ solution, and m (g) is the weight of adsorbent. (See drogels. The amount of CS also has a certain effect, indicating that the
Fig. S2 in SI before and after adsorption of ions). functional groups of CS have great influence on the adsorption of heavy
metal ions.

2.6. Characterization of GL/CS hydrogels

3.2. GL/CS hydrogel properties
The synthesis of GL/CS hydrogel was completed in KQ-100 ultra-
sonic cleaner. In order to characterize the functional groups on the 3.2.1. Photographs and SEM
surface of GL/CS hydrogels before and after adsorption of heavy metal From a theoretical point of view, it can be analyzed that the cross-
ions, Nicolet-Nexus 470 (Nicolet, USA) Fourier transform infrared linking of the monomers will produce a hydrogel with a three-dimen-
spectrometer was used. To observe the morphology of GL/CS hydrogel, sional network structure. From the photographs of the hydrogels
JSM-7001F scanning electron microscopy was utilized. The thermal (Fig. 2(A) and (B)), it is shown that the GL/CS hydrogel has a highly
analysis of GL/CS hydrogel was carried out by STA 449 C integrated developed three-dimensional structure of pale brown-yellow honey-
thermal analyzer. comb morphology accompanied by a large number of folds, and the

47
C. Jiang, et al. Composites Part B 169 (2019) 45–54

Fig. 2. Photographs and SEM images of GL/CS (A–D); Macrostructure of GL/CS (E–F); FT-IR spectra of CS (a), GL (b), GL/CS (c) (G), after adsorption heavy metal
ions (d = Cu, e = Co, f = Ni, g = Pb, h = Cd) (H); TG and DTG curves of GL, CS and GL/CS (I).

hydrogel is translucent and has a thin wall. As shown in Fig. 2(C) and 1560 cm−1. The specific peaks of glucan and chitosan are found in GL/
(D), the hydrogel is rich in pores of various sizes, and the surface is CS, indicating that two monomers were successfully grafted into GL/CS.
relatively smooth, but some gully-like cracks are distributed on the Fig. 2(H) d∼h are the FT-IR spectra of GL/CS adsorbed heavy metal
surface. The tri-dimensional structure of the hydrogel was obtained by ions. It is clear that some of the absorption peaks after the adsorption of
cross-linking three monomers (acrylic acid, chitosan, glucan) with a heavy metal ions are offset. For example, -OH shifts from 3423 cm−1 to
crosslinking agent (NMBA). The pore structure on the surface is caused about 3500 cm−1. Some similar absorption peaks produce a degeneracy
by the loss of moisture of the hydrogel during vacuum drying. Because of the Fermi resonance effect, for example, the -NH2 characteristic
water will remain in the structure of the hydrogel during the process of absorption peak and C-O are degenerate at a position of about
synthesis. Under the condition of vacuum drying, the water in the 1300 cm−1. The phenomenon of the deviation and degeneracy of these
system will accelerate to the environment, which will lead to pores on absorption peaks is due to the fact that during the adsorption process,
the surface of the hydrogel. And it is also speculated that the honey- heavy metal ions M2+ will chelate with O, N and form coordination
comb-like hollow structure will appear inside the hydrogel, which is bonds, which makes the electron cloud density change and causes the
confirmed by Fig. 2(A) and (B). The water content of each part of the vibration band shift of the bond.
hydrogel is different. Because of the water loss, the collapse of each part
is different, resulting in a wrinkled structure on the surface. Fig. 2(E) 3.2.3. TG/DT
and (F) is a partial enlarged view of the inner wall of the tunnel, the It can be clearly seen from Fig. 2(I) that the decomposition tem-
surface of the inner wall is rugged, and many short rods and short peratures of CS, GL and GL/CS are 317 °C, 295 °C and 443 °C, respec-
pieces are randomly stacked to form a plurality of smaller microspores. tively. After thermal decomposition from 25 °C to 800 °C, the final re-
This porous special structure of the hydrogel makes it exhibit ex- sidual mass fractions of CS, GL and GL/CS were 10%, 29% and 49%,
cellent performance in terms of adsorption. Its three-dimensional respectively. From Fig. 2(I), it can be found that CS and GL lose weight
structure, pore structure and surface folds are beneficial to increase the by 10% and 12%, respectively, at around 70 °C, which is caused by the
specific surface area and provide more adsorption sites for the adsorbed loss of moisture when heated. The second stage is the thermal decom-
substances, thereby effectively improving its adsorption performance. position of CS and GL molecules, and CS begins thermal decomposition
at 282 °C until the weight drops to 10%, while GL thermally decom-
3.2.2. FT-IR poses from 258 °C until it falls to 29% by weight. Compared to CS and
In this paper, the monomers and synthesized samples were tested by GL, the thermal stability of GL/CS is significantly improved. First, GL/
FT-IR spectroscopy. In Fig. 2(G) a, 3467 cm−1 is a stretching vibration CS loses its moisture at 87 °C. In the second stage, GL/CS begins to
absorption peak of -OH; 2869 cm−1 and 1659 cm−1 are the stretching thermally decompose at around 400 °C until it reduce to 49% of the
vibration absorption peaks of -NH2, respectively; the absorption peak of weight. GL/CS hydrogel formed by crosslinking CS, GL and acrylic acid
the ether bond in chitosan appears at 1598 cm−1; the peak at about is more stable than that of other monomers.
661 cm−1 is assigned to the C-H vibration absorption. In Fig. 2(G) b,
3443 cm−1 is related to the stretching vibration absorption peak of -OH 3.3. Adsorption properties of GL/CS hydrogels
and 847 cm−1 is the glycoside bond absorption peak. It can be seen
from Fig. 2(G) c that a glucosidic bond unique to glucan appears at 3.3.1. Swelling behaviors of the GL/CS
856 cm−1 in GL/CS, and a stretching vibration peak of -NH2 occurs at In the fields of industry, agriculture and medical treatment, the

48
C. Jiang, et al. Composites Part B 169 (2019) 45–54

Fig. 3. (A) Effect of time on water absorption performance of GL/CS; (B) Effect of pH on ions adsorption behavior of GL/CS; (C) Effect of adsorbent dosage on ions
adsorption behavior of GL/CS.

swelling properties of the hydrogels is an important indicator of hy- of hydrogels. In this range, with the increase of the amount of ad-
drogels. Liquid-solid contact time is one of the parameters for hydrogel sorbents, the adsorbents will provide more adsorption sites and increase
application in water absorption and swelling. Fig. 3 (A) shows that the the adsorption capacity of the hydrogel. However, when the amount of
water absorption rate of GL/CS hydrogel increases rapidly in 40 min GL/CS hydrogel exceeds 0.02 g, the adsorption capacity decreases as
and reaches saturation slowly after 60 min. The swelling process of GL/ the amount of GL/CS hydrogel increases. This is because the con-
CS hydrogels can be divided into two stages: initial fast stage and final centration of the metal ions remains unchanged, the amount of the
slow stage. Initially, the hydrogel contains a large number of binding adsorbent increases, and the number of free adsorption sites increases,
sites, which can bind to water rapidly, and the water absorption rate is resulting in a decrease in the overall adsorption capacity of the hy-
very fast. In the slow stage, fewer binding sites lead to lower adsorption drogel. At the same time, the content of the adsorbent in the solution is
rate and finally saturation. too high, so that agglomeration occurs between them, causing some
adsorption sites to disappear, thereby reducing the adsorption amount
of the hydrogel. It is also observed from the diagram that the adsorption
3.3.2. Effect of pH and adsorbent dosage on adsorption properties
properties of the hydrogels are in the best state when the amount of
The pH value in industrial wastewater is often not 7, so the impact
adsorbents is up to 0.02 g, no matter which kind of ions. And the ad-
of pH on adsorption performance is also particularly important. As is
sorption capacity of Cu2+ is 365 mg g−1, Co2+ is 251 mg g−1, Ni2+is
clear from Fig. 3(B), qe increase with an increase in pH value and the
207 mg g−1, Pb2+ is 424 mg g−1, and Cd2+ is 356 mg g−1.
minimum value of qe is at pH = 1. The effect of pH on the five ions is
basically the same. At pH = 7, the difference of the adsorption capacity
of the five ions is larger, but with the gradual decrease of the pH value,
3.4. Adsorption thermodynamic
the difference will become smaller. In the adsorption process of heavy
metal ions, there are both chelation of the hydrogel and heavy metal
It can be seen from Fig. 4 that the adsorption capacity of GL/CS
ions, as well as ion exchange. The adsorption of heavy metal ions by
hydrogels increases with the increase of temperature, because the ad-
hydrogels is a reversible process. H+ is easily bonded to some polar
sorption process is an endothermic process, and the increase of tem-
functional groups (-COO-, -NH-, -O-), and therefore, H+ competes with
perature can move the adsorption equilibrium to the direction of strong
heavy metal ions. The decrease in pH causes an increase in H+ con-
adsorption. In order to study thermodynamics, the obtained data are
centration in water. As H+ increases, the position of the hydrogel
fitted by the following formulas, the results are shown in Fig. 4 and the
capable of binding to heavy metal ions is reduced, resulting in a de-
corresponding thermodynamic parameters ΔG0, ΔS0 and ΔH0 are shown
crease in the amount of adsorption of heavy metal ions.
in Table 2 (A).
As shown in Fig. 3(C), when other conditions remain unchanged,
and the amount of adsorbents is in the range of 0–0.02 g, the increase in ΔG 0 = ΔH 0 − T ΔS 0 (3)
the amount of adsorbents in the solution is beneficial to the adsorption

49
C. Jiang, et al. Composites Part B 169 (2019) 45–54

Fig. 4. Thermodynamic fitting of the five kinds of ions adsorbed by GL/CS and the influence of temperature on adsorption of the ions.

Table 2
(A) Adsorption thermodynamic parameters.
Thermodynamic △H0 △S0 △G0 (KJ mol−1)

Parameters (KJ mol−1) (J mol−1 K−1) 293.15K 303.15K 313.15K 323.15K 333.15K
Cu2+ 6.923 43.72 −5.89 −6.33 −6.77 −7.21 −7.64
Co2+ 17.02 70.55 −3.66 −4.36 −5.07 −5.78 −6.48
Ni2+ 21.08 81.78 −2.89 −3.70 −4.53 −5.34 −6.16
Pb2+ 4.953 41.40 −7.18 −7.60 −8.01 −8.43 −8.84
Cd2+ 10.41 49.86 −4.21 −4.71 −5.21 −5.71 −6.21

Kinetic models and parameters Cu2+ Co2+ Ni2+ Pb2+ Cd2+

qe,exp (mg g−1) 342.6 232.8 185.5 395.2 269.8

Pseudo-first-order kinetics
qe (mg g−1) 1625 495.4 241.1 703.2 461.7
k1 (min−1) 0.060 0.035 0.026 0.038 0.030
R2 0.717 0.787 0.979 0.705 0.908
Pseudo-second-order kinetics
qe (mg g−1) 381.7 285.7 234.7 436.7 343.6
k2 (g mg−1min−1) × 105 121.6 8.137 8.623 10.55 5.602
R2 0.999 0.998 0.991 0.999 0.995

50
C. Jiang, et al. Composites Part B 169 (2019) 45–54

Fig. 5. Effect of adsorption time on adsorption ion behavior of GL/CS (F); and the pseudo-first-order kinetic fitting (a∼e), pseudo-second-order kinetic fitting (A∼E).

ΔS 0 ΔH 0 Pseudo-first-order kinetic model:

In (qe / Ce ) = −
R RT (4)
In (qe − qt ) = Inqe − k1 t (5)
Where, qe (mg g−1) is the adsorption capacity of adsorbent, and Ce (mg
Pseudo-second-order kinetic model:
L−1) is the concentration of adsorbate in the equilibrium of adsorption.
R (J K−1 mol−1) is the universal constant of gas and T (K) is the tem- t
=
1
+
1
perature of reaction. qt k2 qe2 qe (6)
From Table 2(A), it can be seen that the ΔG0 is negative, the ad- −1
Where, qe (mg g ) is the theoretical equilibrium adsorption capacity, t
sorption process is a spontaneous process, and the temperature rise is
is the adsorption time, qt (mg g−1) is the adsorption capacity at time t,
beneficial to the adsorption, which is consistent with the trend of the qe-
and k1 (min−1) is the pseudo first-order kinetic model rate constant, k2
T diagram. ΔH0 is a positive value, indicating that the adsorption pro-
(g) is the pseudo-second-order kinetic rate constant, and the adsorption
cess is accompanied by endothermic process. The fitting of thermo-
kinetic parameters obtained by the model are listed in Table 2(B).
dynamic curve shows that the adsorption process by which GL/CS ad-
The pseudo-first-order kinetic model is based on the membrane
sorbs ions is accompanied by a spontaneous endothermic reaction.
diffusion theory, and it is considered that the adsorption reaction rate of
the adsorbate is proportional to the square of the difference between
3.5. Adsorption kinetics the equilibrium adsorption amounts in the system. The pseudo-second-
order kinetic model is established on the adsorption rate limiting step,
By studying the influence of time on the adsorption of the five ions including the adsorption mechanism, electron sharing or electron
by GL/CS, the kinetic model was fitted and the dynamic mechanism transfer between the adsorbate and the adsorbent. The degree to which
was explored. Fig. 5 shows the effect of adsorption time on the ad- the correlation coefficient (R2) is close to 1 reflects the closeness of the
sorption of the ions and adsorption kinetics of GL/CS. It can be seen actual situation to the model. From the results of the fitted parameters,
from Fig. 5(F) that the adsorption capacity increases rapidly with in- the theoretical adsorption capacity obtained by pseudo-second-order
creasing adsorption time from 0 to 60 min, and the adsorption capacity kinetics is closer to the actual measurement results than that of the first-
increases slowly after 60 min until the adsorption equilibrium reaches order kinetics, and the correlation coefficient (R2) of the pseudo-
180 min later. In order to further explore the kinetics of adsorption, the second-order kinetic model is higher. These results indicate that the
pseudo-first-order kinetic model and the pseudo-second-kinetic model pseudo second-kinetic model is more in line with the process of de-
were used to study this process. scribing heavy metal ions adsorbed by GL/CS hydrogels.

51
C. Jiang, et al. Composites Part B 169 (2019) 45–54

Fig. 6. Effect of heavy metal ions concentration on the adsorption of GL/CS and the isotherm model.

3.6. Adsorption isotherm Ce C 1

= e +
qe qm, L KL qm, L (7)
As can be seen from Fig. 6, the adsorption capacity of GL/CS hy- −1
drogel increases gradually with the increase of initial heavy metal ion Where, Ce (mg L ) is the concentration of adsorbate at equilibrium, qe
concentration until the final adsorption capacity of the hydrogel tends (mg g−1) is the adsorption capacity of adsorbent at equilibrium, qm,L
to be stable. This is due to the fixed amount of hydrogel, the number of (mg g−1) is the theoretical maximum adsorption capacity, and KL (L
adsorption sites is certain, and the increase of metal ion concentration mg−1) is the Langmuir adsorption constant.
leads to fewer and fewer adsorption sites. Finally, the adsorption ca- Freundlich adsorption isotherm assumes that the adsorbent surface
pacity of the adsorbent reaches saturation. In order to further study the is heterogeneous, the adsorbate adsorption is multi-layered, and there is
adsorption mechanism, the relationship between adsorption capacity interaction between adsorbents.
and metal ion concentration was discussed by using adsorption iso- 1
Inqe = InKF + InCe
therms. n (8)
The Langmuir adsorption isotherm model assumes that there is no −1
Where, Ce (mg L ) is the concentration of adsorbate at equilibrium, qe
saturated atomic force field on the surface of the adsorbent. Once the
(mg g−1) is the adsorption capacity at equilibrium, KF (L g−1) is the
surface is covered by a layer of adsorbate molecules, the force field will
adsorption constant related to adsorption capacity, and n is the ad-
be saturated and the adsorption will not occur, so the adsorption is
sorption constant related to surface inhomogeneity.
monolayer adsorption. The linear Langmuir adsorption isotherm
Temkin adsorption isotherm model discussed the interaction be-
equation is as follows:
tween adsorbent and adsorbate, assuming that the heat of adsorption
decreases with the degree of adsorption process.

52
C. Jiang, et al. Composites Part B 169 (2019) 45–54

Table 3 The correlation coefficient R2 is above 0.99, which is better than the
Adsorption isotherm parameters. correlation coefficient of other isotherm models. This shows that the
Parameters Cu2+ Co2+ Ni2+ Pb2+ Cd2+ process of adsorption of heavy metal ions by GL/CS is mainly in ac-
cordance with the chemical adsorption of the single molecular layer of
Langmuir Langmuir. Combined with the parameter 1/n in the Freundlich model,
qm,L (mg g−1) 469.5 332.2 287.4 552.5 329.0
it can be inferred that the adsorption process is more likely to occur.
KL (L mg−1) 0.202 0.028 0.013 0.031 0.027
R2 0.993 0.998 0.992 0.998 0.997
Based on the fitting results of the thermodynamic and kinetic models, it
Freundlich is concluded that the whole adsorption process is mainly endothermic
KF (L g−1) 251.1 144.1 100.5 301.6 209.2 chemical adsorption with single molecular layer and spontaneous re-
1/n 0.081 0.121 0.130 0.083 0.058 action. (The other three isotherm fitting curves can be found in Figs. S3,
R2 0.831 0.997 0.943 0.956 0.734
S4, and S5 of SI).
Temkin
A (mg L−1) 947.5 19.32 4.442 1078 94792
B 31.97 33.44 31.43 38.46 17.03 4. Conclusion
R2 0.798 0.992 0.913 0.938 0.723
D-R
The polysaccharide-based hydrogel GL/CS with excellent adsorp-
qm,D-R (mg g−1) 417.1 296.3 246.1 507.0 301.4
β(mol2 KJ−2) × 10−5 3.330 12.01 19.72 1.943 4.179
tion performance was successfully prepared by a high-efficiency, en-
R2 0.383 0.670 0.527 0.640 0.223 vironmentally friendly, inexpensive, and easy-to-use ultrasonic-assisted
polymerization method. It was used to adsorb five heavy metal ions,
When the amount of adsorbent is 0.01 g, the GL/CS hydrogel exhibits excellent such as Cu2+, Co2+, Ni2+, Pb2+ and Cd2+. The adsorption experiments
adsorption performance in a neutral solution at 20 °C, and its adsorption ca- showed that GL/CS had the best adsorption performance under neutral
pacity for Cu2+, Co2+, Ni2+, Pb2+ and Cd2+ is 342 mg g−1, 232 mg g−1, conditions. The kinetics, thermodynamics and adsorption isotherms of
184 mg g−1, 395 mg g−1 and 269 mg g−1, respectively. As shown in Table 4,
the hydrogel adsorption process indicate that the adsorption of the five
GL/CS hydrogels have outstanding adsorption properties for heavy metal ions
ions conforms to the pseudo-second-order kinetic model and Langmuir
compared with other adsorbents, taking Cu2+ adsorption as an example.
isotherm model, which proves that the adsorption process is a sponta-
neous endothermic chemical monolayer adsorption. In addition, GL/CS
Table 4
hydrogel also has good water absorption performance, and the water
Comparison of adsorption capacities of several adsorbents for Cu2+.
adsorption capacity is 1566 g g−1, indicating that GL/CS also has a
Adsorbent Adsorption capacity(mg g−1) References good development prospect in water absorption.
PE-PD/GO 87 [4]
BAS 18 [6] Acknowledgments
M-CS-AnGS 83 [7]
Cellulosic biopolymer 76 [10] We gratefully acknowledge the Natural Science Foundation of
Claymineral 43 [14]
Jiangsu Province (BK20131249), the Senior Personnel Scientific
NIPAM-co-AA 108 [17]
HMO-P(HMAm/HEA) 54 [18] Research Foundation of Jiangsu University (15JDG084), Natural
SBM 64 [23] Science Fund Project of Colleges in Jiangsu Province(16KJB430008)
CCS 299 [24] and the College Students Innovative Practice Fund of Jiangsu University
Fe3O4-SC 73 [26] Industrial Center (ZXJG2018114) for financial support of this research.
nZVMn 181 [30]
GL/CS 342 This study
Appendix A. Supplementary data

qe = BInA + BInCe (9) Supplementary data to this article can be found online at https://
doi.org/10.1016/j.compositesb.2019.03.082.
where, Ce (mg L−1) is the concentration of adsorbate at equilibrium, qe
(mg g−1) is the capacity of adsorbent at equilibrium, A (mg L−1) is the
References
equilibrium constant related to binding energy, and B is the equilibrium
constant related to adsorption heat.
[1] Coukouma AE, Asher SA. Increased volume responsiveness of macroporous hydro-
Dubinin-Radushkevich (D-R) isotherm model is based on Polanyi gels. Sensor Actuator B Chem 2018;255:2900–3.
potential energy theory. It is pointed out that the adsorption space on [2] Fu L, Wang A, Lyv F, Lai G, Zhang H, Yu J, Lin CT, Yu A, Su W. Electrochemical
the adsorbent surface is constant, and the adsorption potential is in- antioxidant screening based on a chitosan hydrogel. Bioelectrochemistry
2018;121:7–10.
dependent of temperature. [3] Rajaee S, Salehi MB, Moghadam AM, Sefti MV, Mohammadi S. Nanocomposite
hydrogels adsorption: experimental investigation and performance on sandstone
Inqe = −βε 2 + Inqm, D − R (10) core. J Pet Sci Eng 2017;159:934–41.
−1 [4] Dong Z, Zhang F, Wang D, Liu X, Jin J. Polydopamine-mediated surface-functio-
where, qe (mg g ) is the adsorption capacity of the adsorbent at nalization of graphene oxide for heavy metal ions removal. J Solid State Chem
equilibrium, qm,D-R (mg g−1) is the theoretical maximum adsorption 2015;224:88–93.
capacity, β (mol2 KJ−2) is the adsorption constant related to the ad- [5] Liu X, Lee DJ. Thermodynamic parameters for adsorption equilibrium of heavy
metals and dyes from wastewaters. Bioresour Technol 2014;160:24–31.
sorption energy, and Ɛ is the adsorption potential. [6] Maaloula N, Oulegob P, Rendueles M, Ghorbal A, Díaz M. Novel biosorbents from
almond shells: characterization and adsorption properties modeling for Cu(II) ions
Ce + 1 ⎞
Among them, ε = RTIn ⎛⎜ ⎟
from aqueous solutions. J Environ Chem Eng 2017;5:2944–54.
Ce ⎠ [7] Liu T, Han X, Wang Y, Yan L, Du B, Wei Q, Wei D. Magnetic chitosan/anaerobic
⎝ (11)
granular sludge composite: synthesis, characterization and application in heavy
−1 metal ions removal. J Colloid Interface Sci 2017;508:405–14.
Where, Ce (mg L ) is the concentration of adsorbate at equilibrium, R
[8] Wang R, Wang W, Ren H, Chae J. Detection of copper ions in drinking water using
(J K−1 mol−1) is the universal constant of gas, and T (K) is the tem- the competitive adsorption of proteins. Biosens Bioelectron 2014;57:179–85.
perature of reaction. [9] Raval NP, Shah PU, Shah NK. Adsorptive removal of nickel(II) ions from aqueous
Table 3 is the process of GL/CS adsorption of the five kinds of ions, environment: a review. J Environ Manag 2016;179:1–20.
[10] Singha AS, Guleria A. Chemical modification of cellulosic biopolymer and its use in
and the corresponding isotherm model parameters are obtained by removal of heavy metal ions from wastewater. Int J Biol Macromol
fitting. It is clear from the table that the process of GL/CS adsorption of 2014;67:409–17.
heavy metal ions is more consistent with the linear fitting of Langmuir. [11] Cui Y, Ge Q, Liu XY, Chung TS. Novel forward osmosis process to effectively remove

53
C. Jiang, et al. Composites Part B 169 (2019) 45–54

heavy metal ions. J Membr Sci 2014;467:188–94. [30] Dada AO, Adekola FA, Odebunmi EO. Liquid phase scavenging of Cd (II) and Cu (II)
[12] Šæiban M, Klašnja M, Škrbiæ B. Adsorption of copper ions from water by modified ions onto novel nanoscale zerovalent manganese (nZVMn): equilibrium, kinetic and
agricultural by-products. Desalination 2008;229:170–80. thermodynamic studies. Environ Nanotechnol Monitoring Manage 2017;8:63–72.
[13] Zeng G, Wan J, Huang D, Hua L, Huang C, Cheng M, Xue W, Gong X, Wang R, Jiang [31] Vázquez G, Freire MS, González-Alvarez J, Antorrena G. Equilibrium and kinetic
D. Precipitation, adsorption and rhizosphere effect: the mechanisms for Phosphate- modelling of the adsorption of Cd2+ ions onto chestnut shell. Desalination
induced Pb immobilization in soils—a review. J Hazard Mater 2017;339:354–67. 2009;249:855–60.
[14] El-Bayaa AA, Badawy NA, AlKhalik EA. Effect of ionic strength on the adsorption of [32] Taurino R, Sciancalepore C, Collini L, Bondi M, Bondioli F. Functionalization of PVC
copper and chromium ions by vermiculite pure clay mineral. J Hazard Mater by chitosan addition: compound stability and tensile properties. Compos B Eng
2009;170:1204–9. 2018;149:240–7.
[15] Han YL, Lo YC, Cheng CL, Yu WJ, Nagarajan D, Liu CH, Li YH, Chang JS. Calcium [33] Nešovića K, Janković A, Kojić V, Vukašinović-Sekulić M, Perić-Grujića A, Rhee KY,
ion adsorption with extracellular proteins of thermophilic bacteria isolated from Mišković-Stanković V. Silver/poly(vinyl alcohol)/chitosan/graphene hydrogels –
geothermal sites—a feasibility study. Biochem Eng J 2017;117:48–56. synthesis, biological and physicochemical properties and silver release kinetics.
[16] Keshtkar AR, Tabatabaeefar A, Vaneghi AS, Moosavian MA. Electrospun poly- Compos B Eng 2018;154:175–85.
vinylpyrrolidone/silica/3-aminopropyltriethoxysilane composite nanofiber ad- [34] González PG, Pliego-Cuervo YB. Adsorption of Cd(II), Hg(II) and Zn(II) from aqu-
sorbent: preparation, characterization and its application for heavy metal ions re- eous solution using mesoporous activated carbon produced from Bambusa vulgaris
moval from aqueous solution. J Environ Chem Eng 2016;4:1248–58. striata. Chem Eng Res Des 2014;92:2715–24.
[17] Mizoguchi K, Ida J, Matsuyama T, Yamamoto H. Straight-chained thermo-re- [35] Abdolali A, Ngo HH, Guo W, Lu S, Chen SS, Nguyen NC, Zhang X, Wang J, Wu Y. A
sponsive polymer with high chelating group content for heavy metal ion recovery. breakthrough biosorbent in removing heavy metals: equilibrium, kinetic, thermo-
Separ Purif Technol 2010;75:69–75. dynamic and mechanism analyses in a lab-scale study. Sci Total Environ
[18] Zhu Q, Li Z. Hydrogel-supported nanosized hydrous manganese dioxide: synthesis, 2016;542:603–11.
characterization, and adsorption behavior study for Pb2+, Cu2+, Cd2+ and Ni2+ [36] Gautam RK, Mudhoo A, Lofrano G, Chattopadhyaya MC. Biomass-derived biosor-
removal from water. Chem Eng J 2015;281:69–80. bents for metal ions sequestration: adsorbent modification and activation methods
[19] Liu H, Wang C, Liu J, Wang B, Sun H. Competitive adsorption of Cd(II), Zn(II) and and adsorbent regeneration. J Environ Chem Eng 2014;2:239–59.
Ni(II) from their binary and ternary acidic systems using tourmaline. J Environ [37] Nur T, Loganathan P, Kandasamy J, Vigneswaran S. Removal of strontium from
Manag 2013;128:727–34. aqueous solutions and synthetic seawater using resorcinol formaldehyde poly-
[20] Samuel MS, Subramaniyan V, Bhattacharya J, Parthiban C, Chand S, Singh NDP. A condensate resin. Desalination 2017;420:283–91.
GO-CS@MOF [Zn(BDC)(DMF)] material for the adsorption of chromium (VI) ions [38] Kesenci K, Say R, Denizli A. Removal of heavy metal ions from water by using poly
from aqueous solution. Compos B Eng 2018;152:116–25. (ethyleneglycol dimethacrylate-co-acrylamide) beads. Eur Polym J
[21] Zheng L, Zhu C, Dang Z, Zhang H, Yi X, Liu C. Preparation of cellulose derived from 2002;38:1443–8.
corn stalk and its application for cadmium ion adsorption from aqueous solution. [39] Xie H, Zhao Z, An S, Jiang Y. The influence of the surface properties of silicon–-
Carbohydr Polym 2012;90:1008–15. fluorine hydrogel on protein adsorption. Colloids Surf, B 2015;136:1113–9.
[22] Sun JH, Chen Y, Yu HQ, Yan LG, Du B, Pei ZG. Removal of Cu2+, Cd2+ and Pb2+ [40] Chethan PD, Vishalakshi B. Synthesis of ethylenediamine modified chitosan mi-
from aqueous solutions by magnetic alginate microsphere based on Fe3O4/MgAl- crospheres for removal of divalent and hexavalent ions. Int J Biol Macromol
layered double hydroxide. J Colloid Interface Sci 2018;532:474–84. 2015;75:179–85.
[23] Witek-Krowiak A, Reddy DHK. Removal of microelemental Cr(III) and Cu(II) by [41] Wang Y, Zheng Y, He W, He W, Wang C, Sun Y, Qiao K, Wang XY, Gao L.
using soybean meal waste-Unusual isotherms and insights of binding mechanism. Preparation of a novel sodium alginate/polyvinyl formal composite with a double
Bio Technol 2013;127:350–7. crosslinking interpenetrating network for multifunctional biomedical application.
[24] Yuan S, Zhang P, Yang Z, Lv L, Tang S, Liang B. Successive grafting of poly(hy- Compos B Eng 2017;114:149–62.
droxyethyl methacrylate) brushes and melamine onto chitosan microspheres for [42] Etaati A, Pather S, Fang ZP, Wang H. The study of fibre/matrix bond strength in
effective Cu(II) uptake. Int J Biol Macromol 2018;109:287–302. short hemp polypropylene composites from dynamic mechanical analysis. Compos
[25] Yin N, Wang K, Xia YA, Li Z. Novel melamine modified metal-organic frameworks B Eng 2014;62:19–28.
for remarkably high removal of heavy metal Pb (II). Desalination 2018;430:120–7. [43] Wang XH, Hou HQ, Li YJ, Wang YY, Hao C, Ge CW. A novel semi-IPN hydrogel:
[26] Wang YY, Wang XH, Ding YM, Zhou ZL, Hao C, Zhou SS. Novel sodium lig- preparation, swelling properties and adsorption studies of Co (II). J Ind Eng Chem
nosulphonate assisted synthesis of well dispersed Fe3O4 microspheres for efficient 2016;41:82–90.
adsorption of copper (II). Powder Technol 2018;325:597–605. [44] Fosso-Kankeu E, Mittal H, Waanders F, Ray SS. Thermodynamic properties and
[27] Albishri HM, Marwani HM. Chemically modified activated carbon with tris(hy- adsorption behaviour of hydrogel nanocomposites for cadmium removal from mine
droxymethyl)aminomethane for selective adsorption and determination of gold in effluents. J Ind Eng Chem 2017;48:151–61.
water samples. Arab J Chem 2016;9:S252–8. [45] Wang XH, Wang YY, He SF, Hou HQ, Hao C. Ultrasonic-assisted synthesis of su-
[28] Yang J, Li Z, Zhu H. Adsorption and photocatalytic degradation of sulfamethoxazole perabsorbent hydrogels based on sodium lignosulfonate and their adsorption
by a novel composite hydrogel with visible light irradiation. Appl Catal B Environ properties for Ni2+. Ultrason Sonochem 2018;40:221–9.
2017;217:603–14. [46] Mallakpour S, Motirasoul F. Ultrasonication synthesis of PVA/PVP/α-MnO2-stearic
[29] Nguyen TAH, Ngo HH, Guo WS, Zhang J, Liang S, Yue QY, Li Q, Nguyen TV. acid blend nanocomposites for adsorbing Cd II ion Ultrason. Sonochem
Applicability of agricultural waste and by-products for adsorptive removal of heavy 2018;40:410–8.
metals from wastewater. Bioresour Technol 2013;148:574–85.

54