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Desalination 263 (2010) 170175

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j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Adsorption behavior of Cu2+ from aqueous solutions onto starch-g-poly

(acrylic acid)/sodium humate hydrogels
Yian Zheng a,b, Shuibo Hua a,b, Aiqin Wang a,

Center of Eco-materials and Green Chemistry, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, China
Graduate University of the Chinese Academy of Sciences, Beijing 100049, China

a r t i c l e

i n f o

Article history:
Received 10 April 2010
Accepted 22 June 2010
Available online 17 July 2010
Sodium humate
Cu2+ adsorption

a b s t r a c t
A series of starch-g-poly(acrylic acid)/sodium humate (St-g-PAA/SH) hydrogels were prepared and used to
adsorb Cu2+ from the aqueous solution. The batch adsorption experiments were carried out by varying
contact times (090 min), initial Cu2+ concentration (0.0030.02 mol/L), and pH values (2.05.0). The
effects of ion strength (5, 10 mmol/L NaCl) and competitive ion (5, 10 mmol/L Pb(NO3)2) on the adsorption
capacity were investigated. The results indicated that the addition of 5% SH into St-g-PAA polymeric
networks could not only improve the initial adsorption rate and nal adsorption capacity for Cu2+, but also
make a remarkable contribution to regeneration ability. St-g-PAA/SH hydrogels exhibited high adsorption
capacity within a wide pH range and the adsorption data could be well described by the pseudo-secondorder kinetic model and Langmuir isotherm model. FTIR spectra before and after adsorption of Cu2+ on the
hydrogels revealed that complexation was considered as the main adsorption mechanism.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Adsorption is a conventional but important separation process and
has been used widely in the chemical, biological, analytical, and
environmental elds [13]. In most cases, the adsorbents have large
internal porosities to ensure adequate surface area for adsorption.
However, the diffusion limitations within the particles lead to
decreases in the adsorption rate and the available capacity [4]. So, it
is interesting to develop a novel adsorbent with a small diffusion
resistance and a high adsorption capacity.
Polymeric hydrogels are crosslinked three-dimensional network
structure of hydrophilic homopolymers or copolymers [57]. Due to
the super-hydrophilicity characteristics, they can swell quickly in the
aqueous solution, which is benecial for shortening the time to reach
the adsorption equilibrium [8]. Polymeric hydrogels can be prepared
with different functional groups such as carboxylic acid, amine,
hydroxyl, amidoxime and sulfonic acid groups. These groups attached
onto the polymeric networks can be tailored easily for a specic
application. Owing to higher adsorption rate and adsorption capacity,
polymer hydrogels can provide many advantages as a novel type, fastresponsive, and high-capacity adsorbent materials in an adsorption
process [9,10].
With the development of polymer hydrogels, an incorporation of
biodegradable, environmentally friendly polysaccharide, such as
starch [1113] cellulose [14,15] or chitosan [16,17], into the polymer

Corresponding author. Tel.: + 86 931 4968118; fax: + 86 931 8277088.

E-mail address: (A. Wang).
0011-9164/$ see front matter 2010 Elsevier B.V. All rights reserved.

hydrogel has been focused on. Starch (St) is an abundant, inexpensive,

renewable and fully biodegradable natural raw material. Considerable
research and technical work have been reported so far, and the
chemical modication of starch or modied starch via vinyl graft
copolymerization constitutes the most important eld for not only
improving the properties of starch and enlarging the range of its
utilization [1820], but also affording corresponding hydrogels with
biodegradability and biocompatibility.
Humic substances, a major component of organic matter, are some
of the most abundant materials on earth. They are formed during the
decomposition of plant and animal biomass in natural systems and
usually include a skeleton of alkyl and aromatic units with functional
groups such as carboxylic acid, phenolic hydroxyl, and quinine groups
attached to them [21]. It was reported that the presence of humic
acid/humates can benet for the adsorption of heavy metals. Hizal and
co-worker found that the clay mineral in the presence of humic acid
probably behaved more like a chelating agent for heavy metal ions
than a simple inorganic ion exchanger, since the stability of the
dominating surface complexes in the presence of humic acid was
higher than that of the corresponding binary metal ion complexes
[22]. Arias et al. concluded that humic substances could be adsorbed
on mineral particles by which they would promote the adsorption of
some heavy metals [23]. Wang et al. reviewed that the presence of
humic acid would result in the complexation of humic acid with metal
ions, promoting the adsorption of Pb2+ and Cu2+ on y ash [24].
Recently, the humates had been introduced into the polymer
hydrogels to enhance their water absorbencies [2527]. However,
only a few literatures were published on the adsorption performance
of hydrogels with humates. In order to know whether these hydrogels

Y. Zheng et al. / Desalination 263 (2010) 170175

are also excellent adsorbents for Cu2+, in this study, a series of starchg-poly(acrylic acid)/sodium humate (St-g-PAA/SH) hydrogels were
prepared and used as adsorbents for Cu2+ adsorption from aqueous
solution. The parameters inuencing the adsorption capacity of the
hydrogel, such as SH content, initial pH values of solution, contact
time and initial Cu2+ concentration were investigated. The effects of
competitive cation of Pb2+ were evaluated and the adsorption
mechanism of Cu2+ onto St-g-PAA/SH was also discussed.

2.1. Materials
Starch (St, Hua'ou Starch Co., Ltd., Inner Mongoulia, China) was
derived from potato. Acrylic acid (AA, chemically pure, Shanghai
Wulian Chemical Factory, Shanghai, China) was distilled under
reduced pressure before use. Ammonium persulfate (APS, analytical
grade, Xi'an Chemical Reagent Factory, Xi'an, China) was recrystallized from water before use. N,N-methylenebisacrylamide (MBA,
chemically pure, Shanghai Chemical Reagent Corp., Shanghai, China)
was used as purchased. Sodium humate (SH, Shuanglong Humic Acid
Co., Ltd., Xinjiang, China) was milled and passed through a 320-mesh
screen prior to use. Other agents used were all analytical grade and all
solutions were prepared with distilled water.
2.2. Preparation of St-g-PAA/SH hydrogels
St-g-PAA/SH hydrogels were prepared according to our previous
reports [27]. 1.44 g St and 30 mL of distilled water were put in a
250 mL four-necked ask equipped with a stirrer, a condenser, a
thermometer, and a nitrogen line. The slurry was gelatinized at 95 C
for 30 min and cooled down to 60 C, while 0.049 g of APS was added.
After 15 min, the mixture containing 10 mL of distilled water, 10.08 g
AA with 60% neutralization degree, 0.01 g MBA and a certain amount
of SH was added dropwise into the ask. The reaction was performed
at 70 C for 3 h and the resulting product was put into 400 mL alcohol
and then dried at 70 C to a constant weight. The adsorbent used for
test had a particle size in the range of 4080 mesh.
2.3. Adsorption and analysis
Adsorption experiments were carried out by agitating 50 mg of
hydrogel with 25 mL Cu2+ ion solution in a shaker at 30 C/120 rpm.
The samples were withdrawn from the asks at predetermined time
intervals and analyzed for Cu2+ content by atomic absorption
spectrometry. The adsorption capacity of the hydrogel for Cu2+ was
calculated through the following equation:

pH values (2.05.0) for 60 min. The pH values were adjusted with

0.1 mol/L HCl or NaOH solutions. During the adsorption process, the
inuences of ion strength on the adsorption capacity were investigated in the solution containing 0.02 mol/L Cu2+ and different
concentrations of NaCl (5, and 10 mmol/L), and the effects of
competitive cation, Pb2+ in this study, were also evaluated at different
Pb2+ concentrations (5 and 10 mmol/L Pb(NO3)2).
2.4. Desorption and regeneration

2. Material and methods



The desorption of Cu2+-loaded hydrogel was done using 0.1 mol/L

HCl as the desorbing agent. A xed amount (50 mg) of each adsorbent
was contacted separately with 30 mL 0.1 mol/L HCl solution. The
bottle was placed in a thermostatic shaker and shaken for 60 min at
120 rpm. At the end of the experiment, the supernatant was discarded
and the solid was washed with distilled water for several times. The
obtained sample was regenerated with 0.1 mol/L NaOH for 30 min
and then washed with distilled water for several times. The recovered
hydrogel was employed for another adsorption. The water adsorbed
during the regeneration process was taken into account when the
adsorption capacity was calculated.
2.5. Characterization
As-prepared hydrogels were characterized and the adsorption
mechanism of Cu2+ onto these hdyrogels was analyzed on a Thermo
Nicolet NEXUS TM spectrophotometer using KBr pellets.
3. Results and discussion
3.1. Adsorption kinetics for Cu2+
The effects of contact time on the adsorption capacities of the
hydrogels with different amounts of SH were studied, as shown in
Fig. 1. To make a convenient comparison, all the adsorption capacities
were represented based on per gram of polymer St-g-PAA. The
results suggest that the time to adsorption equilibrium is measured
to be 30, 10, 30, 30, 60 min for St-g-PAA, St-g-PAA/5% SH, St-g-PAA/
10% SH, St-g-PAA/15% SH and St-g-PAA/20% SH, respectively,
indicating a faster adsorption kinetics, particularly for St-g-PAA/5%
SH. When the adsorption equilibrium is achieved, the adsorption
capacities are found to be 2.80, 2.72, 2.69 and 2.61 mmol/g when 5%
SH, 10% SH, 15% SH and 20% SH is introduced, while the controlled
sample without SH shows an adsorption capacity of 2.76 mmol/g for

where q is the amount of Cu2+ adsorbed at time t or at equilibrium

(mmol/g), C0 and Ce is the initial and nal concentration of Cu2+ (mol/
L), V is the volume of Cu2+ solution used (mL) and m is the mass of the
hydrogel used (g). All assays were carried out in triplicate and the
average was used in the analysis.
For the adsorption kinetic studies, a series of solutions containing
0.02 mol/L Cu2+ were allowed to contact with 0.05 g hydrogel with
different amounts of SH. At different intervals (190 min), 2 mL
aliquot was sampled and analyzed for residual Cu2+ concentration.
When the adsorption equilibrium was achieved, the equilibrium pH
values were also recorded. To investigate the adsorption isotherms, a
series of Cu2+ solutions with different concentrations (0.003
0.02 mol/L) were kept in contact with 0.05 g hydrogel with different
amounts of SH for 60 min. The effects of pH on Cu2+ adsorption were
studied with an initial Cu2+ concentration of 0.02 mol/L and different

Fig. 1. Inuences of contact time on the adsorption capacities of hydrogels with

different amount of SH (initial Cu2+ concentration, 0.02 mol/L; pH, original;
temperature, 303 K; agitation speed, 120 rpm; and adsorbent dose, 50 mg/25 mL).


Y. Zheng et al. / Desalination 263 (2010) 170175

Cu2+. Then, it can be concluded that an appropriate addition of SH

into St-g-PAA can not only improve the adsorption rate, but also
enhance its nal adsorption capacity for Cu2+. This result is
attributed to the improved network structure of St-g-PAA/SH
compared to St-g-PAA. SH can attach to the polymer networks in
the form of grafting by which the network structure is improved [27],
and accordingly, the adsorption rate is improved and the nal
adsorption capacity for Cu2+ is shown to be higher than that of St-gPAA. As SH possesses many ionic functional groups, the ability of SH
to react with metallic cations has long been recognized and the
binding capacity is high, and thus SH can adsorb and trap Cu2+ [28],
which may also be responsible for the improved adsorption capacity.
Yi and co-worker studied the adsorption performance of sodium
humate/polyacrylamide/clay hybrid hydrogels for methylene blue
(MB) and concluded similar results that an appropriate SH content
was critical for improving the adsorption rate for MB [29].
In order to examine the controlling mechanism of adsorption
processes such as mass transfer and chemical reaction, the pseudorst-order and pseudo-second-order equations were used to test the
experimental data:
logqe qt = log qe


k2 qe 2

where qe and qt are the amounts of Cu2+ adsorbed onto hydrogels

(mmol/g) at equilibrium and at time t, respectively. k1 and k2 are the
rate constants of pseudo-rst-order (min 1) and pseudo-second-order
adsorption (g/mmol/min). The straight-line plots of log (qe qt )
against t and t/qt against t were used to determine the rate constant k1
and k2, and correlation coefcient R2 values. The initial adsorption rate
h (mmol/g/min) can be determined using the equation of h = k2q2e.
These parameters were calculated and summarized in Table 1.
The pseudo-rst-order kinetic model has been used extensively to
describe the adsorption of metal ions onto adsorbents, but in most
cases in the literature, the pseudo-rst-order equation does not t
well for the whole range of contact time and is generally applicable
over the initial 20 to 30 min of an adsorption process. The main
disadvantages of this model are (i) that the linear equation does not
give theoretical qe values that agree well with experimental qe values,
and (ii) that the plots are only linear over the rst 30 min,
approximately. Beyond this initial 30 min period the experimental
and theoretical data do not correlate well. The correlation coefcients
R2 for the pseudo-second-order kinetic plots for all the hydrogels
studied are above 0.99, indicating that the pseudo-second-order
kinetic model can describe well the experimental data, and meaning
that the adsorption process of Cu2+ onto these adsorbents is probably
controlled by the chemical process. In addition, it is obvious that when
5% SH is introduced into the hydrogel, the resulting adsorbent has
faster initial adsorption rate and higher nal adsorption capacity. That
is, an appropriate addition of SH into the polymeric networks can
promote the adsorption of Cu2+ onto the hydrogels.

3.2. pH-dependence
It is well known that the changes in pH values of an external
solution can inuence the adsorption behaviors of a metal ion by an
adsorbent. Indeed, pH affects the transition metal speciation and the
charge of functional groups in the polymer hydrogels. Fig. 2 shows the
effects of solution pH on the adsorption capacity of St-g-PAA/SH for
Cu2+. It can be seen that the adsorption capacities of the hydrogels
with different SH content show a rapid increase when pH is increased
from 2.0 to 2.7, beyond which a gradual increase in the adsorption
capacity is observed. St-g-PAA/SH is an ionic polymer matrix and its
surface charge is essentially affected by changing the pH values. At the
lower pH values, the carboxylate anions present in polymeric
networks are converted to protonated form, which can hinder the
interaction of St-g-PAA/SH with metal ion, by which the adsorption
capacities for Cu2+ decrease appreciably. Conversely, at the higher pH
values, more ionized carboxylic groups will be available, thereby
increasing interaction between positively charged Cu2+ and negatively charged carboxylate groups and causing an increase in Cu2+
adsorption. Nevertheless, little changes in the adsorption capacities
are observed when the pH values lie between 4.0 and 5.0. In this
study, the pH value of 0.02 mol/L Cu2+ solution prepared freshly is
determined to be 4.68 and thus the original pH value of Cu2+ solution
is not necessary to be adjusted for further study.
3.3. Adsorption isotherms for Cu2+
As shown in Fig. 3, the amount of Cu2+ adsorbed increases with an
increase in the initial Cu2+ concentration and remains nearly constant
after the initial Cu2+ concentration reaches 0.01 mol/L. In addition, it
can be observed from Fig. 3 that at lower initial Cu2+ concentration
(0.005 mol/L), St-g-PAA/SH shows a higher adsorption capacity for
Cu2+ compared with St-g-PAA regardless of the content of SH in the
hydrogel. Therefore, it can be concluded that the introduction of SH
into the polymer hydrogel is more benecial for the improvement of
adsorption capacity at lower Cu2+ concentration.
Adsorption properties and equilibrium data, commonly known as
adsorption isotherms, describe how pollutants interact with adsorbent materials and so, are critical in optimizing the use of adsorbents.
Then, it is important to establish the most appropriate correlation for
the equilibrium curve. In this study, two typical isotherms were used
for tting the experimental data:
Langmuir equation :

+ e

Freundlich equation : log qe = log K +

log Ce

where qe is the amount of Cu2+ adsorbed at equilibrium (mmol/g), Ce

is the equilibrium concentration of Cu2+ solution (mol/L), qm is the
monolayer adsorption capacity of the adsorbent (mmol/g), and b is
the Langmuir adsorption constant (L/mol) and is related to the free
energy of adsorption. K (mL/g) and n (dimensionless) are the

Table 1
Estimated adsorption kinetic parameters for Cu2+ adsorption.

Pseudo-rst-order model
qe, exp (mmol/g)

qe, cal (mmol/g)

k1 (min 1)


qe, exp (mmol/g)

Pseudo-second-order model
qe, cal (mmol/g)

k2 (g/mmol/min 1)

h (mmol/g/min)












Y. Zheng et al. / Desalination 263 (2010) 170175


Table 2
Estimated adsorption isotherm parameters for Cu2+ adsorption.

Langmuir model

Freundlich model


7.14 10
7.07 103
1.21 104
6.11 103
7.60 103







3.4. Effects of ion strength and coexisting ion



Fig. 2. Effects of pH on the Cu

adsorption (initial Cu
concentration, 0.02 mol/L;
contact time, 60 min; temperature, 303 K; agitation speed, 120 rpm; and adsorbent
dose, 50 mg/25 mL).

Freundlich adsorption isotherm constants, being indicative of the

adsorption extent and the degree of nonlinearity between solution
concentration and adsorption, respectively.
Adsorption equations were obtained from the experimental data
with Eqs. (4) and (5). The isotherm constants and correlation
coefcients R2 were calculated from the linear Langmuir and
Freundlich plots by plotting Ce/qe vs Ce and log qe vs log Ce. The
results were summarized in Table 2. Here it should be mentioned
that during the whole concentration studied, the linearity obtained
from Freundlich was quite poor with the R2 values lying between
0.3300 and 0.5477. As a consequence, we ignored the adsorption
capacity of all the hydrogels at lower initial Cu2+ concentration and
the calculated parameters were listed in Table 2. It is obvious that
the adsorption behavior of Cu2+ onto these hydrogels can be
satisfactorily described by the Langmuir isotherm, and the calculated monolayer adsorption capacity qm for Cu2+ is found to be 2.80,
2.83, 2.75, 2.73 and 2.63 mmol/g for St-g-PAA, St-g-PAA/5% SH, St-gPAA/10% SH, St-g-PAA/15% SH, St-g-PAA/20% SH, respectively. These
data provide powerful evidence that an appropriate addition of SH
(5% in this study) into the hydrogel can improve its adsorption
capacity for Cu2+. In addition, it is clearly observed from Table 3
that as-prepared adsorbent has higher adsorption capacity than
those of other adsorbents reported.

Generally, certain additives such as salts in the solution may

either accelerate or retard the adsorption process [36,37]. Salts may
have two functions: (i) they may screen the electrostatic interaction
of opposite charges in adsorbents and the adsorbate molecules, and
an increase in salt concentration could decrease the amount
adsorbed by an adsorbent; (ii) they may enhance the degree of
dissociation of the adsorbate molecules and facilitate the amount of
pollutants adsorbed. The situation becomes much more signicant
when both the adsorbate and adsorbent are charged bodies. So, the
ionic strength is an important factor in an adsorption process. In
this section, we discussed the effects of NaCl concentration on the
adsorption process. Background electrolytes used in this study were
5 and 10 mmol/L NaCl, as shown in Fig. 4. It seems that the
presence of appreciable quantities of Na+ has no obvious effects on
Cu2+ adsorption. This behavior may be attributed to the facts that
Na+ ion has poor afnity towards the adsorption sites of hydrogels
compared with Cu2+, and accordingly, no visible competition
between Na+ and Cu2+ for the adsorption sites is observed.
Afterward, we introduced some competitive ions, Pb2+ in this
study, to investigate the adsorption capacity of these hydrogels in
the presence of competitive ions (Fig. 4).
Competitive adsorption occurs where the adsorption of a mixture
of adsorbates is carried out on one surface. Some of the components in
the efuent may reduce the adsorption of others or may coadsorb
along with another components. In an effort to further understand the
adsorption process, we evaluated the effects of coexisting competitive
ion, Pb2+ in this study. It can be seen that the presence of Pb2+ in the
solution can affect greatly the adsorption capacity. This is ascribed to
chelation between Pb2+ and COO groups, which can compete
against Cu2+ for available adsorption sites. Nevertheless, St-g-PAA/5%
SH shows basically a higher adsorption capacity compared with St-gPAA without SH.
3.5. Adsorption mechanism
One challenge for the adsorption eld is to clearly identify the
adsorption mechanism, in particular the interactions occurring at the
adsorbent/adsorbate interface. In this work, Cu2+ adsorption onto the
surface of these hydrogels is assumed to occur through ion-exchange

Table 3
Comparison of the adsorption capacities of Cu2+ onto different adsorbents.

Fig. 3. Variation in the adsorption capacity as a function of initial Cu2+ concentration

using hydrogels with different amount of SH (contact time, 60 min; pH, original;
temperature, 303 K; agitation speed, 120 rpm; and adsorbent dose, 50 mg/25 mL).


qm (mmol/g)


Activated nylon-based membrane

Polymer modied pine bark
Thiourea-modied chitosan microspheres
Cu(II) ion imprinted composite adsorbent
St-g-PAA/5% SH


This work
This work


Y. Zheng et al. / Desalination 263 (2010) 170175

and after the adsorption, as stated above; (ii) changes in some

characteristic absorption bands. As shown in Fig. 5, the strong
absorption band at around 1629 cm 1, assigned to the OH group in
the starch, shifts to lower wavenumbers of 1616 cm 1 , and
meanwhile, the absorption band at 1567 cm 1, assigned to the
asymmetric stretching vibration of C O of carboxylate group, is
almost disappeared along with shifting to lower wavenumbers of
1562 cm 1. In addition, the absorption band at 1229 cm 1, assigning to phenolic CO stretching vibration cannot be observed after
the adsorption for Cu2+. All the information suggests that along with
the shift or disappearance of some characteristic groups, the
chelation occurs between the adsorbent and adsorbate. Considering
these discussions, it can be deduced that ion-exchange and chelation
coexist during the whole adsorption process.

Fig. 4. Effects of ion strength and coexisting competitive ion on the adsorption capacity
(initial Cu2+ concentration, 0.02 mol/L; contact time, 60 min; pH, original; temperature, 303 K; agitation speed, 120 rpm; and adsorbent dose, 50 mg/25 mL).

and chelation between positively charged Cu2+ and nonionized or

ionized carboxylic groups within the polymer hydrogels, which can be
schemed as the following equations:

eeCOOH eeCOO + H

eeCOO + Cu

2 +

2 +

eeCOO Cu

The above adsorption mechanism can be conrmed by the

following facts: (i) pH variation of the suspension when the
adsorption equilibrium is achieved. During the experiment, it was
found that the pH value decreased from the original 4.7 to even 3.0.
As we have known, these hydrogels are three-dimensional crosslinked polymer networks and have lots of COOH, which can be
served as the adsorption sites for ion-exchange and chelation. In an
aqueous solution, these COOH groups within the hydrogels
dissociate to yield protons by which the solution pH will decrease.
This has been testied by the pH variation of the suspension before

Fig. 5. FTIR spectra of (a) St-g-PAA, (b) St-g-PAA/5% SH, (c) St-g-PAA/10% SH, (d) St-gPAA/15% SH, (e) St-g-PAA/20% SH after the adsorption and (f) St-g-PAA/20% SH before
the adsorption.

3.6. Regeneration evaluation

Regeneration ability is one of important parameters characterizing
an adsorbent. In this study, we used 0.1 mol/L as the desorbing agent
and 0.1 mol/L NaOH as the regenerating agent to investigate the
regeneration ability of developing hydrogel adsorbent. Here, we can
dene the regeneration ratio as the ratio of re-adsorbed Cu2+ amount
to initial adsorbed one, as shown in Fig. 6. It is obvious that the
regeneration ratio at most cases is higher than 1, particular for
hydrogels with SH. As mentioned in the preparation process of St-gPAA/SH, AA has a neutralization degree of 60%. Accompanying the
regeneration with NaOH solution, some carboxylic groups within the
polymer networks can be transformed into carboxylate groups which
have a stronger afnity for Cu2+. In addition, precipitation adsorption
may be involved due to the stronger basic nature of hydrogel surface
as a result of regeneration treated with alkaline solution, which would
make some contributions to Cu2+ adsorption. During the experiment,
it is found that partial SH can be released from the polymeric
networks with the addition of alkaline solution, by which some micropores have been formed on the surface of an adsorbent [26], which
would afford the chance for Cu2+ entrance and increase the
adsorption capacity for Cu2+. From Fig. 6, it can also be observed
that St-g-PAA/SH with an appropriate addition of SH has higher
regeneration ratio compared with St-g-PAA, meaning that the
addition of SH into the hydrogel is favorable for the design of an
adsorbent for Cu2+ removal.

Fig. 6. The regeneration ability of hydrogels with different amounts of SH.

Y. Zheng et al. / Desalination 263 (2010) 170175

4. Conclusions
In this study, a series of hydrogels containing St and SH were
developed and used to adsorb Cu2+ from the aqueous solution. The
results indicate that 5% addition of SH into St-g-PAA can increase the
initial adsorption rate, improve the nal adsorption capacity and
benet for the regeneration ratio. This kind of hydrogel shows a
higher adsorption capacity with a pH range of 2.75.0 and the
addition of NaCl has no appreciable effects on the adsorption capacity.
The adsorbent material displays an excellent reusable ability for Cu2+
adsorption and after the forth adsorptiondesorption cycle, the
adsorption capacity for Cu2+ shows only a slight decrease compared
with the initial one. The adsorption kinetics data can be described by
the pseudo-second-order model, and the adsorption isotherm agrees
well with the Langmuir model. During the whole adsorption process,
complexation interaction is the governed adsorption mechanism.
The authors thank the joint support by the National Natural
Science Foundation of China (No. 20877077) and Science and
Technology Support Project of Gansu Provincial Science and Technology Department (No. 0804GKCA03A).
[1] G. Crini, Non-conventional low-cost adsorbents for dye removal: a review,
Bioresource Technol. 97 (2006) 10611085.
[2] P.M. Choksi, V.Y. Joshi, Adsorption kinetic study for the removal of nickel (II) and
aluminum (III) from an aqueous solution by natural adsorbents, Desalination 208
(2007) 216231.
[3] C. Gerente, V.K.C. Lee, P. Le Cloirec, G. McKay, Application of chitosan for the
removal of metals from wastewaters by adsorption-mechanisms and models
review, Crit. Rev. Env. Sci. Tec. 37 (2007) 41127.
[4] M.-H. Liao, D.-H. Chen, Preparation and characterization of a novel magnetic
nano-adsorbent, J. Mater. Chem. 12 (2002) 36543659.
[5] S. Kiatkamjornwong, K. Mongkolsawat, M. Sonsuk, Synthesis and property
characterization of cassava starch grafted poly [acrylamide-co-(maleic acid)]
superabsorbent via -irradiation, Polymer 43 (2002) 39153924.
[6] W.-F. Lee, C.-T. Huang, Immobilization of trypsin by thermo-responsive
hydrogel for the afnity separation of trypsin inhibitor, Desalination 234
(2008) 195203.
[7] Y. Zheng, P. Li, J. Zhang, A. Wang, Study on superabsorbent composite XVI.
Synthesis, characterization and swelling behaviors of poly(sodium acrylate)/
vermiculite superabsorbent composites, Eur. Polym. J. 43 (2007) 16911698.
[8] H. Kagz, A. Durmu, A. Kagz, Enhanced swelling and adsorption properties of
AAm-AMPSNa/clay hydrogel nanocomposites for heavy metal ion removal,
Polym. Adv. Technol. 19 (2008) 213220.
[9] Y. Zheng, A. Wang, Enhanced adsorption of ammonium using hydrogel
composites based on chitosan and halloysite, J. Macromol. Sci. A 47 (2010) 3338.
[10] Y. Bulut, G. Akay, D. Elma, I.E. Serhatl, Synthesis of clay-based superabsorbent composite and its sorption capability, J. Hazard. Mater. 171 (2009)
[11] S.E. Abdel-Aal, Y.H. Gad, A.M. Dessouki, Use of rice straw and radiation-modied
maize starch/acrylonitrile in the treatment of wastewater, J. Hazard. Mater. 129
(2006) 204215.
[12] Q. Chang, X. Hao, L. Duan, Synthesis of crosslinked starch-graft- polyacrylamideco-sodium xanthate and its performances in wastewater treatment, J. Hazard.
Mater. 159 (2008) 548553.


[13] A. Li, J. Zhang, A. Wang, Utilization of starch and clay for the preparation of
superabsorbent composite, Bioresource Technol. 98 (2007) 327332.
[14] C. Demitri, R.D. Sole, F. Scalera, A. Sannino, G. Vasapollo, A. Maffezzoli, L. Ambrosio,
L. Nicolais, Novel superabsorbent cellulose-based hydrogels crosslinked with
citric acid, J. Appl. Polym. Sci. 110 (2008) 24532460.
[15] F. Lionetto, A. Sannino, A. Maffezzoli, Ultrasonic monitoring of the network
formation in superabsorbent cellulose based hydrogels, Polymer 46 (2005)
[16] J. Zhang, L. Wang, A. Wang, Preparation and properties of chitosan- g-poly(acrylic
acid)/montmorillonite superabsorbent nanocomposite via in situ intercalative
polymerization, Ind. Eng. Chem. Res. 46 (2007) 24972502.
[17] Y. Zheng, J. Zhang, A. Wang, Fast removal of ammonium nitrogen from aqueous
solution using chitosan-g-poly(acrylic acid)/attapulgite composite, Chem. Eng. J.
155 (2009) 215222.
[18] Kh.M. Mostafa, A.A. El-Sanabary, Graft polymerization of different monomers onto
carbamated starches derived from native and hydrolyzed starches, J. Appl. Polym.
Sci. 88 (2003) 959965.
[19] D. Trimnell, E.I. Stout, Grafting acrylic acid onto starch and poly(vinyl alcohol) by
photolysis, J. Appl. Polym. Sci. 25 (1980) 24312434.
[20] M.I. Khalil, Kh.M. Mostafa, A. Hebeish, Graft polymerization of acrylamide onto
maize starch using potassium persulfate as initiator, Angew. Makromol. Chem.
213 (1993) 4354.
[21] D.L. Sparks, Environmental Soil Chemistry, Academic Press, San Diego, CA, 1995.
[22] J. Hizal, R. Apak, Modeling of cadmium(II) adsorption on kaolinite-based clays
in the absence and presence of humic acid, Appl. Clay Sci. 32 (2006)
[23] M. Arias, M.T. Barral, J.C. Mejuto, Enhancement of copper and cadmium
adsorption on kaolin by the presence of humic acids, Chemosphere 48 (2002)
[24] S. Wang, T. Terdkiatburana, M.O. Tad, Single and co-adsorption of heavy metals
and humic acid on y ash, Sep. Purif. Technol. 58 (2008) 353358.
[25] A. Li, J. Zhang, A. Wang, Preparation and slow-release property of a poly(acrylic
acid)/attapulgite/sodium humate superabsorbent composite, J. Appl. Polym. Sci.
103 (2007) 3745.
[26] Y. Zheng, T. Gao, A. Wang, Preparation, swelling, and slow-release characteristics
of superabsorbent composite containing sodium humate, Ind. Eng. Chem. Res. 47
(2008) 17661773.
[27] S. Hua, A. Wang, Preparation and properties of superabsorbent containing starch
and sodium humate, Polym. Adv. Technol. 19 (2008) 10091014.
[28] E.M. Logan, I.D. Pulford, G.T. Cook, A.B. Mackenzie, Complexation of Cu2+ and Pb2
by peat and humic acid, Eur. J. Soil Sci. 48 (1997) 685696.
[29] J.-Z. Yi, L.-M. Zhang, Removal of methylene blue dye from aqueous solution by
adsorption onto sodium humate/polyacrylamide/clay hybrid hydrogels, Bioresource Technol. 99 (2008) 21822186.
[30] Z.-Y. He, H.-L. Nie, C.B. White, L.-M. Zhu, Y.-T. Zhou, Y. Zheng, Removal of Cu2+
from aqueous solution by adsorption onto a novel activated nylon-based
membrane, Bioresource Technol. 99 (2008) 79547958.
[31] M. Sprynskyy, B. Buszewski, A.P. Terzyk, J. Namisnik, Study of the selection
mechanism of heavy metal (Pb2+, Cu2+, Ni2+, and Cd2+) adsorption on
clinoptilolite, J. Colloid Interf. Sci. 304 (2006) 2128.
[32] M.E. Argun, S. Dursun, M. Karatas, Removal of Cd(II), Pb(II), Cu(II) and Ni(II) from
water using modied pine bark, Desalination 249 (2009) 519527.
[33] L. Zhou, Y. Wang, Z. Liu, Q. Huang, Characteristics of equilibrium, kinetics studies
for adsorption of Hg(II), Cu(II), and Ni(II) ions by thiourea-modied magnetic
chitosan microspheres, J. Hazard. Mater. 161 (2009) 9951002.
[34] Y. Ren, M. Zhang, D. Zhao, Synthesis and properties of magnetic Cu(II) ion
imprinted composite adsorbent for selective removal of copper, Desalination 228
(2008) 135149.
[35] H. Xhen, A. Wang, Adsorption characteristics of Cu(II) from aqueous solution
onto poly(acrylamide)/attapulgite composite, J. Hazard. Mater. 165 (2009)
[36] G. Crini, P.-M. Badot, Application of chitosan, a natural aminopolysaccharide, for
dye removal from aqueous solutions by adsorption processes using batch studies:
a review of recent literature, Prog. Polym. Sci. 33 (2008) 399447.
[37] Y. Zheng, A. Wang, Evaluation of ammonium removal using a chitosan-g-poly
(acrylic acid)/rectorite hydrogel composite, J. Hazard. Mater. 171 (2009)