Reactive and Functional Polymers 131 (2018) 64–74

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Reactive and Functional Polymers

journal homepage: www.elsevier.com/locate/react

A new low-cost polymeric adsorbents with polyamine chelating groups for T

efficient removal of heavy metal ions from water solutions
⁎
Michał Cegłowskia, , Błażej Gierczyka, Marcin Frankowskia, Łukasz Popendab
a
Faculty of Chemistry, Adam Mickiewicz University in Poznan, Umultowska 89b, 61-614 Poznań, Poland
b
NanoBioMedical Centre, Adam Mickiewicz University in Poznań, Umultowska 85, 61-614 Poznan, Poland

A R T I C LE I N FO A B S T R A C T

Keywords: Two new low-cost polymeric adsorbents have been obtained in a simple reaction of diethylenetriamine (DETA)
Low-cost adsorbent or pentaethylenehexamine (PEHA) with 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazinane-2,4,6-trione (HDI-IC).
Chelating polymer The reagents used for the synthesis are inexpensive and are produced yearly in high quantities to be applied in
Adsorption various industrial processes. The resulting HDI-IC-DETA and HDI-IC-PEHA polymers possess ethyleneamine
Heavy metal ion
chains of various lengths therefore they are capable of forming polyamine chelating complexes with heavy metal
ions. The composition, properties and morphology of the two polymers were investigated by Fourier transform
infrared spectroscopy, elemental analysis, thermogravimetric analysis, solid state nuclear magnetic resonance,
and scanning electron microscopy. The influence of parameters such as pH, initial concentration, contact time,
and temperature on the adsorption of Cd2+, Co2+, Cr3+, Cu2+, and Ni2+ ions was investigated. The adsorption
isotherm data were well fitted by Langmuir model, whereas the adsorption kinetics followed the pseudo-second-
order kinetic model. The values of maximum amount of ions adsorbed, calculated using the Langmuir model for
adsorption of Cd2+, Co2+, Cr3+, and Cu2+ ions on HDI-IC-PEHA polymer, were at least twice higher than those
calculated for HDI-IC-DETA polymer. The findings reported indicate that HDI-IC-DETA and HDI-IC-PEHA
polymers are excellent adsorbents for efficient removal of heavy metal ions from aqueous solutions.

1. Introduction
Pollution with heavy metal ions is a serious environmental problem
in view of their toxicity, persistence and non-biodegradable nature. The
release of heavy metal ions caused by extensive industrialization and
indiscriminate disposal, results in contamination of aquatic ecosystems,
atmosphere and soil. These ions tend to accumulate in the biosphere
and enter living organisms through the alimentary chain which results
in their circulation in the environment [1]. As a result, the presence of
heavy metal ions in the ecosystem is a major and long-term environ-
mental hazard. Many of these ions pose a serious threat to human
health even at very low concentrations. Some of them like iron, cobalt,
zinc, and copper are required in human diet in small quantities, how-
ever their presence at higher concentration leads to toxic effects. The
removal of heavy metal ions from the environment has therefore re-
ceived much attention in recent years and is considered as an important
subject of environmental chemistry [2].
Various techniques such as adsorption, ion exchange, dialysis pre-
cipitation and extraction have been applied to remove excess heavy
metal ions from water solutions. Among these techniques adsorption
has received much attention due to high environmental friendliness and
low cost of adsorbents production [3, 4]. The additional benefit of using
adsorption is the possibility to easily remove adsorbent from a purified
solution which significantly reduces the overall cost of purification
process. Moreover, usually under appropriate conditions the adsorbed
pollutant can be desorbed which allows the adsorbent reuse.
The adsorption properties of particular adsorbent are closely related
to its specific surface area, internal structure and presence of accessible
functional groups. These factors affect the types of interaction that are
taking place between adsorbate and adsorbent and ultimately control
the effectiveness of adsorption process. As a result, numerous materials
with various adsorption properties can be obtained to meet specific
needs. Among the commonly synthesized adsorbents one can find
functional polymers [5–12], activated carbon [13–16], zeolites
[17–19], modified silica [20–25] and metal oxides [26–28]. Functional
polymers have received much interest due to their vast surface area,
perfect skeleton strength and the fact that their basic physicochemical
properties such as pore size distribution or internal surface area can be
adjusted by varying the polymerization conditions [29]. The possibility
to introduce various functional groups into the polymeric matrices

⁎
Corresponding author.
E-mail address: ceglowski.m@gmail.com (M. Cegłowski).

https://doi.org/10.1016/j.reactfunctpolym.2018.07.006
Received 2 November 2017; Received in revised form 13 May 2018; Accepted 7 July 2018
Available online 12 July 2018
1381-5148/ © 2018 Elsevier B.V. All rights reserved.
M. Cegłowski et al.
allows their use as adsorbents that can effectively trap many organic
and inorganic pollutants. Moreover, the exhausted adsorbents can be
regenerated under mild conditions usually by treatment with acidic or
alkaline solution [30].
A good heavy metal ion adsorbent designed for large-scale appli-
cation, besides showing adequate adsorption properties, must be in-
expensive in preparation. The main drawback of activated carbons and
many functional polymers is their high production cost, caused by the
necessity of altering their structure by introduction of functional groups
or complexing units [31]. In recent years, the search for low-cost ad-
sorbent for heavy metal ions has become a very important research
focus. Various materials such as agricultural wastes, industrial by-
products and wastes of natural substances have been studied as ad-
sorbents of heavy metal ions [30]. For instance, pecan shell-based
granular activated carbons pretreated with HCl were used for removal
of metal ions (Cu2+, Pb2+, Zn2+) from water solutions [32]. Rice husk
treated with K2HPO4 was used for removal and recovery of Cd2+ from
wastewater [33]. Hydrous titanium oxide obtained by TiCl4 hydrolysis
was used for purification of industrial waste contaminated with chro-
mium (VI) [34]. Clay sorbent treated with hydrochloric acid was used
for removal of nickel, copper, and zinc ions from wastewater [35].
In this study, a simple reaction of polyamines, particularly diethy-
lenetriamine (DETA) and pentaethylenehexamine (PEHA), with 1,3,5-
tris(6-isocyanatohexyl)-1,3,5-triazinane-2,4,6-trione (HDI-IC) was used
to obtain two polymeric adsorbents. The obtained polymers can be
regarded as low-cost adsorbents of heavy metal ions, as the reagents
used for their synthesis are inexpensive and are produced yearly in high
quantities to be applied in various industrial processes [36–38].
Moreover, most low-cost adsorbents need some additional pretreatment
before they can be applied in adsorption of heavy metal ions, therefore
a reaction that takes only 2 h can be regarded as low time-consuming
process. The materials obtained were characterized and their adsorp-
tion properties towards Cd2+, Co2+, Cr3+, Cu2+, and Ni2+ ions were
tested. The influence of factors affecting the adsorption of these ions
such as pH, concentration, contact time, and temperature was in-
vestigated. The polymeric adsorbents obtained were applied for the
removal of heavy metal ions from real wastewater samples.
2. Experimental
2.1. Materials and chemicals
Diethylenetriamine, pentaethylenehexamine, ethylenediaminete-
traacetic acid disodium salt (EDTA), acetonitrile, ethyl acetate, metal
perchlorates: Cd(ClO4)2 × 6H2O, Co(ClO4)2 × 6H2O, Cr
(ClO4)3 × 6H2O, Cu(ClO4)2 × 6H2O, and Ni(ClO4)2 × 6H2O were ob-
tained from Sigma-Aldrich (St. Louis, MO, USA) and were used without
further purification. 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazinane-
2,4,6-trione (HDI-IC) was obtained from Covestro (Leverkusen,
Germany). Wastewater samples were obtained from PRESSEKO
(Bolechowo near/Poznan, Poland) company.
2.2. Instruments
A Shimadzu ICPE-9820 Inductively Coupled Plasma Optical
Emission Spectrometer (ICP-OES) with the mini-torch technology was
used for determination of Cd2+, Co2+, Cr3+, Cu2+, and Ni2+ ions
concentrations. Each measurement was performed in 3 replications,
and the % RSD did not exceed 5%. The FTIR spectra of the resins were
recorded on a Bruker IFS 66s spectrometer (Billerica, MA, USA) using
KBr pellets (about 1.5 mg of sample in 200 mg of KBr). 13C and 15N CP-
MAS NMR spectra were recorded on an Agilent DD2 spectrometer
(Santa Clara, CA, USA) equipped with Wide Bore Triple Resonance T3
MAS XY{1H-19F}, 4 mm probehead, using standard cross polarization
sequence (tancpx) with 1H decoupling, operating at frequencies 100.66
and 40.58 MHz, respectively. The following parameters were used:
65
Reactive and Functional Polymers 131 (2018) 64–74
sample rotation – 8000 Hz, relaxation delay – 7 s, acquisition time –
0.05 s, cross-polarization contact time – 0.9 ms. The spectra were re-
ferred to the methylene signal of external glycine (43.30 ppm for 13C
and −347.60 ppm for 15N, respectively). Elemental analyses were
carried out on a Vario EL III Element Analyzer (Hanau, Germany).
Thermal data were obtained by using a Setaram Setsys 1200 (Caluire,
France). The thermal stability of the resin was investigated by ther-
mogravimetric analysis in air stream at a heating rate of 5 °C min−1.
The pH measurements were performed using Elmetron CP-505 appa-
ratus (Zabrze, Poland) equipped with a combined pH electrode.
Scanning electron microscopy (SEM) images were obtained on a Hitachi
Scanning Electron Microscope SU3500 (Tokyo, Japan).
2.3. Synthesis of polymeric adsorbents
A portion of 10 g of HDI-IC (0.02 mol) was dissolved in ethyl acetate
or acetonitrile (100 mL) and 0.03 mol of the corresponding amine (3.1 g
of DETA or 7.0 g PEHA) was added upon vigorous stirring. The mixtures
obtained were mixed for 1 h and the precipitated resin was filtered off,
washed with ethyl acetate or acetonitrile, dried at room temperature,
grounded using mortar and pestle, and sieved using a 30-mesh sieve.
2.4. Adsorption experiments
The adsorption of Cd2+, Co2+, Cr3+, Cu2+, and Ni2+ ions on HDI-
IC-DETA and HDI-IC-PEHA polymers was examined using batch ex-
periments. The relations between the adsorption properties and the pH
of the solution were studied in the pH range from 2 to 6. The pH of the
solutions was adjusted with buffers containing KCl/HCl (pH 2) and
acetic acid/sodium acetate (pH 3–6). To prepare each sample 10 mL of
buffered solution was used with the initial metal ion concentration
equal to 1 mM. To each solution 10 mg of HDI-IC-DETA or HDI-IC-
PEHA polymers were added and the obtained mixture was stirred for
24 h at room temperature. The exact concentration of metal ions before
and after adsorption was measured by ICP-OES.
To prepare adsorption isotherms, a series of samples containing
10 mg of HDI-IC-DETA or HDI-IC-PEHA polymers were equilibrated
with 10 mL buffered (pH = 6) solutions containing various concentra-
tions (0.1–20 mM) of Cd2+, Co2+, Cr3+, Cu2+, or Ni2+ ions. The so-
lution was shaken at room temperature for 24 h. The starting (C0;
mg L−1) and equilibrium (Ceq; mg L−1) concentrations of metal ions
were measured by ICP-OES. The amount of metal ions adsorbed (qe;
mg g−1) after equilibration was calculated using the following equa-
tion:
(C0 − Ceq ) V
qeq =
m (1)
where m is the mass of the polymer (g) and V is the volume of the
solution (L).
For the adsorption kinetic studies, 50 mg of HDI-IC-DETA or HDI-IC-
PEHA polymers were stirred at room temperature in 50 mL of buffered
(pH = 6) metal ion solution with the initial concentration of 1 mM. The
metal ion concentration was measured at preset time intervals using
ICP-OES by withdrawing samples (200 μL) from the release medium.
The amount of adsorbed metal ions at time t (h), qt (mg g−1) was cal-
culated from:
(C0 − Ct ) V
qt =
m (2)
−1
where m is the mass of the polymer (g), C0 (mg g ) is the initial
concentration, Ct (mg g−1) is the concentration at time t, and V is the
volume of the solution (L).
Thermodynamic studies were performed for a set of samples con-
taining 10 mg of HDI-IC-DETA or HDI-IC-PEHA polymers and 10 mL of
buffered (pH = 6) metal ion solution at the initial concentration of
1 mM. The samples were shaken at 296 ± 1 K, 303 ± 1 K, 313 ± 1 K,
M. Cegłowski et al. Reactive and Functional Polymers 131 (2018) 64–74

and 323 ± 1 K for 24 h. Other experimental details were as for iso-

therm determination.
Adsorption/desorption experiments were performed in 12 h inter-
vals for the sets of samples containing 10 mg of HDI-IC-DETA or HDI-IC-
PEHA polymers and 10 mL of buffered (pH = 6) metal ion solution at
the initial concentration of 1 mM. Afterwards, the solution was dec-
anted, the polymers were washed with water and immersed in 10 mL of
0.1 M EDTA water solution. The starting and final concentrations of
metal ions were measured by ICP-OES. To test the reusability of the
polymers, the adsorption/desorption cycles were repeated five times
using the same adsorbent.
Glass column of an inner diameter of 0.75 cm was filled with 1 g of
powdered polymer. The 1 mM buffered (pH = 6) solution of corre-
sponding metal perchlorate was passed through the bed with a flow of
1 mL min−1. The concentration of metal in eluate (Ct) was determined
by ICP-OES. The breakthrough point (BTP) was chosen arbitrary at
0.1 mM concentration of the metal ion in filtrate. The breakthrough
curves were presented as (Ct/C0) plotted against time (t). The break-
through curves were analyzed using Thomas model:
C KT q0 m Fig. 2. FT-IR spectra of HDI-IC-DETA and HDI-IC-PEHA.
ln ⎛ 0 − 1⎞ = − KT C0 t
⎝C ⎠ Q (3)

where C0 is initial concentration of feeding solution (mg L−1), Ct –
concentration of metal ions (mg L−1) in filtrate at time t (min), KT –
Thomas rate (L min−1 mg−1), Q – flow rate (L min−1), q0 – adsorption
capacity (mg g−1) and m – mass of the polymer (g).
The bed adsorption capacity qbed (mg g−1) was determined by in-
tegration of breakthrough curve:
t
Q ∫ (C0 − Ct ) dt
o polymers form a white solid that can be easily ground to desired grain
qbed =
m (4)
Experiments with real wastewater samples were performed by
adding 10 mL of wastewater sample to 50 mg of HDI-IC-DETA or HDI-
IC-PEHA polymers. After shaking for 24 h the starting and final con-
centrations of metal ions were measured by ICP-OES.
2.5. Statistical analysis
The obtained data was examined using one-way analysis of variance
(ANOVA). The adequacy of the regression model (R2 values) were ex-
amined using lack-of-fit test by comparing calculated F values with F
values obtained from statistic tables.
3. Results and discussion
3.1. Synthesis and characterization of the HDI-IC-DETA and HDI-IC-PEHA
polymers
Both HDI-IC-DETA and HDI-IC-PEHA polymers were obtained in
one simple reaction between isocyanate groups of HDI-IC monomer and
amine groups of DETA or PEHA polyamines (Fig. 1). As a result, the two
polymers are polyamides which comprise free amine groups in their
structure. For the synthesis of HDI-IC-DETA and HDI-IC-PEHA two
different amines of various length of ethyleneamine chain were used,
therefore the polymers differ in the amount and accessibility of amine
groups in their structure. The presence of these free amine groups is the
polymers' structure is the main reason for the high adsorption proper-
ties towards the heavy metal ions. HDI-IC-DETA and HDI-IC-PEHA
size which is an additional benefit for a good heavy metal ion ad-
sorbent. The results of elemental analysis are (%): C, 54.04; H, 8.58; N,
19.16 for HDI-IC-DETA and C, 52.79; H, 8.36; N, 20.03 for HDI-IC-
PEHA. The results were compared to the values calculated for models in
which different polymer composition was assumed. It was established
that HDI-IC-DETA polymer was obtained with almost quantitative
yield, whereas HDI-IC-PEHA polymer was obtained with ca. 83% yield.
Two different solvents (acetonitrile, ethyl acetate) were used for poly-
condensation reaction, resulting in polymers of the same spectroscopic
and adsorption properties towards metal ions.
The FT-IR absorbance spectra (Fig. 2) confirm the structure of the
resins obtained. The signals at 3360, 1631, 1560 and 1250 cm−1 cor-
respond to disubstituted urea moieties, and are assigned to νNH, νC]O
(amide I band), amide II and amide III bands, respectively. The iso-
cyanuric acid core gives signals at 1695, 1465 and 765 cm−1, identified
as νC]O, ring stretching and γC]O (out-of-plane bending) modes. The
presence of polyamine chain is confirmed by the bands at
3400–3500 cm−1 (νNH) and 1250 cm−1 (νCeN, overlapped with amide
III mode).
The 13C NMR spectra of both resins show characteristic signals

Fig. 1. Scheme of synthesis of HDI-IC-DETA and HDI-IC-PEHA.

66
M. Cegłowski et al. Reactive and Functional Polymers 131 (2018) 64–74

Fig. 3. Results of thermogravimetric analysis for HDI-IC-DETA and HDI-IC-

PEHA.

assigned to C]O carbon atoms, first at 145 ppm (isocyanuric acid ring)
and 155 ppm (N,N′-disubstituted urea). The methylene carbon atoms of
1,6-hexylene moiety give the signals at 24 and 39 ppm, while those of
the ethylene groups of polyamine chains are assigned to a broad signal
with maximum at ca. 45 ppm. The 15N NMR spectra of both resins show
three signals, the first one at ca. -239 ppm, assigned to isocyanuric acid
core, the second one at −298 ppm (NH-CO-NH moiety) and the last one Fig. 4. SEM images of HDI-IC-DETA and HDI-IC-PEHA.
between −348 and − 355 ppm (primary and secondary amine nitrogen
atoms).
pH 6, therefore all subsequent experiments were performed in solutions
The results of thermogravimetric analysis of HDI-IC-DETA and HDI-
with a pH of 6.
IC-PEHA polymers are presented in Fig. 3. The HDI-IC-DETA polymer
undergoes two decomposition steps. The first one starts at around 350
3.3. Adsorption isotherms
°C and ends at 480 °C. It is probably connected to a continuous de-
composition of the polymer, because the mass loss at the end of this
Adsorption isotherms were used to characterize the adsorption
process is around 75%. The second step starts at 480 °C and ends at 620
properties of HDI-IC-DETA and HDI-IC-PEHA polymers at the equili-
°C. During this step all organic residue is oxidized, as the mass loss at
brium state. Both polymers obtained can form complexes with heavy
the end of this step is almost exactly 100%. The HDI-IC-PEHA polymer
metal ions using free amine groups and amide groups (Fig. 6). For metal
undergoes three decomposition steps. In comparison to HDI-IC-DETA
adsorption studies, perchlorate salts were used to avoid formation of
polymer, the additional step takes place in the 80–180 °C temperature
mixed complexes as perchlorate ions are very poor complexing agents.
range and is probably connected to desorption of the residual solvent.
Moreover, perchlorate salts show very low reactivity as oxidants. The
The two subsequent steps in the 350–480 °C and 480–620 °C ranges are
relationship between the equilibrium concentration of the heavy metal
almost identical to the ones observed for HDI-IC-DETA polymer. It is a
ions and the amount of metal ions adsorbed is presented in Fig. 7. To
result of a high similarity of the two polymers structure.
characterize the adsorption process, Langmuir, Freundlich, and Temkin
The SEM images of HDI-IC-DETA and HDI-IC-PEHA polymers are
adsorption isotherm models were considered.
presented in Fig. 4. Both polymers present similar, rough surface with a
The Langmuir adsorption isotherm was applied in the linearized
wide distribution of particle sizes ranging in micrometers. Their rough
form:
surface contributes to increased surface area which is beneficial for
increased adsorption properties of the polymers. Ceq Ceq 1
= +
qeq qm Kqm (5)
−1 −1
3.2. Influence of pH on adsorption where K (L mg ) is the binding equilibrium constant; qm (mg g ) is
the maximum amount of ions adsorbed; Ceq (mg L−1) is the equilibrium
One of the most important factors that affect the adsorption of concentration of ions, and qeq (mg g−1) is the amount of ions adsorbed
heavy metal ions is the pH value of the solution. The influence of pH on at the concentration Ceq. The calculated values of qm, K and correlation
the qeq values calculated for HDI-IC-DETA and HDI-IC-PEHA polymers coefficients (R2) are given in Table 1. The R2 values obtained for the
is illustrated in Fig. 5. For both polymers and all heavy metal ions ex- adsorption of heavy metal ions on both HDI-IC-DETA and HDI-IC-PEHA
amined, the highest qeq values are observed at pH 6. HDI-IC-DETA and polymers are above 0.99, which indicates that the experimental data is
HDI-IC-PEHA polymers possess multiple amine groups that are re- very well fitted with the Langmuir adsorption model. This fact was also
sponsible for strong interactions with heavy metal ions. At pH 6 the confirmed by calculations made for ANOVA lack-of-fit test. For both
overall amount of free amine groups in the polymers structures is high, polymers and all metal ions examined the calculated F values are lower
therefore at this pH the adsorption properties of both polymers towards than the ones obtained from tables, which confirms that the data fits the
heavy metal ions are very good. At lower pH, amine groups are pro- model. The effectiveness of heavy metal ions removal was evaluated on
tonated which results in poorer adsorption properties. Finally, at pH 2 the basis of the calculated qm parameter, which represents the max-
almost all amine groups are protonated which reduces the adsorption of imum amount of ions adsorbed. According to the values of this para-
heavy metal ions to minimum. The highest qeq values were observed for meter, the HDI-IC-DETA polymer shows the highest adsorption

67
M. Cegłowski et al.
Fig. 5. The pH influence on the sorption ability of (a) HDI-IC-DETA and (b)
HDI-IC-PEHA.
properties towards Cu2+ ions, good adsorption properties for Cd2+ and
Ni2+ ions and moderate and poor adsorption properties towards Co2+
and Cr3+, respectively. On the other hand, HDI-IC-PEHA polymer ad-
sorbs the Cd2+ and Cu2+ ions most effectively, shows good adsorption
properties towards Co2+ and Ni2+ ions, and poor adsorption properties
towards Cr3+ ions. The qm values characterizing the adsorption of
Cd2+, Co2+, Cr3+, and Cu2+on the HDI-IC-PEHA polymer are at least
twice higher than those values calculated for the HDI-IC-DETA polymer.
This observation can be explained by the fact that HDI-IC-PEHA
polymer possesses longer ethyleneamine chains in its structure which
have increased flexibility. These chains due to high flexibility and
presence of multiple nitrogen donor atoms can adapt to geometries of
coordination spheres of various ions. As a result, the polymer can ad-
sorb more heavy metal ions than its counterpart possessing shorter
ethyleneamine chains. The increase in adsorption of Ni2+ ions by HDI-
IC-PEHA polymer over HDI-IC-DETA polymer was only around 25%.
This phenomenon may be caused by the increased engagement of amide
groups over amine groups into formation of complexes with Ni2+ ions
[39]. As the number of amide groups is similar in both polymers, only a
moderate increase in adsorption is observed when longer ethylenea-
mine chains are present in the structure.
The Freundlich adsorption isotherm is mathematically expressed as:
1/ n
qeq = Kf Ceq (6)
1 are distributed consistently up to some maximum binding energy. The
log qeq = log Kf + log Ceq
n (7)
68
Reactive and Functional Polymers 131 (2018) 64–74
Fig. 6. Possible adsorption mechanism of heavy metal ions by HDI-IC-DETA
and HDI-IC-PEHA.
where Kf and n represent the Freundlich constants, Ceq (mg L−1) is the
equilibrium concentration of ions, and qeq (mg g−1) is the number of
ions adsorbed at the concentration Ceq. The calculated values of Kf, 1/n
and correlation coefficients (R2) are given in Table 1. The R2 values
obtained for adsorption of heavy metal ions on HDI-IC-DETA polymer
are in the range 0.863–0.945, whereas for HDI-IC-PEHA polymer they
are in the range 0.893–0.983. These values indicate that the Freundlich
adsorption model only partly fits the adsorption of heavy metal ions on
both polymers. The calculations of F values made for ANOVA lack-of-fit
test allowed to verify this observation. The calculated F values obtained
for adsorption of all metal ions by HDI-IC-DETA polymer are higher
than the tabular ones, indicating that the data does not fit the Freun-
dlich adsorption model. On the other hand, the same analysis per-
formed for HDI-IC-PEHA polymer showed that data obtained for ad-
sorption of Cd2+, Co2+ and Cu2+ ions fitted the model. Nevertheless,
the parameters calculated from Freundlich adsorption model can be
used to characterize the adsorption process to some extent. The 1/n
values for all ions adsorbed and both polymers have similar values and
are in the range 0.289–0.488. The 1/n parameter ranging between 0
and 1 is a measure of adsorption intensity or surface heterogeneity.
Then 1/n values closer to 0 indicate a more heterogeneous surface [40].
All obtained values are lower than one which indicates a normal
Langmuir isotherm [41].
The Temkin adsorption isotherm is described by equations:
RT
qeq = ln(Kf Ceq)
b (8)
qeq = B ln Kt + B ln Ceq (9)
where R is a gas constant, T is temperature, Kt is the equilibrium con-
stant (L g−1) related to the maximum binding energy and B is related to
the heat of adsorption. The assumption in the Temkin adsorption model
is that the heat of adsorption of the adsorbate molecules in a layer
decreases linearly with increasing coverage, which is caused by ad-
sorbent-adsorbate interactions [42]. Moreover, the bonding energies
obtained R2 values for both polymers and all metal ions examined are in
M. Cegłowski et al. Reactive and Functional Polymers 131 (2018) 64–74

IC-PEHA the values are higher, 1.109 L g−1 and 1.788 L g−1, respec-
tively, however the origin of this effect is unclear. B values show higher
differences and are in the range 0.631–11.45 J mol−1 indicating that
the heat of adsorption is much dependent on the metal ion – polymer
combination. The calculated values of Kt, B and correlation coefficients
(R2) are given in Table 1.

3.4. Adsorption kinetics

The change in adsorption capacity with interaction time was studied

to characterize the adsorption kinetics. The experimental results were
compared to those described by three kinetic models: the pseudo-first-
order, pseudo-second-order, and the intraparticle diffusion. The
pseudo-first-order model given by Langergren and Svenska is mathe-
matically expressed as:
k1
log(qe − qt ) = log qe − t
2.303 (10)

Fig. 7. Adsorption isotherms of metal ions onto (a) HDI-IC-DETA and (b) HDI-
IC-PEHA.
the 0.923–0.974 range, therefore ANOVA lack-of-fit test was used to
examine whether the data fits the model. The calculated F values ob-
tained for adsorption of Cd2+ and Cu2+ metal ions by HDI-IC-DETA
polymer are lower than the tabular ones, meaning that the data ob-
tained for these ions fits Temkin adsorption model. For both polymers
and most of the metal ions examined the values of Kt constants are of
the same order of magnitude and are in the range 0.125–0.617 L g−1.
For the adsorption of Cr3+ ions by HDI-IC-DETA and Ni2+ ions by HDI-
where qe and qt are the amount of metal ions adsorbed (mg g−1) at
equilibrium and at time t (h), respectively, and k1 (h−1) is the rate
constant. The calculated values of k1 and correlation coefficients (R2)
are given in Table 2, whereas the plot of log(qe – qt) versus t is presented
in Fig. 8. The R2 values are in the 0.967–0.987 range for HDI-IC-DETA
polymer and in the 0.825–0.974 range for HDI-IC-PEHA polymer.
Comparison of the values obtained and those calculated for pseudo-
second-order model suggests, that the adsorption of metal ions on both
polymers does not follow pseudo-first-order kinetics. This observation
was also confirmed by the fact that for both polymers and all metal ions
examined the calculated F values are higher than the tabular ones,
which clearly indicates that the data obtained does not fit the pseudo-
first-order kinetic model.
The pseudo-second-order model is based on the equilibrium ad-
sorption and can be expressed as:
t 1 1
= + t
qt k2 qe2 qe (11)
−1 −1
where k2 (g mmol h ) is the rate constant of second-order adsorp-
tion model. The calculated values of k2 and correlation coefficients (R2)
are given in Table 2, whereas the plot of t/qt versus t is presented in
Fig. 9. The R2 values for both polymers and all metal ions adsorbed are
greater than 0.99 which clearly indicates that the pseudo-second-order
kinetic model can be applied to describe the adsorption of metal ions
onto HDI-IC-DETA and HDI-IC-PEHA polymers. This was also con-
firmed by the fact that for both polymers and all metal ions examined
the calculated F values are lower than the tabular ones, which confirms
that the kinetic data fits the pseudo-second-order model.
The intraparticle diffusion model is based on the theory proposed by
Weber and Morris and is mathematically expressed as:
qt = kp t 1/2 + x i (12)

Table 1
Parameters of metal ion adsorption by HDI-IC-DETA and HDI-IC-PEHA polymers.
Polymer Metal ion Langmuir Freundlich Temkin

qm (mg g−1) K (L mg−1) R2 Kf (mg g−1 (L mg−1)1/n) 1/n R2 Kt (L g−1) B R2

HDI-IC-DETA Cd2+ 23.09 0.007 0.999 0.880 0.460 0.942 0.126 4.017 0.964
Co2+ 15.87 0.019 0.997 0.908 0.456 0.890 0.297 2.875 0.923
Cr3+ 4.12 0.043 0.999 0.659 0.302 0.863 1.109 0.631 0.965
Cu2+ 27.19 0.017 0.998 2.342 0.374 0.945 0.434 4.264 0.974
Ni2+ 21.16 0.017 0.999 1.406 0.422 0.936 0.313 3.632 0.951
HDI-IC-PEHA Cd2+ 69.46 0.006 0.995 2.086 0.488 0.955 0.125 11.45 0.954
Co2+ 31.67 0.016 0.993 2.939 0.358 0.968 0.523 4.675 0.952
Cr3+ 9.80 0.012 0.994 0.510 0.451 0.978 0.238 1.631 0.953
Cu2+ 62.68 0.015 0.995 4.985 0.379 0.983 0.617 8.723 0.936
Ni2+ 26.43 0.042 0.999 4.398 0.289 0.893 1.788 3.656 0.968

69
M. Cegłowski et al. Reactive and Functional Polymers 131 (2018) 64–74

Table 2
Kinetic parameters calculated for pseudo-first-order, pseudo-second-order and intraparticle diffusion models.
Polymer Metal ion Pseudo-first-order model Pseudo-second-order model Intraparticle diffusion model

−1 −1 −1
k1 (h ) R 2
k2 (g mg h ) R 2
kp (mg g−1 h1/2) xi

2+
HDI-IC-DETA Cd 0.398 0.987 0.173 0.996 2.023 1.955
Co2+ 0.415 0.983 0.137 0.992 1.963 1.147
Cr3+ 0.339 0.969 0.556 0.995 0.584 0.610
Cu2+ 0.402 0.986 0.082 0.994 2.952 1.661
Ni2+ 0.417 0.975 0.187 0.996 1.989 1.986
HDI-IC-PEHA Cd2+ 1.041 0.963 0.105 0.993 5.212 7.231
Co2+ 0.970 0.974 0.217 0.999 2.726 4.170
Cr3+ 0.548 0.833 1.866 0.999 0.589 1.312
Cu2+ 1.399 0.906 0.264 0.999 4.460 9.362
Ni2+ 0.810 0.825 0.328 0.999 3.612 6.646

Fig. 8. Pseudo-first-order kinetic model for metal ion adsorption by (a) HDI-IC- Fig. 9. Pseudo-second-order kinetic model for metal ion adsorption by (a) HDI-
DETA and (b) HDI-IC-PEHA. IC-DETA and (b) HDI-IC-PEHA.

where kp (mg g−1 h1/2) is the intraparticle diffusion rate constant and xi
is the intercept. The calculated values of kp and xi are given in Table 2,
whereas the plot of qt versus t1/2 is presented in Fig. 10. The in-
traparticle diffusion model assumes that the metal ions are transported
from the solution though the interface between the solution and the
adsorbent followed by a rate-limiting intraparticle diffusion step which
drives them into the pores of the particles in the adsorbent [43]. The
multilinear plot, such as the one presented in Fig. 10, suggests that two
or more steps are involved in the adsorption process [44]. As follows
from the plots obtained for adsorption of all metal ions on HDI-IC-DETA
and HDI-IC-PEHA polymers, a three phase adsorption process is ex-
pected. The initial steep section represents surface or film diffusion, the
second one is connected with a gradual adsorption stage, whereas the
third section is the final equilibrium stage [45]. The value of intercept xi
gives the information about the boundary layer, in particular higher
values of the intercept suggest greater effects of the boundary layer
[46].

70
M. Cegłowski et al. Reactive and Functional Polymers 131 (2018) 64–74

Fig. 11. Plot of ln Kd versus 1/T for adsorption of metal ion onto (a) HDI-IC-
DETA and (b) HDI-IC-PEHA.

Fig. 10. Intraparticle diffusion plots for metal ion adsorption onto (a) HDI-IC-
is probably the effect of release of water molecules from the hydration
DETA and (b) HDI-IC-PEHA.
shell of heavy metal ions [43]. The negative values of ΔG prove that the
adsorption of metal ions on both polymers is a spontaneous process
3.5. Adsorption thermodynamics which is even more favorable at higher temperatures. Taking into ac-
count all the calculated values it can be concluded that increase in
To evaluate the influence of temperature on the adsorption process, entropy, caused by releasing water molecules from the hydration shell
the changes in enthalpy (ΔH), entropy (ΔS), and Gibbs free energy (ΔG) of adsorbed metal ions, is the driving force of observed adsorption
were considered. The values of ΔH and ΔS were calculated using the process of these ions onto HDI-IC-DETA and HDI-IC-PEHA polymers.
equation:
∆S ∆H 3.6. Adsorption/desorption experiments
ln K d = −
R RT (13)
The HDI-IC-DETA and HDI-IC-PEHA polymers were examined in
where R (8.314 J mol−1 K−1) is the universal gas constant, T (K) is the
order to estimate their ability to retain adsorption properties after
solution temperature and Kd is the distribution coefficient which can be
several adsorption/desorption cycles. A 0.1 M EDTA solution was used
defined as:
as a desorption agent to achieve complete removal of heavy metal ions
CAe from polymers' structure. The adsorption capacity values calculated for
Kd =
Ce (14) five subsequent adsorption/desorption cycles are summarized in
−1
where CAe is the amount of ions adsorbed on solid (mg g ) and Ce is Table 4. After five cycles, the HDI-IC-DETA and HDI-IC-PEHA polymers
the equilibrium concentration (mg mL−1). The ΔH and ΔS values were retained more than 90% of their initial adsorption capacity for all ions
calculated from the slope and intercept of the plot of ln Kd versus 1/T examined. These results clearly indicate that both polymers can be ef-
(Fig. 11). The ΔG value was calculated using the equation: fectively used in continuous adsorption/desorption cycles.

∆G = −RT ln K d
The calculated values of ΔH, ΔS, and ΔG are gathered in Table 3.
The positive values of enthalpy changes (ΔH) clearly indicate that the
adsorption is an endothermic process. The positive values of ΔS suggest
that the randomness is increasing during the adsorption process, which
(15)
3.7. Column experiments
The adsorption performance of the HDI-IC-DETA and HDI-IC-PEHA
polymers towards examined metal ions in fixed-bed columns was
evaluated in a series of column experiments and the obtained

71
M. Cegłowski et al. Reactive and Functional Polymers 131 (2018) 64–74

Table 3
Thermodynamic parameters obtained for metal ion adsorption.
Polymer Metal ion ΔH (kJ mol−1) ΔS (J mol−1 K−1) ΔG (kJ mol−1)

296 K 303 K 313 K 333 K

HDI-IC-DETA Cd2+
25.80 124.70 −11.05 −11.72 −12.63 −13.93
Co2+ 13.63 87.49 −12.31 −12.49 −13.06 −13.77
Cr3+ 30.53 137.74 −9.90 −11.33 −11.96 −13.52
Cu2+ 28.80 143.41 −13.33 −14.68 −15.26 −16.75
Ni2+ 16.96 99.78 −12.59 −12.91 −13.56 −14.44
HDI-IC-PEHA Cd2+ 16.37 102.40 −13.90 −14.39 −14.82 −15.76
Co2+ 12.42 88.65 −13.76 −14.18 −14.50 −15.18
Cr3+ 31.35 142.42 −10.50 −11.91 −12.52 −14.20
Cu2+ 26.58 142.59 −15.55 −16.25 −17.20 −18.51
Ni2+ 17.04 107.93 −14.80 −15.42 −15.85 −16.76

Table 4
Values of qeq for five cycles of adsorption/desorption of metal ions using 0.1 M
EDTA as desorption agent.
Polymer Cycle qeq (mg g−1)

Cd2+ Co2+ Cr3+ Cu2+ Ni2+

HDI-IC-DETA 1 8.68 7.55 2.50 11.55 8.55

2 8.56 7.34 2.41 11.36 8.34
3 8.37 7.22 2.43 11.11 8.11
4 8.25 6.91 2.32 10.83 7.95
5 8.09 6.83 2.25 10.55 7.72
HDI-IC-PEHA 1 23.28 12.31 3.15 22.35 17.30
2 22.67 12.02 3.04 22.01 17.01
3 22.16 11.73 3.03 21.66 16.65
4 21.68 11.40 2.96 21.24 16.34
5 21.29 11.15 2.85 20.63 15.92

breakthrough curves are shown in Figs. 12. It can be clearly seen that
each of the breakthrough curves shows an adsorption zone and a mass
transfer zone before the BTP is reached, indicating that the both poly-
mers can be applied in a fixed-bed column to effectively remove heavy
metal ions from aqueous solution. The breakthrough curves were ana-
lyzed with the Thomas model to evaluate the performance of the HDI-
IC-DETA and HDI-IC-PEHA polymers in fixed-bed columns and the
obtained results are summarized in Table 5. As shown, the correlation
coefficients (R2) are higher than 0.98 for most of the polymer – ion
pairs, indicating that the experimental data fit fairly well to the Thomas
model. The calculated adsorption capacities (qbed) are found in a very
good agreement with the maximum adsorption capacity (qm) calculated
from Langmuir model, which also confirms very good fitting.

3.8. Treatment of real wastewater samples

Real wastewater samples were obtained from PRESSEKO Company,

which specializes in neutralization of hazardous wastes. The samples
obtained were the wastes left after various electrochemical processes,
therefore they contained high concentrations of heavy metal ions.
Chromium was present in the mixture as Cr3+ ions, because the was-
tewater that contained chromium was produced during trivalent chro-
mium plating. Table 6 shows the concentration of Cr3+, Cu2+, and
Ni2+ before and after purification with the use of HDI-IC-DETA or HDI-
IC-PEHA polymers. The HDI-IC-DETA polymer reduced the initial
concentration of Cr3+, Cu2+, and Ni2+ by ca. 49%, 53%, and 10%,
respectively. The HDI-IC-PEHA polymer reduced the initial concentra-
tion of Cr3+, Cu2+, and Ni2+ by ca. 77%, 90%, and 41%, respectively.
The results clearly indicate that the HDI-IC-PEHA polymer is more ef-
fective in purification of real wastewater samples, which is in ac-
cordance with the results obtained from adsorption isotherms. The re-
latively high adsorption of chromium ions is presumably a result of
faster kinetics of adsorption of chromium ions over Cu2+ and Ni2+ ions.
Fig. 12. Breakthrough curves obtained for (a) HDI-IC-DETA and (b) HDI-IC-
PEHA.
3.9. Comparison of HDI-IC-DETA and HDI-IC-PEHA polymers with other
adsorbents and cost analysis
A comparison of the maximum adsorption capacities with other
results obtained for various adsorbents is presented in Table 7. The HDI-
IC-DETA polymer shows similar adsorption properties to other ad-
sorbents for adsorption of Cd2+, Co2+, Cu2+, and Ni2+ ions. On the
other hand, HDI-IC-PEHA polymer shows greater maximum adsorption
capacities for Cd2+, Co2+, Cu2+, and Ni2+ ions than any other listed
adsorbent. This clearly indicates that both polymers can be effectively
used as adsorbents for heavy metal ions and that the HDI-IC-PEHA
polymer can be considered as a very efficient adsorbent of these ions.

72
M. Cegłowski et al. Reactive and Functional Polymers 131 (2018) 64–74

Table 5
Results obtained for column experiments using Thomas model and values of breakthrough points.
Metal ion HDI-IC-DETA HDI-IC-PEHA

−1 −1 −1
Kt [L min mg ] qbed [mg g ] R 2
BTP [L] Kt [L min−1 mg−1] qbed [mg g−1] R2 BTP [L]

2+ −4 −4
Cd 2.6 × 10 27.1 0.995 0.15 0.8 × 10 57.8 0.941 0.35
Co2+ 4.0 × 10−4 13.3 0.988 0.19 3.5 × 10−4 25.4 0.987 0.36
Cr3+ 18.2 × 10−4 3.6 0.983 0.05 6.6 × 10−4 9.2 0.972 0.13
Cu2+ 3.8 × 10−4 28.4 0.993 0.35 1.6 × 10−4 63.1 0.965 0.92
Ni2+ 2.9 × 10−4 18.6 0.964 0.26 3.1 × 10−4 23.2 0.981 0.32

Table 6 performed in ethyl acetate, which is a low-cost compound that is also

The metal ion concentration in wastewater sample before and after purification considered as a green solvent. Time of the reaction is around 1 h, which
with HDI-IC-DETA and HDI-IC-PEHA polymers. is also an additional advantage for the potential application.
Metal ion Initial concentration Concentration after purification with
(mg L−1) (mg L−1) 4. Conclusions

HDI-IC-DETA HDI-IC-PEHA In summary, we have obtained two new low-cost polymer ad-
Cr3+
11.96 5.78 2.76 sorbents from inexpensive reagents that are produced yearly in high
Cu2+ 38.80 18.04 3.60 quantities. Both polymers were characterized by chemical and spec-
Ni2+ 150.0 135.0 88.8 troscopic methods and showed satisfactory thermal and chemical sta-
bilities. The adsorption properties of the polymers obtained towards
Cd2+, Co2+, Cr3+, Cu2+, and Ni2+ ions were investigated. The ad-
Table 7 sorption of these ions onto both HDI-IC-DETA and HDI-IC-PEHA poly-
Comparison of maximum adsorption capacities with results obtained for var- mers was best described by the Langmuir model. The sorption kinetics
ious adsorbents.
of all metal ions investigated were best modeled by a pseudo-second-
Mn+ Adsorbent Adsorption References order model. The negative ΔG values but positive ΔH and ΔS values
capacity indicate that the adsorption of metal ions is a spontaneous process for
(mg g−1)
which the driving force is entropy. The HDI-IC-PEHA polymer showed
Cd2+ Fe3O4-poly(L-cysteine/2-hydroxyethyl 19.59 [47] around two times higher maximum adsorption capacities for Cd2+,
acrylate) Co2+, Cr3+, and Cu2+ ions examined than HDI-IC-DETA polymer,
Hydrous manganese dioxide 43.39 [48] which is probably a result of possessing longer ethyleneamine chains.
nanoparticles
Both polymers were effective in removal of heavy metal ions from real
HDI-IC-DETA 23.09 Present study
HDI-IC-PEHA 69.46 Present study wastewater samples. On the basis of these results, HDI-IC-DETA and
Co2+ 3-aminopropyltriethoxysilane 25.91 [49] HDI-IC-PEHA polymers may be an excellent potential low-cost poly-
functionalized montmorillonite meric adsorbent for efficient removal of heavy metal ions from aqueous
Ammonium 9.43 [50] solutions containing a mixture of heavy metal ions.
molybdophosphate–polyacrylonitrile
HDI-IC-DETA 15.87 Present study
HDI-IC-PEHA 31.67 Present study Acknowledgement
Cr3+ Graphene oxide based inverse spinel 45.46 [51]
nickel ferrite The authors thank PRESSEKO Company for providing samples of
Mn3O4 nanomaterial 41.7 [52]
hazardous wastes.
HDI-IC-DETA 4.12 Present study
HDI-IC-PEHA 9.80 Present study This research did not receive any specific grant from funding
Cu2+ Dowex M-4195 50.77 [53] agencies in the public, commercial, or not-for-profit sectors.
Hydrous manganese dioxide 33.93 [48]
nanoparticles References
HDI-IC-DETA 27.19 Present study
HDI-IC-PEHA 62.68 Present study
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