Reactive and Functional Polymers 147 (2020) 104451

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Reactive and Functional Polymers

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A Cr(VI)-imprinted-poly(4-VP-co-EGDMA) sorbent prepared using T

precipitation polymerization and its application for selective adsorptive
removal and solid phase extraction of Cr(VI) ions from electroplating
industrial wastewater
Yantus A.B. Neolakaa, , Yosep Lawaa, Johnson N. Naata, Arsel A. Pau Riwue,
⁎

Handoko Darmokoesoemob, , Ganden Supriyantob, , Clovia I. Holdsworthc, ,

⁎ ⁎ ⁎
d e,⁎
Andrew N. Amenaghawon , Heri Septya Kusuma
a
Department of Chemical Education, Faculty of Education and Teachers Training, University of Nusa Cendana, Kupang 85001, Nusa Tenggara Timur, Indonesia
b
Department of Chemistry, Faculty of Science and Technology, Airlangga University, Surabaya, Mulyorejo 60115, Indonesia
c
Discipline of Chemistry, School of Environmental and Life Sciences, University of Newcastle, Callaghan, NSW 2308, Australia
d
Department of Chemical Engineering, Faculty of Engineering, University of Benin, PMB 1154 Benin City, Nigeria
e
Analytical Chemistry Research Group, Department of Chemical Education, Faculty of Education and Teachers Training, University of Nusa Cendana, Kupang 85001,
Nusa Tenggara Timur, Indonesia

ARTICLE INFO ABSTRACT

Keywords: A Cr(VI)-imprinted-poly(4-VP-co-EGDMA) (IIP) was proposed to be used in the process of selective extraction of
Cr(VI) low concentration of Cr(VI) ion from aqueous solution. The polymer was synthesized by using Cr(VI) ion as a
Cr(VI)-imprinted-poly(4-VP-co-EGDMA) template, 4-vinylphiridine (4-VP) as complexion agent and monomer, ethylene glycol dimethyl acrylate
Solid phase extraction (EGDMA) as cross-linker, benzoyl peroxide (BPO) as initiator and ethanol/acetone as a porogen. Non ion-im-
Electroplating industrial wastewater
printed-poly(4-VP-co-EGDMA) (NIP) as a control polymer was prepared too. The synthesis was conducted by
Ion imprinting polymer
using precipitation polymerization method. The prepared of IIP unleached, IIP leached and NIP were char-
acterized by XRD, FTIR, SEM-EDX and BET-BJH instrument. Based on the characterization data, it can be found
that all of this imprinting material have a micro and mesopore structures. The effect of sorbent dosage, pH,
contact time and temperature on Cr(VI) adsorption from aqueous solution were investigated. The result shows
that the adsorption of Cr(VI) ion was highest at pH 2 with 30 min contact time at 313 K with an initial con-
centration of Cr(VI) 14 mg/L. The selective studies shows that the IIP material was a very selective to adsorp Cr
(VI) even in water was found interfering ion such as Ni(II) and Cr(III) respectively. Kinetic and isotherm
modeling were also studied by using 5 models in each. The result of modeling kinetic shows that Cr(VI) ad-
sorption fit with the Pseudo-second-order model while modeling isotherm followed the Freundlich model. The
application of this material to adsorb Cr(VI) from electroplating industrial waste which reaches 96% and the
reusability testing also shows that this adsorbent has good stability even though it was used 10 times repeatedly.

1. Introduction because it is used in the metabolism of glucose while Cr(VI) is a highly

Chromium is one of the heavy metal elements that is produced from
industrial activity such as electroplating, metallurgy, fusion, battery
fabrication, factory, pigment manufacture, pesticides, printing and
photographic industries [1]. Chromium can acquire variable oxidation
states depends on pH conditions, however, it existence is mainly either
as Cr(III) or Cr(VI). Cr(III) is a rare essential element for human bodies
toxic and carcinogenic element [2]. The Cr(VI) was not found in water
as free ions but in complex form it depends on the pH of water. Ex-
ample, in pH 1.0, Cr(VI) was found as H2CrO4, while at pH 1 to 6 was
found in the form of Cr2O72− and HCrO4−. At pH 7, Cr(VI) was only
found as CrO42− [3].
Generally, Cr(VI) was not detected directly in the sample if the
existence of Cr(VI) is < 1 μg/L [4]. Several methods have been

Corresponding authors.
⁎

E-mail addresses: yantusneolakaunc@gmail.com (Y.A.B. Neolaka), handoko.darmokoesoemo@gmail.com, handoko-d@fst.unair.ac.id (H. Darmokoesoemo),

ganden-s@fst.unair.ac.id (G. Supriyanto), clovia.holdsworth@newcastle.edu.au (C.I. Holdsworth), heriseptyakusuma@gmail.com (H.S. Kusuma).

https://doi.org/10.1016/j.reactfunctpolym.2019.104451
Received 5 September 2019; Received in revised form 9 December 2019; Accepted 11 December 2019
Available online 16 December 2019
1381-5148/ © 2019 Elsevier B.V. All rights reserved.
Y.A.B. Neolaka, et al.
developed for detection or extraction of Cr(VI) from an aqueous solu-
tion such as solvent extraction [5], ion-exchange [6], and solid phase
extraction (SPE) [7]. SPE is a commonly used as a method for pre-
concentration or isolation of heavy metal ion analyte from aqua sample.
This method has advantages such as its sorbent is simple to prepare,
using small solution, high extraction efficiency, relatively fast, simple
phase separation process and can be combined with several detection
techniques like different in both on-line and off-line modes [8]. The SPE
method was developed to minimize the use of solvent in a large scale to
extract metal ion by using the liquid-liquid extraction method [9].
In the SPE system, the selection of suitable sorbent material is an
important factor for obtaining a large extraction efficiency. Several
reports have shown that the development of the advanced SPE sorbent
was used in the preconcentration of Cr(VI) namely: artificial ad-
sorbents, activated carbon, sephiolite [10], graphene, carbon nanotubes
[11], Fe3O4@SiO2@DPC [12] and thermally reduced graphene (TRG)
modified silica-supported 3-aminopropyltriethoxysilane (SiO2-APTES)
composite [13]. However, those sorbent material has disadvantages like
low selectivity and sensitivity for the process of preconcentration or
extraction of small ion targets in the complex matrix samples. Other
sorbent types that can be used as solid-phase sorbent are based on
molecule or ion imprinting polymer (MIP or IIP) sorbent. In MIP, the
template molecule interacts with a functional monomer (such as AA,
MAA, HEMA or VP) through hydrogen bonds or Van der Waals inter-
actions. In an IIP, a ligand is required to form a complex of the template
ion to create the selective binding sites after metal leaching out from a
matrix of IIP [14,15]. Especially for IIP, it is one of the most promising
SPE sorbent to be used for selective extraction of Cr(VI) ion because of
its high selectivity, good stability, simplicity and low cost [16]. A
variation of these IIP materials have been reported [4,17–22]. The
developments of IIP, especially used in SPE systems for preconcentra-
tion or identification of metal ions in water have been frequently re-
ported. For example, some of the reports are as follows: preparation of
IIP for the analysis of Pb2+ from water samples [23], Novel Hg2+-im-
printed polymers based on thymine–Hg2+–thymine interaction for
Hg2+ preconcentration from water sample [24] and Cr(VI) removal
from water environment by using iron oxide nanoparticle-multiwalled
carbon nanotube composites [25].
IIP can be synthesized by using bulk polymerization, suspension,
emulsion polymerization, dispersion and precipitation polymerization
[26]. Especially in bulk imprinting, the functional monomer and cross-
linked are polymerized (usually by radical polymerization), in the
presence of the template molecule or ion, in a small volume of poro-
genic solvent [14]. However, bulk polymerization method has a
weakness because the grinding and sieving processes in the step of bulk
polymerization method could also change the mimic of template ion in
a matrix of polymer and will cause the decrease of selectivity and
sensitivity of the IIP material [27,28].
Previously some researchers have synthesized metal ion-imprinting
polymer that can be applied to metal ion removal [29]. As an example
Bayramoglu & Arica, (2011) made the IIP by using bulk polymerization
method, with 4-vinyl pyridine (4-VP) as a complex agent, 2-hydro-
xyethyl methacrylate (HEMA) as functional monomer, ethylene glycol
dimethacrylate (EGDMA) as cross-linker, AIBN as an initiator and water
and isopropyl alcohol as a porogen under long-wave UV radiation [4].
However, the polymerization process with UV radiation may cause
degradation of polymer which is formed because UV radiation may the
damage polymer chains, reduce the molecular weight and produce ra-
dicals at the same time with the produce of IIP. Tavengwa et al., (2013)
synthesized the magnetic IIP material to adsorp Cr(VI) in low con-
centration (1 mg/L – 20 mg/L) with best low initial concentration of Cr
(VI) is 5 mg/L [20]. However, the contact time was still > 30 min. Kong
et al., (2014) has prepared the IIP by using bulk polymerization method
for Cr(VI)-imprinted polymer particles made from 4-vinylpyridine (4-
VP) and N,N-diethyl aminoethyl methacrylate (DEAEM) as functional
monomers, and ethylene glycol dimethacrylate (EGDMA) as cross-
2
Reactive and Functional Polymers 147 (2020) 104451
linker and AIBN as initiator and acetone as porogen [30]. They use
100 mL of Cr(VI) ion solution with an initial concentration from
100 mg/L to 1000 mg/L and get maximum adsorption capacity of IIPs
about 286.56 mg/g. Velempini, et al., (2017) was prepare IIP obtained
from natural polymers like CMC and carboxymethyl chitosan for ad-
sorption Cr(VI) from aqueous solution. However, the selectivity for
competitive adsorption between Cr(VI) and anion ion such as SO42−,
PO43−, F−, NO3− and Cl− are still unsatisfactory [31].
Although the removal of ions Cr(VI) by using IIP has been widely
reported, however there are still limited reports on the direct use of 4-
VP as the complexing agent and monomer. Besides that, competitive
adsorption between Cr(VI) ion and other cations such as Pb(II), Cr(III),
Ni(II) and Mn(II)) have not yet been fully investigated. This is im-
portant because these cations are commonly found together with Cr(VI)
ion in aqueous solution.
In this paper, we report about a simple preparation which directly
produce an IIP (Cr(VI)-imprinted-poly(4-VP-co-EGDMA) material in
granular form (without requiring grinding process and of highly uni-
form size of material) for fast, selective and efficient extraction, pre-
concentration and determination of low range concentration of Cr(VI)
in aqueous solution. The IIP was synthesized using precipitation
method where Cr(VI) was used as template ion, 4-VP used both as a
complexing agent and monomer, EGDMA as a cross-linker, benzoyl
peroxide (BPO) as an initiator and ethanol/acetone as a porogen. The
complexing agent and template ion are assembled by non-covalent in-
teractions. Physical characterization of IIP and NIP particles was pro-
vided by XRD, FTIR, SEM-EDX and BET-BJH analyses. The effect of
adsorption parameters such as IIP dosage, pH, contact time, initial
concentration of Cr(VI) samples and temperature were investigated.
Selectivity of the IIP towards Cr(VI) was also determined by competi-
tive adsorption studies with a single competitor such as Cr(III) or Ni(II)
ion.
2. Material and methods
2.1. Materials
4-Vinyl pyridine (4-VP), ethylene glycol dimethacrylate (EGDMA),
benzoyl peroxide (BPO), potassium dichromate (K2Cr2O7) were ob-
tained from Sigma-Aldrich (Bukit Merah, Singapore). Acetone, 1,5-di-
phenylcarbazide (DiPC), ethanol, HCl, HNO3, H2SO4 and chloroform
were purchased from Merck (Jakarta, Indonesia). Ultra High Purity
(99.999%) nitrogen gas was supplied by UD. Wonokoyo Prima Gas
(Surabaya, Indonesia), RO water were purchased in our laboratory.
2.2. Preparation of Cr(VI)-imprinted Poly(4-VP-co EGDMA)
Cr(VI)-imprinted poly(4-VP-co EGDMA) (IIP) was synthesized by
using precipitation technique. Here, Cr(VI) (1 mmol; 0.3 g) was allowed
to complex with 4-VP (12 mmol; 1.3 mL) in ethanol/acetone (2:1)
(200 mL) for 30 min without stirring in a 250-mL Schott (Duran) glass
bottle. After this period, EGDMA (60 mmol; 11.3 mL) and 1% BPO
(0.1 g in 10 mL chloroform) were added into the bottle. The mixture
was purged with nitrogen gas for ten minutes and polymerized in a
water bath at 6 °C for one hour and 80 °C for a further five hours. After
polymerization, the solid polymer was filtered and stirred in ethanol:
RO water (70: 30) for 6 h to remove the excess of the reagents. The
imprinted anion was removed by stirring the solid polymer in 4 M
HNO3 for 6 h. The solid polymer was filtered through a 0.45 μm filter
paper and a fresh nitric acid solution was added to the solid polymer.
This process was continued until Cr(VI) is not detected using UV-VIs at
540 nm. The presence of Cr(VI) in the acidic filtrate was tested by
UV–Vis spectrophotometer by measuring the absorbance at 540 nm
attributed to the complex formed between DiPC (added to the filtrate)
and Cr(VI). The solid polymer was then collected and washed several
times with RO water until neutral pH was observed and dried at 55 °C.
Y.A.B. Neolaka, et al.
Non-imprinted poly(4-VP-co-EGDMA) (NIP) was also prepared by using
an identical procedure without the addition of Cr(VI) for comparison.
2.3. Colorimetric determination of hexavalent chromium
The colometric determination of hexavalent chromium was based
on reaction betwen Cr(VI) ion and DiPC. The DiPC will reduce Cr(VI) to
Cr(III) and form a magenta colored complex. The chemical equation for
Cr(VI) reacts with diphenylcarbazide to form complex is:
2
2CrO4 + 3C13 H14 N4 O + 8H+ [Cr+3 (C13 H12 N4 O) 2]+
Chromate ion DiPC Acid Cr(III) DiPC complex.
The magenta-colored complex then measured spectromatically by
using UV–Vis spectrophotometer at 540 nm. Here, the optimum ab-
sorbance of complex betwen Cr(VI) and DiPC is 540 nm which is ob-
tained from calibration curve data. The calibration curve was found out
by using 0.5 mg/L K2Cr2O7 and added with 2.0 mL 1.5-diphe-
nylcarbazide solution and mix. The solution then was added with
H2SO4 to give a pH of 2 ± 0.5, dilute to 100 mL with RO water, and let
stand 5 to 10 min for full color development. The solution then mea-
sured by using UV–Vis spectrophotometer at a wavelength range from
600 to 450 nm.
The standard curve of Cr(VI) where found out by using a series of
initial concentration of Cr(VI) solution from 0 mg/L to 3 mg/L. Each
sample then complexted with DiPC and is measured with UV–Vis at
540 nm. The linear of the standard curve of this studies could be de-
scribed as:
A = 0.0576 C + 0.0003 (1)
Where A is the absorbance and C is analyte concentration. The
correlation coefficient R2 = 0.999.
2.4. Optimization of adsorption parameter studies
The optimum conditions for Cr(VI) adsorption onto IIP and NIP, was
studied by using several parameters such as adsorbent dosage, pH,
contact time and temperature. This study was conducted by using batch
system. The adsorbent dosage was determined from 10 to 200 mg of IIP
and NIP. Meanwhile, the pH was studied from pH 1 to 9 and contact
time was studied from 0 to 120 min. All of these experiments were
conducted by using 25 mL of 14 mg/L Cr(VI) solution. Temperature
condition for Cr(VI) adsorption onto surface of IIP was studied from
303 K to 343 K with initial Cr(VI) ion solution ranging from 6 to 14 mg/
L. The concentration of Cr(VI) was analyzed spectrophotometrically
(Shimadzu UV 1240) at 540 nm using 1,5-diphenylcarbazide as the
complexion agent.
Cr(VI) adsorption capacities were calculated using the following Eq.
2 [32]:
(Co Ce ) V
qe =
(2)
W
where Co and Ce are the initial and equilibrium concentrations of Cr(VI)
in solution, V is the volume (L) and W is the weight (g) of the adsorbent
respectively.
2.5. SPE of Cr(VI) from electroplating industrial wastewater
Previously, it needs to prepare a cartridge containing 0.08 g IIP
which is later conditioned by RO water. Then, 1.415 mg/L sample so-
lution that has been conditioned at pH 2 is flowed into the cartridge.
After that, the cartridge is washed using RO water for several times.
Moreover, the cartridge is flowed by HNO3 4 M and eluet is stored into
a 10 mL volumetrix flask and added with RO water until it attaches to
the limit of flask. Furthermore, eluet is spectrophotometrically mea-
sured at 540 nm using 1.5 diphenyl carbacide as a complex agent.
3
Reactive and Functional Polymers 147 (2020) 104451
2.6. Physical characterization of IIP and NIP particles
The structures of IIP and NIP were characterized by using X-ray
diffraction (Philips X'pert type) and FTIR 8000 (Shimadzu). Their sur-
face morphologies were examined by using SEM-EDX (JEOL, JMS 5600,
Tokyo, Japan). The surface area, total pore volume and pore size dis-
tribution were determined by N2 adsorption isotherm with the re-
lationship between N2 adsorbed volume at standard conditions using
Quantachrome Instruments NOVA 1200 (High-Speed Gas Sorption
Analyzer Versions 10.0–10.03).
3. Results and discussion
Cr(VI)-imprinted poly(4-VP-co-EGDMA) has been prepared by the
non-covalent (self-assembly) approach by using precipitation method
employing Cr2O72− as a template ion. The non-covalent approach re-
quires first covalent synthesis step as in polymerization with the
covalent approach. This treatment is useful to get the bonding of O from
K2Cr2O7 and N from 4-VP. An advantage of imprinting ion by using
precipitation method that resulted IIP is not swell or is not supple when
the polymerization process proceeds [14]. 4-VP was used as the com-
plexing monomer because 4-VP has a high affinity for metal ions [4].
Benzoyl peroxide was used as the thermal initiator. Ethanol/acetone
was chosen as the porogen because the ratio of the two solvents can
dissolve the monomers and ionic templates. After polymerization, the
template ion was leached, i.e. extracted, with HNO3. The schematic of
the ion imprinting process is illustrated in Fig. 1.
3.1. Physical characterization of Cr(VI)-imprinted Poly(4-VP-co-EGDMA)
by XRD characterization
XRD characterizations were performed to confirm the change of
polymer structures before and after leaching processes. XRD char-
acterization of IIP unleached, IIP leached and NIP are presented in
Fig. 2. XRD spectra in Fig. 2 show that IIP and NIP structures were
identified as amorphous structures. Generally, it is known that the
polymers have the amorphous structure. As seen in Fig. 2, for example
the appearance of K2Cr2O7 is identified by the peaks at 2θ = 24.38;
25.65; 27.07; 29.76; 31.12 and the compounds, were not further
characterized after leached process of IIP. Based on XRD spectra it can
be said that the imprinting process of Cr(VI) in a polymer matrix suc-
cessfully created. XRD spectra of IIP leached shows the deceased of
crystallinity of IIP after leaching process. It is identified by a peak at
between 0o to 10o, it was confirmed that dissolution of polymer residue
and crosslinking did not react to form the IIP.
The obtained XRD is supported by BET-BJH data which only shows
the change of pore diameter average of unleached IIP, but after
leaching it does not specifically change the IIP pore structure. This is
clearly seen from the pore diameter vs dV/dD graphs at Fig. 6 that still
sticks in range of 5 nm to 30 nm indicating that the obtained IIP is
categorised into mesopore group. This result also indicates that the Cr
(VI) leaching process from the IIP just decreased the crystalinity degree
of IIP and it does change the crystal structure of the IIP itself. These data
are also supported by FTIR Spectra where the Cr(VI) leaching process of
IIP does change the functional group of IIP. Therefore, it can be con-
cluded that IIP crystalinity only decreases its intensity without being
followed by the change of pore size (still in the mesoporic group).
3.2. FTIR analysis
FTIR characterization was conducted to see the form of IIP and NIP
after synthesis by using precipitation method. FTIR characterization of
IIP unleached, IIP leached and NIP are presented in Fig. 3. As shown in
Fig. 3 that a characteristic stretching vibration band at 3500 cm−1 for
–OH, which belongs to the crosslinking agent, EGDMA. Band at
2991.29 cm−1 is peak of methylene vibration (CeH) and ester
Y.A.B. Neolaka, et al. Reactive and Functional Polymers 147 (2020) 104451

Fig. 1. Schematic of the Cr(VI) ion imprinting process

Fig. 3. FTIR spectra of IIP unleached, leached and NIP

configuration peak in EGDMA (=CH2-COOR). Band at 2360.58 cm−1 is

Fig. 2. XRD spectra of IIP unleached, IIP leached and NIP the peak of vibration of the 4-VP ring after making complex formation
with Cr(VI) ion. This peaks do not appear in NIP so that it reinforces the
IIP synthesis results which contains the metal ions. Adsorption band at

4
Y.A.B. Neolaka, et al.
Fig. 4. UV–Vis Absorbance spectra of K2Cr2O7, 4-VP, EGDMA and K2Cr2O7–4-
VP-EGDMA
1761.99 cm−1 is the carbonyl group of EGDMA and the band at
1636.53 cm−1 is a new peak in IIP indicates that this band was re-
inforced the characteristic stretching vibration of pyridine groups
(C=N) absorption after complexion of Cr(VI) anions. The band at
1597.92 cm−1 is the peak of the pyridine group in IIP and NIP, while
adsorption band at 941.46 cm−1 to 784.38 cm−1 is the aromatic ring of
4-VP. This FTIR spectra confirm that Cr(VI) anions from complex with
4-VP in the polymer structure of IIP unleached. These results are con-
sistent with some previous researchers report by Bayramoglu & Arica,
(2011) and Yiǧitoǧlu & Arslan, (2009) [4,33].
3.3. UV–Vis analysis
The formation of the K2Cr2O7–4-VP complex was confirmed by
UV–Vis absorption spectral studies in ethanol: acetone as a porogen.
The UV–vis absorption spectra of K2Cr2O7, 4-VP, EGDMA, and
K2Cr2O7–4-VP-EGDMA solution is shown in Fig. 4. As shown in Fig. 4
there are two typical absorbance spectra of K2Cr2O7 emerging at the
wavelength of 313 nm and 350 nm. Whereas, 4-VP has maximum ab-
sorbance spectra at 304 nm and 308 nm. EGDMA were found in two
maximum absorbances are at 304 nm and 314 nm. Based on K2Cr2O7–4-
VP-EGDMA absorbance spectra, it is seen that the 4-VP peak does not
appear and an absorbance peak for EGDMA remains at 304 nm. This
result confirms the existence of the K2Cr2O7–4-VP complex in the
polymerizing solution.
3.4. SEM-EDX chracterization
The IIP unleached, IIP leached and NIP were characterized by using
SEM in other to know the morphological image and EDX was used to
know the composition of elements especially chromium contain in IIP
unleached and leached. SEM-EDX characterization of IIP unleached, IIP
leached and NIP are presented in Fig. 5.
As seen in Fig. 5, the SEM image of IIP unleached, IIP leached and
NIP were also obtained at 5000× magnification. The SEM image at
Fig. 5 shows that IIP unleached (Fig. 5a) has a rough surfaces com-
paring with IIP leached (Fig. 5b) and NIP (Fig. 5c). The rough surface of
IIP unleached may be due to the presence of Cr(VI) ion in matrix of
polymer structures which is more numerous than in NIP and IIP leached
[4]. It is known that the density of metal ions in the polymer matrix and
salts of metal ions will cause the surface of a polymer to be more rough
and porous [34–36] The formation of bright contrasts in mikrograph
SEM, confirmed the presence of heavy metal ions of Cr (VI) in the
matrix. This is because the heavy metal ions have a possibility of
backscattering electron-emitting greater than the elements with atomic
5
Reactive and Functional Polymers 147 (2020) 104451
numbers lower in the polymer matrix. The spectra and Table data of
EDX at Fig. 5a); Fig. 5b) and c) confirms the presence of Cr(VI) ion in
both polymer structures. During extraction with HNO3 4 M, the Cr(VI)
ion templates on the polymer structures are extracted, however it has
approximately 40% of the Cr(VI) ion was not leached from the polymer
structures. However, in the leaching processes of Cr(VI) from the
polymer matrix which only reached 40% because of the IIP where re-
sulted has a rigid chemical bond so the leaching out of Cr(VI) with acid
being does not maximal [37]. This result was similar to the previous
report where the percentage of template ions that were not released
from imprinting polymer particles was close to 20% [4].
3.5. BET-BJH characterized
BET-BJH characterization was used to find out the surface area,
pore diameter, pore size, pore volume from IIP unleached, IIP leached
and NIP. N2 adsorption and pore diameter are presented in Fig. 6. BET
surface area, pore total volume, micro volume, meso volume and pore
size average were summarized in Table 1.
As seen in Fig. 7, adsorption proses follows isotherm adsorption IV
type which is called hysteresis loop. This type of isotherm in general is
identic for adsorption N2 at mesopore materials. Generally mesopore
material has hysteresis loop at P/P0 between 0.75 and 0.95. Table 1
shows that pore size distribution of IIP unleached and IIP leached are
6.520 nm and 4.848 nm while size pore distribution of NIP is 5.888 nm
respectively.
As seen in Table 1, BET surface area of IIP was increased after
leaching processes while pore total volume and mesopore volume was
decreased. Average of pore size volume becomes smaller after leaching
proses to IIP. This result indicated that this material has a mesopore and
micropore canal structures.
3.6. Batch adsorption studies
In order to evaluate the optimum condition of IIP and NIP to adsorp
Cr(VI) from aqueous solution there were several parameters used such
as the effect of adsorbent dosages, pH, contact time and a temperature.
This study was performed by using batch system and the adsorption
capacities which were calculated by using eq. (2). All of this studies
were conducted by using 25 mL of Cr(VI) ion solution 14 mg/L. The
adsorbent dosage was found out by using differences variation of IIP
leached NIP amount from 10 to 200 mg and optimation process used
25 mL of Cr(VI) ion solution 14 mg/L at pH neutral respectively. Next,
pH was studied from 1 to 9, contact time was studied from 0 min to
120 min use 0.08 g of adsorbent dosages. Temperature condition was
studied from at 303 K to 343 K with the difference several initial Cr(VI)
ion solution with a concentration from 6 to 14 mg/L. Based on the
optimation result it was known that optimum condition to adsorp Cr
(VI) from aqueous solution that occurs at pH 2 of at 301 K sample
condition in contact time of 30 min with the best adsorbent dosages was
0.08 g respectively. The detail of this work was shown at Fig. 7 to
Fig. 11.
3.6.1. Effect of adsorbent dosage
The effect of adsorbent dosage on adsorption Cr(VI) ion on the IIP
was studied with different dosage value from 0.01 to 0.20 g, by using
25 mL Cr(VI) solution 14 mg/L. The result of this studies was shown in
Fig. 7.
Based on Fig. 8 adsorption capacity of those materials maximum
which used 0.08 g dosages with capacity adsorption of Cr(VI) onto IIP
and NIP are 4.145 mg/g and 3.798 mg/g. respectively. As seen that Cr
(VI) adsorption onto IIP is higher than NIP particles. This result in-
dicated that maximum adsorption Cr(VI) ion in the IIP and NIP particles
it may occur with small dosage of this material.
Y.A.B. Neolaka, et al.
Fig. 5. SEM-EDX of: (a) IIP unleached, (b) IIP leached and (c) NIP was amplified 5000×.
3.6.2. Effect of pH value in the adsorption process
The effect of pH in Cr(VI) adsorption onto IIP and NIP particles was
studied with different pH value from 1 to 9 by using 25 mL Cr(VI)
solution 14 mg/L. The effect of pH in adsorption of Cr(VI) onto IIP and
NIP are shown in Fig. 8.
pH is one of important parameters that will cause the high ad-
sorption of Cr(VI) ion onto sorbent particles. In aqueous solution, Cr(VI)
has several forms depend on solution pH. For example, in lower pH 1.0
Cr(VI) in the form of acid chromate ion in the form of H2CrO4, while at
pH 1 to 6 as HCr2O72− and HCrO4− [38]. When the pH increases from
6 to 7, the Cr(VI) will be changed into CrO4− and Cr2O72−. At pH 7 Cr
(VI) is only in the form of CrO42− [39]. Cr(VI) will be in the form of Cr
(OH)6 when solution is in base condition. Based on Fig. 8, adsorption
capacity of Cr(VI) onto IIP and NIP particles are maximum at pH 2 with
value are 3.461 and 2.983 respectively. It can be seen that adsorption
6
Reactive and Functional Polymers 147 (2020) 104451
capacity of Cr(VI) onto IIP is higher than onto NIP as control. In pH 2, it
may be the Cr(VI) is in the form as HCrO4−. The same result was re-
ported by Ma et al. (2014) [40].
3.6.3. Effect of contact time
Effect of contact time was studied by using 0.08 g of IIP and NIP in
25 mL of Cr(VI) sample solution with concentration of 14 mg/L. The
solution was adjusted at pH 2 and adsorption was studied with different
contact time from 15 to 120 min. The effect of contact time on ad-
sorption Cr(VI) in the surface of IIP and NIP are shown in Fig. 9.
As shown in Fig. 9, adsorption capacity of IIP and NIP increased
slightly. It can be seen that the maximum adsorption capacity of Cr(VI)
in IIP and NIP occur at 30 min with the adsorption capacities are
3.61786 mg/g and 3.241 mg/g respectively. This result indicates that
adsorption of Cr(VI) onto IIP and NIP particles is fasted at low time
Y.A.B. Neolaka, et al.
Fig. 6. N2 adsorption isotherm and pore size distribution of: a) IIP unleached,
b) IIP leached and c) NIP.
contact. However, after 30 min of contact time, there was a decrease in
the adsorption capacity. Because the availability of active sites in the
adsorbent is decreasing and there is a possibility of release back of Cr
(VI) from the surface of the IIP to the solution due to the weak inter-
action between the adsorbent and the ion target. The results were linear
with the reports on paper the optimum contact time in adsorption of Cr
(VI) ions using chitosan-CDTA-GO nanocomposite adsorbents [41].
7
Reactive and Functional Polymers 147 (2020) 104451
3.6.4. Effect of initial concentration and temperature condition
The effect of initial concentration and temperature condition were
studied by using 25 mL initial concentration of Cr(VI) ion between 6
and 14 mg/L at variation temperature from 303 to 343 K. Studies were
conducted by using 25 mL of initial Cr(VI) solution with variation from
6 mg/L to 14 mg/L and 0.08 g of sorbent. The sample solution were
adjusted at pH 2 and adsorption was conducted by using batch system
of contact time for 30 min. The effect of initial concentration and
temperature condition of adsorption Cr(VI) in surface of IIP and NIP are
shown in Figs. 10 and 11 respectively. Fig. 10 shows the representative
plots of variation of temperatures versus adsorption capacity of Cr(VI)
ion onto surface of IIP and NIP particles. It was found that the ad-
sorption of Cr(VI) ions was steady constant with an increasing in tem-
perature from 303 to 343 K. As seen that the adsorption capacities was
optimum at 313 K for those sorbent and occur with 14 mg/L of initial
concentration of sample solution. The adsorption capacities of Cr(VI)
onto IIP and NIP particle of this studies are 3.280 mg/g and 2.941 mg/g
respectively.
Based on the result of optimation parameters such as pH, contact
time, temperature, it can be seen the best adsorption of Cr(VI) on IIP
and NIP was found at condition of pH 2 with contact time is 30 min and
the temperature was set at 313 K. In this optimum condition, it is
known that, the surface of adsorbent would also surrounded by hy-
dronium ions which enhance ions interactions with binding site of the
sorbent particles by greater attractive force [42].
The optimum condition of Cr(VI) adsorption onto some of modified
of imprinted adsorbents are presented in Table 2. Table 2 shows that
material produced was effective and was competitive if it was compared
with the same materials which was found in previous research. This is
seen from the contact time of Cr(VI) in the low concentration with high
speed of 30 min to remove all concentration of Cr(VI) from water
sample by using least adsorbent mass.
3.6.5. Selectivity adsorption of Cr(VI) ion onto IIP and NIP
Selectivity adsorption was studied to know the competitive ad-
sorption between Cr(VI) ion and competitor ion onto IIP or NIP particle.
Distribution, selectivity coefficient and relative selectivity coefficient
were calculated using Eqs. 3, 4 and 5 below [48,49]:
Ci Cf V
Kd =
Cf m (3)
Where Kd, Ci, Cf, V and m are distribution coefficient, initial con-
tration (mg/g), final concentration (mg/g), volume of solution (L) and
adsorbent dosage (g) respectively. Selectivity coefficient was fine out
use Eq. 4:
K d (template ion)
k=
K d (interferent ion) (4)
Where k is coefficient selectivity. In order to evaluate the imprinting
effect on the selectivity, comparison k value of IIP and NIP was evaluate
by use Eq. 5 [48,50]:
k (imprinted)
k =
k (non imprinted) (5)
Where k’ is selectivity coefficient resulting from comparison k value
of IIP and NIP. Selectivity of IIP and IIP was studied by doing single ion
competitive adsorption between Cr(VI)/(Cr(III) and Cr(VI)/Ni(II) use
batch system method. Competitive adsorption studies was conducted by
adding the interfering ion with different concentration between 2 and
16 mg/L in to the 50 mL of Cr(VI) ion sample solution 14 mg/L. 0.08 g
of IIP and NIP were use in this work. The result of the adsorption ca-
pacities for each ions onto IIP or NIP particle was shown in Table 3.
As seen in Table 3, adsorption capacities of Cr(VI) ion onto IIP are
7.703 mg/g and 7.431 mg/g even it was found of Ni(II) or Cr(III) as a
competitor ion in sample solution which were separated respectively. In
Y.A.B. Neolaka, et al. Reactive and Functional Polymers 147 (2020) 104451

Table 1
Surface area and pore character of IIP unleahed, IIP leached and NIP based from BET-BJH method.
Sample S BETa (m2/g) Pore total volumeb (cm3/g) Micro volumec (cm3/g) Meso volume (cm3/g) Pore size average (nm)

IIP unleached 40.382 0.110 0.000 0.110 6.520

IIP leached 41.458 0.032 0.013 0.019 4.848
NIP 34.799 0.051 0.011 0.040 5.888

a
Multy point of BET.
b
Pore total volume at P/P0 = 0.99376 (IIP unleached); 0.99376 (IIP leached), 0.99086 (NIP).
c
meso volume = Pore total volume – micro volume.

Fig. 7. Effect of adsorbent dosage for adsorption Cr(VI) onto IIP and NIP par-
ticle (Experimental conditions: initial concentration: 14 mg/L, temperature:
25 °C).
Fig. 9. Effect of contact time for adsorption Cr(VI) onto IIP and NIP articles
(Experimental conditions: initial concentration: 14 mg/L, pH: 2, temperature:
25 °C; adsorbent dosage: 0.08 g).

Fig. 8. Effect of pH for adsorption Cr(VI) onto IIP leached particle
(Experimental conditions: initial concentration: 14 mg/L, temperature: 25 °C;
adsorbent dosage: 0.08 g).
Table 3, it was also found that adsorption capacities of Cr(VI) onto IIP
particles are bigger than capacities adsorption of Cr(VI) onto NIP par-
ticle even in the sample there is Ni(II) or Cr(III) as an interfering ion.
The form data from Table 3, then were used to calculate the value of
coefficient distribution (Kd), selectivity coefficient (k) and the relative
selectivity coefficient (k’) and the result was shown in Table 4.
Table 4 shows that adsorption of Cr(VI) ion in the IIP particle was
more selective comparing with adsorption Cr(VI) ion onto NIP particle
even Cr(VI) exist together with Ni(II) or Cr(III) as a competitor ion
respectively. Kd value of Cr(VI) adsorption in the competitive adsorp-
tion between Cr(VI)/NI(II) or Cr(VI)/Cr(III) onto IIP was higher than on
Fig. 10. Effect of temperature condition for adsorption Cr(VI) onto IIP particles
(Experimental conditions: initial concentration: 6 mg/L to 14 mg/L, pH: 2,
adsorbent dosage: 0.08 g).
the NIP particle. The k value of competitive adsorption between Cr(VI)/
NI(II) or Cr(VI)/Cr(III) for IIP as sorbent was greater than NIP as sor-
bent. The k’ value for Cr(VI)/NI(II) or Cr(VI)/Cr(III) onto IIP was much
higher than on the NIP particle. Value of k’ showed that adsorption of
Cr(VI) ion onto IIP particles in the competitive adsorption between Cr
(VI)/NI(II) or Cr(VI)/Cr(III) system are 3.824 and 22.884 times larger
than onto NIP particles. The result proves that the IIP has a very high
selectivity degree to adsorption the Cr(VI) ion even Ni(II) or Cr(III) exist
together in sample solution.
3.6.6. Modeling adsorption kinetics
The calculation of real-time ionic adsorption should be done in
order to determine the effect of time to adsoption process and to
identify what mechanisms that control the very reactions such as mass

8
Y.A.B. Neolaka, et al. Reactive and Functional Polymers 147 (2020) 104451

Table 3
Competitive adsorption of Cr(VI)/Ni(II) and Cr(VI)/Cr(III) onto IIP and NIP.
Competitive Ions qe (mg/g)

Mean Standard Mean Standard

deviation deviation

IIP NIP

Cr(VI)/Ni(II) Cr(VI) 7.703 0.060 2.311 0.054

Ni(II) 0.419 0.043 0.096 0.093
Cr(VI)/Cr(III) Cr(VI) 7.431 0.020 0.639 0.062
Cr(III) 0.634 0.020 0.263 0.006

Experiment condition: Each competitor ion is made with a concentration of 2 to

16 mg/L in to the 50 mL of Cr(VI) ion sample solution 14 mg/L.

plotting t/qt versus t with h = k2 qe 2 (mg/g.min) is initial adsorption

Fig. 11. Effect of temperature condition for adsorption Cr(VI) onto NIP parti- rate t → 0 [53,54,57–59].
cles (Experimental conditions: initial concentration: 6 mg/L to 14 mg/L, pH: 2, Weber and Morris formulate the intra-particle diffusion model to
adsorbent dosage: 0.08 g). locate the migration of adsorbates from the surface of adsorbent into its
internal pores because of stirring process as follows:
transfer and chemical reactions. The authors used five kinetic models to
qt = ki t 0.5 + C (11)
observe adsorption process of a contaminant into adsorbents, which are
pseudo-first order model, pseudo-second order model, Bangham model, where qt (mg/g) is the number of adsorbates on the surface of ad-
intra-particle diffusion model and Elovich model. srobent, ki (mg/g) min0.5) is the constant of intra-particle diffusion, t
Pseudo-first order kinetic equation is expressed by Lagergren as (min) is time and C (mg/g) is the intercept. The value of ki is obtained
follows: by plotting qt versus t0.5. Adsorption system will follow this model if the
dqt linear line crosses the zero (C = 0). On the other hand, if it does not
= k1 (qe qt ) follow, the adsorption rate will not be controlled by intra-particle dif-
dt (6)
fusion, but will be controlled by other possible processes [52–55]. C is
Integration at t = 0 – t and qt = 0 − qt′ results: the thickness of limit border formed by adsorption process. The bigger
qe the thickness, the bigger the limit border will be [57].
ln = k1 t Bangham equation is used to study the time phases where adsorp-
qe qt (7) tion system is happened as described as follows:
and its linear form will be:
Co ko m
ln(qe qt ) = ln qe k1 t (8) log log = log + log t
Co qt m 2.303 V (12)
where qe and qt are the number of adsorbate adsorbed at equilibrium
and at time t (mg/g) respectively, k1 is pseudo-first order constant Where Co is the initial concentration of adsorbates (mg/L), V is the
(min−1) of adsorption process. The value of qe and k1 should be de- solution volume (mL), m is the mass of adsorbent per liter of solution
termined by plotting ln(qe – qt) versus t with k1 is the slope and qe is the (g/L), qt (mg/g) is the amount of adsorbates remains at time t and at α
intercept [51–56]. (< 1), and ko is the constant.
Some adsorption cases will follow pseudo-second kinetic order ex- Elovich kinetic model is used to study the adsorption rate based on
pressed as follows: the capacity of adsorpsi on heterogenous surface and can be expressed
with Eq. 13 as follows:
dqt
= k2 (qe qt ) 2
dt (9) dqt
= exp( qt )
dt (13)
Limiting the expression at t = 0 - t and qt = 0 − qt′ in the in-
tegration will result: where α is initial adsorption rate (mg/g. min) and β is desorption rate
t 1 1 (g/mg) that refers to the locating the reaction process on the surface of
= + t adsorbate and chemisorption activation rate [59–61]. By determining
qt k2 qe 2 qe (10)
the limit at t = 0 – t, qt = 0 – qt. and assuming that (α·β) > > t, this
Parameter qe (mg/g) and k2 (g/mg.min) should be determined by equation can be simplified into:

Table 2
Optimum condition use the different adsorbent for Cr(VI) ion from batch studies.
Adsorbent Adsorbent dosage (g) pH Initial Cr(VI) concentration (mg/L) Time contact (min) Reference

IIP 4-VP/HEMA 0.1 4.0 200 40 [4]

PGME-deta 0.5 1.8 0.1 30 [43]
Magnetic Polymer (Cr-(IIP)) 0.02 4 5 40 [20]
Cr(VI)-IIPs 0.1 2 600 3 [21]
Cr(VI)-IIP 0.1 2 600 3 [44]
Electrospun chitosan nanofibers 0.05 3 100 60 [45]
CNFb-S-TEA 0.05 4.5 125 720 [46]
Cr(VI)-PCGA 0.5 3 400 30 [47]
Cr(VI)-imprinted-poly(4-VP-co-EGDMA) 0.08 2 14 30 Present study

9
Y.A.B. Neolaka, et al. Reactive and Functional Polymers 147 (2020) 104451

Table 4 using Elovich model is smaller than 0.95 so that this tells us Cr(VI)
The coefficient distribution (Kd), selectivity coefficient (k) and the relative se- adsorption is not completely dominated by chemisorption process. To
lectivity coefficient (k’) values for the solid phase. determine whether our adsorption process is also controlled by diffu-
Competitive Ions IIP NIP k’ sion rate, the intra-particle diffusion kinetic model is used. This model
results R2 > 0.95 for IIP which means Cr(VI) adsorption on the surface
Kd (L/g) k Kd (L/g) k of four adsorbents is also affected by intra-particle distribution. The
calculation for NIP shows that adsorption rate is not affected by intra-
Cr(VI)/Ni(II) Cr(VI) 4.599 – 0.224 – –
Ni(II) 0.180 25.540 0.034 6.679 3.824 particle distribution because R2 < 0.95. Another factor that could
Cr(VI)/Cr(III) Cr(VI) 3.522 – 0.049 – – affect Cr(VI) adsorption is the adsorption rate where based on Bangham
Cr(III) 0.320 11.020 0.102 0.482 22.844 kinetic model, the value of R2 of IIP is higher than 0.95. In conclusion,
base on five kinetic models show that Cr(VI) adsorption on the surface
of IIP is controlled by chemisorption, intra-particle distribution, and
1 1 time. On the other hand, adsorption by NIP is controlled only by che-
qt = ln( )+ ln t
(14) misorption.

Slope and intercept should be obtained by plotting qt versus ln t and

3.6.7. Isotherm adsorption modeling
can be utillized to calculate β and α.
Isotherm equations such as Langmuir, Freundlich, Tempkin, DKR
Modeling adsorption kinetic is necessary to know whether the ad-
and BET models were used to describe the equilibrium of adsorption.
sorption mechanism follows the chemical or physical properties of the
Langmuir parameters are determined by following equation:
adsorbent. Generally, these models can be conducted using batch
system. This paper reports the study of adsorption mechanism using qmax K Ce
q=
synthesized ionic imprinting polymer with five kinetic models which 1 + K Ce (15)
are pseudo-first order, pseudo-second order, intra-particle distribution
model, Bangham model, and Elovich model. Pseudo-first kinetic order qmax (mg/L) and K (L/mg) are monolayer capacity at high concentra-
model, pseudo-second kinetic order order, and Elovich model were tion and equilibrium constant respectively. Ce is concentration of so-
selected to be used in this paper to study adsorption system Cr(VI) on lution at equilibrium (mg/L) and q shows the amount of adsorbate
ionic imprinting polymer with the assumption that adsorption rate was adsorbed at equilibrium (mg/g).
controlled by chemisorption [53,59]. Intra-particle diffusion model was Ce 1 1
used to observe the adsorption system controlled by diffusion = + Ce
q K qmax qmax (16)
[53,55,62]. Bangham Model was used to study the steps when ad-
sorption system was appeared. Graphs of kinetic model were produced Freundlich parameters are determined by following equation:
from studied kinetic models using IIP and NIP as the adsorbent. The
q = KF Ce1/ n (17)
graphs are shown on Table 5.
Based on Table 5, it is seen that IIP and NIP have R2 > 0.95 for KF and 1/n show Freundlich capacity factor and Freundlich intensity
pseudo-second kinetic order model, which shows that the adsorption of parameter respectively. Ce is the concentration of solution at equili-
Cr (VI) ions occurs at certain active sites of the localized Cr (VI)-im- brium (mg/L) and q shows the amount of adsorbate adsorbed at equ-
printed-poly (4-VP-co-EGDMA) sorbent [63]. The result shows that the librium (mg/g).
increase of adsorbed concentration to these 2 adsorbents is faster than
1
the decrease of Cr(VI) concentration in sample solution. This result is on log q = log KF + log Ce
n (18)
the same page with the research done by Debnath et al. (2008) [64].
Elovich Model can also be used to support the result whether the ad- Dubinin-Radushkevich Isotherm (DKR) Isotherm is used to de-
sorption is dominated by chemisorption process by studying its R2. termine the pseudo-energy of adsorbed adsorbates on the surface of
Using Elovich model, R2 for IIP is higher than 0.95 so that suffice to say adsorbent. The linear equation of DKR is expressed as follows:
that this adsorption system is controlled by chemisorption. R2 of NIP
ln qe = ln Xm 2
(19)
Table 5
1
Parameter values of adsorption kinetics of Cr(VI) on IIP and NIP. = R T ln 1 +
Ce (20)
Kinetics modeling Parameters Sorbents
Where qe is adsorbed substances (mg/g); β is the activity coefficient
IIP NIP constant at specific energy absorbance, ε is Polanyi's potential, R is the
Pseudo-first-order k1/10−3 min−1 0.285 0.185 gas constant (J/mol·K) and T is the temperature (K). Parameters of DKR
qe. mg/g 7.202 0.450 are calculated by plotting the graph of ln qe versus ε2 with β is obtained
R2 0.612 0.414 from the slope and Xm is obtained from its intercept. The number of β is
Pseudo-second-order k2/10−3 g/mg min−1 2.654 3.463 proportional to the transferred energy (E (kJ/mol)) in solution onto the
qe. mg/g 1.034 0.938
surface of adsorbent, following the expressed equation:
h/10−2 mg/g min−1 2.838 3.250
R2 0.999 0.999 1
Intra-particle distribution ki/10−2 mg g−1 min-0.5 0.014 0.130 E= 1
C. mg g−1 2.438 2.481 ( 2 )2 (21)
R2 0.973 0.788
Bangham km (mL/(g/L)) 4.630 4.649 If E > 8, then the adsorption process of adsorbate follows chemi-
Α 1.255 1.249 sorption process [65].
R2 0.984 0.876 Tempkin isotherm model describes the interaction of adsorbent with
Elovich α /10−2 mg g−1 min−1 28,872.626 44,440.873 the adsorbate. This model assumes the adsorption occurs in all mole-
β. g mg−1 3.859 3.995
R2 0.982 0.878
cules of surface of adsorbent and the interactions will linearly be de-
creased. In addition, the adsorption is characterized until its maximum
Exp: The condition of experiment was carried out according to the optimum energy. Parameters of Tempkin model are determined by following
condition which was gained in the Batch adsorption studies. equation:

10
Y.A.B. Neolaka, et al. Reactive and Functional Polymers 147 (2020) 104451

R T Table 7
qe = ln AT Ce
BT (22) Thermodynamic parameters of Cr(VI) adsorption on IIP and NIP.

Its linear model is: T (K) ∆G0 (kJ/mol) ∆H0 (kJ /mol) ∆S0 (kJ /mol)

R T R T IIP NIP IIP NIP IIP NIP

qe = ln AT + ln Ce
BT BT (23) 303 −16.318 −14.707 −20.757 −9.924 −0.015 0.016
313 −16.171 −14.865
This equation can also be written in another form as follows: 323 −16.025 −14.865
333 −15.878 −15.181
qe = B1 ln Kt + B1 ln Ce (24) 343 −15.732 −15.181

Where Kt = AT and B1 = RT/bT. The slope of qe versus ln Ce is used

Exp: The thermodynamic calculation base on optimation temperature experi-
to determine the value of Kt and the intercept is used to determine B1. ment data.
Ce is concentration of solution at equilibrium (mg/L) and q represents
the number of adsorption equilibrium (mg/g). Kt is suitable equilibrium of n. If n ≥ 1, the system is homogeny and if n ≤ 1, the system is
constant (L/mol) for maximum energy bond and B1 is related to the heterogeny. Based on the value of n, suffice to say that there is homo-
adsorption part itself [66]. genous system of adsorption on IIP and NIP. These data share synergic
Brunauer-Emmett-Teller (BET) isotherm refers to the expansion of result with [69].
Langmuir theory. BET assumes that adsorbate molecules can form more In validating whether the isotherm is controlled by chemisorption or
than one layer of adsorbates on its surface. In this isotherm, the ad- physisorption process, the value of b from Tempkin isotherm should be
sorption mechanism for every process is different. Langmuir isotherm is considered. The indication whether the adsorption is happened via ion
mostly suitable for chemical adsorption while BET isotherm is more exhange can be determined by calculating the value of b of Tempkin
appropriate to be implemented in physical adsorption. BET Isotherm isotherm between 8 and 16 kJ/mol. If the value is less than −40 kJ/
can be explained with the eq. 25. mol, the adsorption follows physisorption process [70]. Table 7 shows
Ce 1 (B 1) Ce that the value of b on IIP and NIP indicate the process tends to be
= +
[(C0 Ce ) qe ] B qm B qm C0 (25) happened via chemisorption process. DKR isotherm calculation shows
that the values of β for all solid phases are lower than 8 kJ/mol so that it
The plot of Ce
versus Ce
will result a linear graph where qm can be concluded that some part of the adsorption process was con-
[(C0 Ce ) qe ] C0
and B can be calculated using resulted slope and intercept [67]. trolled by physisorption. BET isotherm model itself can be used to de-
The modeling of adsorption isotherm can be conducted to under- termine whether the adsorption process is occured in multilayer or else.
stand the phenomenon of immobility or mobility of an analyte in Table 6 shows that the process in IIP and NIP is dominated by chemi-
aquatic environment to a solid phase at constant pH and temperature sorption via monolayer homogenous system.
[66]. Isotherms of adsorption can also be studied to determine the ef-
fects of parameters of physics-chemistry on adsorption process. In this
3.7. Thermodynamic adsorption
research we used five models of adsoprtion isotherm to study the pro-
cess of Cr(VI) adsorption on a prepared solid surface. Data from various
Thermodynamic parameters are also evaluated by conducting the
models of Cr(VI) adsorption on the surface of IIP and NIP are shown by
binding in various temperatures, ∆H0 (enthalpy), ∆S0 (entropy) of ions
and Table 6.
adsorption. Free Gibbs energy is calculated using expressed equation as
Table 6 shows that the adsorption isotherm for IIP and NIP follow
follows:
Freundlich isotherm with the R2 of 0.962 and 0.884 respectively with
the adsorption capacity (Xm) of 3.443 mg/g and 2.825 mg/g respec- G0 = n R T ln K (26)
tively. Freundlich Isotherm assumes that the adsorption on the surgace
The value of K is determined by plotting ln (qe/Ce) versus qe and the
of prepared IIP was done on hotoregenous surface and the adsorption
intercept will be the desired value. Each variation results different va-
capacity that is proportional to the concentration of Cr(VI) at equili-
lues of K in order to determine the plot of ln K versus 1/T. Slope and
brium [68]. Heterogeneity in Freundlich isotherm is shown by the value
intercept of resulted curves were used to calculate ∆H0 (enthalpy) and
∆S0 (entropy). K is the thermodynamic equilibrium constant (L/g), R is
Table 6
The value of Cr(VI) isotherm parameters.
the gas constant (8.314 J/mol.K) and T is the absolute temperature (K).
Thermodynamic study is needed to determine whether Cr(VI) ad-
Kinetics modeling Parameters Sorbents sorption on the surface of prepared adsorbents was spontaneous or not.
IIP NIP
Experimental data from various temperature were processed using
Van't Hoff equation to create the plot of 1/T versus ln K as shown by
Langmuir qmax (mg/g) 1.352 2.004 Fig. 12. Then, the linear equations shown by Fig. 12 were used to
KL (L/mg) −0.810 −0.556 calculate ∆H0, ∆G0 and ∆S0 from each variation of temperature shown
R2 0.726 0.799
Freundlich n 1.371 2.124
by Table 7.
KF (mg/kg) 1.223 1.556 Table 7 shows that ∆G0 of Cr(VI) adsorption in the surface of IIP and
R2 0.962 0.884 NIP (303Ke333K) are negative so that in conclusion, the adsorption of
Kt 1.845 4.191 Cr(VI) is a spontaneous process wihout any initial induction period
Tempkin b (kJ/mol) 26.330 17.320
[71]. If the reaction is done in spontaneous process, it will produce
R2 0.926 0.826
Xm (mg/g) 3.443 2.825 supporting effect for electrostatic interactions or complex compound
DKR β (kJ/mol) -4 × 10−10 -2 × 10−10 formation of Cr(VI) and the adsorbent easily [72]. These data support
R2 0.926 0.698 our calculation by using DKR isotherm model. Negative ∆H0 of Cr(VI)
B 0.965 1.018 adsorption on the surface of IIP and NIP indicates that this adsorption is
BET qmax (mg/g) 3.623 11.876
R2 0.269 0.169
naturally exothermic. Our result is also proportional to previous re-
searches conducted by Hu et al. (2011), Wang et al. (2012) and Maksin
Exp: The condition of experiment was carried out according to the optimum et al. (2012) [43,68,70]. Positive ∆S0 of Cr(VI) adsorption on NIP sur-
condition which was gained in the Batch adsorption studies. face shows the increase of disorder degree of liquid-solid interface in

11
Y.A.B. Neolaka, et al.
Fig. 12. Plot of 1/T versus ln K: a) IIP and b) NIP.
Table 8
Recovery (%) of electroplated sample of Cr(VI) using SPE system.
Sorbents Sample type Initial concentration (mg/L)
IIP Electroplating 1.415
NIP
the adsorption process. Different process was happened on IIP that has
negative ∆S0, showing the decrease of disorder degree of liquid-solid
interface [1].
3.8. Recovery and enrichment factor of Cr(VI) extraction from
electroplated wastewater using SPE system
Application of prepared solid phase for Cr(VI) recovery from elec-
troplated wastewater sample using SPE system is shown by Table 8.
Recovery of Cr(VI) was studied using 10 mL of electroplated sample
that was flown to 4 catridges of SPE with the diameter of 3 mm and
have been filled 1 g of IIP and NIP. Recovery analysis is shown by
Table 8.
Based on aforementioned table, the recovery of eluted analyte (Cr
(VI) on the surface of solid phase IIP is up to 95.89% while the recovery
of NIP is 45.60% in 1.415 mg/L electroplated wastewater. Acceptance
percentage of Cr(VI) recovery, which is 76–116%, using IIP as the solid-
phase to concentrate Cr(VI) is said to be excellent [73]. This result
shows that IIP can be used in the concentrating process of low con-
centration Cr(VI) in wastewater.
3.9. Reusability
Reusability is one of pivotal factors in the implementation of ma-
terial in industries. Based on Fig. 13, it is shown that variations of re-
covery (%) of electroplated wastewater Cr(VI) using IIP by ten times of
repetitions are statistically equal. There is some decrease about 4.47%
that means there are about 0.22 mg of Cr(VI) could not be leached out
of IIP adsorbent after the third until tenth utillization. In coonclusion,
aforementioned variations are remarkable small so that this adsorbent
can be regenerated and be utillized up to ten times.
4. Conclusions
The adsorbent is based on IIP which was synthesized successfully to
be used in the process of selective removal and solid phase extraction of
Cr(VI). This ionic imprinting polymer was made from Cr(VI) ion as a
12
Reactive and Functional Polymers 147 (2020) 104451
Fig. 13. Reusability of IIP and NIP.
Cads (mg/g) R (%) EF theory EF true
2.087 96.667 5.000 4.833
1.601 60.347 5.000 3.017
template ion, 4-VP as complexion agent and monomer, EGDMA as cross
linker agent, BPO as initiator and ethanol/acetone as a porogen was
successfully synthesized by using precipitation method. The result
shows that the IIP adsorbent have a micro and mesopores structure with
average of pore size of IIP unleached, leached and NIP such as: 6.520,
4.848 and 5.888 nm respectively. The adsorption of Cr(VI) ion was
found relatively fast and condition for Cr(VI) ion adsorption was op-
timum in such condition at pH 2, 0.08 g adsorbent dosage, adsorption
time 30 min at 323 K temperature condition. The best initial Cr(VI) ion
solution concentration of this study was found at 14 mg/L. This ma-
terial is very selective to adsorp Cr(VI) ion even in water environment
contains interfering ion such as Ni(II) and Cr(III) respectively. Modeling
kinetic of Cr(VI) adsorption in this material fit with the Pseudo-second-
order model while modeling isotherm followed the Freundlich model.
The application of this material to adsorp Cr(VI) from electroplating
industrial waste which reaches 96%. The reusability testing shows that
this adsorbent has good stability even it was used 10 times repeatedly.
Finally, in the future this material is expected to be used as one of solid
phase materials in SPE system for preconcentration or extraction of Cr
(VI) from water sample in low concentration.
Acknowledgement
The First authors acknowledges a Fundamental Research Grand of
the Ministry of Research, Technology and Higher Education, Republic
of Indonesia.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time due to technical or time limitations.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Y.A.B. Neolaka, et al.
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