Journal of Environmental Chemical Engineering 3 (2015) 1416–1425

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Preparation of granular hydrogel composite by the redox couple for

efficient and fast adsorption of La(III) and Ce(III)
Yongfeng Zhu a,b , Yian Zheng a , Aiqin Wang a,c, *
a
Center of Eco-material and Green Chemistry, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Tianshui Middle Road 18#, Lanzhou
730000, PR China
b
Graduate University of the Chinese Academy of Sciences, Beijing 100049, PR China
c
Center of Xuyi Palygorskite Applied Technology, Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Xuyi 211700, PR China

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

Article history: A series of granular grafted hydrogel composites were prepared at room temperature and atmospheric
Received 25 June 2014 conditions by aqueous radical polymerization initiated by the redox couple Vc/H2O2 using chitosan (CTS)
Accepted 28 November 2014 as the backbone, acrylic acid (AA) as the monomer, and attapulgite (APT) as the inorganic component, and
Available online 2 December 2014
the resulting products, labeled as CTS-g-PAA/APT, were then applied as the adsorbent to adsorption La(III)
and Ce(III) from aqueous solution. The variables affecting the adsorption capacity for La(III) and Ce(III)
Keywords: were investigated, including the contact time, initial concentration, pH, and APT content, etc. The results
Granular
show that the as-prepared adsorbent has fast adsorption rate and high adsorption capacity for La(III) and
Hydrogel composite
Redox couple
Ce(III) in a wide pH range. The adsorption equilibrium for La(III) and Ce(III) can be reached within 40 min
Adsorption and the maximum adsorption capacity for La(III) and Ce(III) is 333.33 and 243.90 mg/g, respectively. An
La(III) appropriate addition of APT is beneficial for the adsorption process, Finally, the regeneration ability was
Ce(III) evaluated for the hydrogel composite, with the observation that after five consecutive adsorption–
desorption cycles, the composite still has a good adsorption capacity for La(III) and Ce(III). These
information imply that the hydrogel composite can be used as an effective adsorbent for the removal and
recovery of La(III) and Ce(III) from aqueous solution.
ã 2014 Elsevier Ltd. All rights reserved.

Introduction
In recent year, hydrogels known as 3-D crosslinked polymer
networks have attracted special attentions for their wide
applications in drug delivery [1–3], tissue engineering [4,5],
removal of metal ions [6,7] and dyes [8,9], and biomolecules
separation [10,11], etc. Due to the presence of metal-binding
functional groups in the polymeric networks, such as amide,
amine, carboxylic acid and ammonium groups, the hydrogels can
bind with heavy metal ions and function as good adsorbents in
water purification processes [12,13]. Comparing with other
adsorption materials involving activated carbon [12], zeolites
[13,14], silica gel [15], biocarbon [16], biomass [17] and inorganic
mineral [18], the 3-D structured hydrogels have the advantages of
* Corresponding author at: Center of Eco-material and Green Chemistry, Lanzhou
Institute of Chemical Physics, Chinese Academy of Sciences, Tianshui Middle Road
18#, Lanzhou 730000, PR China. Tel.: +86 931 4968118; fax: +86 931 8277088.
E-mail address: aqwang@licp.cas.cn (A. Wang).
simplicity, high efficiency and easy recovery, and are receiving
increasing interests for water environmental remediation.
Conventional hydrogel adsorbents are generally obtained in the
form of gel, which requires more energy consumption during the
processes of drying, smashing and granulating [19,20]. To reduce
the energy consumption, the resulting hydrogels are expected to
form with granules. Up to now, various polymerization techniques
have been developed for preparing granular hydrogels, such as
suspension polymerization, inverse suspension polymerization,
aqueous solution polymerization, and so on. Liu et al. [21] prepared
a series of 3-D crosslinked nanocomposite microgels using inverse
suspension polymerization and investigated their adsorption
properties for the heavy metals. The nanocomposite microgel
exhibited better mechanical stabilities and selective adsorption
ability for Pb2+. Nevertheless, the inverse suspension polymeriza-
tion required large amounts of toxic organic solvents. Comparing
with other polymerization process, aqueous solution polymeriza-
tion can be considered as a green polymerization process. In
previous studies, Wang et al. [22] prepared the granular alginate-
based hydrogels via grafting and crosslinking reactions in an
aqueous solution, and the resulting hydrogel has satisfactory

http://dx.doi.org/10.1016/j.jece.2014.11.028
2213-3437/ ã 2014 Elsevier Ltd. All rights reserved.
 Y. Zhu et al. / Journal of Environmental Chemical Engineering 3 (2015) 1416–1425
adsorption capacities, adsorption rates, and recovery capacities for
the target metal ions.
Generally, the polymerization of vinyl monomer-based hydro-
gels is initiated by a water-soluble free-radical initiator with the
assistance of heating [23,24], this reaction process also requires
more energy consumption. Therefore, a polymerization reaction
that can be carried out at mild conditions (lower temperature) by
water-soluble redox initiators is expected, such as APS/sodium
pyrosulfite, APS/sodium bisulfite and Fenton reagent, by which less
energy consumption and unpredictable self crosslinking will be
avoided and then is more appropriate for the thermally unstable
moieties. Zheng et al. [25] prepared granular hydrogel under an
ambient temperature in air atmosphere using Fenton reagent as
the redox initiator. The obtained hydrogels were investigated as
the adsorbents for removal of heavy metals from the aqueous
solution. The applicability of the adsorbent in real electroplating
effluent suggests that the granular hydrogel is an efficient
adsorbent for the removal of Cu(II) and Ni(II) from industrial
effluents.
Based on the above background, a granular hydrogel composite,
chitosan-g-poly (acrylic acid)/attapulgite (CTS-g-PAA/APT), was
prepared at room temperature and atmospheric conditions using
H2O2/Vc as the initiator. H2O2/Vc is a redox initiator, which can
initiate the polymerization reaction at lower temperature and
acidic conditions. The resulting hydrogel composites were then
used to adsorb La(III) and Ce(III), two common rare earth elements
used for advanced new materials such as superalloys, catalysts,
special ceramics and organic synthesis [26]. The adsorption
isotherms, adsorption kinetics, as well as the effects of initial
pH on the adsorption capacity were investigated. In addition, the
effects of APT content (wt%) on adsorption properties were also
studied.
Material and methods
Acrylic acid (AA, chemically pure, Shanghai Shanpu Chemical
Factory, China), chitosan (CTS, Zhejiang Yuhuan Ocean Biology Co.,
China, degree of deacetylation is 0.85, the average molecular
weight is 3
105), N,N-methylenebisacrylamide (MBA, chemically
pure, Shanghai Yuanfan additives plant, China) were used without
further purification. Ascorbic acid (Vc, analytical grade) and
hydrogen peroxide solution (H2O2, analytical grade) were supplied
by Sinopharm Chemical Reagent Co., Ltd. Natural attapulgite (APT,
industrial grade, the R&D Center of Xuyi Attapulgite Applied
Technology, Lanzhou Institute of Chemical Physics, CAS) was
milled and sieved through a 200-mesh screen prior to use.
A stock standard La(III) or Ce(III) solution at 1000 mg/L was
prepared by dissolving an appropriate amount of analytical grade
nitrates in distilled water. The working solutions containing
different concentrations of La(III) and Ce(III) were prepared by
stepwise dilution of the stock solution. The pH values were
adjusted by addition of 0.1 and 1.0 mol/L NaOH or HCl solution to a
designed value (Mettler, Toledo FE20 pH-meter). Other reagents
used were all analytical grade and all solutions were prepared with
distilled water.
Preparation of hydrogel composites
A series of hydrogels were prepared according to the following
procedure: 3.6 g AA and 0.15 g MBA were added into a 250 mL
three-neck flask containing 45 mL distilled water, and then 0.3 g
CTS was added in the flask and dispersed for 30 min. After that, a
certain amount of APT (0.18 g for 1:20 to AA, 0.36 g for 1:10 to AA,
0.6 g for 1:6 to AA, 1.2 g for 1:3 to AA and 1.8 g for 1:2 to AA) was
added and stirred for 60 min. Later, the required quantities of Vc
and freshly prepared H2O2 solution (3%) were added. Immediately,
1417
the granular hydrogel was formed, and then the reaction was
carried out for 1 h at room temperature. The granular hydrogel was
immersed into 2.0 mol/L NaOH solution to neutral solution pH and
then dehydrated with industrial alcohol and dried at room
temperature. The blank sample without APT was marked as
CTS-g-PAA/APT(AA/APT = 1/0), and other adsorbent was labeled as
CTS-g-PAA/APT(AA/APT = a/1) (a = 20, 10, 6, 3, 2). All hydrogel
samples used for adsorption had a particle size in the range of 40–
80 mesh.
Characterizations
FTIR spectra were determined by a Nicolet NEXUS FTIR
spectrometer in 4000–400 cm1 wavenumber region using KBr
pellets. The morphologies of the adsorbents with and without APT
were observed by JSM-6701F field emission scanning electron
microscopy (SEM) (JSM-5600, LVJEOL Ltd.) with an acceleration
voltage of 20 kV. Before the sample was observed, all the samples
were coated with gold film.
Batch adsorption studies
The adsorption studies were conducted by mixing 25 mg
adsorbent with 25 mL of La(III) or Ce(III) solution at desired
concentration. The mixtures were shaken in a thermostatic orbital
shaker (THZ-98A) with a constant speed of 120 rpm and constant
temperature of 30  C for a given time, and then the adsorbents
were separated by direct filtration. After that, the concentration of
La(III) or Ce(III) in the residual solution was measured by
ultraviolet spectrophotometry with a Specord 200UV/vis spectro-
photometer at the maximum absorbency wavelength (670 for La
(III) and 665 nm for Ce(III)) using chlorophosphonazo mA (CPA-
mA) as the complexing agent. The adsorption capacity of the
hydrogel was calculated from the following equation:
½ðC 0  C e Þ
V
Qe ¼ (1)
m
where Qe is the adsorption capacity for La(III) or Ce(III) at any time
(mg/g), C0 and Ce are the initial and final concentration of La(III) or
Ce(III) (mg/L), V is the volume of solution used (mL) and m is the
weight of absorbent (mg).
To optimize the adsorption conditions, batch adsorption
experiments were carried out, such as pH, adsorption kinetics
and adsorption capacity. To maintain pH value at the desirable
range during adsorption experiments, the initial pH was adjusted
by 0.1 mol/L NaOH or HCl solution. For adsorption kinetic studies, a
series of adsorbents were immersed into 400 mg/L La(NO3)3 or Ce
(NO3)3 solution at 30  C, and were separated from the solution for
predetermined intervals of time. The sorption isotherms for metal
ions were established as follows: 25 mg adsorbent was dipped into
25 mL of La(NO3)3 or Ce(NO3)3 solution with various initial
concentration, and shaken at 30  C until adsorption saturation.
After filtration, all the supernatant was left for further analysis to
obtain the corresponding adsorption capacity.
Desorption and regeneration
In order to figure out the optimum condition using HCl solution
as the desorbing agent for La(III) or Ce(III)-loaded composite, the
influences of different HCl concentration and desorption time on
desorption efficiency were firstly studied. The CTS-g-PAA/APT
composite with a ratio of APT to AA of 1:20 was selected to reach
the adsorption saturation by La(III) or Ce(III) at optimum pH for 2 h.
The representative La(III) or Ce(III)-loaded sample was filtered and
washed with distilled water. Then, the sample was put into a 50 mL
conical flask containing 25 mL of HCl solution with different
1418 Y. Zhu et al. / Journal of Environmental Chemical Engineering 3 (2015) 1416–1425
Fig. 1. The digital images of CTS-g-PAA, CTS-g-PAA/APT (APT/AA = 1/6), CTS-g-PAA/
APT (APT/AA = 1/3) from the left to right.
concentrations from 0.1 to 2 mol/L and stirred for 2 h. The
concentration of rare earth ions was measured by ultraviolet
spectrophotometry. The desorption ratios were expressed by the
mass ratio of the eluted ions to the adsorbed ions. The desorption
kinetics was conducted using optimum concentration of desorbing
agent for predetermined intervals of time.
Once the optimum condition of desorption process was chosen,
the reusability of the adsorbent was evaluated according to the
following procedures: 25 mg adsorbent was mixed with 25 mL La
(NO3)3 or Ce(NO3)3 solution (400 mg/L) for 1 h. After the
adsorption equilibrium, the adsorbent was separated from
solution. Later, the adsorbent was dispersed into 25 mL optimum
concentration of HCl for 1 h to desorb the La(III) or Ce(III) adsorbed
on the adsorbent. Afterwards, the adsorbent was separated from
the HCl solution, neutralized with 10 mL 0.1 mol/L NaOH solution
for 10 min, washed with distilled water for several time and the
recovered adsorbent was then used for another adsorption process
from a similar adsorption procedure. The adsorption–desorption
process was performed for five times.
Results and discussion
Characterization of CTS-g-PAA/APT
In this study, a granular adsorbent, CTS-g-PAA/APT composite
was prepared at room temperature and atmospheric conditions
with Vc/H2O2 as the initiator and MBA as the crosslinker. As
observed from digital images (Fig. 1), the resulting hydrogel is
granular with good uniformity. With the addition of APT, the
sample color changes from white to gray. As we have known, it is
Fig. 2. FTIR spectra of CTS-g-PAA (a), CTS-g-PAA/APT (20/1) (b), CTS-g-PAA/APT(6/1) (c) and APT (d) (e) from top to bottom.
difficult for the production of granular hydrogel using green
aqueous radical polymerization. In current work, we can obtain the
granular hydrogel using CTS as the backbone to graft the poly
(acrylic acid) and the resulting hydrogel will suffer from a facile
post-treatment to achieve the final product and this procedure will
save much energy compared to conditional gel-like product which
requires more energy to dry, smash and granulate. Moreover, this
hydrogel can be achieved under mild polymerization conditions
without additional heat and expensive catalyst, and this process
shows obvious advantages over other polymerization processes
involving high temperature or toxic organic reagents. Furthermore,
this adsorbent was firstly used for the removal of rare earth metals
and some variables affecting the adsorption capacity will be
discussed in the following section.
FTIR analysis
Fig. 2 was illustrated the FTIR spectra of CTS-g-PAA (a), CTS-g-
PAA/APT (20/1) (b), CTS-g-PAA/APT(6/1) (c) and APT (d). In the
nanocomposite, the characteristic peaks at 1723–1727 cm1,
1455 and 1410 cm1 were attributed to C¼O stretching of —COOH
and symmetric stretching of —COO groups, respectively. Com-
pared to the FTIR spectrum, the characteristic peaks of APT at
3550 cm1 (the stretching vibrations of (Al)O—H) and 1652 cm1
(the —OH bending vibration) disappeared in the spectrum of
nanocomposite. But the characteristic peaks at 1031 and 983 cm1
(SiOSi stretching vibration), 512 and 470 cm1 (Si—O—Si
bending vibration) were obviously enhanced with the increase
of APT content. The information indicated that APT participated in
the graft copolymerization reaction through its activated silanol
groups [27].
Surface morphologies
SEM micrographs of the APT (a), CTS-g-PAA (b), CTS-g-PAA/APT
(6/1) (c), CTS-g-PAA/APT (3/1) (d) were shown in Fig. 3. It is clearly
observed that the APT shows a nanorod-like structure and single
crystals of attapulgite aggregate as crystal bundles and aggregates,
due to the existence of van der Waals force and hydrogen bonds
[28] (Fig. 3a). For the hydrogel without APT, the sample exhibits an
undulant and dense surface (Fig. 3b). However, when APT is
introduced into the CTS-g-PAA matrix, the samples show a coarse
surface (Fig. 3c and d), and the randomly arranged nano-scale rod
of APT was uniformly dispersed in the polymer matrix. Also, with
increasing the APT content, the surface roughness of CTS-g-PAA/
APT is increased. This can be attributed to the fact that among the
hydrophilic polymer chains, the hydrogen-bonding interaction for
 Y. Zhu et al. / Journal of Environmental Chemical Engineering 3 (2015) 1416–1425 1419

Fig. 3. SEM images of APT (a), CTS-g-PAA (b), CTS-g-PAA/APT (6/1) (c), CTS-g-PAA/APT (3/1) (d).

APT can be reduced [29]. Therefore, the incorporation of a proper
amount of APT is beneficial to improve the surface structure of the
nanocomposite.
pH-dependence
The initial pH has an enormous impact on the adsorption
capacity of heavy metal ions for an adsorbent, as it influences the
surface properties of the adsorbent and ionization/dissociation
states of the adsorbate molecule [30–32]. To obtain the optimal pH
range for the adsorption of La(III) and Ce(III), a series of
experiments were performed with an initial La(III) or Ce(III)
concentration of 400 mg/L and contact time of 2 h. To avoid the
hydrolyzed species of La and Ce, the pH range was investigated
from 1 to 7, as shown in Fig. 4.
From Fig. 4, it can be seen that the major trend of each pH-curve
is the same: the adsorption capacity of La(III) and Ce(III) increases
with increasing initial pH. And the trend of each pH-curve can
divide into three stages: at the strong-acid condition (2  pH < 3),
at the weak acid condition (3  pH < 4), at close to neutral and
neutral condition (4  pH  7). At the strong-acid condition (2 
pH < 3), the adsorption capacities of CTS-g-PAA/APT composite for
La(III) and Ce(III) were very low. The amount adsorbed of CTS-g-
PAA/APT (AA/APT = 20/1, 10/1, 1/0, 6/1, 3/1, 2/1) were 78.39, 83.50,
93.03, 92.23, 81.93 and 80.97 mg/g for La(III) and 48.64, 26.92,
31.69, 45.83, 37.29 and 55.69 mg/g for Ce(III) at pH 1.0. But at the
weak acid condition (3  pH  4), the adsorption capacity greatly
increased. The amount adsorbed of CTS-g-PAA/APT (AA/APT = 20/1,
10/1, 1/0, 6/1, 3/1, 2/1) were 320.26, 316.38, 313.14, 289.02, 272.34,
255.35 mg/g for La(III) for La(III) and 225.75, 219.86, 218.77, 209.87,

Fig. 4. Effect of initial pH on the adsorption capacity of CTS-g-PAA/APT composite for La(III) (a) and Ce(III) (b). Adsorption experiments: C0: 400 mg/L; sample dose: 25 mg/
25 mL; temperature: 30  C; equilibrium time: 120 min.
1420 Y. Zhu et al. / Journal of Environmental Chemical Engineering 3 (2015) 1416–1425

Fig. 5. Variation of the adsorption capacity of CTS-g-PAA/APT composites at different contact time (a for La(III), b for Ce(III)). Adsorption experiments: C0: 400 mg/L; sample
dose: 25 mg/25 mL; pH: 6; temperature: 30  C.

177.63, 160.66 mg/g for Ce(III) at pH 6.0, respectively. And at close
to neutral and neutral condition (4  pH  7), the adsorption
capacity for La(III) and Ce(III) showed a platform and no
appreciable changes were observed. All the adsorbents have
similar change trend within the pH range studied. The variation
trend can be explained by the interaction between H+ and —COO,
—NH2 at different pH values. At low pH values (high acidic),
carboxyl groups retain their protons (—COOH) which can reduce
the number of binding sites available for metal ions uptake [28],
while the amino groups of chitosan in the composite was
protonated (NH3+) which will result in electrostatic repulsion
between metal ions and protonated amino groups with the same
charges. Moreover, the H+ ions in the solution can compete with
metal ions to make the ion-exchange reaction. As the pH increased
from high (2  pH < 3) to less acidic regions (3  pH  7), two main
adsorption interactions occur: (1) chelation between amino groups
and metal ions; (2) electrostatic interaction between carboxylate
groups and metal ions. In this case, the number of available binding
sites has greatly increased, so the amount adsorbed shows a
remarkable increase. Considering the formation of La(OH)3 or Ce
(OH)3 precipitation when the pH value of La(III) or Ce(III) solution
exceeds 7.5, the pH 6 was selected as the initial pH value of La(III) or
Ce(III) solution for the following adsorption experiments, though a
wide pH range can be applied.
 
k1
log ðqe  qt Þ ¼ log qe  t (2)
2:303
t 1 t
¼ þ (3)
qt ðk2
q2e Þ qe
where qt and qe are the amount adsorbed (mg/g) for La(III) and Ce
(III) at the time t and adsorption equilibrium, respectively. k1 and k2
are the constants of the pseudo-first-order equation (min1) and
pseudo-second-order equation (g/mg min), respectively. The
related parameters and correlation coefficients R2 can be obtained
by the regression of the experimental data and were listed in
Tables 1 and 2.
From Tables 1 and 2, it can be found that the correlation
coefficient R2 of pseudo-second-order models for all the adsorb-
ents exceeded 0.99, but the linear correlation coefficients (R2) for
the pseudo-first-order kinetic model were all low. Moreover, for
the pseudo-second-order kinetic model, the calculated qe values
(qe, cal) slightly differ from the experimental qe values (qe,exp),, but
there are large difference between the qe,exp and qe, cal for pseudo-
first-order kinetic model. All this indicates that, the pseudo-
second-order kinetic model can describe well the adsorption
experimental data.

Adsorption kinetics

Contact time is a very important parameter which was used to

Table 1
evaluate the adsorption kinetics of an adsorbent. The effects of Estimated adsorption kinetic parameters for La(III) and Ce(III) by pseudo-first-order
contact time on the adsorption capacity of La(III) or Ce(III) were models.
investigated with 25 mg CTS-g-PAA/APT in 25 mL of 400 mg/L La
qe,exp qe,cal k1 R2
(III) or Ce(III) solution at 30  C. The results are shown in Fig. 5.
(mg/g) (mg/g) (min1)
The plot clearly indicated that the adsorption capacity
La(III) AA/APT=20/1 319.77 12.51 3.29
102 0.1142
increased rapidly with elongating the contact time from 0 to
AA/APT=10/1 309.65 36.72 5.27
102 0.2547
30 min, and more than 90% of the adsorption was achieved within AA/APT=1/0 314.92 22.07 5.57
102 0.2128
30 min, suggesting that the adsorption of La(III) and Ce(III) onto the AA/APT=6/1 300.97 19.28 3.62
102 0.1759
CTS-g-PAA/APT was rapid. In addition, there are no obvious AA/APT=3/1 273.68 49.22 3.66
102 0.7344
AA/APT=2/1 262.63 129.03 8.31
102 0.9598
differences in the adsorption rate for La(III) and Ce(III), and this fact
may be explained that La(III) and Ce(III) have the same hydrated Ce(III) AA/APT=20/1 232.41 213.3 4.70
102 0.371
ionic radius (4.52 Å) [33]. AA/APT=10/1 221.65 138.48 8.63
102 0.9398
To evaluate the control factors of the adsorption process, the AA/APT=1/0 225.36 28.03 6.47
102 0.4045
adsorption kinetics based on the pseudo-first-order equation and AA/APT=6/1 211.56 106.46 8.63
102 0.9794
AA/APT=3/1 178.33 84.12 3.85
102 0.9166
pseudo-second-order equation were applied, as expressed in the
AA/APT=2/1 163.21 21.75 4.79
102 0.3003
following Eqs. of (2) and (3).
 Y. Zhu et al. / Journal of Environmental Chemical Engineering 3 (2015) 1416–1425 1421

Table 2 Different from the Langmuir isotherm model, Freundlich

Estimated adsorption kinetic parameters for La(III) and Ce(III) by pseudo-second
isotherm model is used to describe the adsorption on the
models.
heterogeneous adsorbent surface. The linearized equation is
qe,exp qe,cal k1 R2 expressed as following:
(mg/g) (mg/g) (g/mg min)
1.07
103
1
La(III) AA/APT=20/1 319.77 330.33 0.9994 log qe ¼ log K F þ
log C e (5)
AA/APT=10/1 309.65 312.53 1.13
103 0.9996 n
AA/APT=1/0 314.92 322.58 1.46
103 0.9996 Like in the Langmuir adsorption isotherm, qe and Ce are the
AA/APT=6/1 300.97 303.03 1.82
103 0.999
equilibrium adsorption capacity (mg/g) and the equilibrium
AA/APT=3/1 273.68 277.77 2.27
103 0.9997
AA/APT=2/1 262.63 267.27 1.78
103 0.9996 concentration (mg/L) in the solution, respectively. KF is the
Freundlich constant (L/g) and n is a dimensionless constant. KF
Ce(III) AA/APT=20/1 232.41 238.06 1.14
103 0.9992 and n can also be calculated by the slope (1/n) and intercept (log KF)
AA/APT=10/1 221.65 227.27 1.30
103 0.9994
of plot (log qe) versus log Ce. The Langmuir and Freundlich isotherm
AA/APT=1/0 225.36 232.56 6.47
103 0.9998
AA/APT=6/1 211.56 217.39 9.32
104 0.9996
models for the adsorption of La(III) and Ce(III) onto CTS-g-PAA/APT
AA/APT=3/1 178.33 185.19 1.16
103 0.9994 at 30  C and pH 6 are presented in Tables 3 and 4.
AA/APT=2/1 163.21 169.49 1.19
103 0.999 The results RL2 were higher than RF2, indicating that the
adsorption of La(III) and Ce(III) onto CTS-g-PAA/APT can be
evaluated by Langmuir models. The results from Langmuir models
Adsorption isotherms also gave the facts that the CTS-g-PAA/APT had homogeneous
surface. Namely, it explain the adsorption procedure of La(III) and
The adsorption isotherms of La(III) and Ce(III) were shown in Ce(III) onto the CTS-g-PAA/APT composite as a homogeneous
Fig. 6. It can be seen that the adsorption capacity was increased adsorbent.
with increasing initial concentration for both of La(III) and Ce(III). Hybrid hydrogels have several advantages as adsorbents for
This is because that the higher initial concentration generated water treatment [34,35]. The incorporation of the natural materials
stronger driving force resulting from the concentration gradient, into hybrid hydrogels cannot only lower the cost of water
which increased the diffusion tendency of metal ions into the treatment, but also can satisfy various situations for water
adsorbent. When the initial concentration reached about 400 mg/ treatment. Moveover, most of hybrid hydrogels have good
L, the active adsorption sites of the adsorbent were almost mechanical properties and tolerance agonist external, vigorous
completely occupied by La(III) and Ce(III), and thus the adsorption stirring, a dominant characteristic for the reuse of an adsorbent.
capacity reached the maximum and kept constant. APT is a crystalline hydrated magnesium silicate with a fibrous
Adsorption data for a wide range of adsorbate concentrations morphology, large specific surface area and moderate cation
are most conveniently described by the adsorption isotherms. exchange capacity. The introduction of APT clay into CTS-g-PAA
Langmuir and Freundlich are the mostly used isotherms for the polymeric network can generate a coarse surface, which may
study of the adsorption of cationic species to materials such as accelerate the adsorption process and simultaneously reduce the
hydrogel in this study. cost of the hybrid hydrogel. Moreover, APT can react with the CTS-
Langmuir adsorption isotherm is based on the assumption that g-PAA polymer and the introduction of APT into the polymer may
the surface of adsorbent is energetically identical and has only one improve the adsorption ability of the polymer to some extent. Also,
type of binding sites, and the linearized equation can be expressed the introduction of rigid APT may prevent the collapse of polymeric
as following: network during drying.
From Fig. 6, it also can be seen that when an appropriate
Ce Ce 1
¼ þ (4) amount of APT is introduced into the hydrogel (AA/APT = 20/1), the
qe Q m ðQ m
bÞ resulting composite shows a slight increase in the adsorption
where qe is the equilibrium adsorption capacity (mg/g) of metal capacity for La(III) and Ce(III). This fact may be ascribed to that the
ions and Ce is the equilibrium concentration (mg/L) in the solution. APT powder can participate in the formation of three-dimensional
Qm is the maximum adsorption capacity (mg/g), b is the Langmuir network structure, and the introduction of rigid APT will greatly
constants (L/mg), which can be calculated by the slope (1/ Qm) and decrease the hydrogen bonding interaction among hydrophilic
intercept (1/Qm
b) of plot (Ce/qe) versus Ce. groups and restrained the entanglement of polymer chains, which

Fig. 6. Effect of the initial La(III) or Ce(III) concentration on the adsorption capacity of CTS-g-PAA polymer and CTS-g-PAA/APT composites. Adsorption experiments: sample
dose: 25 mg/25 mL; pH: 6; temperature: 30  C; equilibrium time: 60 min.
1422 Y. Zhu et al. / Journal of Environmental Chemical Engineering 3 (2015) 1416–1425

Table 3 changed significantly. The major differences were shown as

Isotherm constants for La(III) adsorption onto CTS-g-PAA/APT composite.
follows: (i) the wide absorption band at near 3440 cm1,
Adsorbent Langmuir equation Freundlich equation corresponding to the stretching vibration of —NH2 groups and
Qm(mg/g) b (L/mg) RL 2
KF (L/g) n RF2
—OH groups, widened; (ii) the absorption band at 1560–
1590 cm1, assigned to the asymmetric vibration of carboxylate
AA/APT = 20/1 333.33 0.4615 0.9998 99.56 3.97 0.6412
AA/APT = 10/1 322.58 0.6595 0.9992 110.28 4.44 0.6748
group, was enhanced obviously and shifted to the lower wave
AA/APT = 1/0 322.58 0.62 0.9999 108.62 4.23 0.7044 numbers; the absorption band at 1409–1454 cm1, attributed to
AA/APT = 6/1 303.03 0.66 0.9998 112.9 4.98 0.6769 symmetric vibration absorption bands of carboxylate, was
AA/APT = 3/1 277.28 0.2176 0.9993 94.79 4.98 0.7938 reduced. The results indicated the chelating interaction of
AA/APT = 2/1 256.41 0.2378 0.9993 96.32 5.66 0.6809
carboxylate to La(III) or Ce(III) ion. The formation of coordination
bond of carboxylate with metals will diminish the charge density
on the carboxylate oxygen and thus decrease the force constant of
it. All of these changes in FTIR spectra of the CTS-g-PAA and CTS-g-
Table 4
Isotherm constants for Ce(III) adsorption onto CTS-g-PAA/APT composite. PAA/APT(20/1) composite before and after La(III) or Ce(III)
adsorption indicate that —NH2, —OH and —COOH groups in the
Adsorbent Langmuir equation Freundlich equation composites are all involved in the adsorption process.
qm(mg/g) b (L/mg) RL2 K (L/g) n RF2
AA:APT = 20/1 243.9 0.3388 0.9999 62.03 3.71 0.6844 Desorption and reusability
AA:APT = 10/1 222.22 0.5844 0.9999 74.66 4.63 0.6808
AA:APT = 1/0 227.27 0.647 0.9999 73.94 4.41 0.7051 Reusing ability of an adsorbent during regeneration process is
AA:APT = 6/1 208.33 0.4174 0.9997 71.94 4.43 0.7113
an important parameter to evaluate the properties of an adsorbent.
AA:APT = 3/1 188.68 0.2314 0.9999 55.68 3.95 0.8404
AA:APT = 2/1 169.49 0.295 0.9997 59.33 5.05 0.7169 Due to lower adsorption capacity at high acidity, we used HCl as the
desorbing agent to evaluate the desorption efficacy of the as-
prepared adsorbent. Firstly, the effect of HCl concentration on the
desorption ability of CTS-g-PAA/APT was investigated. Later, the
can form more suitable adsorption sites. Further increase in APT desorption rate was observed at the optimum HCl concentration.
content would result in a monotonic decrease in the adsorption As shown in Fig. 9, when the HCl concentration was gradually
capacity for both of La(III) and Ce(III) compared with that without increased, there was an increase of the desorption efficiency. As the
APT. One can speculate that excessive APT nanoparticles will be HCl concentration further increased to 0.5 mol/L for La(III) or
present in the polymeric networks in the form of physical filler. The 1.0 mol/L for Ce(III), the desorption efficiency of La(III) or Ce(III)
adsorption capacities of APT for La(III) and Ce(III) are determined to showed no obvious changes. This is an indication that the
be 40.25 and 16.24 mg/g, respectively, and are quite lower than interaction between carboxylate (—COO), amino group (—NH2)
those of CTS-g-PAA. Furthermore, the higher the APT content is, the and La(III) or Ce(III) can be weaken and subsequently metal ions
lower the content of carboxyl groups in the composite is, and are released from the adsorbent into the desorbing medium. From
accordingly, an appreciable decrease in the adsorption capacity the experimental results, 0.5 mol/L HCl solution is selected for La
will be observed. In addition, we compared the adsorption capacity (III) desorption, while 1.0 mol/L HCl solution is chosen for Ce(III)
and adsorption kinetics of La(III) and Ce(III) onto different desorption to further investigate the desorption ability at different
adsorbents, as summarized in Table 5. The comparative results times, as shown in Fig. 10. It is clearly observed that within 40 min,
demonstrate that the CTS-g-PAA/APT composite shows higher there appears a rapid desorption rate and the balance of
adsorption capacity and faster adsorption kinetics than other adsorbing–desorbing is reached at 60 min. At that time, the
adsorbents reported [36–45]. desorption ratio for La(III) and Ce(III) were found to be 89.12% and
In order to illustrate the adsorption mechanism of CTS-g-PAA/ 87.55%, respectively.
APT composite for La(III) or Ce(III), the FTIR spectra of the The adsorption–desorption process was performed for five
representative CTS-g-PAA/APT composite before and after La(III) or times with 0.5 mol/L HCl solution for La(III) and 1.0 mol/L HCl
Ce(III) adsorption were given in Figs. 7 and 8. solution for Ce(III). After eluted with HCl, the adsorbent was
Combined with Figs. 7 and 8, it is clearly observed that after La activated with 0.1 mol/L NaOH solution and used again for La(III)
(III) or Ce(III) adsorption, the FTIR spectra of the adsorbents have and Ce(III) adsorption. As Fig. 11 shown, the adsorption capacities

Table 5
Comparison of La(III) and Ce(III) adsorption capacity among different adsorbents.

Adsorbents Adsorption capacity Adsorption time Adsorption conditions

(mg/g) (min)

La Ce La Ce
Platanus orientalis leaf powder [36] 28.65 32.05 60 60 C0
:100 mg/L, dosage:.0.1 g/0.025 L, pH 4.0
Fish scale [37] 200 240 C0:300 mg/L, dosage: 0.3 g/L, pH 6.0
Neem sawdust [37] 160.2 180 C0:250 mg/L, dosage: 0.2 g/L, pH 6.0
Iron oxide loaded calcium alginate beads [38] 123.5 480 C0:138 mg/L, dosage: 1.0 g/L, pH 5.0
Mesoporous conjugate adsorbent [39] 192.31 25 C0: 5 mg/L, dosage: 8 mg /30 mL, pH 3.5
Activated carbon [40] 175.4 60 C0: 50 mg/L, dosage: 30 mg/10 mL, pH 3.5
Activated carbon [41] 9. 66 10 C0: 10 mg/L, dosage: 10 mg/5 mL, pH 4.0
SnO2–TiO2nanocomposites[42] 65.6 60 C0: 125.0 mg/L, dosage: 25 mg, pH 5.0
Magnetic ZnO clay nanocomposite hydrogel [43] 58.8 80 C0: 42 mg/L, dosage: 30 mg/30 mL, pH 5.0
Ce(III)-imprinted polymer [44] 130 Without test
Magnetic alginate–chitosan gel beads [45] 97.1 600 C0: 138 mg/L, dosage: 50 mg/50 mL, pH 5.0
This study 333.33 243.9 40 40 C0: 400 mg/L, dosage: 25 mg/25 mL, pH 6.0
 Y. Zhu et al. / Journal of Environmental Chemical Engineering 3 (2015) 1416–1425 1423

Fig. 7. FTIR spectra of the representative CTS-g-PAA and CTS-g-PAA/APT (20/1) composite before (a and b) and after (c and d) La(III) adsorption.

Fig. 8. FTIR spectra of the representative CTS-g-PAA and CTS-g-PAA/APT (20/1) composite before (a and b) and after (c and d) Ce(III) adsorption.

Fig. 9. Effect of HCl concentration on the desorption ability of CTS-g-PAA/APT Fig. 10. Desorption time of CTS-g-PAA/APT(20/1) saturated with La(III) and Ce(III).
composite. Adsorption experiments: sample dose: 25 mg/25 mL; pH: 6; equilibrium Adsorption experiments: sample dose: 25 mg/25 mL; pH: 6; 30  C/120 rpm; time:
time: 120 min., 30  C/120 rpm; desorption experiments: 30  C/120 rpm/2 h. 120 min. Desorption experiments: 30  C/120 rpm.
1424 Y. Zhu et al. / Journal of Environmental Chemical Engineering 3 (2015) 1416–1425
Fig. 11. The amount adsorbed for La(III) and Ce(III) as a function of adsorption–desorption cycle. Adsorption experiments: sample dose: 25 mg/25 mL; pH: 6; 30  C/120 rpm;
time: 60 min. Desorption experiments: time: 60 min., 30  C/120 rpm.
of all the adsorbent in the second and third cycles were higher than
the initial one, suggesting that some adsorption sites can be
created during the regeneration process, and similar phenomenon
is also found in our earlier studies [46,47]. After the third cycle, the
adsorption capacity for La(III) and Ce(III) began to decrease.
Nevertheless, during the five-time consecutive adsorption–de-
sorption processes, the average desorption efficiency of each CTS-
g-PAA/APT composite is determined to be above 95% for La(III) and
Ce(III), meaning that CTS-g-PAA/APT composite has excellent
reusability.
Economic evaluation
Hydrogel is a crosslinked functional polymer material with
unique 3D network structure and large amounts of functional
groups. Generally, the polymerization of vinyl monomer-based
hydrogels needs the assistance of heating and the resulting
adsorbent is bulk hydrogel which must be ground before use, and
accordingly, the energy consumption cannot be ignored by the
users. In this study, a granular adsorbent is directly obtained by
aqueous radical polymerization at room temperature, without
additional heating and inert gas protection. And this preparation
method will save much energy compared to conditional gel-like
product which requires more energy to dry, smash and granulate.
Furthermore, the materials used in this reaction are common. CTS
produced by deacetylation of chitin, is the world’s second most
abundant natural hydrophilic biomacromolecule. It is estimated
that approximately 10 billion tons of chitin can be synthesized in
nature each year [48]. APT is a natural hydrated magnesium
aluminum silicate and acrylic acid is a commonly used chemical
reagents.
As an adsorbent, the superhydrophilic 3D network and tailored
chelating groups of hydrogels endow them with faster adsorption
kinetics and higher adsorption capacities for different kinds of
adsorbates compared to other adsorbents. Moreover, the adsor-
bent can be easily separated after the adsorption, and the
corresponding adsorbates (La3+ and Ce3+ in this study) can be
effectively desorbed for subsequent enrichment and recovery. As
we have known, rare earth elements and their compounds are in
demand, and are often crucial for, a broad and rapidly expanding
range of applications that rely upon their chemical, catalytic,
electrical, magnetic, and optical properties. And they are also
becoming uniquely indispensable in many high-tech industries
such as new energy, new materials, energy conservation,
environmental protection, electronic information, and defense
technologies [49]. In recent years, the preconcentration and
purification of rare earth metals increasingly become a critical
issue for expanding the demand along of cutting-edge materials
and new industries. Therefore, it is no doubtable that the as-
prepared hydrogel will be a potential adsorbent for commercial
recycling of rare earth elements.
Conclusions
In this study, a granular hydrogel composite was firstly
prepared at room temperature and atmospheric conditions. This
is a great advance for the preparation of hydrogels by aqueous
radical polymerization. The resulting CTS-g-PAA/APT composite
was then used to adsorb the rare earth metal ions La(III) and Ce(III).
When an appropriate amount of APT was added (AA/APT = 20/1),
the resulting composite was shown to have an improved
adsorption capacity, with the maximum adsorption capacity of
328.51 mg/g for La(III) and 250.04 mg/g for Ce(III). The adsorption
equilibrium can be achieved within 40 min, and in the wide pH
range of 3–7, the adsorbent shows higher adsorption capacity for
La(III) and Ce(III). After consecutive five adsorption–desorption
processes, there appears only a slight decrease in the adsorption
capacity for both of La(III) and Ce(III). All the information implies
that the as-prepared composite is an effective adsorbents for
removal of La(III) and Ce(III) from aqueous solution.
Acknowledgements
The authors thank the joint support by the National Natural
Science Foundation of China (21107116 and 21377135, 21477135,
51403221) and “863” Project of the Ministry of Science and
Technology, China (2013AA032003).
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