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Role of Ionic Moieties in Hydrogel Networks to Remove Heavy Metal

Ions from Water
Noman Chowdhury, Solaiman, Chanchal Kumar Roy, Shakhawat H. Firoz, Tahmina Foyez,
and Abu Bin Imran*
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ABSTRACT: A variety of methods for removing heavy metal ions from wastewater have been developed but because of their low
efficiency, further production of toxic sludge or other waste materials, high expense, and lengthy procedures, limited progress has
been achieved to date. Polymeric hydrogel has been attracting particular attention for the effective removal of heavy metal ions from
wastewater. Here, ionogenic polymeric hydrogels were prepared by free-radical copolymerization of a neutral acrylamide (AAm)
monomer with an ionic comonomer in the presence of a suitable initiator and a cross-linker. Different types of ionic comonomers
such as strongly acidic: 2-acrylamido-2-methylpropane sulfonic acid, weakly acidic: acrylic acid (AAc), and zwitterionic: 2-
methacryloyloxy ethyl dimethyl-3-sulfopropyl ammonium hydroxide with varying amounts were incorporated into the poly(AAm)
networks to fabricate the hydrogels. The heavy metal ions (Fe3+, Cr3+, and Hg2+) removal capacity of the fabricated hydrogels from
an aqueous solution via electrostatic interactions, coordination bond formation, and a diffusion process was compared and
contrasted. The poly(AAm) hydrogel containing weakly acidic AAc groups shows excellent removal capacity of heavy metal ions.
The release and recovery of heavy metal ions from the hydrogel samples are also impressive. The compressive strength of hydrogels
was found to be significantly high after incorporating heavy metal ions that will increase their potential applications in different
sectors.

■ INTRODUCTION
Heavy metal ions and many other toxic elements originating
from various industries are continuously contaminating water,
soil, and air. They are prevailing in water from various industries
such as electroplating, tanning mills, steel production, wood
processing, plastic manufacturing, metallurgical and mining
operations, nuclear power plants, dyes and pigments, ceramic,
paints, and fertilizer industries.1,2 Iron, lead, cadmium, arsenic,
mercury, aluminum, antimony, chromium, cobalt, copper,
manganese, selenium, gold, thallium, uranium, and so forth are
the most common heavy metal ions responsible for the
poisoning. The main problem with heavy metal ion contami-
nation is that they are not biodegradable and thus persist in
living organisms’ bodies, causing dangerous diseases and severe
cell abnormalities. Excessive vomiting, abdominal pain, reduced
sense of touch, sight, vision, and taste, fatigue or lack of physical
stamina, tremors and incoordination, anemia, autoimmune
disorders, weakened or inefficient renal function, hyper-
allergenic symptoms, and compromised metabolism of vitamin
© 2020 The Authors. Published by
American Chemical Society
836
D are the common effects of heavy metal ion poisoning.3,4
Various heavy metal ion removal techniques have been widely
employed to date, for example, chemical precipitation
(hydroxide precipitation, sulfide precipitation, and chelating
precipitation), ion exchange, adsorption, membrane filtration
(ultrafiltration, reverse osmosis, nanofiltration, and electro-
dialysis), coagulation and flocculation, electrochemical treat-
ment, and so on.5−9 While all the above-mentioned techniques
could be used for the treatment of wastewater-containing heavy
metal ions, the selection of the most suitable treatment
techniques based on the initial metal ion concentration, removal
Received: November 6, 2020
Accepted: December 11, 2020
Published: December 31, 2020
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efficiency, hazardous sludge production, material recovery,
wastewater component, capital expenditure and operating
cost, the durability of the plant, reliability, and environmental
impacts, and so forth are not yet materialized.10 The adsorption
process is usually favored to eliminate heavy metal ions because
of its high performance, ease of handling, availability of various
adsorbents, and cost-effectiveness.11−13
Hydrogels, cross-linked polymeric materials that absorb
significant volumes of water without dissolving in any solvent,
can be treated as unique, incredibly versatile, and high-capacity
adsorbent materials for extracting heavy metal ions from
wastewater.14,15 They have many advantages over conventional
methods, including hydrophilic composition, suitable for task-
specific functional modification, greater chemical penetration
due to their three-dimensional structure, controllable dimen-
sional synthesizability, differences in the functional group, eco-
friendliness due to rapid biological decomposition, and the
possibility of reuse due to the controlled desorption
process.16−19 Metal ion-chelating polymers, referred to as
polychelatogens, contain one or more electron donor atoms,
such as N, S, O, and P, which may form coordinate bonds with
most toxic heavy metal ions. Amide, amine, carboxylic acid,
sulfonic acid, and/or ammonium moieties containing hydrogels
can chelate metal ions and be powerful polychelatogens for
wastewater treatment. Various hydrogel synthesis and their
adsorption activity for the elimination of heavy metal ions have
been investigated. The poly(ethyleneglycol dimethacrylate-co-
acrylamide) hydrogel beads have the following sequence of
elimination of heavy metal ions Pb(II) > Cd(II) > Hg(II).20
Essawy and Ibrahim reported the poly(vinylpyrrolidone-co-
methylacrylate) hydrogel with the following order of heavy
metal ion removal Cu(II) > Ni(II) > Cd(II).21 The poly(3-
acrylamidopropyl)trimethyl ammonium chloride hydrogels are
capable of removing As(V).16 Hydrogels comprised of acrylic,
vinyl, and other functional monomers such as acrylic acid (AAc),
acrylamide (AAm), 2-acrylamido-2-methyl-1-propane sulfonic
acid (AMPS), hydroxyl ethyl methacrylamide (HEMA), N-vinyl
imidazole (NI), and 4-vinyl pyridine have proven to be strong
adsorbents to heavy metal ions.22−27 Magnetic hydrogels based
on poly(AMPS-co-NI) for the removal of heavy metal ions have
also been reported.28 Recently, Morán-Quiroz et al. synthesized
superabsorbent poly(AAc-co-AAm) hydrogels using a redox
initiator and used them to remove Cu(II) ions from aqueous
solutions.29 The poly(AAm-co-sodium methacrylate) hydrogels
prepared by free-radical copolymerization using poly(ethylene
glycol) diacrylate as a cross-linker can remove Cu(II) ions and
Cd(II) ions at pH 5.0.30 Evren et al. fabricated poly(AMPS-co-
itaconic acid) hydrogels to remove heavy metal ions.31 The
hydrogels made of poly(AAm-AAc) could bind metal ions such
as Cu(II) and Cd(II) stronger than alkali or alkaline earth ions.32
After a subtle change in the pH values of the medium, the
ionogenic hydrogels containing ionizing side groups may
contribute to major changes in the degree of swelling. The
side groups ionize and electrostatic repulsive forces occur
between polymer chains in the aqueous medium to increase the
degree of adsorption and swelling.33−35 The nature and
dissociation ability of ionizing side groups should strongly
influence their heavy metal ion removal capacity. It is obvious
from the literature that the use of anionic moiety, poly-
ampholyte, and polyzwitterion have been studied to prepare
hydrogels as heavy metal ion adsorbents by various research
groups. Still, unfortunately, the effects of ionic moieties
(strongly acidic, weakly acidic, and zwitterionic) present in the
837
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same polymer networks on heavy metal ion removal capacity
have been neglected or scarcely explored.
Here, we report the fabrication of poly(AAm) hydrogels by
incorporating different types of weakly dissociating, strongly
dissociating, and zwitterionic moieties into polymer networks to
precisely control the removal of heavy metal ions (Fe3+, Cr3+,
and Hg2+) from aqueous samples. The heavy metal ion removal
capacity and kinetics, release, and recovery have been studied
extensively. In addition, the substantial increment of compres-
sive strengths after adsorbing heavy metal ions has been
investigated.
■
RESULTS AND DISCUSSION
Poly(AAm-AAc) hydrogel, poly(AAm-AMPS) hydrogel, poly-
(AAm-AAc-AMPS) hydrogel, and poly(AAm-MEDSA) hydro-
gel are prepared by free-radical polymerization, one of the most
common and facile polymerization techniques for hydrogel
synthesis. The free-radical polymerization of the AAm main
monomer along with one or more from AAc, AMPS, and
MEDSA as comonomers in the presence of the N,N-
methylenebisacrylamide (BIS) cross-linker and potassium
persulfate (KPS) initiator easily produces the hydrogels. The
weakly dissociating AAc and strongly dissociating AMPS can
effectively remove various types of heavy metal ions as the
anionic charges have a strong affinity toward positively charged
heavy metal ions. AAc is a weakly dissociable acid, and its pKa is
4.25 at 25 °C.36 If the pH increases above the pKa, the carboxyl
group of the AAc becomes deprotonated, leading to a strong,
attractive interaction with heavy metal ions. AMPS contains a
strongly ionizable sulfonate group with a pKa value of 1.5, which
gives its hydrogel’s high chelating ability and dissociates entirely
in the whole pH range.37,38 MEDSA contains both anionic and
cationic moieties used to synthesize electrically neutral
polyzwitterionic hydrogels to remove heavy metal ions and
their counterparts from water. 39,40 The importance of
zwitterionic comonomers is their selectivity because of the
interaction between ions and positive and negative charges
within the chain.41,42
In the Fourier transform infrared (FT-IR) spectra of
poly(AAm-AAc), poly(AAm-AMPS), poly(AAm-AAc-AMPS),
and poly(AAm-MEDSA) hydrogels, the absorbance at 2930
cm−1 is originated from −CH2 stretching frequency, and the
broad absorption band around 3100−3500 cm−1 is ascribed to
the overlapping peaks of the −NH and −OH groups (Figure 1).
The presence of a carbonyl group in the hydrogels is confirmed
Figure 1. FT-IR spectra of poly(AAm-AAc), poly(AAm-AMPS),
poly(AAm-AAc-AMPS), and poly(AAm-MEDSA) hydrogels.
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Figure 2. Swelling behaviors with varying temperatures for (a) poly(AAm-AAc) (1.9/0.1) M, poly(AAm-AMPS) (1.9/0.1) M, poly(AAm-AAc-
AMPS) (1.9/0.05/0.05) M, and poly(AAm-MEDSA) (1.9/0.1) M hydrogels. (b) Poly(AAm-AAc) (1.6/0.4) M, poly(AAm-AMPS) (1.6/0.4) M,
poly(AAm-AAc-AMPS) (1.6/0.2/0.2) M, and poly(AAm-MEDSA) (1.6/0.4) M hydrogels.

Figure 3. Swelling behaviors with varying pH for (a) poly(AAm-AAc) (1.9/0.1) M, poly(AAm-AMPS) (1.9/0.1) M, poly(AAm-AAc-AMPS) (1.9/
0.05/0.05) M, and poly(AAm-MEDSA) (1.9/0.1) M hydrogels. (b) Poly(AAm-AAc) (1.6/0.4) M, poly(AAm-AMPS) (1.6/0.4) M, poly(AAm-AAc-
AMPS) (1.6/0.2/0.2) M, and poly(AAm-MEDSA) (1.6/0.4) M hydrogels.

from a band observed at 1665 cm−1. The symmetric stretching
vibrations of the carboxylate group indicated by a band observed
at around 1451 cm−1 confirm the successful incorporation of
AAc into the poly(AAm-AAc) hydrogel network. The SO
asymmetric stretching is observed at 1390 cm−1 for poly(AAm-
AMPS), poly(AAm-AAc-AMPS), and poly(AAm-MEDSA)
hydrogels. The absorption bands around 1700−1600 cm−1 are
because of amide I, amide II, and amide III from AMPS. The
presence of the absorption bands at 1039 and 1370 cm−1
corresponding to sulfonate (SO3−)-stretching vibration and
the quaternary ammonium group of MEDSA, respectively,
confirms that the fabrication of the poly(AAm-MEDSA)
hydrogel was successful.43
The swelling behavior of an ionic hydrogel mainly depends on
the concentration of the ionic groups, the degree of ionization,
the pH, the ionic strength of the surrounding media, the valence
and the nature of the counterion, and the composition of the
swelling medium. If the content of ionic groups (AAc, AMPS) in
the hydrogel system increases, the hydrophilicity of the polymer
network increases. The swelling ratio of the poly(AAm-AMPS)
(1.6/0.4) M hydrogel in water is found to be higher than that of
the poly(AAm-AMPS) (1.9/0.1) M hydrogel (Figure 2). The
strong dissociation power of the ionic groups (−SO3H) of
AMPS provides more electrostatic repulsion of negative charges
leading to increased swelling. The poly(AAm-AAc) hydrogel
does not show any prominent temperature sensitivity, but the
poly(AAm-AMPS) hydrogel containing much amount of AMPS
shows detectable temperature sensitivity. At higher temper-
atures, the ionic groups (−SO3H) present in the poly(AAm-
AMPS) (1.6/0.4) M hydrogel prefer to interact among
themselves than associating with water molecules, forcing the
polymer chains to contract in their size and repelling water
molecules.
838
The swelling ratio of the poly(AAm-AAc-AMPS) hydrogel
does not show any temperature sensitivity and it is an
intermediate swelling ratio between poly(AAm-AMPS) and
poly(AAm-AAc) hydrogels. Incorporation of both AAc and
AMPS into the poly(AAm-AAc-AMPS) networks averages the
hydrophilicity of the polymer chains to exhibit an intermediate
swelling ratio. The swelling ratio of the poly(AAm-MEDSA)
hydrogel is the lowest and slightly responds to temperature as
the ionic moieties of the MEDSA are undissociated under most
environmental conditions.
The poly(AAm-AAc) hydrogel shrinks considerably as
carboxylate groups are protonated in a highly acidic environ-
ment (Figure 3). However at pH > 4.5, the dissociation of
carboxylic acids occurs and increases the swelling ratio of the
hydrogel. The poly(AAm-AAc) hydrogel shows the maximum
swelling ratio at pH 9. AMPS remains in the dissociated state in
the pH range of 2−12. Consequently, because of a strong
swelling driving force created by electrostatic repulsion between
the ionized sulfonate groups at a wide pH range, the poly(AAm-
AMPS) hydrogel swells quickly. The sulfonic acid groups are
associated, collapsed, and have a relatively low swelling ratio at
pH values lower than the pKa value. In contrast, because of the
dissociation of the sulfonic groups and the destruction of
hydrogen bonding, the swelling ratio increased at pH values
greater than the pKa value. The increase in the AMPS content
increased the dissociated groups, thus increasing electrostatic
repulsion leading to an extension of the hydrogel network.44 At
pH < pKa of AMPS and AAc, the excess hydrogen cations shield
the repulsive pendant anions to reduce the swelling capacity.45
The swelling ratio of poly(AAm-AAc) and poly(AAm-AMPS)
hydrogels at a particular pH increases with increasing AAc and
AMPS concentration.
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The swelling ratio of the poly(AAm-AAc-AMPS) hydrogel is
found to be an intermediate between those of poly(AAm-AAc)
and poly(AAm-AMPS) hydrogels, and it increases with
increasing pH. The poly(AAm-AAc-AMPS) hydrogel contains
both AAc and AMPS moieties in the network; therefore, the
polymer networks experience greater extensibility because of the
repulsive force of ionic groups to increase the swelling ratio. The
poly(AAm-MEDSA) hydrogels do not show any noticeable pH
sensitivity. With increasing pH, anionic groups become
deprotonated and cationic groups become protonated states.
Consequently, there is no net change of repulsive force on
polymer networks with varying pH to exhibit any pH
sensitivity.46−49
The heavy metal ion removal capacity of hydrogels was
analyzed by cyclic voltammetry. The observed cathodic peak
current was normalized with the initial peak current and plotted
against time for different hydrogels in Figure 4. A decrease in the
Figure 4. Fe3+ removal kinetics of poly(AAm-AAc) (1.6/0.4) M,
poly(AAm-AMPS) (1.6/0.4) M, poly(AAm-AAc-AMPS) (1.6/0.2/
0.2) M, and poly(AAm-MEDSA) (1.6/0.4) M hydrogels from aqueous
solutions by cyclic voltammetry.
normalized peak current of Fe3+ with time has been observed for
the presence of all types of hydrogels in the aqueous solution of
Fe3+. The decrease in the value of peak current indicates the
elimination of Fe3+ from the solution. The poly(AAm-AAc)
hydrogel shows the fastest current decrement compared with
others. The hydrogel networks containing high AAc and AMPS
contents demonstrated good removal capacity of Fe3+ from
water (Figures S1−S4). The presence of the anionic carboxylate
(−COO−) group of AAc and the sulfonate (−SO3−) group of
AMPS in the polymer network enhances the binding capacity
with the metal ions. The coordination bond and electrostatic
interactions might be responsible for these strong binding
capacities. The poly(AAm-AAc-AMPs) hydrogel shows moder-
ate Fe3+ removal capacity compared to poly(AAm-AAc) and
poly(AAM-AMPS) hydrogels. The Fe3+ removal capacity of the
poly(AAm-MEDSA) hydrogel is the lowest compared with
those of the other two hydrogels. MEDSA contains both anionic
and cationic moieties, the anionic part in the poly(AAm-
MEDSA) hydrogel can effectively form a complex with Fe3+ by
electrostatic attraction but simultaneously experience repulsion
of bound Fe3+ with cationic parts of the network. A calibration
curve of concentration (mM) versus current (A) is plotted in
(Figure S5). The concentration of the Fe(III) ion solution at
different times can be determined by observing the peak current
values, applying the same scan rate in a fixed potential window
with a fixed three-electrode system. The removal capacity of Fe3+
for the poly(AAm-AAc) (1.6/0.4) M hydrogel is 276 mg/g,
poly(AAm-AMPS) (1.6/0.4) M hydrogel is 92 mg/g, poly-
(AAm-AAc-AMPS) (1.6/0.2/0.2) M hydrogel is 210 mg/g, and
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poly(AAm-MEDSA) (1.6/0.4) M hydrogel is 55 mg/g. The
hydrogel containing large AAc shows the highest capacity to
remove Fe3+ as carboxylic (−COOH) functional groups can
effectively bind with Fe3+ than other ionic moieties of
monomers. An excess of hydrogen ions can compete effectively
with metal ions for binding sites at a lower pH, resulting in a
lower degree of metal ion uptake. Owing to the Fe(III)
hydroxide’s insolubility formed via hydrolysis of Fe(III) ions,
the adsorption experiment could not be carried out at high pH.
The maximum binding of all metal ions occurred within the first
3 h and remained unchanged over the entire 24 h. The removal
process of the Fe(III) ions will be more complex at higher pH. It
will be difficult to differentiate between the adsorption and
precipitation of Fe(III) ions removed from solutions.50
A significant decrease in the peak current of Hg2+ for all types
of hydrogels is observed after 24 h (Figure 5). Similar to Fe3+
Figure 5. Cyclic voltammograms of the HgCl2 solution at a scan rate of
0.1 Vs−1 after equilibrating with a fixed amount of different types of
hydrogels for 24 h.
ions, the poly(AAm-AAc) hydrogel shows the most and the
poly(AAm-MEDSA) hydrogel shows the least removal capacity
of Hg2+ ions. The poly(AAm-AMPS) hydrogels and poly(AAm-
AAC-AMPS) hydrogels also show good capacity because of the
presence of AAc and AMPS anionic monomers. The hydrogels
containing more anionic moieties showed good Hg2+ removal
capacities.
Chromium has a characteristic UV−vis peak at 300 nm. The
poly(AAm-AAc), poly(AAm-AMPS), and poly(AAm-AAc-
AMPS) hydrogels containing more AAc or AMPS show more
removal capacity of Cr3+, similar such results were also obtained
in the cyclic voltametric study. In an aqueous solution, the
deprotonation of anionic moieties gives more negatively charged
ions, and thereby, Cr3+ can easily bind with them by attractive
electrostatic forces. The Cr3+ removal capacity of the poly(AAm-
MEDSA) hydrogel also increases with increasing MEDSA
content in the polymer network. For a quantitative analysis of
the amount of Cr3+, a calibration curve of concentration (M)
versus absorbance (au) has been plotted. The Cr3+ removal
capacity of the poly(AAm-AAc) (1.6/0.4) M hydrogel,
poly(AAm-AMPS) (1.6/0.4) M hydrogel, poly(AAm-AAc-
AMPS) (1.6/0.2/0.2) M hydrogel, and poly(AAm-MEDSA)
(1.6/0.4) M hydrogels is 139, 129, 129, and 84 mg/g,
respectively. The poly(AAm-AAc) hydrogel shows the quickest
and poly(AAm-MEDSA) hydrogel shows the slowest Cr3+
removal capacities (Figure 6).
Generally, hydrogels remove heavy metal ions by diffusion,
adsorption, and forming a coordination complex with metal
ions. The hydrogels containing anionic−COOH and −SO3H
functional groups dissociate and electrostatically attract metal
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Figure 6. Decay of the Cr3+ concentration with time for poly(AAm-
AAc) (1.6/0.4) M, poly(AAm-AMPS) (1.6/0.4) M, poly(AAm-AAc-
AMPS) (1.6/0.2/0.2) M, and poly(AAm-MEDSA) (1.6/0.4) M
hydrogels by UV−vis spectra analysis.
ions to show adequate removal capacity. The zwitterionic
poly(AAm-MEDSA) hydrogel shows poor removal capacity as
its anionic part forms a complex with Cr3+ by electrostatic force,
but its cationic part simultaneously repulses with heavy metal
ions.
The prepared hydrogel exhibits greater chelating ability at low
metal ion concentration, which means that to adsorb this,
electrostatic attraction (physical adsorption) is employed. On
the other hand, the adsorption is relatively low at high metal ion
concentrations, indicating that the chelating interaction
(chemical adsorption) occurs in the adsorption process. This
may be because of the interaction with the external transport
paths of highly concentrated metal ions through the boundary
layer from the solution to the adsorbent and the adsorption of
metal ions to the pores and voids of the inner surfaces of
hydrogels.51 Langmuir isotherm is most commonly employed
for measuring the chelating ability of heavy metal ions by the
polymeric hydrogel.
A variety of kinetics models are suggested to establish and
interpret the dynamics of metal ion adsorption processes and the
key parameters governing sorption kinetics. The kinetic model
of the pseudo-first-order suggests that the rate of adsorption is
proportional to the number of adsorption sites. In comparison,
the kinetic model of the pseudo-second-order assumes that the
adsorption rate is proportional to the square of the available
number of adsorption sites. Figure 7 shows the fitting for the
Figure 7. Fitting curves for the adsorption of Fe3+ on different types of hydrogels using (a) pseudo-first-order kinetic model and (b) pseudo-second-
order kinetic model.
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adsorption of Fe3+ on poly(AAm-AAc), poly(AAm-AMPS),
poly(AAm-AAc-AMPS), and poly(AAm-MEDSA) hydrogels
using the pseudo-first-order kinetics and pseudo-second-order
kinetics, respectively.
The pseudo-first-order expression of Lagergren is a
fundamental kinetic model proposed for the sorption process
in solid/liquid systems. The adsorption kinetics described by a
pseudo-first-order equation is as follows
k1t
log(qe − qt ) = log qe −
2.303
where qe and qt (mg/g) represent the amount of Fe3+ adsorbed
at equilibrium and at any adsorption time t, and k1 (min−1) is the
pseudo-first-order constant. The adsorption rate constant k1 can
experimentally be determined from the slope of linear plots of
log(qe − qt) versus t.
The pseudo-second-order kinetics model of Ho can also
interpret the kinetic data. This model is based on the assumption
that the second-order chemisorption precedes by the sorption.
The adsorption kinetics described using a pseudo-second-order
equation is as follows
t 1 t
= +
qt k 2qe 2 qe
where qe (mg/g) and qt (mg/g), k2 (min−1) represent the
amount of Fe3+ adsorbed at equilibrium, the amount of Fe3+
adsorbed at equilibrium after time t, and pseudo-first-order rate
constant, respectively. From the slope of the linear plot t/qt
versus t, the adsorption rate constant k2 was experimentally
calculated. Table S5 summarizes all kinetic parameters obtained
by linear regression of the kinetic models. The higher values of
the coefficient of correlation (R2) and the good agreement
between the measured qe,exp and the calculated qe,cal suggest a
better fit of the results obtained using the pseudo-first-order
kinetic model. When adsorption occurs on the hydrogel’s
surface at the beginning of the process, a rapid adsorption rate
was observed after that; when adsorption takes place on the
inner surface of the polymer networks, the adsorption rate was
slow.
The recovery of heavy metal ions under acidic conditions was
excellent (Figure S10). At low pH, the polymer−metal complex
becomes unstable because of the competing affinity of H+ to the
anionic segment of the network. H+ replaces the metal ions and
thereby releases them from the hydrogel sample. All fabricated
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Figure 8. Uniaxial compressive test of different types of poly(AAm-AAc) (1.6/0.4) M, poly(AAm-AMPS) (1.6/0.4) M, poly(AAm-AAc-AMPS) (1.6/
0.2/0.2) M, and poly(AAm-MEDSA) (1.6/0.4) M hydrogels. (a) Stress−strain curves, (b) photographs of fragile poly(AAm-AAc) (1.6/0.4) M
(without Fe3+), strong poly(AAm-AAc) (1.6/0.4) M (with Fe3+), and fragile poly(AAm-MEDSA) (1.6/0.4) M (with Fe3+) hydrogels during
compressive tests.

Table 1. Young’s Modulus, Compressive Strength, and Toughness Values of Poly(AAm-AAc) (1.6/0.4) M, Poly(AAm-AMPS)
(1.6/0.4) M, Poly(AAm-AAc-AMPS) (1.6/0.2/0.2) M, and Poly(AAm-MEDSA) (1.6/0.4) M Hydrogels before and after
Adsorption of Fe3+
Young’s modulus (MPa) compressive strength (MPa) toughness J/m3
name of the hydrogel before after before after before after
poly(AAm-AAc) (1.6/0.4) M 1.30 10.02 27.72 70.33 0.12 3.96
poly(AAm-AMPS) (1.6/0.4) M 1.54 0.59 26.24 53.56 0.011 0.71
poly(AAm-AAc-AMPS) (1.6/0.2/0.2) M 0.86 3.77 29.22 69.74 0.09 13.07
poly(AAm-MEDSA) (1.6/0.4) M 0.90 0.70 26.08 42.40 0.07 0.59

ionogenic hydrogels release about 90% of heavy metal ions at pH
1 within 3 h, at room temperature.
Thermal analysis was carried out to measure the thermal
stability and pyrolysis behavior of poly(AAm-AAc-AMPS) and
poly(AAm-AAc-AMPS)@Fe3+ hydrogels (Figure S11). All the
samples show a slight weight loss at low temperatures (<150 °C)
because of the release of weakly adsorbed water molecules from
the hydrogels. In the case of the poly(AAm-AAc-AMPS)
hydrogel, the initial degradation starts at 225 °C (25%), and a
to give a strong compressive response. However, in the case of
poly(AAm-AMPS) hydrogel and poly(AAm-MEDSA) hydro-
gels, the polymer networks form a complex with a lower amount
of Fe3+ to give relatively poor compressive strength. Thus, a
tougher hydrogel may be obtained by increasing the degree of
cross-linking, but it compromises the percent of elongation.
Therefore, in order to obtain a sufficiently strong and ductile
hydrogel, the optimization of the degree of cross-linking is
prerequisite.

drastic change appears up to 365 °C (27%) because of the
degradation of oxygen-containing groups. The final degradation
of poly(AAm-AAc-AMPS) hydrogels starts at 460 °C, and after
that temperature, only carbon residue exists. However after Fe3+
adsorption, the initial degradation starts at 210 °C. With
increasing temperature, degradation occurs uniformly and
slowly in the region of 210−740 °C where oxygen-containing
groups are degraded, and about 37% weight loss has occurred in
that region. The poly(AAm-AAc-AMPS) (1.6/0.2/0.2) M
hydrogel after equilibrium incorporation of Fe3+ shows better
thermal resistance, and no drastic degradation pattern is
observed. The high ash residue at high temperatures is because
of the presence of much amount of nondecomposed Fe3+ in the
hydrogel.
The as-prepared poly(AAm-AAc) hydrogel exhibits poor
compressive strength. After incorporating Fe3+ into the
poly(AAm-AAc) hydrogel, the compressive strength is incred-
ibly increased (Figure 8 and Table 1). The poly(AAm-AAc-
AMPS)@Fe(III) hydrogel also shows good compressive
strength, but poor compressive strengths are observed for
poly(AAm-AMPS) and poly(AAm-MEDSA) hydrogels. The
acrylate group may form a strong complex with Fe3+, which acts
as an additional physical cross-linking to the hydrogel network
841
■
CONCLUSIONS
We have successfully synthesized different ionogenic hydrogels
containing weakly and strongly dissociating anionic moieties
and zwitterionic moieties via a simple free radical polymerization
method. AAm is used as a main monomer; one or more from
AAc, AMPS, and MEDSA are used as comonomers to make
poly(AAm-AAc), poly(AAm-AMPS), poly(AAm-AAc-AMPS),
poly(AAm-MEDSA) hydrogels with varying monomer and
comonomer concentrations. Synthesized hydrogels are con-
firmed by FT-IR spectral analysis. The swelling ratios of
synthesized hydrogels increase with incorporating the ionic
monomer into the network because of their electrostatic
repulsion forces. The hydrogels exhibit temperature and pH
sensitivity. The reported hydrogels can remove heavy metal ions
(Fe3+, Hg2+, and Cr3+) from aqueous samples, which are
analyzed and compared by UV−visible spectroscopy and cyclic
voltammetry. The weakly dissociating AAc containing hydrogels
show great heavy metal ion removal capacities. Hydrogels
remove metal ions from the samples by electrostatic attraction
forces and entrap inside polymer networks. The adsorbed heavy
metal ions from hydrogels can be recovered at low pH so that
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ACS Omega http://pubs.acs.org/journal/acsodf
they can be further used for water treatment. The enhanced
compressive strength and thermal stability of hydrogels with the
incorporation of metal ions will expand their area of applications
and open up windows to further investigate the mechanical
property improvement of conventional hydrogels using metal
ions as an additional cross-linker. The synthesized hydrogels can
possibly be used for the treatment of industrial wastewater, water
purification, and so on.
■
EXPERIMENTAL SECTION
Chemicals and Reagents. The chemicals, which were
mainly used in this work are as follows AAm (Sigma-Aldrich,
Germany), AAc (Scharlab, Spain), 2-methacryloyloxy ethyl
dimethyl-3-sulfopropyl ammonium hydroxide (MEDSA)
(Sigma-Aldrich, Germany), 2-acrylamido-2-methylpropane sul-
fonic acid (AMPS) (Sigma-Aldrich, Germany), BIS (Acros
Organics, USA), KPS (Acros Organics, USA), tetramethylethy-
lenediamine (TEMED) (Sigma-Aldrich, Germany), iron
trichloride (FeCl3) (Sigma-Aldrich, Germany), mercuric
chloride (HgCl2) (Sigma-Aldrich, Germany), and chromium-
(III) nitrate (Cr(NO3)3) (Sigma-Aldrich, Germany). Analytical
standard chemicals and reagents were directly used without
further purification. Deionized water was used as a solvent,
unless otherwise stated, to prepare most of the solutions.
Fabrication of Hydrogels. The following four types of
hydrogels (i) poly(AAm-AAc), (ii) poly(AAm-AMPS), (iii)
poly(AAm-AAc-AMPS), and (iv) poly(AAm-MEDSA) were
prepared using AAm as a major monomer, one or more
comonomers from AAc, AMPS, and MEDSA, BIS as a cross-
linker, KPS as an initiator, TEMED as an accelerator, and
deionized water as a solvent. The recipes of all hydrogels with
varying concentrations of monomers and other gel precursors
(e.g., cross-linker, initiator, and solvent) are shown in Tables
S1−S4, and the detailed procedure has been reported
elsewhere.52,53 Briefly, a solution of monomer, BIS, and
TEMED in H2O was prepared into a test tube, and nitrogen
(N2) gas was bubbled for 30 m to remove any dissolved oxygen.
In another container, a 2.96 mM KPS solution was prepared and
N2 bubbled. The two solutions were then mixed inside an ice
bath, and free-radial polymerization was carried out at room
temperature for 24 h. The fabricated hydrogel was then
immersed in distilled water and washed for 3 days to eliminate
any unreacted monomer, cross-linker, and initiator. The distilled
water was changed every 6 h.
Swelling Study of Hydrogels. The temperature-depend-
ent swelling of hydrogels was observed in the temperature range
from 10 to 60 °C. A piece of preweighed dry hydrogel was
immersed in a jacketed glass cell containing distilled water, and
the cell was attached to a circulating water bath to control the
temperature. The hydrogel sample was kept 3 h at a certain
temperature to reach an equilibrium swelling state, and weight
was measured. The swelling ratio was calculated using the
following equation
swelling ratio = Wwet /Wdry
here, Wwet is the weight of the swollen hydrogel after
equilibrium, and Wdry is the weight of the dry hydrogel. The
pH dependency of hydrogels was observed in buffer solutions of
pH 2, 5, 7, and 9 at 30 °C.
Cyclic Voltammetry Analysis. The cyclic voltametric
analysis was carried out using an electrochemical analyzer, 797
VA Computrace, Metrohm, Switzerland. To investigate heavy
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Article
metal ion removal capacity, 1−2.5 g dry hydrogel was immersed
in an aqueous solution of 0.1 M heavy metal ion at room
temperature. To maintain homogeneity, the solution was stirred
at a fixed 150 rpm. After a certain interval, 0.5 mL heavy metal
ion solution was withdrawn from the solution and taken for
cyclic voltametric analysis. Three electrode cells with disk shape
Pt as the working electrode having a surface area of 0.071 cm2,
Ag|AgCl (aq) as a reference electrode, and Pt wire as the counter
electrode were used for the cyclic voltametric analysis. A
concentration of 0.1 M KCl solution was maintained for the
experiments. Calibration curves of cathodic peak current versus
concentration were drawn with different concentrations of
heavy metal ion solution at a fixed scan rate of 0.1 Vs−1. Removal
capacities of heavy metal ions were calculated from the following
expression
removal capacity (mg/g) = (Co − Cf ) × V /m
where Co and Cf are the initial and final concentrations (mg/L)
of heavy metal ions, V is the volume of the solution (L), and m is
the mass (g) of hydrogel samples used as an adsorbent. The
cyclic voltammograms of Fe3+ and Hg2+ were obtained with the
aqueous solution of FeCl3 and HgCl2.
UV−Visible Spectrophotometric Analysis. Heavy metal
ion removal capacities were analyzed using a UV−visible
spectrophotometer, Shimadzu-1800, Japan. A carefully dried 10
mg hydrogel sample was transferred into 10 mL of 0.01 M heavy
metal ion solution at room temperature. Deionized water was
chosen as the reference or baseline. The concentrations of
remaining heavy metal ion solutions after adsorption were
measured from the calibration curve.
Mechanical Strength Test. The mechanical strength of
hydrogels was tested using a universal testing machine (UTM
Model-100P250-12, TestResources Inc., USA) at room temper-
ature. The cylindrical-shaped hydrogel with a 10 mm diameter
was immersed into a 100 mL 0.1 M heavy metal ion solution and
was kept undisturbed for 24 h to reach equilibrium swelling
state. The equilibrium swelled gel was placed in the UTM base
for the compressive test. The crosshead speed was 50 mm/min.
To maintain reproducibility, each specimen was tested at least
three times. From the recorded force and area data, the
compressive stress (σ) of the hydrogels was obtained, while the
strain (%) was computed from the ratio of the change in length
(Δl) and the original length (l0) of the sample (ε = Δl/l0 × 100).
The Young’s modulus was calculated from the initial 10%
deformation slope of the stress−strain curves. The toughness of
each specimen was also calculated from the integral area under
the stress−strain curves.54
FT-IR Spectral Analysis. The infrared spectra were studied
using a FT-IR spectrophotometer (FT-IR 8400, Shimadzu,
Japan) in the region of 4000−400 cm−1. The hydrogel samples
were oven dried at 50 °C and ground well to obtain powder
form. The samples were then uniformly mixed with KBr crystals.
A sample pellet was made using a hand-press pellet maker and
placed carefully in the path of the IR beam for analysis.55
Thermogravimetry and Differential Thermal Analysis.
The thermal stability of hydrogels was analyzed using a
thermogravimetric analyzer (DT/TGA 7200, HITACHI,
Japan). Approximately, 5 mg of the previously dried and the
powdered sample was taken in a platinum pan for each test and
analyzed from 25 to 800 °C at a heating rate of 10 °C/m under a
constant flow of nitrogen at a flow rate of 10 mL/m. Before the
data acquisition, the sample was equilibrated at 25 °C for 5 m to
obtain an isothermal condition.
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ACS Omega 2021, 6, 836−844
ACS Omega
■
http://pubs.acs.org/journal/acsodf
ASSOCIATED CONTENT
* (16-157 RG/CHE/AS_I-FR3240293340) for the funding.
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsomega.0c05411.
Recipes to synthesize poly(AAm-AAc), poly(AAm-
AMPS), poly(AAm-AAc-AMPS), and poly(AAm-
MEDSA) hydrogels, cyclic voltammograms of the FeCl3
solution at a scan rate of 0.1 V s−1 after swelling of
poly(AAm-AAc), poly(AAm-AMPS), poly(AAm-AAc-
AMPS), and poly(AAm-MEDSA) hydrogels, calibration
curve of cathodic peak current (μA) versus concentration
(mM) of Fe3+, successive UV−vis spectra of Cr3+ removal
capacity for poly(AAm-AAc), poly(AAm-AMPS), poly-
(AAm-AAc-AMPS), and poly(AAm-MEDSA) hydrogels,
parameters for the fitting of the adsorption of Fe3+ on
different types of hydrogels using the pseudo-first-order
and pseudo-second-order kinetic models, mechanical
properties of different ionogenic hydrogels before and
after adsorbing heavy metal ions (Fe3+), pictorial
representation of release and recovery of Fe3+ from
hydrogels, and thermogravimetric analysis of the poly-
(AAm-AAc-AMPS) hydrogel and poly(AAm-AAc-
AMPS) hydrogel after equilibrium incorporation of Fe3+
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
Abu Bin Imran − Department of Chemistry, Faculty of
Engineering, Bangladesh University of Engineering and
Technology, Dhaka 1000, Bangladesh; orcid.org/0000-
0001-8920-8921; Email: abimran@chem.buet.ac.bd
Authors
Noman Chowdhury − Department of Chemistry, Faculty of
Engineering, Bangladesh University of Engineering and
Technology, Dhaka 1000, Bangladesh
Solaiman − Department of Chemistry, Faculty of Engineering,
Bangladesh University of Engineering and Technology, Dhaka
1000, Bangladesh
Chanchal Kumar Roy − Department of Chemistry, Faculty of
Engineering, Bangladesh University of Engineering and
Technology, Dhaka 1000, Bangladesh
Shakhawat H. Firoz − Department of Chemistry, Faculty of
Engineering, Bangladesh University of Engineering and
Technology, Dhaka 1000, Bangladesh; orcid.org/0000-
0002-1771-462X
Tahmina Foyez − Department of Pharmaceutical Sciences,
School of Health and Life Sciences, North South University,
Dhaka 1229, Bangladesh
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.0c05411
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
A.B.I. gratefully acknowledges the support of the Capacity
Utilization Program under Special Allocation for Science and
Technology (BS-182 and PHY’S-467) from the Ministry of
Science and Technology, the People’s Republic of Bangladesh.
The author is also thankful to the Committee for Advanced
Studies and Research (CASR) in BUET and The World
843
Article
Academy of Sciences (TWAS), Italy and a program of UNESCO
■
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