International Journal of Biological Macromolecules 127 (2019) 511–519

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International Journal of Biological Macromolecules

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

Superadsorbent hydrogel based on lignin and montmorillonite for Cu(II)

ions removal from aqueous solution
Xiao-Feng Sun a,⁎, Yiwei Hao a, Yingyue Cao b, Qihang Zeng a
a
Department of Applied Chemistry, College of Science, Northwestern Polytechnical University, Xi'an 710129, China
b
KunLun College, QingHai University, XiNin 810016, China

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

Article history: Superadsorbent hydrogel was prepared from lignin and montmorillonite for Cu(II) ions removal, and the chem-
Received 26 October 2018 ical structure and morphology of the hydrogel were characterized by FT-IR, XRD, SEM and XPS. The swelling ki-
Received in revised form 28 December 2018 netics of the prepared hydrogel was investigated, and the result showed that the swelling process fit the Schott
Accepted 11 January 2019
second-order dynamic equation. The influences of pH, contact time, Na+ concentration, and initial Cu(II) ion con-
Available online 18 January 2019
centration on adsorption were studied, and the maximum adsorption value was 1.17 mmol/g, and the adsorption
Keywords:
was rapid during the initial 5 h period, and copper ions adsorption on the superadsorbent hydrogel is a favorable
Lignin process. The results also indicated that the adsorption kinetics was in accordance with the pseudo-second-order
Superadsorbent kinetic model and the adsorption isotherm conformed to the Freundlich model. FT-IR and XPS analysis revealed
Montmorillonite that the adsorption behavior was mainly due to ion exchange. The desorption ratios of copper ions from the
Cu(II) ion superadsorbent were N0.8, and the regeneration efficiency was N80% after five cycles reuse, and the results
Adsorption show the excellent desorption performance and reusability of the prepared hydrogel.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction
Biomaterials based on natural polymers such as lignin and cellulose
from biomass have gained considerable interest for practical applica-
tions due to their biocompatibility and biodegradation. Cellulosic bio-
polymer and agricultural waste biomass have been chemically
modified for removal of toxic heavy metal ions from aqueous solution
[1–3]. Lignin, a major component of lignocellulose, is the largest source
of aromatic building blocks on the earth and has great potential to serve
as starting material for the production of bio-based products [4,5]. Lig-
nin is frequent available in huge amount as byproduct of industrial
waste, but it has antioxidant, antimicrobial, biodegradable, and CO2
neutral advantages [6]. Lignin has been studied as main bio-based alter-
native for the production of carbon fiber precursor [7–9]. Recently
lignin-based hydrogels have attracted great attention in academia,
showing excellent performance for removal of various pollutants from
water [6,10]. The adsorption properties of lignin-based hydrogels can
further be improved by using a combination of nanomaterials and lignin
that results in promising hydrogel nanocomposites [10].
The application of lignin polymer in hydrogels can not only obtain
hydrogels with specific properties, but also achieve high-value utiliza-
tion of lignin. Previous studies pointed out that the addition of lignin
into the hydrogel is beneficial to improve the strength of the hydrogel,
⁎ Corresponding author.
E-mail address: xf001sn@nwpu.edu.cn (X.-F. Sun).
realizing the slow release of hydrophilic drugs [10,11]. The lignin from
plant fibers is nontoxic and biodegradable and does not affect the bio-
compatibility of materials [12,13]. Therefore, hydrogels based on lignin
are expected to be used for controlled drug release and medical polymer
materials. Lignin contains lots of phenolic hydroxyl and carboxyl groups
which can have electrostatic interactions with heavy metal ions and cat-
ionic dyes [14]. As a consequence, hydrogels based on lignin were also
be used in the treatment of wastewater containing heavy metals and
dyes [10].
Cu(II) ion is a common heavy metal ion in wastewater, and improper
disposal of heavy metal ion may cause serious environmental pollutions
[15]. The conventional methods in removing and recycling metal ions
from aqueous solutions include adsorption [14], ion exchange [16],
chemical precipitation [17], reverse osmosis [18], and so on. In these
methods, adsorption was considered to be a cost-effective method in
wastewater treatment [15,17]. Hydrogels have been proved as an excel-
lent adsorbent for heavy metal ions removal [10,15]. However, there are
many drawbacks in conventional hydrogels, such as low mechanical
strength, poor biocompatibility and bad biodegradability [19,20].
Lignin-based hydrogels could overcome the above drawbacks, while
retaining the good adsorption performance of hydrogels.
In order to improve adsorption and mechanical performances,
montmorillonite (MMT) was introduced in lignin nanocomposites
[21]. MMT, a layered aluminium silicate composed of an aluminium oc-
tahedral sheet and two silica tetrahedral sheets [22], has been widely
used to improve the properties of hydrogels. MMT also has good

https://doi.org/10.1016/j.ijbiomac.2019.01.058
0141-8130/© 2019 Elsevier B.V. All rights reserved.
512 X.-F. Sun et al. / International Journal of Biological Macromolecules 127 (2019) 511–519
biocompatibility without toxic side effects [23]. Therefore, MMT cannot
change the environmental friendliness of lignin-based hydrogels, but it
can improve the properties of lignin-based hydrogels.
In this paper, a superabsorbent hydrogel was prepared using lignin
and MMT. The structure and morphology of the hydrogel was character-
ized by FT-IR, SEM, XPS, and XRD, and its swelling property was studied.
The influences of pH, contact time, Na+, and initial copper ions concen-
tration on Cu(II) ion adsorption were studied. The adsorption kinetics
and adsorption isotherms of Cu(II) ions on the prepared hydrogel
were also discussed. Desorption and reusability studies of the prepared
adsorbent were conducted.
2. Experimental section
2.1. Materials
Lignin was isolated from wheat straw according to our previous
method [24], and it had a weight-average (Mw), 2820 g mol−1 and
number-average (Mn), 1740 g mol−1 molecular weight. Acrylic acid
was purchased from Tianjin Dongli District Tianda Chemical Reagent
Company (China). Potassium persulfate and anhydrous sodium sulfite
were purchased from Tianjin Fuchen Chemical Reagent Company
(China). N,N-methylene bisacrylamide (BIS) and ditiocarb sodium
were purchased from J&K Chemical LTD. Montmorillonite (MMT) and
copper sulfate pentahydrate were purchased from China National Med-
icines Corporation LTD. All reagents used were of analytical grade.
2.2. Preparation of composite hydrogel
0.5 g of lignin and 0.2 g of MMT were placed in 50 mL of distilled
water and stirred at 60 °C in a water bath. The redox initiator K2S2O8-
Na2SO3 (0.06 g) was added into the solution. After 5 min, the acrylic
acid (2 mL) and the crosslinking agent, N,N′-methylene-bis-acrylamide
(0.05 g), were added into the solution and stirred vigorously. After hy-
drogel was formed, the hydrogel was cut into uniform size of pieces
and then immersed in distilled water at room temperature for 48 h,
and the distilled water was changed regularly to remove any unreacted
reactants. Finally, the composite hydrogel was pre-frozen at −20 °C and
then freeze-dried at −50 °C for 48 h.
2.3. Characterizations of composite hydrogel
The dried composite hydrogel samples were analyzed using an FTIR
spectrometer (Nicolet 510, USA) within the frequency range
4000–400 cm−1 after the samples were milled, mixed with KBr, and
laminated.
XRD patterns were obtained by X-ray diffraction meter (Philips,
PW3040), and a conventional copper target X-ray tube set to 36 kV
and 20 mA. The X-ray source was Cu Kα radiation (λ = 1.54056 A).
Data were collected from 2θ of 5° to 20° with a step width of 0.02°.
The surface morphology of prepared hydrogel was observed using
SEM (VEGA 3 LMH, TESCAN, Czech). The samples that swollen to equi-
librium sate were pre-frozen at −20 °C for 5 h and then freeze-dried
under vacuum at −50 °C for 24 h to completely remove the water in
the network of hydrogel. The freeze-dried samples sputtered with
gold were then observed by SEM at an accelerating voltage of 10 kV.
The hydrogel sample before and after adsorption of Cu(II) ions were
analyzed using XPS (Axis Ultra, Kratos Analytical Ltd., UK) with an Al Kα
X-ray source (1486.71 eV of photons). All binding energies were refer-
enced to the neutral C 1s peak at 284.6 eV to compensate for surface
charging effects.
2.4. Swelling test
A known mass of the hydrogel sample was immersed in 100 mL of
distilled water at room temperature. After certain time intervals, the
hydrogel was taken out and weighed after the removal of excess
water on the surface. All tests on the swelling ratios of the samples
were conducted in triplicate. The swelling ratio at time t was calculated
with the following Eq. (1):
wt −wd
St ðg=gÞ ¼ ð1Þ
wd
where Wt (g) is the weight of the swollen hydrogel at time t (min) and
Wd (g) is the weight of the dry hydrogel.
2.5. Determinations of Cu(II) ions and other metal ions
In this work, the exact amount of copper sulfate solution and
2.00 mL EDTA solution (2%, m/v) were moved into 10 mL colorimetric
tube. Then, 1.50 mL DDTC solution (2%, m/v) was added to form com-
plex with Cu(II) ions. The complex solution was placed for 5 min and
measured the absorbance at 450 nm by UV–Visible spectrophotometer
(752B, Prius, Tianjin, China) [25]. The blank absorbance of reagents was
corrected before each determination. In the range of 10–70 mg/L, the
linear equation of standard curve is A = 0.00802ρ + 0.00700 (R2 =
0.9992, n = 7), where A is the absorbance and ρ is the concentration
of copper sulfate. The concentrations of Cd(II) and Pb(II) ions solutions
were determined using acetylene air flame Atomic Absorption Spec-
trometer (Beijing PERSEE TAS-990).
2.6. Batch adsorption experiment
200 mg of hydrogel sample was soaked in 100 mL of copper sulfate
solution under different conditions such as various pH, contact time,
and ion concentrations. The remaining copper ions concentration in
the solution was subsequently analyzed using above method. The
amount of adsorbed Cu(II) ions per unit mass of hydrogel sample, q
(mg/g), was calculated by using Eq. (2):
ðC o −C t ÞV
q¼ ð2Þ
m
where Co and Ct (mg/L) are the concentrations of copper ions before and
after adsorption, respectively; V (L) is the volume of copper ion solution,
and m (g) is the weight of the dry hydrogel.
2.7. Desorption and reusability test
For the desorption experiment, the used hydrogel with adsorbed Cu
(II) ions was placed in certain concentration NaCl solution and stirred
for 24 h at 298 K. Desorption ratio (Ds) was expressed using the follow-
ing Eq. (3):
Cd
Ds ¼ ð3Þ
C 0 −C e
where C0 is the initial copper ion concentration (mg/L); Ce is the equilib-
rium copper ion concentration (mg/L); and Cd is the equilibrium copper
ion concentration in elution medium (mg/L). All desorption solutions
were 100 mL.
The regenerated adsorbent was reused, and five cycles of consecu-
tive adsorption-desorption-adsorption were carried out to validate the
reusability of the prepared hydrogel. The regeneration efficiency (ER,
%) was determined by comparing the adsorption capacity of fresh and
regenerated adsorbents using the following Eq. (4):
qR
ER ¼  100% ð4Þ
qF
where qF and qR are the adsorbed Cu(II) ions amount (mg/g) of fresh
and regenerated adsorbents.
 X.-F. Sun et al. / International Journal of Biological Macromolecules 127 (2019) 511–519 513

3. Results and discussion
3.1. Synthesis and FT-IR analysis of composite hydrogel
The proposed mechanism for the synthesis of the composite hydro-
gel based on lignin and MMT is shown in Fig. 1. Wheat straw lignin with
low molecular weight-average (Mw, 2820 g mol−1), possessing a char-
acteristic alkali solubility, contained some aliphatic and phenolic hy-
droxyl groups as well as carboxylic groups that serve as active sites.
Firstly, the redox initiator system (NH4)2S2O8-Na2SO3 captured hydro-
gen atoms from the hydroxyl groups of lignin followed by the genera-
tions of free radicals as active sites, and poly(acrylic acid) (PAAc) was
grafted to lignin. The FT-IR spectra of wheat straw lignin and lignin-g-
PAAc are shown in Fig. 2, and the absorption peak of the O\\H
stretching in lignin-g-PAAc became weak in comparison with the spec-
trum of lignin biopolymer because of the grafting reactions on the hy-
droxyl groups of lignin, and the absorption intensity of the C_O
stretching vibration in the carboxyl groups increased, and previous
studies had also proved the successful grafting of the monomer on lig-
nin [26,27]. After the cross-linker BIS and MMT were added, a three-
dimensional network structure hydrogel, lignin-g-PAAc/MMT compos-
ite hydrogel, was formed because BIS could react with two active sites
to form the hydrogel network and MMT could act as a physical cross-
linker. FT-IR spectroscopy was applied for studying the preparation
mechanism of the lignin-g-PAAc/MMT composite hydrogel.
The FT-IR spectra of MMT, lignin, PAAc, lignin-g-PAAc, and lignin-g-
PAAc/MMT composite hydrogel are shown in Fig. 2. The two peaks at
3630 cm−1 and 3421 cm−1 in MMT spectrum were originated from
the O\\H stretching of Al\\OH and absorbed interlayer water, respec-
tively [28]. The absorption peak at 1638 cm−1 in the spectra of MMT
and lignin-g-PAAc/MMT composite hydrogel was attributed to the de-
formation vibration of the hydroxyl groups, and the two absorption
peaks at 914 and 798 cm−1 are assigned to Al\\Al\\OH and Si\\O\\Al
bending vibrations of MMT, respectively [28]. The broad and strong ab-
sorption at 3421 cm−1 that originated from the O\\H stretching of hy-
droxyl groups in the spectra of lignin and PAAc became weak in
lignin-g-PAAc spectrum and changed into two peaks at 3610 cm−1
and 3360 cm−1 resulting from the graft copolymerization of acrylic
acid onto lignin. The strong absorption peak at 1720 cm−1 in the spectra
of lignin-g-PAAc and lignin-g-PAAc/MMT composite hydrogel was due
to the C_O stretching vibration in the carboxyl groups [29]. The peaks
observed at 2927 cm−1 were assigned to the stretching band of C\\H,
and the peaks observed at 1411 cm−1 and 1115 cm−1 were assigned
to the stretching band of aromatic nucleus and C\\O or C\\O\\C
bonds, respectively [13]. Therefore, it could be concluded that the
lignin-g-PAAc/MMT composite hydrogel was synthesized successfully.
3.2. XRD analysis of composite hydrogel
The XRD pattern profiles of the dried hydrogel and MMT powder are
shown in Fig. 3. The peak at 6.02° of 2θ was the characteristic diffraction
peak of MMT. According to Bragg equation, lamellar spacing of MMT is
1.467 nm, showing that the MMT has a typical structure of nano-
materials [30]. In comparison with MMT, the peak at 6.02° disappeared
in the XRD pattern of the lignin-g-PAAc/MMT composite hydrogel, indi-
cating the exfoliations of laminated layers of MMT in the hydrogel, and

HO CH2 HO CH2
HC O HC O
HC OH HC OH
H2 H H2
Initiator system O C C C CH2
n

+ COOH COOH COOH

H2 H H2
OH O C C C CH2
n
Lignin COOH COOH

COOH COOH COOH COOH

H2 H H H
O C C C C C C C CH2
O O H H H
O O O
N N HN
H H HN
HN HN
montmorillonite O
O O
H2 H H H
O C C C C CH C C CH 2
H H

COOH COOH COOH COOH

Polyacrylic acid

Crosslinking point O O
N N
lignin chain H H

montmorillonite

Fig. 1. The preparation diagram of composite hydrogel.

514 X.-F. Sun et al. / International Journal of Biological Macromolecules 127 (2019) 511–519

the adsorption properties. The effect of time on the swelling ratio of

the hydrogel is shown in Fig. 4. To explain the swelling mechanism of
the prepared hydrogel, the two empirical equations, Fickian diffusion
equation [31] and Schott second-order dynamic equation [32], were
used to analyze the experimental data as follows:

St
Fickian diffusion equation : In ¼ Ink þ nInt ð5Þ
S∞

t
Schott second‐order dynamic equation : ¼ A þ Bt ð6Þ
St

where St and S∞ are the absolute cumulative water penetrated into the
network at time t, and infinite time, respectively; k1 is a constant indicat-
ing the structural and geometric properties of the matrix, and n is the dif-
fusion exponent that indicates the transport mechanism of water taken
up. A = 1 / k2, k2 is the initial swelling rate of the hydrogel; B = 1 / Seq,
Seq is the theoretical equilibrium swelling ratio of the hydrogel.
The R2 values of the Fickian fitting curve and Schott second-order dy-
namic fitting curve (Fig. S1) were 0.9749 and 0.9983, respectively, indi-
cating that the swelling process better fitted the Schott second-order
dynamic equation. This is due to the Fickian diffusion equation only ap-
plies to the initial swelling process, and the Fickian diffusion belongs to
the first-order dynamic equation, which assumes that the diffusion coef-
ficient and film thickness in the swelling process do not change [33,34].

3.4. Effects of pH and contact time and adsorption kinetics study

The pH value of aqueous solution is an important factor for metal

Fig. 2. IR spectra of MMT, PAAc, lignin, lignin-g-PAAc, lignin-g-PAAc/MMT hydrogel before
adsorption (e) and after adsorption (f).
the delaminated layers of MMT were individually dispersed in a contin-
uous polymer matrix.
3.3. Analysis of swelling kinetics
The swelling kinetics of hydrogels is important for their application
in heavy metal adsorption because the swelling ratio directly affects
Intensity
ions removal, and metal ions are generally soluble in acidic solution
but precipitate in alkaline condition. The effect of pH on copper ion re-
moval was investigated over a range from pH 1 to 5 with a contact
time of 8 h at 303 K. The obtained results are shown in Fig. 5(a), and it
is evident that the adsorption amount of Cu(II) ions increased with in-
creasing pH value from 1 to 5. When the pH value increased to 5, the ad-
sorption amount of Cu(II) ions on the lignin-g-PAAc/MMT composite
hydrogel was 64.8 mg/g; however, the adsorption amount of Cu(II)
ions was not detected at pH 1, and it was only 2.2 mg/g at pH 2. At pH
b3.0, the active sites of the hydrogel became more positively charged
because of presence of enormous H+ ions, and thus metal ions with pos-
itive charge had difficulties to approach the binding sites due to electro-
static repulsion [1]. In addition, because copper hydroxide chemical
precipitation occurs in alkaline condition, adsorption behavior did not
work.

(a)

(b)

6 8 10 12 14 16

2©(degree)

Fig. 3. XRD patterns: (a) montmorillonite; (b) the prepared hydrogel. Fig. 4. Effect of time on the swelling ratio of the hydrogel.
 X.-F. Sun et al. / International Journal of Biological Macromolecules 127 (2019) 511–519 515

Fig. 5. The influence factors of adsorption: (a) pH; (b) contact time; (c) Na+ ion concentration; (d) initial copper ion concentration.

The effect of contact time on copper ion adsorption using the pre-
pared composite hydrogel is presented in Fig. 5(b). It was observed
that the adsorption amount of copper ions on the lignin-g-PAAc/MMT
composite hydrogel increased from 17.8 mg/g to 57.8 mg/g as the con-
tact time increased from 0.25 h to 12 h at pH 5.0 with copper ions con-
centration of 400 mg/L, and the uptake of copper ions was rapid during
the initial 5 h period, and then it proceeded at a slower rate and
sustained stable. The reason can be explained by the fact that the initial
adsorption occurred between the adsorption sites of the hydrogel sur-
face and the copper ions and the continuous adsorption only appeared
in the internal adsorption sites of the hydrogel, leading to a slow growth
rate of the adsorption amount.
In order to study the adsorption process of copper ions on the lignin-
g-PAAc/MMT composite hydrogel, three adsorption kinetic models
were used to analyze the obtained experimental data as follows [35]:
k1
The pseudo‐first‐order model : lgðqe −qt Þ ¼ lgqe − t ð7Þ
2:303
t 1 1
The pseudo‐second‐order model : ¼ þ t
qt k2 qe 2 qe
1 1
Elovich equation model : qt ¼ ln ðabÞ þ ln t
b b
(h), and k1, k2, a and b are the rate constants of the corresponding
model.
Fig. S2 displays the fitted plots of the pseudo-first-order model,
pseudo-second-order model, intraparticle-diffusion model, and Elovich
equation, and Table 1 lists the kinetics factors for copper ions adsorption
on the prepared hydrogel. It is clear that the adsorption process can be
described using the pseudo-second-order kinetic model after compar-
ing the values of correlation coefficient R2 of the three kinetic models.
The model indicated that the adsorption process consisted of the ad-
sorption on the surface of the hydrogel, the diffusion of copper ions
from the surface into the internal of the hydrogel and the final adsorp-
tion equilibrium process, which is consistent with the experimental
results.
3.5. Effects of Na+ ion and initial copper ion concentrations and adsorption
isotherm study
Other ions or impurities in wastewater may influence the adsorption
of copper ions on the prepared hydrogel, and Na+ ion concentration
was studied as an important parameter influencing adsorption
ð8Þ
Table 1
Kinetics parameters for copper ion adsorption.
ð9Þ
Pseudo-first-order Pseudo-second-order Elovich equation

qe k1 R2 qe k2 R2 a b R2
where qt and qe are the adsorption amount per unit mass of hydrogel at
0.6696 0.4571 0.9948 0.9846 1.1113 0.9984 3.2324 5.5862 0.9839
time t and infinite time, respectively (mmol/g); t is the adsorption time
516 X.-F. Sun et al. / International Journal of Biological Macromolecules 127 (2019) 511–519

Table 2
Isotherms parameters for copper ions adsorption.
Langmuir Freundlich Temkin
KL qmax R2 KF n R2 A B
(mmol/g)
0.0164 1.1708 0.9824 0.1357 2.8632 0.9975 −0.2944 0.2195 0.9536
behavior. It can be seen from Fig. 5(c) that adsorption amount de-
creased rapidly when increasing the Na+ ions concentrations of solu-
tions, and this was due to the competition between enormous Na+
ions and Cu(II) ions for the same active adsorption site in the composite
hydrogel. Thus, the presences of other ions or impurities in wastewater
can cause a decrease in the removal of particular metal ion in compari-
son with clean water.
The effect of initial copper ion concentration on the adsorption using
the superadsorbent hydrogel is presented in Fig. 5(d). It can be observed
that the adsorption amount of copper ions on the hydrogel increased
from 21.0 mg/g to 64.2 mg/g as the initial concentration of copper ion
solution increased from 80 mg/L to 560 mg/L at pH 5.0. Higher initial
concentration led to more active site combining with copper ions in
comparison with lower initial concentration, and more concentrated
copper ion solution can accelerate the diffusion of copper ions into the
hydrogel as a result of an increase in the driving force of concentration
gradient.
To study the adsorption isotherms, three adsorption isotherm
models were used to analyze the experimental data as follows [36–38]:
Table 3 lists the maximum adsorption capacities of various lignin ad-
sorbents for Cu(II) ions removal. Compared with other lignin adsor-
bents, the lignin-g-PAAc/MMT composite hydrogel has higher
R2
maximum adsorption capacity, and the adsorption capacity of the pre-
pared hydrogel is also higher than that of cellulose-g-poly(acrylic
acid) and activated carbon prepared from hazelnut husks. The compar-
ative studies indicated that the lignin-g-PAAc/MMT composite hydrogel
is a superadsorbent for the removal of Cu(II) ions from aqueous
solution.
3.6. Adsorption performance of the prepared hydrogel for other heavy metal
ions
To study adsorption performance of the prepared hydrogel for other
heavy metal ions removal, the hydrogel sample was used to removal Cd
(II) and Pb(II) ions from aqueous solution at pH 5.0 with contact time of
12 h. It can be seen from Fig. 6 that the adsorption amounts of Cd(II) and
Pb(II) ions on the lignin-g-PAAc/MMT composite hydrogel increased
with increasing initial concentration, and this result was the same as
Cu(II) ions. The adsorption amount of Cd(II) ions was relatively higher
than that of Cu(II) ions, and the adsorption amount of Pb(II) ions was
slightly lower than that of Cu(II) ions; However, the adsorption
amounts of the three heavy metal ions were N1.1 mmol/g when the ini-
tial concentration was 400 mg/L. The obtained results indicated that the
prepared superadsorbent hydrogel can be used for other heavy metal
ions removal.
3.7. Adsorption mechanism

Ce Ce 1 To understand the adsorption mechanism of copper ions on the pre-

Langmuir equation ½36 : ¼ þ ð10Þ
qe qmax K L qmax pared composite hydrogel, FT-IR spectra of the hydrogel before and
after adsorption are presented in Fig. 2(e) and (f), respectively. The ab-
1 sorption peak at 433 cm−1 in Fig. 2(f) was probably due to the Cu\\O
Freundlich equation ½37 : lgqe ¼ lgK F þ lgC e ð11Þ
n stretching vibration, and the absorption peaks at 1720 cm−1 and
1115 cm−1, originated from carboxyl groups, became weak because of
Temkin equation ½38 : qe ¼ A þ B ln C e ð12Þ the electrostatic interactions between \\COO− anions and copper
ions. In addition, the pH value of the copper ions solution decreased
where Ce is the concentration of remained copper ion solution at ad- from 5.0 to 3.2 after adsorption. This result indicated that the adsorption
sorption equilibrium (mmol/L); qe are the adsorption amount per unit of copper ions on the hydrogel mainly depended on ion exchange.
mass of hydrogel at adsorption equilibrium (mmol/g); qmax represents Fig. 7 presents the SEM images of the composite hydrogel before and
the theoretical maximum adsorption capacity (mmol/g); KL is the Lang- after adsorption. It can be seen that the micro pores in the hydrogel after
muir constant related to the affinity of binding sites; KF is the Freundlich adsorption could be not observed and the pore wall with copper ions
constant (mmol1−n·g−1·L−n); n represents indicator of adsorption in- was thicker than the one without copper ions. This is due to the
tensity; A and B are the Temkin constants.
Fig. S3 presents the adsorption isotherm curves fitted using experi-
mental data, and the adsorption parameters and correlation coefficients
are provided in Table 2. It can be seen that the Freundlich adsorption
isothermal model could better describe the adsorption behavior after
comparing the R2 data in Table 2. This revealed that the adsorption pro-
cess conformed to the multilayer adsorption behavior [39]. The value of
n is N1, indicating that copper ions adsorption on the lignin-g-PAAc/
MMT composite hydrogel is favorable process, and the prepared hydro-
gel is a superadsorbent for copper ions removal.

Table 3
Comparative studies of the maximum adsorption capacities of various lignin adsorbents
for the removal of Cu(II) ions from aqueous solution.

Adsorbents qmax qmax pH References

(mg/g) (mmol/g)

Lignin-g-PAAc/montmorillonite hydrogel 74.35 1.17 6.5 This work

Activated carbon 6.65 0.10 5.7 [40]
Kraft lignin 5.94 0.09 4.4 [41]
Amino lignin 26.4 0.42 – [42]
Sulfonated amine lignin 48.5 0.76 6.0 [43]
Cysteine-functionalized lignin 68.9 1.08 6 [44]
Fig. 6. Comparative studies of the adsorption amounts of Cu(II), Cd(II), Pb(II) ions on the
Cellulose-g-poly(acrylic acid) 15.2 0.24 – [45]
prepared hydrogel.
 X.-F. Sun et al. / International Journal of Biological Macromolecules 127 (2019) 511–519 517

Fig. 7. SEM micrographs of the hydrogel: (a) before adsorption; (b) after adsorption.

electrostatic interactions between\\COO− anions and copper ions and
the strong adsorption of the composite hydrogel, which reduced the re-
pulsive forces in the hydrogel network.
To further study the adsorption mechanisms of copper ions on the
lignin-g-PAAc/MMT composite hydrogel, XPS was used for analyzing
the interactions between adsorbates and adsorbents [46]. Fig. 8 presents
the XPS wide scan spectra of the hydrogel before and after copper ions
adsorption. Comparing with two spectra, a peak at 932.7 eV in the
wide scan spectrum of the hydrogel after adsorption is attributed to
the Cu 2p orbital, and the peak at 932.7 eV provided the evidence of cop-
per ions being adsorbed on the hydrogel. The Cu 2p spectrum of the hy-
drogel after adsorption is also presented in Fig. 8(c). There are three BE
peaks in the Cu 2p spectrum, which are due to copper ions bindings
with the carboxyl groups and MMT and the sulfur‑oxygen bond of cop-
per sulfate. This result confirmed that the chemisorptions are the main
adsorption mechanism.

Fig. 8. The XPS wide scan spectra of the prepared hydrogel before adsorption (a) and after adsorption (b) and the Cu 2p spectra of the hydrogel after adsorption (c).
518 X.-F. Sun et al. / International Journal of Biological Macromolecules 127 (2019) 511–519
CNaCl
Fig. 9. The influences of the NaCl solution concentration (a) and temperature (b) on desorption and the regeneration efficiencies of the prepared hydrogel (c).
3.8. Desorption and reusability study
Desorption and reusability are important for evaluating potential ap-
plications of the adsorbent [47]. The desorption study found that the
copper ions can be easily desorbed from the superadsorbent hydrogel
using NaCl solution. Fig. 9(a) shows that the desorption amount of cop-
per ions increased as the NaCl solution concentration increased, and this
suggested that the increase of ionic strength of the solution can be fa-
vorable for the desorption process due to the presence of NaCl. Fig. 9
(b) shows that the desorption amount increased with an increase in
the temperature, indicating the desorption is in favor of higher temper-
ature. The desorption ratios were N0.8 under high NaCl concentrations
and the highest desorption ratio was 0.91. The evidence seems to indi-
cate that the prepared hydrogel has excellent desorption performance
and can be reused or used for collecting metal ions from wastewater.
The reusability of the prepared lignin-g-PAAc/MMT hydrogel for Cu
(II) ions adsorption was studied, and the obtained result is shown in
Fig. 9(c). After five cycles of consecutive adsorption-desorption-
adsorption, the regeneration efficiency (ER, %) of the prepared adsor-
bent was still N80%, and the adsorption amount slightly decreased
after each cycle. It is clear therefore that the prepared hydrogel has ex-
cellent reusability.
4. Conclusions
A superabsorbent hydrogel was prepared from lignin and MMT for
Cu(II) ions removal. The structure of the lignin-g-PAAc/MMT hydrogel
was characterized by FT-IR, XRD, SEM and XPS, and the swelling kinetic
study revealed that the swelling process of the hydrogel fit the Schott
T
second-order dynamic equation. Adsorption studies indicated that pH,
contact time, Na+, and initial Cu(II) ion concentration influenced the
adsorption amount of copper ions on the superabsorbent, and the ad-
sorption process conformed to the pseudo-second-order kinetic model
and Freundlich adsorption isotherm model, and the prepared
superadsorbent hydrogel can be used for other heavy metal ions re-
moval. FT-IR and XPS analysis revealed that the adsorption behavior
was mainly due to ion exchange. The desorption and reusability studies
shows the excellent desorption performance and reusability of the pre-
pared superabsorbent hydrogel.
Acknowledgements
The authors appreciate the supports by the National Natural Science
Foundation of China (No. 20707016), Natural Science Basic Research
Plan in Shaanxi Province of China (No. 2017JM2003), and the Seed
Foundation of Innovation and Creation for Graduate Students in North-
western Polytechnical University (No. Z2019204).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ijbiomac.2019.01.058.
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