Colloids and Surfaces A: Physicochem. Eng.

Aspects 416 (2013) 8694

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Colloids and Surfaces A: Physicochemical and
Engineering Aspects
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Review
Recent progress on study of hybrid hydrogels for water treatment
Guanghui Jing, Li Wang

, Haojie Yu, Wael A. Amer, Lei Zhang

State Key Laboratory of Chemical Engineering, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Peoples Republic of China
h i g h l i g h t s
Hybrid hydrogels as adsorbents for
water treatment.
High mechanical strength, low cost,
easily recovered.
Outstanding adsorption capacity for
metal ions and dyes especially.
The incorporation of clay can reduce
the cost and improve the adsorption
capacity.
g r a p h i c a l a b s t r a c t
a r t i c l e i n f o
Article history:
Received 16 May 2012
Received in revised form7 September 2012
Accepted 21 September 2012
Available online 28 September 2012
Keywords:
Hybrid hydrogel
Adsorption
Water treatment
Heavy metals
Dyes
a b s t r a c t
In recent years, hybrid hydrogels have gained great attention as effective adsorbents due to their high
water retention and low cost. This paper gives an overview of the principal results obtained during
the treatment of water utilizing hybrid hydrogels for the removal of metal cations, radionuclides, dyes,
anions and other miscellaneous pollutants from water. It is evident from the literature survey that hybrid
hydrogels have shown good potential applications for the removal of various aquatic pollutants.
2012 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
2. Hybrid hydrogels for the removal of metal ions and radionuclides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3. The hybrid hydrogels for dyes removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4. The hybrid hydrogels for anions removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5. The hybrid hydrogels for other pollutants removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
6. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

Corresponding author. Tel.: +86 571 8795 3200; fax: +86 571 8795 1612.
E-mail address: opl wl@dial.zju.edu.cn (L. Wang).
1. Introduction
With the rapid development of metal plating facilities, mining
operations, leather tanning, and pesticides industries, heavy met-
als wastewater and organic compound wastewater are directly
0927-7757/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2012.09.043
G. Jing et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 416 (2013) 8694 87
or indirectly discharged into the environment increasingly. Most
of the pollutants in wastewater are known to be toxic and car-
cinogenic and hence their presence in the environment should
be controlled. Many techniques have been used for the removal
of toxic pollutants from water such as chemical precipitation,
ion exchange, membrane ltration, adsorption, coagulation,
occulation, otation, and electrochemical treatment.
Adsorption process is often considered one of the most appro-
priate methods for the removal of both inorganic and organic
pollutants. Furthermore, the adsorption process is convenient,
cheap, effective and possesses few troubles [1,2]. However, the
adsorption efciency mainly depends on the type of adsorbents.
Gels can be used as adsorbents for water treatment. Gel is a
non-uid colloidal network or polymer network that is expanded
throughout its whole volume by a uid and it has a wide range of
applications [38]. When the uid is water, this kind of gels can
be dened as hydrogel. Owing to the high water content and the
porous network structure, which allow solute diffusion through
their structure, hydrogels have attractedspecial attentionfor water
treatment. However, the poor mechanical properties and the low
kinetics properties hinder their practical applicationinwater treat-
ment.
Hybridmaterial is thematerial composedof anintimatemixture
of inorganic and/or organic components. The components usually
interpenetrate on a scale of less than 1m. So, hybrid hydro-
gels can be dened as water-swollen materials, which maintain a
distinct three-dimensional structure simultaneously and they are
composed of polymeric material and inorganic material or dif-
ferent polymeric materials. Hybrid hydrogels can overcome the
disadvantages of hydrogels by combining the advantages of the
components and sometimes hybrid hydrogels can be prepared as
a part of efforts to reduce the excessive consumption of petroleum
resources and the environmental impact resulting fromindustrial
polymers. Hybrid hydrogels have several advantages as adsorbents
for water treatment. First, incorporation of the natural materials
into hybrid hydrogels can lower the cost of water treatment, which
is the focus of water treatment industry. Second, the incorporat-
ing of different materials into hydrogels can formdifferent kinds of
hybrid hydrogels to satisfy various situations for water treatment.
For example, incorporating TiO
2
and Fe
3
O
4
into hydrogels can form
photocatalyzed hybrid hydrogels and magnetic hybrid hydrogels,
respectively [912]. Third, most of hybrid hydrogels have good
mechanical properties and tolerance of external, vigorous stirring,
this, is important for the reuseof adsorbents [13,14]. Owingtothese
advantages, hybrid hydrogels canbe potentially used as adsorbents
for water treatment.
Consequently, this review aims to serve as a summary of the
work reported in the literatures on hybrid hydrogels from the
perspective of their application for removal of various aquatic pol-
lutants e.g. metal ions, dyes, anions and so on.
2. Hybrid hydrogels for the removal of metal ions and
radionuclides
Heavy metals are not biodegradable and tend to accumulate in
living organisms and many heavy-metal ions are toxic or carcino-
genic [15]. Various toxic heavy-metal ions constituting one type of
the major pollutants in water, such as Cu
2+
, Pb
2+
, As
5+
and Cr
6+
, are
discharged into the environment during process industries, min-
ing, mineral processing, leather tanning, wood preservation and so
forth.
Among these metal pollutants, evidences showthat copper may
be a human carcinogen and can cause harmto the aqueous fauna,
although copper is very important for the human beings as an
essential trace element. Recently, Bhatnagar et al. have reviewed
Fig. 1. The chemical structure of CS.
the chitosan-basedadsorbents, whichhave shownthe highadsorp-
tion capacities for water treatment [2]. The chemical structure of
chitosan (CS) is shown in Fig. 1. Owing to its low cost and high
contents of hydroxyl and amino functional groups, CS can be used
as an adsorbent for water treatment. Dai et al. [16] have used glu-
taraldehyde(GLA) as cross-linker for thepreparationof poly(acrylic
acid) (PAA) blend CS (CS/PAA) hydrogel beads by one-step method.
For comparison, CS-GLA beads without PAA have been also pre-
pared. The GLA cross-linked CS/PAA beads had better stability in
lower pHsolutions and possessed higher mechanical strength than
CS-GLA beads without PAA. In addition, the adsorption capacity of
CS/PAA-GLA beads for copper ions was greater than that of CS-GLA
beads. As shown in Fig. 2, the efcient effects of CS/PAA-GLA beads
on removal of Cu
2+
resulted fromthe fact that carboxyl groups are
facile to form bidentate carboxylates with metal ions reversibly.
Owing to the efcient desorption of Cu
2+
from the hybrid hydro-
gel beads at pH below 4.0 and the improved mechanical strength,
the adsorption capacity of regenerated beads had no loss up to six
cycles.
The stimuli-responsive interpenetration network (IPN) gel of
poly(N-isopropylacrylamide) (PNIPAm) and poly(sodiumacrylate)
(PNaAA) have been synthesized for the removal of heavy metal
ions [17]. The structure of the IPN is depicted in Fig. 3. The rst
network of PNIPAm and the second network of PNaAA are inde-
pendent of each other. So the IPN hydrogel of PNIPAmexhibited a
thermosensitive volume-phase transition behavior in spite of the
presence of PNaAA that is well known to prevent PNIPAm from
shrinking when the temperature is above its lower critical solution
temperature (LCST). As shown in Fig. 4, the IPN gel adsorbed Cu
2+
sufciently belowits LCST but not above the LCST. Furthermore, the
IPNgel releasedwater without releasingheavymetal ions whenthe
temperature is above LCST. The adsorbed Cu
2+
can be desorbed by
means of acid treatment (0.01NHCl) of the IPNgel in swollen state
at 20

C and the IPN gel-adsorbent has been easily regenerated by

means of alkali treatment in the swollen state.
Cost is always the focus of water treatment industry. Clay can
be potentially used as an alternative of the activated carbon for
water treatment industry. Porous inorganic materials possess high
surface area and have a mechanical strength that is appropriate to
the industrial use [18]. The negative charge on the structure of clay
minerals gives clay the capability to attract metal ion [19]. Com-
pared with clay, CS is more expensive in cost. Moreover, CS also
requires complexing agents to improve its removal performance
for heavy metals. Therefore, in order to reduce the cost of hydrogel
adsorbents manykinds of clayhave beenincorporatedrecentlyinto
polymer matrices matrixes to form hybrid hydrogels. Attapulgite
(APT) is a magnesium aluminum phyllosilicate. Its brous mor-
phology, large specic surface area and moderate cation exchange
capacity are benecial for the adsorption of heavy metals from
solutions. Novel chitosan-g-poly(acrylic acid)/APT (CS-g-PAA/APT)
composites have been reported as adsorbents for the removal
of Cu
2+
from aqueous solutions [20]. More than 90% equilibrium
adsorptioncapacity of the hybridhydrogel for Cu
2+
occurredwithin
15min, and the adsorption process would get the maximumequi-
libriumlevel in 60min. The introduction of APT clay into CS-g-PAA
88 G. Jing et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 416 (2013) 8694
Fig. 2. (a) The structure of CS-GLA and (b) the postulated mechanismof adsorption and desorption of Cu
2+
by CS/PAA-GLA.
polymeric network generated a loose and porous surface, which
may accelerate the adsorption process and at the same time reduce
the cost of the hybrid hydrogel.
Sodium humate (SH) is black crystal, which contains a large
number of functional groups, such as carboxylates and phe-
nolic hydroxyls. A series of CS-g-poly(acrylic acid)/APT/sodium
humate(CS-g-PAA/APT/SH) hybrid hydrogels incorporated with
various amounts of APT have been prepared as adsorbents for the
removal of Pb
2+
fromaqueous solution [21]. The adsorption capac-
ity of the CS-g-PAA/APT/SH hybrid hydrogels for Pb
2+
increased
with increasing pH and concentration of Pb
2+
solution, and also
the adsorptioncapacity increasedwithdecreasing the particles size
of the hybrid hydrogels. However, considering the conditions in
actual application, such as energy use and the separation of adsor-
bent fromliquid phase (40100) mesh was an appropriate choice.
The adsorbed Pb
2+
ion can be desorbed by using 0.05M HCl solu-
tion as a desorbing agent. The experiment results have indicated
that the introduced APT and SH were benecial for recycling of
the hybrid hydrogel. Furthermore, the adsorption capacity of the
hybrid hydrogel was higher than 590mg/g after ve consecutive
adsorption desorption processes.
A pectin based hybrid hydrogel has been prepared by incor-
porating poly(2-acrylamido-2-methylpropanesulfonicacid)
(PAAmPSA) [22]. The incorporation of PAAmPSA improved
the hydrogels water adsorption capability and the ion sorp-
tion properties. The loading of Fe
2+
ion on biopolymers-based
hydrogels results in efcient anion sorption. So, rstly the hybrid
hydrogel was loaded with Fe
2+
and then the dried Fe
2+
-loaded
hybrid hydrogel was immersed in solution to uptake As
5+
. The
high Fe
2+
uptake by this hydrogel results in the corresponding
high adsorption of As
5+
. The As
5+
sorption process is exothermic
and pH dependent. In addition, the As
5+
-loaded hybrid hydrogel
was found to be biodegradable, so it causes no problem of waste
generation.
Application of polymeric hydrogels for the removal of heavy
metals has been hampered by difculties in separation by ltration
[12]. A magnetic cationic hydrogel was synthesized by poly-
merization of (3-acrylamidopropyl)-trimethylammoniumchloride
(APTMCl) via radical polymerization in the presence of 10nm
-Fe
2
O
3
nanoparticles [12]. Chromiumhas many industrial appli-
cations suchas woodpreservation, leather tanning, metal nishing,
pigment and refractory industries [23]. Therefore, the waste gener-
ated by these industries is rich in hexavalent Cr
6+
or trivalent Cr
3+
forms of chromium. Removal of Cr
6+
from contaminated water is
essential because it is carcinogenic and more toxic to the living
organisms than Cr
3+
. The poly(APTMCl)/-Fe
2
O
3
hybrid hydrogel
can be chosen as an adsorbent for removal of Cr
6+
and the adsorp-
tion was found to be independent on the pH of solution. The Cr
6+
Fig. 3. (a) The chemical structure of cross-linked PNIPAAmand (b) the schematic structure of IPN of PNIPAAmand PNaAA.
G. Jing et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 416 (2013) 8694 89
Fig. 4. The recyclable application of stimuli-responsive IPN gel for heavy-metal ion
adsorption.
Reprinted with permission fromRef. [17], copyright 2003 John Wiley and Sons.
removal kinetics was improved drastically by grinding the bulk
hydrogel intopowder form. The incorporationof magnetic particles
intothe polymer matrixprovideda magnetic propertyfor fast sepa-
ration. The inhibition fromcommon background electrolytes (such
as Cl

, SO
4
2
, and PO
4
3
) for Cr
6+
adsorption onto the magnetic
hydrogel is insignicant within the anions relevant concentration.
Regeneration of the magnetic hydrogel can be easily achieved by
washing the Cr
6+
-loaded hydrogel with 0.5MNaCl solution with a
recovery rate of about 90% [12].
Radioactive waste is a waste product containing radioactive
materials, and it is usually produced in a nuclear process such
as nuclear ssion [24]. Radioactivity diminishes over time, so the
waste will seriously inuence the environment for a period of
time until it no longer poses a hazard. This may mean hours to
years for some common medical or industrial radioactive wastes
or thousands of years for high-level wastes from nuclear power
plants.
Polyelectrolyte hybrid hydrogels used for the sorption of uranyl
ion (UO
2
2+
) have been prepared by the polymerization of acryla-
mide (AAm) with 2-acrylamido-2-methyl-1-propanesulfonic acid
(AMPS) and clay such as bentonite (Bent) [24]. The swelling ratio
of AAm/AMPS/Bent hybrid hydrogels can reach 15,400% in aque-
ous solution. The adsorption capacity for UO
2
2+
on the hybrid
hydrogels increased with the AMPS content increase and reached
0.49g/g. The maximum removal efciency of the hybrid hydrogel
was 25.23%. The main interactions between the hydrogel systems
and the uranyl ions were thought to be hydrophobic and hydrogen
bonding.
Because of the relatively long half-life time of cobalt, it can be
seemed as a radioactive waste. Magnetic CS hybrid hydrogel has
Fig. 5. The chemical structure of MB.
been used as adsorbent for the removal of cobalt and the modica-
tion of CS with xanthate improved the adsorption capacity of this
hybrid hydrogel [25].
A summary of adsorption capacities of hybrid hydrogels for dif-
ferent metal ions has beenpresentedinTable 1. Fromthe summary,
it can be found that fewsmart hybrid hydrogels have been studied
for the removal of heavy metals.
3. The hybrid hydrogels for dyes removal
The primary pollution of textile efuent emerges fromthe dye-
ing process. Dyeing and nishing wastes in textile industry are
highly colored and have high organic content [27]. Almost all dye
varieties are toxic, carcinogenic, and mutagenic so they can cause
health problems to human beings. Removal of dyes before the
discharge of wastewater into natural water bodies is extremely
important. The clean methods with low price and biodegradable
adsorbents could be good tools to minimize the environment
impact caused by the manufacturing and by textile efuents. Fur-
thermore, the adsorption process is also widely used for color
removal because of its low cost, effectiveness, simplicity, environ-
mental friendliness, and trouble fewer [2831].
Methyl blue (MB) has a wide range of applications, suchas color-
ing paper, temporary hair colorant, dyeing cottons and wools. The
chemical structure of MB is shown in Fig. 5. The harmful effects
of MB include heart beat increase, vomiting, shock, cyanosis, jaun-
dice, and tissue necrosis in humans. Yi et al. [32] have synthesized a
type of hybrid hydrogels fromSH, polyacrylamide, and hydrophilic
laponite (LP) clay. The hybrid hydrogel was used as an adsor-
bent to remove MB and the maximum adsorption concentration
of MB was 800mg/L/g of hydrogel. The adsorption concentration of
the hybrid hydrogel increased with increasing SH or clay content.
A chitosan-g-poly(acrylic acid)/halloysite (CS-g-PAA/HT) hybrid
hydrogel with 50% HT content has been prepared and the response
surface methodology has been employed to optimize the adsorp-
tionparameters anda highadsorptioncapacityof 1336.05mg/ghas
been achieved [33].
Montmorillonite (MMT), a layered aluminum silicate with
highly exchangeable cations and reactive groups on its surface,
Table 1
The adsorption capacities of hybrid hydrogels for various metal ions removal fromwater.
S. no. Adsorbent Adsorbate Adsorption capacity Percent uptake Sensitivity Reference
1 CS/PAA-GLA Cu
2+
121.55mg/g [16]
2 IPN gel of PNIPAmwith PNaAA Cu
2+
0.25mmol/g Thermal sensitive [17]
3 CS-g-PAA/APT Cu
2+
303.03mg/g [20]
4 CS-g-PAA/SH Pb
2+
845mg/g [21]
5 CS-g-PAA/APT/SH Pb
2+
810mg/g [21]
6 Pectin/poly(AAmPSA) As
2+
126mg/g [22]
7 Poly(APTMCl)/-Fe
2
O
3
Cr
2+
200mg/g [12]
8 Carboxymethylated pine needles Fe
2+
99.48 [26]
90 G. Jing et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 416 (2013) 8694
has also been widely used to improve water absorption ratio of
hydrogels. Starch-graft copolymers have great demand in industry
due to their low-cost, biodegradable properties and environmental
friendliness. Starch-g-acrylic acid/Na-MMT (S-g-AA/MMT) hybrid
hydrogels have been synthesized by graft copolymerization reac-
tion of starch and acrylic acid using N,N

-methylenebisacrylamide
(NMBA) as a cross-linker and cerium ammonium nitrate as an
initiator in the presence of Na-MMT micropowder [27]. This
hybrid hydrogel has been used to remove safranine T from
aqueous solutions. Increasing the ratio of Na-MMT/monomers
up to 1% has improved the ability of water absorbency,
but further increase of Na-MMT caused a decrease in water
absorbency.
IPN hybrid hydrogel can also be used in the application of dye
removal from water [34,35]. Anirudhan et al. have synthesized
IPN hybrid hydrogel and poly(methacrylic acid) grafted cellu-
lose/bentonite (PMAA-g-Cell/Bent) by the graft copolymerization
reaction[34]. Owing to the signicant mechanical properties of cel-
lulose, this hybrid hydrogel has sustainable stability over repeated
MB loading and stripping.
Among the photocatalysts, TiO
2
is believed to be the most
promising photocatalyst due to its superior photocatalytic activity,
nontoxicity, long-termstability, robustness against photocorrosion
and lowprice [36]. Incorporating TiO
2
nanoparticles into hydrogels
matrices can form hybrid hydrogels for photocatalytic removal of
dyes [9,10]. The strong binding of dyes to TiO
2
surfaces is an impor-
tant requirement for high efciency in solar energy conversion
systems [37].
The treatment of acidic waste water is usually difcult because
it can corrode the purication facilities resulting in their malfunc-
tion. Yun et al. [10] have employed the electrospining method
for the fabrication of photocatalytic nanobrous pH-sensitive
hybrid hydrogel frompoly(N,N-dimethylaminopropyl acrylamide)
(PDMAPAAm), poly(vinyl alcohol) (PVA) and TiO
2
for treatment of
acidic waste water. TiO
2
did not inuence the swelling rate and the
swelling kinetics of the hybrid hydrogel signicantly. The sonica-
tion in the nanobers preparation improved the dispersion degree
of TiO
2
in the hydrogel. The good dispersion degree of TiO
2
in
the hydrogel matrix lead to high efciency of dye decomposition
The mechanism of dyes removal was suggested in Fig. 6, the dyes
can be absorbed into the highly swollen PVA/PDMAPAAm hybrid
hydrogel under the acidic conditions and then the dyes can be
Fig. 6. The suggested mechanism of organic compound degradation by
PVA/PDMAPAAmhybrid hydrogel.
Reprinted with permission fromRef. [9], copyright 2010 Elesvier.
decomposed effectively by the photocatalytic activity of TiO
2
with
the UV light.
Generally, for improving the mechanical properties and
exhibiting the pH-sensitive swelling behavior of hydrogel,
PVA and PAA were selected as the components, respectively.
Photocatalytic activity was heightened greatly in the basic
medium and a large surface area of hydrogel was available
for TiO
2
by using nanober supports [38]. The hybrid hydrogel
poly(N-isopropylacrylamide)/TiO
2
(PNIPAAm/TiO
2
) was prepared
via seeded emulsion polymerization of N-isopropylacrylamide
(NIPAAm) in the presence of N,N

-methylene-bis(acrylamide)
(MBA) which acts as the cross-linking monomer [39]. The pres-
ence of TiO
2
nanoparticles in the composite did not inuence the
excellent thermosensitivity of PNIPAAm. The hybrid hydrogel has
potential application in the remediation of wastewater streams.
A photocatalytically degradable TiO
2
/poly[acrylamide-co-
(acrylic acid)] (TiO
2
/poly[AAm-co-AA]) hybrid hydrogel was
reported for textile dye degradation [40]. The TiO
2
particles were
dispersed throughout the hybrid hydrogel (TiO
2
/poly[AAm-co-
AA]). Without photodegradation, the hybrid hydrogel adsorbed up
to 85% of the MB froma 5mg L
1
MB solution within 15min. Com-
bining the effect of photodegradation and the effect of adsorption,
the hybrid hydrogel can photocatalytically degrade 91% of the
total MB in aqueous solution. In addition, the hydrogel composite
can be photodegradable under UV irradiation, so it does not
cause the second pollution into the water. TiO
2
(P25)-graphene
hybrid hydrogel can be also used as adsorbent to remove MB [41].
Compared to the bare P25 hydrogel, TiO
2
(P25)-graphene hybrid
hydrogel has a higher reaction rate in the decomposition of MB,
which may be attributed to the three-dimensional structure of the
hybrid hydrogel that improves the attachment of MB to TiO
2
.
CS-based hydrogels have higher adsorption for various dyes
than those of commercial activated carbon. However, the poor
mechanical properties of CS-based hydrogels are serious imped-
iments to their practical application. Carbon nanotubes (CNT) is
considered one of the most promising nano-llers used to enhance
the mechanical properties of polymer matrices. Moreover, CNT is
an effective adsorbent. Interpenetrating CNT into the CS hydro-
gel matrix can improve the mechanical properties as well as the
hydrogels adsorption capacity [13,42]. The addition mode of CNT
for the production of CS/CNT hybrid hydrogel beads affects their
adsorption for anionic dyes. For example, Chatterjee et al. [43] have
synthesized CNT-impregnated CS beads by four different strate-
gies for dispersing CNT: (a) in CS solution, (b) in sodium dodecyl
sulfate (SDS) solution, (c) in CS solution containing cetyltrimethy-
lammonium bromide (CTAB), and (d) in SDS solution for gelation
with CTAB-containing CS solution. Due to the presence of CNT on
the outer surface of the CS/CNT beads synthesized by strategy (d),
they exhibited maximum adsorption capacity (375.94mg/g) for
Congo red. Increasing the CNT content in CS/CNT hybrid hydrogel
ratio up to 0.01wt% causes an increment in Congo red absorbency,
but further increase of CNT content caused a decrease in Congo
red absorbency. Moreover, the sulfur (%) in the CS/CNT beads has
improved the adsorption property for Congo red [13].
In addition, coreshell membrane structural CS/SDS beads
can be used to remove Congo red from wastewater [44]. The
hybrid hydrogel CS/SDS beads had higher mechanical strength
and acid stability than CS beads formed by alkali gelation.
Hybrid supramolecular hydrogels can also be chosen as adsor-
bents for the removal of dyes formaqueous solutions. Wang et al.
have prepared a hybrid hydrogel through incorporating fmoc-
3-(2-naphthyl)-d-alanine supramolecular hydrogel into agarose
hydrogel [45]. Fig. 7(a) and (b) shows the chemical structures
of fmoc-3-(2-naphthyl)-d-alanine and agarose respectively. The
available mechanism for the removal of MB by the hybrid hydro-
gel is shown in Fig. 7(c). The fracture stress of the hybrid hydrogel
G. Jing et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 416 (2013) 8694 91
Fig. 7. The chemical structures of (a) fmoc-3-(-2-naphthyl)-d-alanine and (b) agarose and (c) the available mechanismof removal of MB by the hybrid hydrogel.
was found to be 12.9kPa which is higher than the fracture stress
of any single hydrogel, supramolecular hydrogel or agarose hydro-
gel. The high efciency of the hybrid hydrogel for removing MB
frompolluted water relies on its hydrophobic part. The analysis of
the interactions between MB with the hybrid hydrogel indicated
that MB had a strong interaction with fmoc-3-(2-naphthyl)-d-
alanine.
A summary of the adsorption capacities of hybrid hydrogels for
different various dyes is presented in Table 2.
4. The hybrid hydrogels for anions removal
Inorganic anions are one of the element classes of aquatic pol-
lutants and many inorganic anions possess harmful effects on
drinkingwater sources. Theremoval of thesepollutants fromdrink-
ing water supplies is an emerging issue. In recent years, many
hybrid hydrogels have been successfully utilized for some anions
removal fromwater [4648].
Nitrogen compounds are necessary elements for living orga-
nisms. Nevertheless, when they are more than needed, they can
lead to accelerated eutrophication of lakes and rivers, dissolved
oxygen depletion and sh toxicity in receiving water, leading a
number of healthproblems involving living species suchas humans
and animals [49]. Nitrate is an inorganic form of nitrogen pollu-
tion and is one of the limiting factors causing eutrophication. The
adsorption of nitrate by poly(dimethyl diallyl ammonium chlo-
ride)/polyacrylamide (PDMAAC/PAAm) hybrid hydrogel has been
examined by Zheng et al. [48]. The adsorption capacity increased
with the increase of contact time up to several minutes. After
the initial increase, the adsorption capacity decreased and the
adsorption process reached its equilibriumat 60min. Additionally,
the adsorption capacity increased with increasing PDMDAAC con-
tent until 50wt% beyond which a sudden decrease was observed.
The calculated maximum adsorption capacity was 19.6mg N/g.
The ion strength and the presence of competitive phosphate ions
have negative effects on the adsorption of hybrid hydrogel with
high content of PDMDAAC. However, this cationic hydrogel had
good adsorption capacities of 5.46mg N/g and 4.9mg N/g that
can be achieved at high saline concentration and competitive
ion solutions (10mmol/L). This hybrid hydrogel also exhibited
good regeneration ability because the adsorbed nitrate ions can
be desorbed efciently in strong acidic or basic media. The zeta
potential and conductivity of the hydrogels increased with the
increase of PDMDAAC content which testied that the electrostatic
attractionplays animportant role duringthe whole adsorptionpro-
cess. It was considered that swelling and electrostatic attraction
were two main adsorption mechanisms for the whole adsorption
process.
Chauhan et al. prepared cation and anion adsorbents from
lignocellulosics using pine needles and their carboxymethylated
forms by network/hydrogel formation with acrylamide and N,N-
methylene bisacrylamide. The hybrid hydrogels were further
functionalized by partial alkaline hydrolysis with 0.5MNaOH. This
hybrid hydrogels had the maximum adsorption capacity when it
Table 2
The adsorption capacities of hybrid hydrogels for dyes removal fromwater.
S. no. Adsorbent Adsorbate Adsorption capacity Removal efciency Reference
1 CS-g-PAA/HT MB 1336.5mg/g [33]
2 S-g-AA/MMT MB 2237mg/g [27]
3 TiO
2
/PVA/PDMAPAAm MB >90% [28]
4 TiO
2
/poly[AAm-co-AA] MB 90% [31]
5 Fmoc-3-(2-naphthyl)-l-alanine/agarose MB 97.7% [35]
6 PVA/TiO
2
Procion blue 92% [27]
7 PVA/TiO
2
Acridine orange 92% [27]
8 TiO
2
/PVA/PAA Coomassie brilliant blue >95% [38]
9 TiO
2
(P25)-graphene MB 87.63mg/g [41]
10 CS/CNT beads Congo red 423.34mg/g [42]
11 magnetic CS/PVA hybrid hydrogel Congo red 470.1mg/g [31]
12 CS/CNT beads Congo red 450.4mg/g [13]
13 CNT-impregnated CS beads Congo red 375.94mg/g [43]
14 CS/SDS beads Congo red 208.3mg/g [44]
92 G. Jing et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 416 (2013) 8694
Table 3
The adsorption capacities of hybrid hydrogels for anions removal fromwater.
S. no. Adsorbent Adsorbate Adsorption capacity Removal efciency Reference
1 Cu
2+
-loaded CS hydrogel beads Phosphate 28.86mg/g [47]
2 PDMAAC/PAAm Nitrate 19.6mgN/g [48]
3 Carboxymethylated pine needles Nitrate 78.9% [26]
was loaded with Fe
2+
and could be used as novel anionic adsorbent
for nitrate [26].
Over the years, the presence of excess amounts of phosphate
anions in water has drawn substantial research attention because
it is believed to be one of the main reasons for eutrophication
and water quality problems. The presence of trace amounts of
phosphate anions, in the treated wastewater from municipalities
and industries, often leads to eutrophication (excess nutrients and
associated effects such as rapid growth of blue green algae and
hyacinth-like plants), which results in short-term and long-term
environmental problems in lakes, coastal areas, and other conned
water bodies [50].
Traditionally, the treatment for disused adsorbents is usually
recovery for recycling or direct discarding. As discussed before, CS
hydrogel beads (CS) are effective bio-adsorbents for the removal
of many heavy metal ions fromaqueous solutions. The disused CS
after the removal of Cu
2+
can be directly applied to adsorb phos-
phate from the aqueous solutions [47]. The pH value of solution
had a great impact on the adsorption capacity of phosphate and
the results indicated that the maximumadsorption capacity (about
28.86mg/g) was achieved at around pH 5.0.
A summary of adsorption capacities of hybrid hydrogels anions
is presented in Table 3.
5. The hybrid hydrogels for other pollutants removal
Much of the natural organic materials found as pollutants in
water come from domestic sewage and the efuents of farms and
food-processing industries. These organic materials are biodegrad-
able. However, the decomposing process of organisms would
exhaust the oxygen in water. This brings about the death of many
animals in the water, and few plants thrive when organic pollu-
tion is severe. Rao et al. synthesized magnetic cationic hydrogel
(MCH) by radical polymerization of (3-Acrylamidopropyl)tri-
methylamoniumchloride(APTMACl) [11]. This MCH canbeusedfor
the removal of natural organic materials and the main mechanism
of this removal was considered to be electrostatic adsorption. With
a dosage of 37.5mg L
1
, the hybrid hydrogel could almost achieve
a 100% removal of Aldrich humic acid. The MCH dosage applied is
comparable with the dosage of coagulants used to remove the nat-
ural organic materials fromdrinking water. However, the MCH can
be regenerated by immersing in NaCl solution.
The hybrid hydrogel of PNIPAm/TBP (tributylphosphate) can be
used to remove the phenol from aqueous solutions because TBP
forms a one-to-one complex with phenol molecule by hydrogen
bonding [51]. Pan et al. [14] reinforced the hybrid hydrogel with a
Fig. 8. Appearance of NIPAM/TBP hybrid gel, composite gel and used composite gel.
Reprinted with permission fromRef. [14], copyright 2008 Elsevier.
thincoatinglayer of calciumalginategel, whichwas cross-linkedby
bivalent calciumions. As shown in Fig. 8, the mechanical strength
of the hybrid hydrogel was apparently improved by the coating
of calcium alginate gel. Meanwhile, the thin coating hardly hin-
dered the diffusion of phenol due to the superior hydrophilicity of
calcium alginate gel. The phenol can be desorbed from the rein-
forced hybrid hydrogel in basic aqueous solution. Owing to the
sufcient durability provided by the coating of calcium alginate,
the hybridhydrogel cancarry out repeatedcycles of adsorptionand
desorption.
Ammonium(NH
4+
) also is an inorganic ion formof nitrogen pol-
lution. At the same time, it is one of the limiting factors causing
eutrophication. A hybrid hydrogel composite CS-g-PAA/rectorite
has been used for the removal of ammonium from aqueous solu-
tions [52]. Although the adsorption capacity decreased with the
increase of content of rectorite in the hydrogel composite, the
incorporation of rectorite into the polymer matrix can reduce the
production cost.
Incorporating HT particles into CS-g-PAA can enhance the
hydrogels adsorption capacity for NH
4+
because the introduc-
tion of the HT particles improved the hydrogels porosity, which
can enhance the contact of the hydrogel with NH
4+
[53]. The
hybrid hydrogel CS-g-PAA/HT had a particle size of 4080mesh.
The well-dened three-dimensional structure and the presence
of the hydrophilic anionic groups on the chains were consid-
ered the governed mechanism for the higher adsorption capacity
Table 4
The adsorption capacities of hybrid hydrogels for other pollutants removals fromwater.
S. no. Adsorbent Adsorbate Adsorption capacity Removal efciency Reference
1 Poly(APTMACl)/-Fe
2
O
3
Aldrich humic acid About 400mg/g About 100% [11]
2 Poly(APTMACl)/-Fe
2
O
3
Suwannee River humic acid About 300mg/g [11]
3 Poly(APTMACl)/-Fe
2
O
3
Suwannee River fulvic acid About 450mg/g [11]
4 PNIPAm/TBP/PVA Phenol >80% [51]
5 PNIPAm/TBP/calciumalginate Phenol >80% [14]
6 PAA/rectorite Ammonium 40110mg N/g [52]
7 CS-g-PAA/HT Ammonium 40.9mg N/g [53]
8 PAA/BT Ammonium 32.87344.47mg N/g [54]
G. Jing et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 416 (2013) 8694 93
for NH
4+
removal. Meanwhile, the hybrid hydrogel showed
pH-independence within the range of 4.07.0. The adsorption
equilibrium can be achieved within 5min with the equilibrium
adsorption capacity of 27.7mg N/g.
As a good adsorbent, it not only needs fast adsorption rate and
high adsorption capacity, but also requires good regeneration abil-
ity for multiple uses. A series of hydrogel composites composed of
biotite (BT) particles and PAA have been prepared at room tem-
perature via a self-induced redox system based on ammonium
persulfate and Fe(II) arisen fromiron-rich BT. After activation with
NaOH, the hydrogel composites can be used as an adsorbent for the
removal of ammonium from aqueous solutions [54]. The hydro-
gel composites were applied in a wide pH range (4.09.0) with the
maximumadsorption capacity of 344.47mg N/g. After six cycles of
adsorptiondesorption processes, there was only a slight decrease
in the adsorption capacity.
A summary of adsorption capacities of hybrid hydrogels for
other pollutants is presented in Table 4.
6. Conclusion
This review mainly covered the recent developments on the
hybrid hydrogels used as adsorbents for water treatment and
reported the main advances. Firstly, many hybrid hydrogels have
high adsorption capacities for aquatic pollutants. The maximum
adsorption capacities of hybrid hydrogels reported in this paper
would provide some ideas of the sorbents effectiveness for each
type of pollutants. The use of hybrid hydrogels for removal of
various pollutants from water and waste water presents many
attractive features such as the outstanding adsorption capacity,
especially for metal ions and dyes, and the fact that these mate-
rials are low cost and nontoxic. Secondly, many of the reported
hybrid hydrogels that have high mechanical durable property can
be regenerated conveniently which can further reduce the cost of
thewater treatment process. However, somehybridhydrogels have
just been testied the feasibility as sorbents for the removal of pol-
lutants from aqueous solutions, so, lots of work need to be done.
Last but not the least, the synthesis of hybridhydrogel is simple and
it is easy to develop new kinds of hybrid hydrogel to suit different
demands.
There are several requirements of hybrid hydrogels for water
treatment: (1) new kinds of hybrid hydrogels with cheaper raw
materials; (2) improving the mechanical properties of hybrid
hydrogels; and (3) functionalization of hybrid hydrogels to make
themenvironmentally responsive. Undoubtedly, hybrid hydrogels
offer a lot of promising benets for commercial purpose in the
future.
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