Separation Science and Technology

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Recent review for removal of metal ions by

hydrogels

Aabid H. Shalla, Zahid Yaseen, Mushtaq A. Bhat, Tauseef A. Rangreez &

Masrat Maswal

To cite this article: Aabid H. Shalla, Zahid Yaseen, Mushtaq A. Bhat, Tauseef A. Rangreez &
Masrat Maswal (2018): Recent review for removal of metal ions by hydrogels, Separation Science
and Technology, DOI: 10.1080/01496395.2018.1503307

To link to this article: https://doi.org/10.1080/01496395.2018.1503307

Published online: 06 Aug 2018.

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SEPARATION SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/01496395.2018.1503307

Recent review for removal of metal ions by hydrogels

Aabid H. Shallaa, Zahid Yaseena, Mushtaq A. Bhata, Tauseef A. Rangreeza, and Masrat Maswalb
a
Department of Chemistry, Islamic University of Science and Technology, Awantipora, Kashmir, India; bGDC Boys Pulwama, Kashmir, India

ABSTRACT ARTICLE HISTORY

A continuous research is going to synthesize the novel adsorbents for removal of toxic metal ions Received 8 March 2018
having high sorption capacity along with non-toxic and biodegradable nature. Ionic impurities Accepted 18 July 2018
have been removed in many ways. However, hydrogels with high sorption capacity, high func- KEYWORDS
tionality, hydrophilicity, regeneration and nontoxicity have made them a good contender for the Hydrogels; biodegradable;
removal of various aquatic pollutants, including heavy metal ions. Moreover, certain modifications sorption capacity; metal
in synthesis of hydrogels, to customize them in response to different stimuli like temperature, pH ions; toxicity
and ionic strength, has added an advantage in waste water treatment. The present review
provides recent progress in the synthesis of the hydrogels for waste water treatment and insight
into increase in selectivity, efficiency and reusability of hydrogels.

Introduction hydrogel have attracted special attention as they have

better mechanical properties and tolerance of external
Urbanization viz-a-viz rapid development of metal plat-
vigorous stirring, which is important for the reuse of
ing facilities, mining operations, leather tanning and
adsorbents. They have attracted considerable attention
pesticides industries results huge discharge of the efflu-
for their potential applications in agriculture, biomedi-
ents containing toxic substance, such as heavy metal
cine and biomedical, cosmetics and food industry
ions, dyes and organic pollutants into the environment
(Fig. 1) but our focus will be application of hydrogel
and in particular water bodies. Owing to toxic and
for waste water treatment.
carcinogenic character of effluents; release of toxic
Hydrogels have physically well-defined three dimen-
waste in the environment should be controlled.
sional porous structures and have chemically respon-
Many techniques have been used for the removal of
sive functional groups, which enable them to readily
toxic pollutants from water, such as chemical precipita-
capture metal ions and dyes from wastewater and to
tion, ion exchange,[1] membrane filtration,[2]
release these toxic pollutants upon changes in aqueous
coagulation,[3] flocculation,[4] flotation,[5] electrochemi-
solution conditions. The hydrophilic character of
cal treatment[6] and adsorption.[7–9] Adsorption is by
hydrogel adsorbents enable to form a flexible network
far the most effective and non-destructive technique
of polymer chains, which allow solutes to quickly pene-
that is widely used for the removal of dyes and metal
trate into the network with water and to form stable
ions from aqueous solutions. Numerous approaches
complexes with functional groups.[23] They are three-
have been made by various researchers to develop
dimensional hydrophilic polymers that absorb large
cheaper and effective adsorbents to remove metal ions
amounts of water, swell to form a solid gel while main-
and dyes from waste water.[10,11] The removal of metal
taining their physical structure without dissolving.
ions from industrial wastewater is considered as an
Due to their high potential for effective removal of
important application of adsorption processes.[12]
heavy metals[22–27] and dyes,[28,29] they are well suited
Flexibility in synthesis and modification of adsorbent,
for waste water treatment. Sorption of heavy metals
regeneration for multiple uses and availability of differ-
and dyes ion is due to the presence of hydrophilic
ent adsorbent materials, such as activated carbon,[13]
functional groups, such as carboxylic acid, amine,
zeolite,[14] clay,[15] ion exchangers,[16] bark,[17]
hydroxyl and sulfonic acid groups that act as complex-
biomass,[18] lignin,[19] chitosan[20] and other polymer
ing agent for the removal of metal ions from aqueous
adsorbents[21,22] have made adsorption a technique of
solutions. Hydrogels swell up to several times of their
choice for treatment of waste waters. In last few years,
original volume in aqueous media which results in

CONTACT Aabid H. Shalla [email protected] Department of Chemistry, Islamic University of Science and Technology, Awantipora, Kashmir, India
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsst.
© 2018 Taylor & Francis
2 A. H. SHALLA ET AL.

between the positively charged metal cations and the

Agricalture
negatively charged active sites distributed everywhere
along the hydrogel structure and these active sites gov-
Applications
Biomedical
Hydrogels

ern the whole uptake of the metal cations by the hydro-

Food Industry gels. The most widely abundant function groups present
in the structure of any hydrogel are hydroxyl groups and
Cosmetic
carbonyl groups.[34] Functional groups like carboxyl
Water treament groups were found to have a very governing role in
removing heavy metal cations that they bind through
salt formation Fig. 2. Besides adsorption mechanism,
there is contribution of the ion exchange mechanism in
Figure 1. Applications of hydrogels. the overall metal uptake by the hydrogels containing
carboxyl groups in their structures. The efficiency of
the native polymer in removing heavy metals from aqu-
interaction and sorption of dyes and metal ions on to eous solutions is not high compared to the semi-inter-
polymers chains that become accessible only after the penetrating polymer network hydrogel. This is due to
hydrogel opens up in aqueous phase. The network of the low accessibility of polymers in the native form,
hydrophilic polymers can swell in water or biological which does not allow the ionic species to migrate to the
fluids and hold a large amount more than 400 times its bulk of the polymer. For example, although native cellu-
original weight more than 20% of their dry weight.[30] lose and native starch contain large number of hydroxyl
Hydrogels can be regenerated as it is insoluble in groups, these hydroxyl groups are not available to
water because of the presence of chemical crosslink, undergo coordination with heavy metals, when in con-
which increases their mechanical strength but at the tact with them in aqueous solutions due to the high
same time decrease the swelling ratio in hydrogels. A crystallinity of the native cellulose and the amylose con-
balance between the selling ration and amount of stituent of native starch. Hydrogels have gained particu-
crosslinking is maintained to obtain the better lar interest in wastewater treatment due to their high
hydrogel.[31,32] These properties are exploited in the adsorption capacities, regeneration abilities and reuse
field of adsorption for the removal of ionic impurities for continuous processes. The adsorption of metal ions
and recalcitrant organic dyes. They are usually pre- by hydrogel is schematically represented in Fig. 3.
pared from polar monomers and according to their El-Naggar et al.[35] irradiate the different ratio of
starting materials; they can be divided into natural mixture of acrylic acid (AA) and sodium aliginate
polymer hydrogels, synthetic polymer hydrogels and after purging with nitrogen to remove oxygen to
combinations of the two classes. Hydrogels can be synthesize the AAc/AG hydrogel. The hydrogel was
classified as physically and chemically cross-linked then tested for the adsorption of metal ions; it was
gels. In the first case, the networks are held together found that AAc/AG hydrogels showed higher affinity
by physical forces, including ionic, Hydrogen bonding for Co+2 and Ni+2 ions, the order of absorption of
or hydrophobic forces, while in the second case, the different metal ions by AAc/AG hydrogels follows the
gel has covalently cross linked networks. order: Cu+2 > Co+2 > Ni+2. The effect of temperature
and pH on the swelling of hydrogel showed that that
the pH-sensitivity increases with increasing the AG
Hydrogels for removal of ionic impurities ratio in the hydrogel up to 10% and then tends to
The ionic impurities are very toxic and non-biodegrad- decrease by increasing the ratio of AG to 15%. Sang
able; hence they can readily be accumulated in an eco- Cheol Lee et al.[23] prepared a composite hydrogel of
logical system to induce irreversible pollution or in hydroxyapatite/polyacrylamide. Hydroxyapatite [Ca10
human body to cause adverse health effects.[33] (PO4)6(OH)2, HAp], a major inorganic constituent of
Recently, there has been increase in synthesis of various the hard tissue (bone and teeth) in the human body, is
hydrogels and their adsorption behavior for heavy usually provided in powder or calcined pellets forms,
metals and dyes were investigated. The hydrogels con- which are disadvantageous. However, high removal
tain functional groups with known affinity for metals, so capacity of hydroxyapatite for divalent heavy metal
it is advisable to test their performance at a range of ions from aqueous solution can be done by converting
concentrations of the particular metal. Adsorption of the it to hydrogel. The gel has been tested for the removal
metal ions by hydrogels takes place by the attraction of hazardous and toxic Pb2+ metal ions. Lead being a
mechanism, depending on the difference in charge potential carcinogen, which causes nerve breakdown, is
 SEPARATION SCIENCE AND TECHNOLOGY 3

Figure 2. Metal ion sorption mechanism on polymeric hydrogel with crosslinker.

always a concern for scientists to remove it from waste from aqueous solutions. Effect of factors like pH value
waters. The equilibrium removal capacities of the com- of the solution, the contact time and the concentrations
posite gels with 30, 50 and 70 wt.% HAp contents are of the adsorbent and adsorbate were studied. The
evaluated to be 123, 178 and 209 mg g−1, respectively. adsorption data agreed with the Langmuir and
The swelling decreases with increase in content of Freundlich isotherms. Essawy and Ibrahim[38] prepared
hydroxyapatite, whereas increase in percentage of poly (vinylpyrrolidone-co-methylacrylate) hydrogel and
hydroxyapatite results increase in absorption of lead studied the tendency of this copolymer gel to extract
ion; this confirms that adsorption is due to the hydro- different metal ions (Cu2+, Ni2+ and Cd2+) from syn-
xyapatite that is responsible for removal of lead ions thetic wastewater under various conditions of pH and
because of increased removal sites. Zhao et al.[36] devel- exposure time. The gel showed better binding capacities
oped a hydrogel based on physical linkage; chitosan for Cu2+ than Cd2+ than for Ni2+ ions. Ju et al.[39]
and CMC was mixed to form Chitosan-CMC hydrogel developed the ion-recognition P(NIPAM-co-BCAm)
was then tested for the adsorption of Cu2+ ions. The hydrogels for removal of Pb2+ ions. The gel developed
adsorption of copper ions on the synthesized hydrogel is thermo-sensitive polymer, exhibits a reversible
was explained on the basis of interaction of copper ion volume change as the surrounding temperature varies.
with carboxyl groups and amino groups. The equili- The hydrogel can be therefore, tuned to adsorb and
brium removal capacities of the composite gels for release the lead ions as and when required by changing
adsorption Cu2+ ions was found to be nearly the external temperature. The mechanism of the release
169.49 mg/g. This gel can be used as efficient adsorbent of the lead ion was explained on the basis of shrinking
for the removal of Cu2+ ions. Ashem et al.[37] prepared of the hydrogel above its lower critical solution tem-
three types of hydrogels through the graft polymeriza- perature (LCST); the mechanism is called as “stretch-
tion of acrylonitrile onto maize starch, and ceric to-shrink” configuration change of copolymer net-
ammonium nitrate was used as the initiator. The works, which is triggered by the change in environ-
hydrogels were used to remove Hg (II) by Hg2+ ions mental temperature (Fig. 4). The utility of the material
4 A. H. SHALLA ET AL.

The results clearly show the advantage of this material

to that of other. The adsorption capacity for Cu2+ ion
reported is 177.9 mg g−1. In comparison with some of
the other hydrogels based on natural polymers
(Table 1), the capacity of natural polymers for uptake
of metal ions was found to be more; may be because of
abundant number of active site available for interac-
tion. Chauhan et al.[44] reported the preparation of
polycarboxylated starch-based hydrogels as Cu2+ ion
sorbents. The studies showed that the sorption of Cu2
+
depended on the structure of the hydrogel and the
external stimuli. The hydrogel prepared from the oxi-
dized starch showed the highest uptake among all the
series of functional starches. Sorption data exhibited
good match with Langmuir and Freundlich isotherms.
Figure 3. Schematic representation of adsorption of metal ions
The authors reported the FTIR spectra of the ion-
by hydrogel. loaded hydrogels, which confirmed the Cu2+ uptake
on hydrogels occurred by chelation of Cu2+ ions with
–CO2H and –C = O or –OH groups of the hydrogel.
was that it was used as adsorbents for removal of lead The maximum sorption capacity of 128.26 mg g−1 was
ions from aqueous solutions and then it also conveni- obtained in 2 h at 40°C, 7.0 pH, and 50 ppm of Cu2+
ently releases the absorbed lead ions as a response to ions.
external stimuli. Dai et al.[45] have used glutaraldehyde (GLA) as
Selva et al.[40] synthesized poly[2-(acrylamido)-2- cross-linker for the preparation of PAA blends CS
methyl-1-propanesulfonic acid-co-itaconic acid] hydro- (CS/PAA) hydrogel beads by one-step method. For
gel. The importance of this hydrogel was its tendency to comparison, CS-GLA beads without PAA have been
remove metal ions under noncompetitive conditions, in also prepared. The GLA cross-linked CS/PAA beads
order to determine the effect of the absence/presence of had better stability in lower pH solutions and possessed
competing metal ions for complex formation with higher mechanical strength than CS-GLA beads with-
functional groups of polymers. Further, it was observed out PAA. In addition, the adsorption capacity of CS/
that as the gel remains for the larger time, acidity of PAA-GLA beads for copper ions was greater than that
aqueous solution containing lead ions increased. This of CS-GLA beads. The efficient effects of CS/PAA-GLA
has been attributed to exchange of H+ ions as a result of beads on removal of Cu2+ resulted from the fact that
ion exchange between metal ions and –SO2OH and – carboxyl groups are facile to form bidentate carboxy-
COOH groups. An interpenetrating network hydrogel lates with metal ions reversibly. Owing to the efficient
was made by Tang et al.[41] The efficiency of the hydro- desorption of Cu2+ from the hybrid hydrogel beads
gel in both swollen and dried condition was studied. below pH 4.0 and the improved mechanical strength,
The author reported that efficiency of removing metal the adsorption capacity of regenerated beads had no
ions using the swollen hydrogel was greater than that loss up to six cycles. The experimental equilibrium
using the dried composite. Ni2+, Cr3+ and Cd2+ were
studied; the maximum adsorption was found to be
102.34 mg g−1 for Ni2+ ions followed by Cr3+. Wang Table 1. Comparative adsorption capacity of some hydrogels
et al.[42] prepared a series of starch-g-poly(acrylic acid) for copper (II) ions.
S. Maximum absorption for
(PAA)/sodium humate (St-g-PAA/SH) hydrogels for No. Hydrogel Cu2+ ions (mg g−1) Reference
adsorption of Cu2+ from the aqueous solution. The 1 Chitosan-CMC hydrogel 170 [38]
[39]
authors reported that the hydrogel exhibited a higher 2 Starch-g-poly (acylic acid) 177
sodium humate
adsorption capacity within a pH range of 2.7–5.0. FTIR 3 Polycarboxylate starch 128.26 [40]

spectra results of hydrogels before and after adsorption based hydrogel

[41]
4 Polyacrylic acid hydrogel 120.27
of Cu2+ ions showed that complexation was the main With linker glutaraldehyde 66.27
adsorption mechanism. The adsorption isotherm was (GLA)
in agreement with the Langmuir model. The author has Without Linker GLA
[43]
5 Cellulose graft 175
compared the adsorption capacities of the synthesized polyacrylamide
hydrogel with other adsorbent for removal of Cu ion. hydroxyapatite
 SEPARATION SCIENCE AND TECHNOLOGY 5

uptakes of Cu (II) on CS-GLA and CS/PAA-GLA beads (4-VP)–based hydrogels with 2-hydroxyethylmetacry-
were average 66.27 and 120.27 mg g−1, respectively. late (HEMA) and magnetic composites were prepared
Melike Fırlak et al.[46] synthesized N-vinyl imida- and tested for use in the removal of UO2+ and Th4+
zole-based uniform porous hydrogels for uptake of ions from aqueous environments. The synthesized
Pb2+. The authors choose the imidazole as the metal hydrogel was used for the removal UO2+ and Th4+
ion chelate as polymers with nitrogen-containing com- from aqueous environments, as 4-VP is an interesting
plex ligands show a great adsorption capacity for poly- material that can complex with metal ions by means
valent metal cations owing to the strong affinity of its nitrogen atom, can be further employed to
between the nitrogen atom and metal cations. As the create charge and hydrophobic groups, and addition-
pH of the medium influence, the amount of adsorption ally can be readily polymerized. The mechanism of
the effect of pH was studied. The adsorption experi- uranium uptake was formulated by the author
ments were carried out in the range of pH 2.0–5.0.The through scheme given in Fig. 6. The pyridine has a
pH of the medium has two kinds of influence on metal strong ability to form the complex ion, which results
uptake: an effect on solubility and speciation of metal in strong interaction of the uranium ions with the
ion in aqueous solution, and an overall charge of the hydrogels. Peng et al.[49] reported a novel porous bio
ligand of the adsorbent. The maximum absorption adsorbent hydrogel system obtained by graft copoly-
capacity was found to be at pH 4.5. The maximum merization of AA and Xylan rich hemicellulose and
absorption capacity for Pb2+ by using the hydrogel successfully employed it for adsorption of heavy metal
was found to be 30.38 mg/g of adsorbent. The mechan- ions (Pb2+, Cd2+ and Zn2+) from aqueous solutions.
ism of lead absorption was very ably explained on the The effects of AA and cross linker amount, pH value
basis of following mechanism given below (Fig. 5). and initial concentration of metal ion on the adsorp-
A superabsorbent polyelectrolytic hydrogels was tion capacity were studied. Equilibrium adsorption
synthesized by Swami et al.[47] for removal of toxic was noted at 60 minutes and adsorption capacities of
metals based on poly(ethylene glycol)-200 and acryloyl Pb2+, Cd2+ and Zn2+ was reported as 859, 495, and
chloride. The metal ion (lead, nickel, copper and iron) 274 mg g−1, respectively. The behavior of Xylan rich
uptake was studied as function of pH and temperature. hemicellulose-g-AA gels was found to be reversible w.
The highest sorption capacity for Pb2+, followed by r.t adsorption of metal ions and could be recycled
Ni2+, Cu2+and Fe2+. The author has explained the easily for a number of adsorption/desorption studies.
high chelating ability, especially for Pb2+ to high-stabi- The adsorption capacities showed a remarkable incli-
lity constant of the lead complex with carboxylic acids nation with increase in pH. The decrease in the
in the entire transition metal series. The importance of absorption at low pH (less than 4.5) values was attrib-
the hydrogel was further augmented by its high recov- uted to conversion of COO− groups into COOH,
ery (>97%) obtained for all the metal ions with 1N HCl hence causing a reduction in their ability to bind a
as eluting agent. positively charged ion. However, at higher pH values
Sahiner et al.[48] reported first time the removal of COOH becomes deprotonated and hence negatively
the rare earth metal ions by using the 4-vinyl pyridine charged ligands easily attract positively charged

Figure 4. Uptake and release of lead ions in response to change in temperature.

6 A. H. SHALLA ET AL.

Figure 5. Pictorial representation of lead uptake.

Figure 6. Pictorial representation of Uranium ion uptake.

metals. Compared with the other hydrogels AA for the removal of copper ions from wastewater.
crosslinked Xylan-rich hemicellulose shows high Celile and Dinc[54] synthesized Epichlorohydrin-
absorption capacity for Pb2+ ion[43,50–52] (Table 2). crosslinked diethylaminoethyl dextran (DEAE-D/
Pliegera et al.[53] reported a chemically modified ECH) hydrogel via intermolecular side chain reaction
pyromellitic dianhydride crosslinked chitosan hydro- of DEAE-D hydroxy unit and ECH as crosslinker.
gel system for adsorption of Cu(II) ions. This study The hydrogel was found to be sensitive to the adsorp-
shows that the prepared hydrogel based on modified tion of metal ions in the order Zn2+ > Mn2+ > Pb2+ >
chitosan could be utilized as an efficient bioadsorbent Cd2+. Study of properties like swelling ability, sorp-
tion capacity and metal recovery was done. This
research was applied for sorption of heavy metal
Table 2. Comparative adsorption capacity of some hydrogels
ions from waters of Orontes River. The researchers
for Lead (II) ions.
S. Absorption Capacity
proposed that DEAE-D/ECH hydrogel can be used
No. Hydrogel For Pb2+ (mg g−1) Reference for removal of chemical substances in environment
1 Acrylic acid and Xylan-rich 859 [49]
and controlled release of fertilizer and pesticide in
Hemicelluloses
2 Hydroxyapatite- 209 [50] agricultural area, and guarantee to be potential sor-
polyacrylamide bents for the treatment of heavy metal ion pollution
[43]
3 Chitosan/magnetite
composite beads
63.33
in (Zn2+, Mn2+ and Pb2+ ions) waste water and aqu-
4 Carrageenan/AA hydrogel 202.0 [51]
eous effluents. Wang and Li[55] prepared Cu2+
[52]
5 4-Vinylpiridine-grafted poly
(acrylic acid) hydrogels
117.9 imprinted composite hydrogel (Cu2+–ICH) hydrogels
6 Chitosan/magnetite 63.33 [43]
with modified properties, such as viscoelasticity,
composite beads mechanical strength. The hydrogels were found to
 SEPARATION SCIENCE AND TECHNOLOGY 7

be suitable for uptake of Cu2+ ions from aqueous Kandile and Nasr[60] have reported a pair (viz. A1,
solutions. The behavior of (Cu2+–ICH) shows pH A2) of biocompatible modified chitosin-based hydro-
dependency and uptake of metal ion was found high- gels. The researchers synthesized this hydrogel via a
est at pH 5.0. The copper imprinted composite reaction of chitosin with [4,4-diformyl-diphenoxy-
hydrogels showed five times higher selectivity than ethane or 4,4-diformyl-2,2-dimethoxy-diphenoxy-
non-imprinted ones for Cu2+ ions. Thus Cu2+ ethane] under variable reaction environments. The
engraved hydrogels prove an efficient sorption system hydrogels were allowed to react with different metals
particularly for Cu 2+ ion. under different pH conditions. This study revealed that
Wu and Li[56] prepared a novel poly(Hydroxyethyl adsorption of metal ions (Cu 2+, Co 2+, Zn 2+, Hg2+ and
methacrylate/Maleamic acid) (p(HEA/MALA)) hydro- Pb 2+ ions) was pH sensitive. Hydrogel (A2) showed the
gel, effective in removal of metal ions like Pb2+, Cd2+, highest sensitivity for Hg2+ ion at pH 5.
Ni2+ and Cu2+ ions, from aqueous solutions. Hua and Li[61] synthesized a Fe3O4-poly(L-cysteine/
Adsorption kinetics of Pb2+, Cd2+, Ni2+ and Cu2+ ions 2-hydroxyethyl acrylate) (Fe3O4-P(Cys/HEA)) mag-
on p(HEA/MALA) followed pseudo-second-order netic hydrogel. The authors successfully used the
kinetic model, and the adsorption rates followed the hydrogel system for removal of Pb2+, Cd2+, Ni2+ and
order Pb2+, Cd2+, Ni2+ and Cu2+ ions. The XPS spectra Cu2+ from aqueous solutions. FT-IR studies showed
of p(HEA/MALA) with and without chelate metal ions that hydrogel is a copolymer of 2-hydroxyethyl acrylate
indicated that Pb2+, Cd2+, Ni2+ and Cu2+ ions were and L-cysteine because of the presence of –NH2 and –
adsorbed via the chelation of –NH2 groups and the SH groups. This sulfhydryl modified magnetic hydrogel
ion-exchange of –COOH groups. According to the for heavy metal ion adsorption under changing pH,
competitive adsorption results, the priority order in temperature, initial heavy metal concentration and the
multi-component adsorption was Pb2+, Cd2+, Ni2+ contact time of adsorbent and heavy metal solutions
and Cu2+ ions pH studies showed that the external showed a pH sensitive behavior but unaffected by tem-
condition play an important role in metal ion adsorp- perature, and the adsorption process followed a
tion. Samaneh et al.[57] reported a cellulose graft poly- pseudo-second-order rate equation fitting Langmuir
acrylamide/hydroxyapatite composite hydrogels, which monolayer adsorption. The authors showed that by
proved to be very effective in adsorption of metal ions employing X-ray photoelectron spectroscopy, the bind-
from their aqueous solutions. This effect has been stu- ing of metal ions with the magnetic hydrogel was
died on Cu2+ ion. The effects on adsorption of varying following a dual reaction; one of chelation and second
the time, pH and initial concentration of Cu2+ solution, of ion-exchange between functional groups and metal
as well as some thermodynamic parameters were also ions. Moreover, Fe3O4-P(Cys/HEA) recycling efficiency
investigated. The maximum adsorption capacity was was found to be 90% using 0.1 M ethylene diamine
found to be 175 mg g−1 of composite hydrogel in tetraacetic acid. Liu et al.[62] prepared a novel hybrid
dried state. Isobe et al.[58] used a novel approach in hydrogels of attapulgite/poly(acrylic acid-co-acryla-
preparation of a metal ion adsorbing hydrogel. They mide) [ATP/P(AA−AM)] with high mechanical
performed a tempo mediated oxidation (nitroxy radical strength via inverse suspension copolymerization of
catalysed oxidation with hypochlorite/bromide) on a AA and acrylamide (AM) and attapulgite (MF-ATP)
cellulose hydrogel prepared by using LiOH/Urea sol- as a crosslinker. The ATP/P(AA−AM) hydrogels were
vent. They successfully transferred carboxylic groups found to be sensitive and selective toward adsorption of
on the hydrogels surface without infringement of its metal ions particularly Pb2+ and Cu2+. The gels were
nanoporous and structural properties. This system reused after many adsorption/desorption cycles.
proved to be very effective in Cu(II) ion adsorption Sanchez et al.[63] synthesized a hemicellulose-based
and binding was found to be reversible. The gel could hydrogels and studied their application for the removal
be used for many adsorption/desorption cycles. This of arsenic and chromium ions from waste water. The
system showed very high adsorption capacity w.r.t authors reported that both ions were adsorbed by the
Zn2+, Fe3+, Cd2+ and Cs+ ions also. A group of hydrogels in considerable amounts and the sorption of
researchers, Abdel-Halim and Al-Deyab[59] prepared Cr ions was highest at pH 3 and pH 9, whereas As ions
PAA/starch hydrogels by graft copolymerization fol- sorbed more at pH 9 compared to acidic pH values.
lowed by crosslinking via treatment with alkaline epi- The authors attributed changes in the sorption capacity
chlorohydrin to get three dimensional hydrogel. The at different pH values for As and Cr to the changing
cross-linked hydrogel was successfully applied for the nature of the metallic ions at different pH values. The
removal of cadmium ions from aqueous solutions by authors claimed that the bio-based hydrogels are of
adsorption. high interest for the mining industries as a sustainable
8 A. H. SHALLA ET AL.

material for the treatment of their highly contaminated electron microscopy (SEM) and thermogravimetric
wastewaters. analysis (TGA). The effect of temperature, contact
Sahiner et al.[64] prepared poly(3-acrylamidopropyl) time, amount of sample, initial concentration of
trimethyl ammonium chloride hydrogels for As(V) metal solution and reaction temperature was explored
removal. As (V) ions are found in the industrial to find out the most suitable condition for maximum
wastewaters and they can be accumulated in the absorption of metal ions. Sun et al.[71] synthesized the
environment and tissues causing various diseases and hydrogel lignin-g-PAA with high absorption capacity
disorders in living organisms. The synthesized hydro- for lead ions; a potential and toxic contaminant in the
gel show excellent capacity for removal of As(V) with waste water from battery industries. The study shows
a removal efficiency of approximately 99.7%. The the high absorption capacity for Pb2+ ions 235 mg g−1,
authors claimed that the removal is basically governed which is comparatively better. Saraydin et al.[72]
by the water diffusion into the hydrogel carrying the reported the hydrogel AM/Crotonic Acid for selective
heavy metals inside especially in the absence of absorption of highly toxic metal ion Hg2+ ions. Since
strongly binding sites. The high adsorption capacity amide compounds readily react with mercuric ions,
of the hydrogel for arsenic removal is very important under ordinary conditions, to give monoamido–mer-
considering hazardous nature of As (V) ions. Other cury or diamido–mercury compounds. It is believed
hydrogels have been synthesized for removal of that mercury–amide linkage is covalent rather than
arsenic ions with adsorption capacity almost similar coordinative. The amide groups in AM have unique
to the poly(3-acrylamidopropyl)trimethyl ammonium mercury binding with extremely high selectivity. On
chloride hydrogels or lower[65–68] (Table 3). Bikiaris the basis of this key principle, the author has envi-
et al.[69] synthesized succinyl-grafted chitosan and saged the polyacrylamide-based hydrogels to synthe-
envisaged its application for the simultaneous removal size and find selective for Hg2+ ions selectively.
of zinc and cationic dye. The modification of chitosan Functionalized carbohydrate gum tragacanth/graphene
was done by grafting the carboxylic groups of succinic oxide and investigated for adsorption of Pb2+, Cd2+
anhydride onto chitosan backbone. The pH studies and Ag+ by Sahraei and Ghaemy.[73] The maximum
confirmed that the optimum pH for the adsorption adsorption capacity (Qm) was 142.50, 112.50 and
of dye, as well as zinc found to be pH 5. The adsorp- 132.12 mg g−1 for Pb2+, Cd2+ and Ag+, respectively.
tion capacity before and after the grafting show The authors also explored influence of pH, adsorbent
improved absorption of dye, as well as zinc increase dosage, contact time and the initial feed concentration
with increase in grafting of succinyl on polymer back- was investigated and the regeneration properties. The
bone. The author explored that absorption capacity maximum removal efficiency was achieved at pH 6. At
remains almost same till 40 cycles, hence confirms low pH, the acidic groups of the hydrogel are mostly
the reusability of the synthesized hydrogels. present in non-ionized form and no interaction can
Zainuddin et al.[70] prepared carboxymethyl sago occur between these groups and the metal ions. With
starch-acid hydrogel for removal of the divalent increasing the pH from 2 to 6, deprotonation of acidic
metal ions like copper, lead and cadmium from the groups increases the probability of interaction
aqueous solutions. The sago starch is a biopolymer between the ionic groups of the hydrogel and metal
that is used for different purposes. The author has ions. However, above pH 6 precipitation of the metal
used this as a eco-friendly material for the adsorption ions occurs so the suitable pH at which adsorption
purpose and was characterized by different technique measurements were done was pH 6. A exhaustive
like Fourier Transform Infrared (FT-IR), scanning study was carried out on a novel superabsorbent
hydrogel (SAHs) composed of AA, sodium alginate
and sodium humate (AAc/NaAlg/SH) by Agnihotri
Table 3. Comparative adsorption capacity of some hydrogels and Singhal.[74] The synthesized SAHs were used for
for As (V) ions. the adsorption of methylene blue (MB), crystal violet
S. Adsorption Capacity (CV) dye molecules and Cu2+/Pb2+/Fe2+ ions. The
No. Materials of As (V) (mg g−1) Reference
1 Poly(3-acrylamidopropyl) 97.0 [64] effects of different experimental parameters, such as
trimethylammonium chloride contact time, concentration and initial metal ions/dyes
hydrogels concentration on the adsorption process were exam-
[65]
2 Nano p(4-vinylpyridine)-based 95.0
hydrogels ined. The hydrogel have a higher value of the absorp-
[66]
3 Iron-PVA hydrogel microspheres 99.4 tion for lead and copper ions compared to that of
[67]
4 Fe (III)-doped alginate gels 94%
5 Chitosan/Cu(OH)2 and chitosan/ >95 [68]
other hydrogels investigated for lead and copper metal
CuO composite absorptions. Recently, a magnetic hydrogel was
 SEPARATION SCIENCE AND TECHNOLOGY 9

synthesized by Pour and Ghamey,[75] based on gela- Acknowledgments

tion of carboxymethyl starch-g-polyvinyle imidazole,
One of the Authors Dr Aabid Hussain Shalla is thankful to
poly(vinyl alcohol) and Fe3O4 mixture in boric acid University Grants Commission for funding under UGC
and was explored for the removal of dyes and metal Major Research Project UGC-MRP-2013-2226, Dr Zahid
ions. Pb2+, Cu2+ and Cd2+ were removed by this Yaseen is thankful for the fellowship granted under DST.
hydrogel. The adsorption equilibrium of a cationic
dye, CV, and an anionic azo dye, congo red (CR)
was also studied and found to follow the Langmuir Funding
adsorption model. The additional feature of the gel This work was supported by the University Grants
was its magnetic sensitivity due the incorporation Commission [UGC-MRP-2013-2226].
nanoparticle of Fe3O4. The maximum absorption
capacity of 95.58 mg g−1 was obtained for Cd2+ions.
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