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Use of super absorbent hydrogels derivative from acrylamide with

itaconic acid and itaconates to remove metal ions from aqueous


solutions
Amal El-Halah,1 Daniel Machado,2 Nain González,1 Jesús Contreras,1 Francisco López-Carrasquero 1
1
Grupo de Polímeros, Departamento de Química, Facultad de Ciencias, Universidad de Los Andes, Mérida, 5101-A, Venezuela
2
Laboratorio de Investigación en Análisis Químico, Industrial y Agropecuario (LIAQIA), Departamento de Química, Facultad de
Ciencias, Universidad de Los Andes, Mérida, 5101-A, Venezuela
Correspondence to: F. López-Carrasquero (E-mail: flopezc@ula.ve)

ABSTRACT: Poly(acrylamide-co-itaconic acid) (AAm/IA) and poly(acrylamide-co-monomethoxyethyl itaconate) (AAm/MEI) hydrogels


(HGs) synthesized at different molar ratios were used to study the adsorption of some metal ions as Cu2+, Ni2+, Pb2+, Cd2+, and Fe3+ in
aqueous solutions at different concentration: 10, 50, 100, 500, and 1000 mg L−1. Statistical analysis was performed and the effect of the
metal ion, ion concentration, and hydrogel (HG) composition, on adsorption and adsorption efficiency, was evaluated for both HGs
studied (AAm/IA and AAm/MEI) and each factor gave rise to significant differences (P ≤ 0.05). The adsorption depends on the type of
ion, its concentration, and also influenced by the type and composition of the HGs. For each system the adsorption efficiencies for all
ions were similar with exception of Fe3+, which showed the highest adsorption efficiency in AAm/MEI HG, but the less for the
AAm/IA. For both systems, the maximum adsorption efficiency was observed when the molar ratio AAm/IA or AAm/MEI is 80/20.
When the adsorption was carried out with individual ions, AAm/MEI HG was more efficient than AAm/IA. For a multielement sample
of Cu2+, Ni2+, Pb2+, and Cd2+, both HGs could adsorb all the ions and their behavioral trend was the same in both cases, in which the
adsorption efficiency was Pb2+ > Cu2+ > Cd2+ > Ni2+. The results of the statistical analysis evidence the advantage of its use in this type
of studies. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46999.

KEYWORDS: hydrogels; ion adsorption; itaconic acid; poly(acrylamide-co-itaconic acid); poly(acrylamide-co-monomethoxyethyl itaco-
nate); statistical analysis

Received 23 March 2018; accepted 4 July 2018


DOI: 10.1002/app.46999

INTRODUCTION
HGs have been widely used in water purification studies, as they
Industrial development has rapidly increased the water pollution have not only been shown to be effective in the adsorption of metal
of the planet. Among the pollutants discharged into the water ions, but also because the synthesis of most of them is relatively
sources, there is a large amount of metal ions as Cu2+, Pb2+, easy, inexpensive, and also these materials can be reused.8–13 Acryl-
Fe2+, Fe3+, Al3+, As5+, Zn2+, Cd2+, Cr3+, and Cr6+ coming from amide HGs that contain low amounts of itaconic acid (IA) and ita-
fabric, automotive, chemical, pharmaceutical, metallurgical, conate units in the structure had received some attention. These
agro-food, mining industries or from the glass, and ceramics HGs were used for swelling studies, cationic dyes, and uranyl
manufacture.1–3 removal and adsorption of bovine serum albumin.14–18 The interest
Currently there are different methods for the decontamination in the preparation of IA or itaconate containing polymers and HGs
of wastewater containing metal ions. The literature make men- is due not only to their structure being similar to that of acrylates
tion of some techniques that are useful for the direct recovery and methacrylates, but also to the fact that IA is a water-soluble nat-
of metal ions, among them, ion exchange, chemical precipita- ural monomer having two carboxylic acid groups which are able to
tion, separation using membranes, and others which involve be esterified selectively.19 Conversely, the IA and its esters have been
adsorption phenomena using substances, such as activated easily copolymerized with AAm, which produce copolymers with
charcoal, zeolites, chelating products, bio-absorbents, and pendant carboxyl groups that are highly hydrophilic. Therefore, if
HGs.4–7 these copolymers are properly cross-linked, they give rise to highly

Additional Supporting Information may be found in the online version of this article.

© 2018 Wiley Periodicals, Inc.

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efficient networks in the absorption of water.20–24 Small amounts of work.25 All the details about the synthesis and characterization
IA in an acrylamide HG increase the degree of swelling of the gel were reported in this reference. The idealized structure of these
network.14,20 Even more, when the proportion of IA or mono- HGs is shown in the Scheme 1.
methoxyethyl itaconate (MEI) in the poly(acrylamide-co-itaconic For the preparation of saline solutions, the following salts were
acid) (AAm/IA) or poly(acrylamide-co-monomethoxyethyl itaco- used: Nickel(II) nitrate hexahydrate, (Ni[NO3]26H2O), copper
nate) (AAm/MEI) HGs is higher than 10 mol %, the swelling (II) nitrate hemihydrate (Cu[NO3]22 1/2H2O), lead (II) nitrate
increases considerably, reaching values near 40 000% when the con- (Pb[NO3]2), cadmium (II) nitrate (Cd[NO3]2), Iron(III) nitrate
tent of itaconate is 30 mol %.25 nonahydrate (Fe[NO3]39H2O), Iron (II) chloride tetrahydrate
IA HGs and their esters have also been proved to be effective for (FeCl24H2O), and Iron (II) hexahydrate (FeCl36H2O), supplied
metal ions adsorption. HGs that contain itaconic acid effectively by Riedel-de Haën.
adsorb Pb2+, Cd2+, Cu2+, and Zn2+ ions.26–29 In addition,
poly(octadecyl diitaconate) has been used as filler material for pre- Swelling Measurements
concentration of cadmium, showing to be a good sorbent material Maximum swelling (Hpmax) was measured using conventional
for Cd2+.30 These studies strongly suggest that these materials, espe- gravimetric procedure. Dry gel samples (Xerogel) were immersed
cially when they have high contents of IA or itaconate units in the in double-distilled water and in a Cu(NO3)2 0.02 M solution at
polymeric chain, could be effective HGs to be used for recover metal 25  C until the equilibrium was reached. Then, the HGs were
ions from contaminated waters. However, in the literature there are removed from the solution, wiped with filter paper, and weighed
few reports in ions adsorption studies with AAm/IA,31,32 while on an electronic balance. The maximum swelling (Hpmax) was
AAm/MEI or poly (acrylamide-co-dimethoxyethyl itaconate) calculated using the following equation25:
(AAm/DEI) HG have not been used for ion adsorption.   
Hpmax = Weq − W0 =W0 × 100 ð1Þ
This article describes the study of the adsorption of some metal ions
as Cu2+, Ni2+, Pb2+, Cd2+, Fe2+, and Fe3+ in aqueous solutions using
poly(acrylamide-co-itaconic acid) (AAm/IA), poly(acrylamide-co- Where Weq is the weight of swollen HG at equilibrium and W0 is
monomethoxyethyl itaconate) (AAm/MEI), and poly(acrylamide- the weight of the dry gel. All swelling measurements were done
co-dimethoxyethyl itaconate) (AAm/DEI) HGs synthetized at differ- by triplicate.
ent molar ratios with the main objective to determinate how the
chemical HG structure and composition influence the adsorption of Metal Ions Adsorption
metal ions. It is noteworthy that amounts of IA and itaconates in The initial and final concentrations of metal ions in solution were
these HGs are higher than those used by others authors.14–18,20 measured with inductively coupled plasma optical emission spec-
The effects of the ion concentration in the solution and the HG troscopy (ICP-OES) equipment; brand ICP-ES LIBERTY SERIE II.
composition on the adsorption for different ions were studied All saline solutions were prepared in water 18.2 MΩ cm−1 at con-
using a multifactorial experimental design and statistical analysis, centrations of about 10, 50, 100, 500, and 1000 mg L−1 and then,
ANOVA, which are useful tools that allows evaluate in the same the initial real concentrations (Conci) were measured by ICP.
experiment the effects of several factors, as the factorial design The initial pH (pHi) of all solutions was also determined.
need less measurements than the classical approximation to
obtain the same precision. The competition on the adsorption of The xerogel samples (pellets) were cut with a very thin steel cutting
some ions in a multielemental solution was also evaluated. blade and weighed, trying to maintain a weight between 30 to
60 mg for all of them. Then, they were immersed in 50 mL of each
EXPERIMENTAL of the separately prepared solutions, allowed to absorb for 24 h.
Experimental Design Then, were removed and weighed. The final concentration (Concf)
To evaluate the effects on adsorption, the experimental design and pH (pHf) of the resulting solutions were measured. The pellets
was a complete factorial arrangement that takes into account the were left dried at room temperature until the samples reach constant
following factors: weight. The procedure was performed by triplicate for all samples.

Data Treatment
1. Metal ion: Cu2+, Ni2+, Fe3+, Cd2+ and Pb2+.
Adsorption Calculation. The adsorption of the ions by the HGs
2. Initial concentration of the metal ion (mg L−1): 10, 50,
was evaluated by the following10:
100, 500, and 1000 (nominal).
3. Composition of the copolymers: HGs of AAm/IA and AAm/MEI
ðConci − Concf ÞV
with a molar ratio of 90/10, 80/20, and 70/30. A= ð2Þ
mHG
This implies 75 combinations (cases) for each HG (AAm/IA and
AAm/MEI). Adsorption and adsorption efficiency were calculated
Where A represents the amount of ion adsorbed in mg of ion per
in three replicates for each case.
gram of HG, Conci, and Concf are the initial and final concentra-
Materials tions (mg L−1) of the saline solution, respectively, V is the volume
The poly AAm, AAm/IA, AAm/MEI, and AAm/DEI HGs used (mL) of the saline solution used and mHG is the weight (g) of the
in this work were synthesized and characterized in our previous dry HG.

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Scheme 1. Idealized structure of the different HGs used in this work.

Adsorption Efficiency. As the changes in the value of A depend Generated Hydrogen Ions. The amount of hydrogen ions gener-
on the initial concentration of the solution, in this work, we pro- ated in the adsorption process was calculated from the difference
pose the use of a parameter E. This value represents the efficiency among initial and final pH.
of the HG to adsorb a metal ion (adsorption efficiency) and can
The pH was measured with a pH meter Thermo Electron Corpo-
be calculated by:
ration Orion 3 star pH Benchtop.
ðConci − Concf Þ 1
E= × ð3Þ
Conci mHG Statistical Analysis. The data analysis was performed using the
classical variance analysis technique, ANOVA33 and the differ-
ences between the means of the analyzed variables (A and E)
Where E is the adsorption efficiency (g−1), Conci and Concf are were evaluated using the “Tukey, HDS” test. For both statistical
the initial and final ion concentration (mg L−1) of the saline solu- analyses a level of significance of 95% (P ≤ 0.05) was used. This
tion, respectively, and mHG is the initial weight (g) of the dry analysis was carried out with the STATGRAPHYCS Centurion
HG. The parameter E has the advantage that allows the compari- XVI program.
son of the adsorption at different initial concentrations and com-
parison between ions with different atomic weight, because E has In the graphs presented below, for the means of A or E variables,
the same calculated value using the concentration in weight (mg the standard error of the mean (SEM) was calculated as:
L−1) or in number of particles (mmol L−1).
S
SEM = pffiffiffi ð5Þ
Adsorbed Metal Ion. Adsorbed ion (mmol) was calculated using n
the data obtained from the ICP-OES equipment using the
following: Where S is standard deviation and n is the number of measures.

ðConci − Concf ÞV
Ion mmoladsorbed = ð4Þ Complex Formation Enthalpies
PA
The complex formation enthalpies (ΔHf) between the different
metal ions and the HG in the adsorption process, was estimated
Where V is the volume of the solution (mL) and PA is the through an exploratory simulation study performed with a com-
atomic weight of the metal ion. putational program for chemical analysis MOPAC 2012 with

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Table I. Maximum Swelling (Hpmax) Reached by AAm, AAm/DEI, AAm/MEI, and AAm/IA 80/20 HG in Water and in a 0.02 M Cu(NO3)2 Solutiona

AAm AAm/DEI AAm/MEI AAm/IA

Water Cu(NO3)2 Water Cu(NO3)2 Water Cu(NO3)2 Water Cu(NO3)2


Hpmax Hpmax Hpmax Hpmax
2534 1919 10 043 10 497 30 329 380 20 330 265
a
The weight of all de HG samples used was of about 50 mg. The volume of water and solution of Cu(NO3)2 used was 100 mL.

semi-empirical method PM7, using the metal ions and the differ- HG dries, the copper salt remains there. But when the HG is sub-
ent monomer involved in the HG structure. merged in water again, the copper salt is release and leaves from
the HG. While for AAm/IA and AAm/MEI a strong chemical
Morphological Study interaction or a complex formation between Cu2+ and the HG
The morphology of xerogels was obtained through SEM images are taking place. Therefore, AAm and AAm/DEI HGs were dis-
from the surface of lyophilized swollen samples. For this purpose, carded for use in the analysis of ion adsorption.
the samples were swollen to equilibrium, cooled in liquid nitro-
Once the HGs to be used were selected, a series of assays were
gen and then lyophilized in a LABCONCO apparatus during
carried out to determine the HG amount, solution volume, con-
24 h. The images were obtained using a scanning electron micro-
centrations, and adsorption times to be used in the adsorption
scope (HITACHI S-2500) operating at 12 kV with a magnifica-
experiments. Samples of about 30–60 mg of HG were chosen.
tion of 500 times. Before the analysis, the aerogel samples were
For these amounts, 50 mL of the Cu(NO3)2 solution was ade-
coated with a thin layer of gold in an ion coater SPI model
quate to carried out all the adsorption experiments. The use of
11430E to provide proper surface conduction.
less volume of solution was not enough for some samples, espe-
The average pore size was calculated from the data obtained with cially those with high content of IA or MEI because they absorb
the SEM images, using the following equations: all the liquid. It was determined that at 24 h, the HG reach the
maximum adsorption and for longer time, 48 and 72 h, it
Spn = 1=ΣðFi =Ti Þ or ΣFi =ΣðFi =Ti Þ ð6Þ remains constant. Therefore, this was the time used in the experi-
ments. The solutions concentrations of 1000, 500, 100, 50, and
Spw = ΣðFi :Ti Þ ð7Þ 10 mg L−1 were the same used by other authors.10,26,34

Where Spn is the number-average pore size, Spw is the weight- Adsorption Studies
average pore size, and Fi is the fraction of pores with a size Ti. Factor Analysis. Once the best experimental conditions were
established, a complete analysis of the effect of the different fac-
RESULTS AND DISCUSSION tors on the adsorption of the metal ions was carried out.
Preliminary Experiments As an example of the obtained results, in Table II, are shown
To determine the HGs that would be used for this work, a pre- the adsorption values for AAm/MEI 80/20 at different concen-
liminary swelling experiment was carried out immersing samples trations. There, it can be observed that the weight of the HGs
of AAm, AAm/DEI, AAm/IA, and AAm/MEI 80/20 HGs, in increases as the concentration of the solution decreases and
water and in 100 mL of a 0.02 M solution of Cu(NO3)2. In the this trend is observed throughout all the concentration gradi-
solution of Cu(NO3)2, AAm and AAm/DEI HGs acquire a very ent. It happens because in the more diluted solutions, the
pale blue color after submerging, while AAm/MEI and AAm/IA water penetration to the network is favored. It was also noted
HGs take a deep blue color. for all solutions, except for iron, that during the adsorption
process take place a decreasing of the pH of the ionic solution.
As explained in Table I, AAm and AAm/DEI HGs, reached
This fact suggests that an ionic exchange occurs between the
almost the same degree of swelling both in the Cu(NO3)2 solu-
metal ion of the outer solution and the hydrogen bounded to
tion and in pure water. Whereas, AAm/MEI and AAm/IA
the acidic groups of the HG. A similar behavior was previously
swelled much less in the Cu(NO3)2 solution than in pure water,
reported by Katime and Rodríguez in 2001, for acrylic acid/ita-
about 2 order of magnitude. Furthermore, when these HGs were
conic acid HGs.26
dried and submerged in water again, the AAm and AAm/DEI
completely loosed the color indicating the output of the ions, Conversely, for all samples analyzed, it was observed that the
while the HGs of AAm/MEI and AAm/IA retained it. In addi- amount of H+ ions generated is at least 1 order of magnitude
tion, AAm and AAm/DEI HG swelled during the process reach- less than the adsorbed metal ions (Table II). This suggests that
ing the Hpmax, whereas AAm/MEI and AAm/IA did not. These the adsorption mechanism is not only related to an ion
results strongly suggest that between AAm and AAm/DEI HGs exchange with the H+ groups associated with the acid groups
and the solvated Cu2+ ion, the interaction process is mainly phys- of the HG structure, but there may also be a chemical interac-
ical; this means that the solvated ions together with the water tion between the metal ion with the oxygens of the carbonyl
penetrate the HG through the pores without practically establish- groups of the itaconate and of the acrylamide, in both cases
ing any type of chemical interaction with the material. Once the forming complex-type interactions, such as it was suggested by

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Table II. Comparative Adsorption Results for AAm/MEI 80/20 at Different Concentrations

Concentration (mg L−1)


HG Initial HG final Mn+ adsorbedg H+ generatedh
n+ −1 e −1 f
M Initial Final weighta (g) weightb (g) pHi c
pHfd A (mgg ) E (g ) (mmol) (mmol)
Cu2+ 1100 1011 0.0394 0.2124 4.42 3.70 113 2.00 6.98E-02 8.00E-03
550 457 0.0382 0.2676 4.86 3.95 122 4.51 7.32E-02 4.96E-03
110 72 0.0422 1.5471 5.27 4.14 45 8.27 2.99E-02 3.33E-03
55 35 0.0334 2.6605 5.49 4.38 30 11.04 1.59E-02 1.92E-03
11 2 0.0389 20.3518 5.72 5.09 12 22.40 7.29E-03 3.08E-04
2+
Ni 1100 1009 0.0384 0.7438 5.70 4.28 118 2.18 7.73E-02 2.54E-03
550 481 0.0387 0.9945 5.69 4.38 89 3.25 5.88E-02 1.98E-03
110 80 0.0339 2.6634 5.95 4.56 44 8.14 2.56E-02 1.31E-03
55 36 0.0344 4.9160 5.89 4.78 28 10.49 1.65E-02 7.59E-04
11 1 0.0363 20.9974 6.25 5.62 14 24.90 8.46E-03 9.18E-05
Cd2+ 937 887 0.0380 0.5374 5.24 4.00 66 1.41 2.23E-02 4.67E-03
469 420 0.0357 1.0197 5.54 4.29 69 3.01 2.20E-02 2.42E-03
94 61 0.0329 4.0459 5.89 4.71 51 10.91 1.48E-02 9.18E-04
47 25 0.0334 7.4387 6.02 4.89 33 14.42 9.87E-03 5.96E-04
9 2 0.0307 18.4709 6.21 5.59 12 26.56 3.25E-03 9.77E-05
Pb2+ 1093 825 0.0348 0.1700 4.76 3.66 121 2.33 2.03E-02 1.01E-02
520 271 0.0370 0.2356 5.14 3.79 134 5.17 2.39E-02 7.75E-03
104 22 0.0411 5.6317 5.47 4.27 61 12.90 1.22E-02 2.50E-03
52 25 0.0358 10.0920 5.78 4.67 38 14.82 6.60E-03 9.94E-04
10 8 0.0376 28.1909 5.26 6.01 2 4.94 4.22E-04 ND
Fe3+ 1176 490 0.0438 0.1237 2.33 2.49 784 13.79 6.15E-01 i

i
572 232 0.0378 0.1309 2.45 2.59 450 15.92 3.04E-01
i
113 28 0.0341 0.3665 2.77 3.04 127 22.23 7.73E-02
i
57 16 0.0369 0.7284 2.93 3.26 55 19.96 3.66E-02
i
13 4 0.0374 4.9705 3.47 4.55 11 17.93 7.62E-03
a
Weight of the dry HG (xerogel).
b
Weight of the swell HG after 24 h.
c
Initial pH of the saline solution.
d
Final pH of the saline solution (after 24 h).
e
Adsorption.
f
Adsorption efficiency.
g
mmols of the adsorbed ion, determined from ICP data.
h
mmols of H+ generated during the adsorption process, calculated with the pH variation. ND Not determined.
i
Generation H+ was not observed.
All results are the average of 3 assays.

El-Hag Ali.10 The physical absorption of the solution of the has been reported,35–40 but at the moment the structure of
solvated ion should also happen together with the other pro- complex between these HG and the metal ions is not complete
cesses. The formation of complex between HG and metal ions clear. At this time in our laboratory, are conducting new

Figure 1. Average adsorption (mg g−1) of all ions concentrations and compositions of the HGs (A) AAm/IA and (B) AAm/MEI, for each metal ion. The
thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present significant differences between them
(“Tukey, HSD,” P ≤ 0.05, n = 45).

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experiments to obtain further experimental evidence that


would allow to determine the nature and structure of each one
of these complexes.
As may be observed in Table II, the adsorption of the ion is
highly dependent of the concentration and nature of the ion.
At this point, AAm/IA and AAm/MEI systems, depending on
the conditions, reach adsorption values as high as 126 and
192 mg g−1 for Cu2+, 35 and 120 mg g−1 for Ni2+, 60 and
Figure 2. Structure obtained by simulation, of the Pb2+complexes with both
455 mg g−1 for Fe3+, 102 and 60 mg g−1 for Cd2+, and 217 and
monomers. (A) IA-Pb2+ and (B) MEI-Pb2+.
144 mg g−1 for Pb2+, respectively. Conversely, the highest
values found in the literature for the adsorption of these metal
ions with others HGs, were 119 mg g−1 for Cu2+ and 204 mg As it can be seen, in all cases the ΔHf follow the sequence MEI <
g−1 for Pb2+ obtained with poly(N-isopropylacrylamide-co- IA < AAm. These values confirm that the complex formation
N,N´-dimethylacrylamide) by García and Alvarez.4 Ozay40 take place mainly with the itaconate or IA units. For both MEI
reported adsorption values of 105.4 for Ni2+, 102 for Fe3+, and IA, the lowers enthalpies were obtained for the Pb2+ ion, sug-
134 for Cd2+, and 126 for Pb2+ with poly(2-acrylamido- gesting that the complex formation between the itaconic unit and
2-methyl-1-propanesufonic acid) HG and Chowdhury and co- this ion is the most favored. Conversely, it can be observed that
workers41 found adsorption values of l38 mg g−1 for Fe3+ with Fe3+ is the ion with the highest ΔHf value indicating that this is
HG based in poly(vinyl alcohol)/polysaccharides. These the less favorable ion to form complex. These facts explain satis-
results, compared with that obtained in this work suggest that factorily the adsorption observed for the system AAm/IA [-
the performance of AAm/IA and AAm/MEI HGs, under the Figure 1(A)], where the Pb2+ is the most adsorbed ion and the
conditions studied, in the most of the cases is as good as or Fe3+ followed by the Ni2+, which showed detection problems at
better than the others. high concentrations, are the less adsorbed. Although these values
were calculated with the monomers and not with the polymer,
The statistical analysis was developed with the purpose of analyz- they satisfactorily explain the obtained results.
ing the effect of each factor (metal ion, ion concentration, and HG
composition) on the dependent variables (A and E). This was eval- Figure 2 shows, as an example, the more stable structure of the
uated for both HGs studied (AAm/IA and AAm/MEI) and each complexes of Pb2+ with both monomers. As may be seen, the
factor gave rise to significant differences (P ≤ 0.05), which means complexes are formed between the metal ions with the oxygens
that all of them affect the studied variables in a significant way. of the carbonyls groups.
The results of these effects are presented graphically below. For AAm/MEI HG the Fe3+ ion showed the highest adsorption,
this fact can not be explained from the point of view of the com-
Metal Ion. Figure 1 shows, in a comparative way, the adsorption plex formation, because here its ΔHf is at least 2.5 times higher
of the different metal ions by both HGs used. From the Figure 1 than the others ions. However, it can be explained because the
(A) is clear that the Pb2+ ion is the most adsorbed with AAm/IA ingress of the solvated ion into the HG should be influenced by
followed by Cu2+, Cd2+, Fe3+, and Ni2+ ion. However, for the the pore size of the HG and the hydrated ionic radius. As may be
AAm/MEI system (Figure 1(B)), the Fe3+ ion is the most observed in Table III, Fe3+ ion has the smaller hydrated ionic
adsorbed, while the other ions were adsorbed more or less in the radius and the results obtained for the SEM micrographs of
same way as with the previous system. AAm/IA and AAm/MEI 90/10 HGs (Figure 3), as it will be
explained after, indicate that the AAm/MEI system has a smaller
As was explained before, the adsorption process may involve a
average pore size than the AAm/IA.
chemical interaction between the carbonyl groups of the mono-
mer units with the metal ions which may produce complex-type In reference to the average pore sizes, they were determined from
interactions. To corroborate this fact, an exploratory simulation the histograms shown in Figure 3 for plot (A) AAm/IA and plot
study to allow determine complex formation enthalpies (ΔHf) (B) AAm/MEI 90/10 HG swelling in water after reaching
was carried out and the obtained results are shown in Table III. equilibrium.

Table III. Hydrated Ionic Radius of the Metal Ions Used in this Work and Their Complex Formation Enthalpy With the Monomers Used in the HGs
Synthesisa

Mn + b Fe3+ (0.66 Å) Fe2+ (0.78 Å) Ni2+ (0.72 Å) Cu2+ (0.94 Å) Cd2+ (0.96 Å) Pb2+ (1.20 Å)
Monomer ΔH (K J mol−1)
AAm 4015 2184 1890 1800 1554 1599
MEI 2597 1844 939 977 722 709
IA 3255 1100 1312 1123 1446 1071
a
The enthalpies were calculated using the program MOPAC2012.
b
The values between parentheses correspond to the hydrated ionic radius of each ion.42

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Figure 3. SEM micrographs and histograms of HG 90/10 (A) AAm/IA and (B) AAm/MEI.

smaller for the last, but it has a considerable less amount of larges
pores than AAm/IA.
At this point, it is necessary to emphasize that in the xerogel the pores
are totally collapsed and in this state their diameters are substantially
smaller than the aerogel. Experimentally it has been observed that
AAm/IA and AAm/MEI HGs have preference for the adsorption of
the ions than for the water, and that during the ion adsorption, the
swelling process practically does not occur (see Table I), therefore the
pores do not expand.28 As it is logical to suppose, the ratio of the pore
diameters between AAm/MEI and AAm/IA must be maintained in
the xerogel, therefore, the pore diameter of the AAm/MEI must be
Figure 4. Adsorption efficiency (E) of AAm/IA and AAm/MEI 80/20 HGs lower than the AAm/IA, this fact strongly suggests that the ions with
with solutions of FeCl2 and FeCl3 of 50 mg L−1. The thin bar represents the
the lowest hydrated ionic radius, as in the case of Fe3+, should enter
standard deviations.
in the MEI/AAm matrix easier than the other ions.
To verify that the size of the ion certainly influences the adsorp-
For AAm/IA the weight and number-average pore size (Spw and tion, a simple study was performed using the FeCl2 and FeCl3 salts
Spn) are 17 μm and 16 μm, respectively, while for AAm/MEI are with a concentration of 50 mg L−1 with both HGs. As may be seen
15 μm and 14 μm. Moreover, the proportion of pores with a size in Figure 4, the Fe3+ ion is the most easily adsorbed for the HG
higher than 17 μm is 47.8% for AAm/IA and only 25.6% for AAm/MEI. It may be due to the fact that its hydrated ionic size is
AAm/MEI, which indicate that not only the average pore size is smaller (0.66 Å) than Fe2+ (0.78 Å). Conversely, for the HG

Figure 5. Average adsorption efficiency (g−1) of all ions concentrations and compositions of the HGs (A) AAm/IA and (B) AAm/MEI, for each metal ion.
The thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present significant differences between
them (“Tukey, HSD,” P ≤ 0.05, n = 45).

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Figure 6. Average Adsorption (mgg−1) of all metal ions and compositions of the HGs (A) AAm/IA and (B) AAm/MEI, for the different concentrations of
the ions. The thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present significant differences
between them (“Tukey, HSD,” P ≤ 0.05, n = 45).

Figure 7. Average Adsorption Efficiency (g−1) of all metal ions and compositions of the HGs (A) AAm/IA and (B) AAm/MEI, for the different concentra-
tions of the ions. The thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present significant differ-
ences between them (“Tukey, HSD,” P ≤ 0.05, n = 45).

AAm/IA, that has a higher pore size, no significant difference was Ion Concentration. For both systems, when the concentration of
found between the adsorption efficiency for Fe2+ and Fe3+. the metal ions increases, the adsorption raises as may be seen in
Figure 6. This occurs because higher concentration of the solu-
The E results obtained are shown in Figure 5. It is clear that both
tion, the ions will be more available. However, as may be seen in
systems show a more or less similar efficiencies for all ions with
Figure 6(A), for the AAm/IA system above 500 mg L−1, the
exception of Fe3+. The Fe3+ shows the highest adsorption effi-
adsorption value does not increase, on the contrary, this seems to
ciency in AAm/MEI HG, but the less in the AAm/IA.
decrease slightly, and this fact strongly suggests that over this
These results indicate that the adsorption depends on the ease concentration value the system becomes saturated.
with which the metal ion interacts with the carboxyl groups pre-
Conversely, adsorption efficiency shows a contrary trend, in this
sent in the HG and also on the relationship between the hydrated
case the efficiency decrease as the concentration raises (Figure 7),
ionic radius and the pore size of the HG.
because the relative adsorption in most diluted solution respect
The chemical interaction (complex formation) is the predomi- to the initial concentration is higher. However, both HGs tested;
nant factor in the ion adsorption. However, the relation between do not show the same behavior, while AAm/IA HGs efficiency is
the pore size and hydrated ion size also influences the ion input. practically equal between concentrations from 10 to 100 mg L−1,

Figure 8. Average Adsorption (mg g−1) of the metals ions and compositions of the different HGs (A) AAm/IA and (B) AAm/MEI, for the different concen-
trations of the ions. The thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present significant dif-
ferences between them (“Tukey, HSD,” P ≤ 0.05, n = 75).

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Figure 9. Average Adsorption Efficiency (g−1) of all the ions and concentrations for the different compositions of the HGs (A) AAm/IA and (B) AAm/MEI.
The thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present significant differences between
them (“Tukey, HSD,” P ≤ 0.05, n = 75).

for AAm/MEI the efficiency increase gradually with the diminu- Finally, taking this fact into account, the maximum adsorption
tion of the concentration. could be reach with HGs with a molar ratio of 80/20, which
has more IA or MEI unit than 90/10 HG, and where the com-
Both, adsorption and efficiency are higher for AAm/MEI than
petition with water is less than the observed with a molar ratio
AAm/IA for each concentration of the solutions.
of 70/30.

Hydrogel Composition. The influence of the HG composition


both in the adsorption and efficiency is shown in Figures 8 and 9. Nature of the Itaconic Co-Monomer. The obtained results indi-
In Figure 8, it can be seen that the 80/20 and 70/30 M ratios reach cate that HGs of AAm/MEI are more effective for ion adsorption
the higher adsorptions for AAm/IA HGs while for AAm/MEI sys- than AAm/IA as it may be seen graphically in Figure 10.
tem, the order in the adsorption is 80/20 > 70/30 > 90/10. This fact is not easy to explain and it is possible that the higher
Conversely, as may be seen in Figure 9, the average adsorption adsorption of the AAm/MEI may be because of the combination
efficiency is significantly higher for the 80/20 ratio than the 90/10 of a series of factors. For all the ions systematically studied in this
and 70/30 ratios for both systems. work, the formation enthalpies (ΔHf) of the complex obtained
with AAm/MEI HG are lower than those obtained with AAm/IA
As mentioned above, the adsorption processes are mainly due to (Table III), this could be favoring the higher adsorption for the
the interaction between the carboxylic acid groups with the metal former. Although the pore size of AAm/MEI HG is lower, is pos-
ions, through an ionic exchange of the metal ion with the sible that at molecular level the presence of a longer side chain
hydroxyl group and also by complex-type interactions with the increase the flexibility of the network allowing that the entry and
oxygen atoms of the carbonyl group. The 90/10 M ratio in both the interaction with the ion occurs more easily. Moreover, in the
systems has fewer itaconate units and therefore less carboxylic case of the AAm/IA HG, the density of hydrogen bonds is higher
groups, for this reason it shows the less adsorption. The HGs making the network more rigid.
with the 70/30 M ratio has the highest proportion of itaconate or
itaconic acid, and then the ion adsorption should be the largest. These results suggest that the side chains of the itaconic unit and
Nevertheless, in this case a competition process between the ion its proportion in the HG could have some influence on the
and water occur. Then, the greater amount of water over the adsorption.
ions, favors the adsorption of the former. This is evident in the
more dilute solutions, especially in the 10 mg L−1, there, HGs Multielement Solution Analysis. Finally, a study was performed
with a co-monomers ratio of 70/30 absorb a large amount of to evaluate the behavior of these HGs in a solution with a mixture
water,25 and in almost all cases, at very dilute concentrations, the of different ions and determinate if any of two showed some kind of
amount of ions that retain these HG are lower than those having selectivity by some of the ions. To do this, two HGs AAm/IA and
a 90/10 M ratio. AAm/MEI 80/20 were used to evaluate a multielement solution

Figure 10. (A) Average adsorption (mgg−1) and (B) average efficiency (g−1) of all metal ions, concentrations ions and HG compositions for HG AAm/IA
and AAm/MEI. The thin bar represents the SEM of the sample. The comparison was made with “Tukey HDS,” P ≤ 0.05, n = 225.

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Figure 11. Adsorption efficiency (E) for each one of the ions in a multielement solution. (A) For AAm/IA and (B) for AAm/MEI. The thin bar represents
the standard deviation of the sample.

Figure 12. Comparison of the adsorption efficiency (E) between the summation averages of E for 500 mg L−1 and 100 mg L−1 in separated ions solutions
with the same ions in a multielement solution. (A) HG AAm/IA 80/20 and (B) to HG AAm/MEI 80/20. The thin bar represents the standard deviation of
the sample.

composed of Cu2+, Cd2+, Ni2+, and Pb2+ ions with a concentration systems, the maximum adsorption efficiency was observed when
of 50 mg L−1 of each one, giving a total concentration of 200 mg the molar ratio AAm/IA or AAm/MEI is 80/20.
L−1. The obtained result indicates that both HGs adsorb all the ions
Each HG shows comparable adsorption efficiency for all ions
and their behavioral trend is the same in both cases.
with exception of Fe3+ which shows the highest adsorption effi-
As may be appreciated in Figure 11, the AAm/IA results more ciency in AAm/MEI HG, but the less for the AAm/IA.
efficient than AAm/MEI system and in both cases the adsorption
AAm/MEI HG is more efficient than AAm/IA when the adsorp-
efficiency is Pb2+ > Cu2+ > Cd2+ > Ni2+. Figure 12 compares the
tion was carried out with single ions. For a multielement sample
adsorption efficiency using the total concentration of the multie-
of Cu2+, Ni2+, Pb2+, and Cd2+, both HGs can absorb all the ions
lement solution (200 mg L−1) with those obtained as an average
and their behavioral trend is the same in both cases, in which the
of the separated solutions for 100 and 500 mg L−1. Although in
adsorption efficiency is Pb2+ > Cu2+ > Cd2+ > Ni2+.
the case of the multielement solution only one concentration and
a molar ratio are being considered, in both cases it is observed The use of the adsorption efficiency (E) of a HG allows to com-
that this solution follows the same tendency showed in Figure 7. pare the adsorption of metal ions with different atomic weight
For HG AAm/IA it is observed that the E value decreases from and evaluate the adsorption in multielement solutions better than
100 to 500 mg L−1. This behavior agrees with the general trend using adsorption (A).
shown in Figure 7(A). For HG AAm/MEI, the observed E value As methodologic point of view, the use of a multifactorial experi-
of the 200 mg L−1 solution is comparable to that of 500, but less mental design with its respective statistical analysis brought
than 100 mg L−1, which is in agreement with that shown in important conclusions about the effects of selected factors on the
Figure 7(B). ions adsorption by HGs. This fact evidences the advantage of
The results obtained in this experiment indicate that these sys- using a statistical approach for this type of studies.
tems are capable of absorbing different metal ions in a multiele-
ment sample. However, additional experiments are needed to ACKNOWLEDGMENTS
obtain more conclusive results and to determine the true poten- The authors gratefully acknowledge the financial support of
tial of these systems for use in remediation of water sources. CDCHTA-ULA, Mérida Venezuela, through grant number
C-2001-18-08-A. The authors also wish to thank to Andres
CONCLUSIONS
E. Mora and Jorge Fernandez of LAQUEM-ULA, for their help
These results indicate AAm/IA and AAm/MEI HGs are effective with the SEM experiments, to Lic. William Velázquez of LARSA-
systems for adsorption ions and their capacity depend on the ion ULA, for his help with the ICP measures and MSc. Eduardo Car-
involved, its concentration and composition of the HGs. For both dozo of the Group of Organometallics of the Chemistry

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46999 (11 of 11) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46999