Journal of Water Process Engineering 53 (2023) 103623

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Journal of Water Process Engineering

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

Development of a new hyper crosslinked resin based on

polyamine-isocyanurate for the efficient removal of endocrine disruptor
bisphenol-A from water
Tauqir Ahmad a, Mohammad Saood Manzar b, Jordana Georgin c, Dison S.P. Franco c,
Sardaraz Khan a, Lucas Meili d, *, Nisar Ullah a, e, **
a
Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
b
Department of Environmental Engineering, Imam Abdulrahman Bin Faisal University, Dammam, Saudi Arabia
c
Universidad de la Costa, CUC, Calle 58 # 55–66, 080002 Barranquilla, Atlántico, Colombia
d
Laboratory of Processes, Center of Technology, Federal University of Alagoas Campus A. C. Simões, Av. Lourival Melo Mota, Tabuleiro dos Martins, Maceió, AL 57072-
970, Brazil
e
Interdisciplinary Research Center for Refining and Advanced Chemicals, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: Bisphenol A (BPA) is a diphenylmethane derivative often used as a building block of polycarbonate in the
Bisphenol A production of plastic and plastic additives. Different sectors of the chemical industry release daily high con­
Adsorption centrations of BPA in treatment plants, leading to polluting the environment. Due to chemical characteristics,
Decontamination
BPA is considered highly toxic to animals and humans health. Adsorption is considered one of the promising
Composites
techniques for the removal of BPA from water. In this study, we report the synthesis of a new polyamine-
isocyanurate-based hyper crosslinked resin (ICYAN-PA) for the adsorptive removal of BPA from aqueous solu­
tion. The porous resin showed good thermal stability with a surface marked by smooth porous layers covered by
particles of different sizes. The resin exhibited optimum removal of BPA at pH 5, with an adsorption capacity of
260 mg g− 1. The isothermal studies suggested that adsorption was favored with increasing temperature (318 K).
The Koble-Corrigan model was more adequate to represent the isothermal data. Moreover, the adsorption process
was favorable, spontaneous, and endothermic (ΔH0 = 50.9 kJ mol− 1). Furthermore, the magnitude of ΔH◦ was
compatible with physical adsorption. The kinetic profiles indicated that the adsorption equilibrium was attained
in <180 min of contact time, and the pseudo-first order model best represented the kinetic data. Given the
relatively fast kinetics and high thermal stability (Td < 220 ◦ C), ICYAN-PA holds a promise in the decontami­
nation of effluents containing BPA.

1. Introduction pretreatment of such effluents is needed before their discharge to water

The rapid growth in industrialization and urbanization has posed a
serious threat to global water contamination. Various contaminants
release into the natural water reservoirs include anthropogenic- and
metalloid pollutants [1,2] pharmaceuticals [3], metal ions [4–6], dyes
[7,8], phenolic compounds [9] and various other pollutants [10,11].
The excessive spike in pollutants concentration in water bodies makes
the water inapt for human health and aquatic life. It also affects mi­
crobial activity which leads to a decrease in soil fertility. Suitable
sources. Moreover, among various indicator parameters for water
quality (i.e. chemical oxygen demand (COD), biochemical oxygen de­
mand, carbon, and nitrogen compounds), COD is considered the most
important quote [12]. Thus, adequate pre-treatment of such effluents is
necessary before discharge into water sources.
Bisphenol A (BPA) is a diphenylmethane derivative frequently used
as a polycarbonate building block in the production of plastic and plastic
additives [13]. It is also used in the synthesis of polycarbonate and is
frequently detected in plastic products, food, water, and paper [14]. The

* Corresponding author.
** Correspondence to: N. Ullah, Interdisciplinary Research Center for Refining and Advanced Chemicals, King Fahd University of Petroleum and Minerals, Dhahran
31261, Saudi Arabia.
E-mail addresses: lucas.meili@ctec.ufal.br (L. Meili), nullah@kfupm.edu.sa (N. Ullah).

https://doi.org/10.1016/j.jwpe.2023.103623
Received 12 January 2023; Received in revised form 23 February 2023; Accepted 28 February 2023
Available online 21 March 2023
2214-7144/© 2023 Elsevier Ltd. All rights reserved.
T. Ahmad et al.
primary source of BPA discharge is chemical industries wherein it is
discharged from effluent treatment plants. It is moderately soluble in
water, with BPA/water partition coefficient is 2.5–4.5. Thus, it adds to
the accumulation, transportation, and adsorption of BPA in sediments,
soils, and related carbon-containing materials in the aqueous environ­
ment which in turn results in their leakage into the food chain [15]. It is
reported that human is exposed to 30.76 nanogram/kg of BPA through
ingestion, dermal exposure, and inhalation. The exposure causes slow
progression and long-term diseases like kidney and cardiovascular
complications, obesity, sexual functionality decline, congenital disabil­
ities, diabetes, and developmental disorders [16]. Moreover, BPA is a
proven endocrine-disrupting compound. It interacts with various phys­
iological receptors like thyroid hormone receptor, androgen receptor,
estrogen receptor α/β, and estrogen-associated receptor γ. In addition, it
harms the neural system, immune system, metabolic systems, and car­
diovascular [17]. Also, it has been linked to causing cancer [18].
Therefore, several alternative options such as bisphenol S, bisphenol F,
etc. have been suggested as an alternative to BPA due to the ban on its
use in baby bottles [19]. But the use of these alternatives is still very rare
and uncommon. As a result, BPA is still commonly used in different
products. Thus, there is a dire need to treat BPA-contaminated effluent
before its discharge into water sources. However, BPA is normally very
stable in the environment and its biodegradability is very low under
natural conditions [20]. In addition, efficient removal of BPA with the
traditional process like sand filtration, coagulation, flocculation, and
sedimentation is difficult as they are normally negatively charged or
neutral in the environmental water. Additionally, treatment techniques
like UV radiation, electrochemical separation, and chemical coagulation
needs the addition of chemical agents or form reactive species which in
turn may be dangerous for aquatic life. Likewise, although ion exchange
and membrane separation are safe, they are economically impractical
due to their high energy demands [21–23].
On the other hand, adsorption is considered an effective and simple
method for the treatment of BPA. Adsorption can efficiently remove
various contaminants from wastewater without the requirement of a
special setup and does not produce unknown byproducts [7]. The
adsorption of the BPA and other contaminants by using various adsor­
bents is more effective and fast as compared to their removal due to its
low cost, simplicity, and fewer chances of producing harmful by-
products [17]. Recently, a wide range of adsorbents including mag­
netic CuZnFe2O4-biochar composite [14], defect-rich porous carbons
[24–27], nitrogen-doped multiwall carbon nanotubes [28,29], beta
zeolite [30], mesoporous silica nanoparticles [31,32] has been suc­
cessfully used for the adsorption of BPA from aqueous solutions. How­
ever, the synthesis of these adsorbents demands high-temperature
heating, solvothermal treatment, and coprecipitation with the target
solvent which demands high energy, time-consuming operations, and
sensitive condition control [33]. Consequently, polymer-based cross-
linked resins have attracted a great deal of attention due to their low
cost, large surface area, high porosity, and good adsorption capacity are
advantageous over other adsorbents. In particular, the ease of regener­
ation and prospects of reusability makes low-cost polymer resin
increasingly attractive for practical utilization.
Continuing our efforts for water remediation via adsorption of pol­
lutants by low-cost and thermally stable hyper crosslinked resins
[7,8,34–36], herein we report the synthesis of pristine hyper-crosslinked
polymer resin (ICYAN-PA), which was achieved in a single step from the
reaction of commercially available 1,2-bis(3-aminopropylamino)ethane
1 with tris(2,3-epoxypropyl) isocyanurate 2. The structural architect of
ICYAN-PA contains isocyanurate core with poly hydroxy- and amine
functions. The chemical structure, surface characterization of ICYAN-PA
was thoroughly performed with the aid of Fourier transform infrared
spectroscopy (FT-IR), powder X-ray diffraction (PXRD), Field emission
scanning electron microscopy (FESEM) energy dispersion spectroscopic
(EDS) and Brunauer-Emmett-Teller (BET) analysis. The thermal stability
of ICYAN-PA was determined by thermogravimetric analysis (TGA). In
2
Journal of Water Process Engineering 53 (2023) 103623
order to determine optimum adsorption conditions, various adsorption
parameters including adsorbent dosage, contact time, pH of dyes solu­
tion and concentration on the adsorptive performance was studied.
Moreover, detailed kinetic and thermodynamic studies were also per­
formed. The ICYAN-PA was able to efficiently remove BPA from the
aqueous solution, with a Qmax value of 260.9 mg g− 1. The ease of syn­
thesis, commercial availability and economically cheap starting mate­
rials make ICYAN-PA very promising to tackle the removal of endocrine-
disrupting compound, BPA, from the aqueous solution.
2. Experimental
2.1. Materials and methods
Details about materials, characterization, and adsorption methods
and models employed are provided in the supplementary file.
2.2. Synthesis of ICYAN-PA
To a stirring solution of 1,2-bis(3-aminopropylamino) ethane (4.6
mL, 25.0 mmol) in CH3CN (100 mL) was added triethylamine (5.24 mL,
37.5 mmol). After being stirred for 30 min, the solution was added to tris
(2,3-epoxypropyl) isocyanurate (9.9 g, 33.3 mmol) and the reaction
mixture was then stirred for 1 h at room temperature under nitrogen,
followed by heating to reflux for 24 h. The reaction was cooled to room
temperature and the solid formed was filtered. The obtained crude
product was then stirred in acetone (25 mL) for 1 h. Filtration of the solid
and then extensive sequential washing with methanol (50 mL) and water
(50 mL) rendered the solid, which was then dried for 12 h at 60 ◦ C under
vacuum to afford ICYAN-PA as a light-yellow solid (8.57 g, 72 %).
2.3. Adsorption models: isotherm, thermodynamics, and kinetics
Adsorption studies are primarily concerned with how the system
behaves in relation to equilibrium and how the initial concentration
affects the time it takes to reach equilibrium. Also, the results from the
isotherms models are used for the determination of the thermodynamic
parameters. For this study, the Langmuir, Freundlich Dubinin-
Radushkevich, and the Koble-Corrigan modes were chosen. Langmuir
model is the most traditional, which considers that the adsorbent con­
tains a fixed number of identical active sites with equal affinity and
adsorption occurs in a monolayer and is the function of the adsorption
and desorption rate [37]. The Freundlich model is an empirical model
that describes that adsorbent possess a non-uniform heat of adsorption
and affinity for the adsorbate molecules, leading to the generation of
multilayer on the surface of the adsorbent [38]. The Dubinin-
Radushkevich model consists of combining the Polanyi and the
Gaussian function for describing the adsorption. This model estimates
the characteristics porosity and apparent free energy of adsorption.
Moreover, it also considers that the increase of the adsorption capacity
depends on diminishing the adsorption energy onto the heterogeneous
surface [39]. Finally, the Koble-Corrigan model considers that the
adsorption is the result of the average between the activated sites be­
tween the adsorbed molecule and the adsorbent [40]. The mentioned
models are presented in the Supplementary material.
To determine thermodynamic parameters, standard Gibbs free en­
ergy change, standard enthalpy, and entropy change were conducted
according to the methodology proposed by Tran and collaborators.
Where different methodologies are needed according to the best-fitted
isotherm model [41]. The employed methodology is shown in the sup­
plementary material. Moreover, for the kinetic models, it was chosen the
pseudo-first order, pseudo-second order, Avrami, and the linear driving
force (LDF) models. The pseudo-first order model takes into consider­
ation that the adsorption occurs based on a pseudo-chemical reaction of
one adsorbate per site of the adsorbent [42]. The pseudo-second order is
an empirical model, which also considers that the adsorption depends on
T. Ahmad et al.
a pseudo-chemical reaction, meaning that the adsorbate needs two
activated sites to be adsorbed [43]. The Avrami model is traditionally
used for nucleation studies, however, due to the formulation of the
model being similar to the structure of the pseudo-first order, it has been
extensively employed in the adsorption studies, considering that the
adsorption depends on the fraction exponent of the model [44]. Finally,
the LDF model was also applied to represent the adsorption; this model
takes into consideration that the rate of adsorption is dependent on the
difference between the adsorption at the equilibrium and the adsorption
capacity at a given time. Moreover, this model also considers that the
adsorption depends upon the surface diffusivity [45]. All the described
models presented in the Supplementary material.
2.4. Parameter estimation, model solution, and evaluation
The parameters estimation, model solution, and evaluation were
performed through Matlab scripting. The estimation of the initial
parameter guest was done through the particleswarm function. For the
final estimation of the parameters, the lsqnonlin and nlinfit were
employed for the model with parameter restrictions and whiteout. Due
to the LDF being a differential equation, the function ode15s was
employed for the resolution with the lsqnonlin for the solution and
parameter estimation. Last, the model fitting was evaluated through
statistical indicators such: as determination coefficient, adjusted deter­
mination coefficient, average relative, and mean squared error, the
equations for the statistical indicators are shown in the supplementary
material.
3. Result and discussion
3.1. Synthesis and characterization of the ICYAN-PA
ICYAN-PA was synthesized by the reaction of 1,2-bis(3-aminopropy­
lamino)ethane 1 and tris(2,3-epoxypropyl) isocyanurate 2 in refluxing
CH3CN, using triethylamine as a base (Scheme 1). The synthesized
ICYAN-PA was extensively washed several times with different solvents
such as acetone and methanol. Moreover, washing was also performed
using cold water and warm water. Washing with water was important to
avoid leaching of ICYAN-PA during the adsorption study since the media
in the adsorption experiments was water.
Scheme 1. Synthesis of resin ICYAN-PA
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Journal of Water Process Engineering 53 (2023) 103623
Likewise, ICYAN-PA was extensively characterized with different
techniques like PXRD, BET, SEM, EDS, FT-IR and TGA. The PXRD
pattern of the neat pristine ICYAN-PA and after BPA loaded resin,
recorded on Bruker XRD D2 Phaser, are given in Figs. 1a. As evident,
humps at 2θ ≈ 20 and small humps at 2θ ≈ 30 and 2θ ≈ 40 indicated the
amorphous nature of the ICYAN-PA. Nevertheless, in the BPA-loaded
resin, these humps were also present but with a small shift in the peak
positions. This suggested that the nature of the BPA-loaded resin did not
change and the adsorption was physisorption in nature.
Similarly, the surface area and porosity of the ICYAN-PA were
studied by BET analysis (Fig. 1b). The BET surface area was found to be
23.4 m2/g with an average particle diameter of 21.3 nm that indicated
the mesoporous nature of ICYAN-PA. In addition, the N2 adsorption-
desorption isotherm of the ICYAN-PA matched type II isotherm ac­
cording to the IUPAC classification of porous materials. In the light of
above, it makes it quite difficult to specify beyond the basic atom group
differences. However, it is pertinent to mention that the adsorbent
physical properties such as the total pore volume, average pore diam­
eter, and specific surface area were not considered in calculating the
effective time. Nevertheless, the textural proprieties of the resin play an
important role during the adsorption process since it is directly involved
with the boundary layer, surface, and pore diffusion [46]. Therefore,
despite the surface area of the resin not being considerably high, other
factors also influence adsorption capacity, justifying the good capacity
of the ICYAN-PA.
Fig. 2a and b indicate the surface morphology of the neat and BPA-
loaded ICYAN-PA. It is evident from these figures that the surface of
ICYAN-PA was composed of different size particles giving a rough
texture to ICYAN-PA. The rough surface of ICYAN-PA is very important
for the adsorption properties as it increases the contact angle. This in
turn decreases the interface hydrophobicity of the resin [47]. As a result,
the decreased hydrophobicity will allow ICYAN-PA to interact most
favorably with MG leading to an enhanced adsorption. However, after
adsorption of BPA onto the surface of the ICYAN-PA leads to a clear
demarcation in the surface morphology of ICYAN-PA, with the
agglomeration of particles on the surface observed. Energy dispersive
spectroscopy (EDS) analysis indicated the presence of C, N & O as the
main elements present in the pristine and BPA adsorbed ICYAN-PA
(Fig. 2c and d).
The FT-IR spectrum of ICYAN-PA (Fig. 3a) reveals absorptions at
T. Ahmad et al. Journal of Water Process Engineering 53 (2023) 103623

Fig. 1. a) XRD of ICYAN-PA, b) BET of ICYN-PA.

Fig. 2. a) FESEM of neat ICYAN-PA, b) FESEM of BPA loaded ICYAN-PA, c) EDS of neat ICYAN-PA, d) EDS of BPA loaded ICYAN-PA.

3660 cm− 1 due to O–H stretching (N–H might be buried underneath),
2977, and 2892 cm− 1 owing to aliphatic-C-H and a peak at 1677 cm− 1
assigned to carbonyl function. However, the FT-IR spectrum of BPA-
loaded ICYAN-PA exhibited an alteration in the position of some
peaks. For example, absorption at 3660 cm− 1 becomes broader and
shifts slightly to a higher frequency (3664 cm− 1) presumably due to the
involvement of O–H in hydrogen bonding (H-bonding). Likewise, the
peak due to carbonyl function at 1677 cm− 1 was also broadened and
shifted to a lower frequency (1640 cm− 1, Fig. 3a). These changes in the
absorption bands suggested the involvement of interaction of ICYAN-PA
functions with the BPA [36].
Moreover, the thermal stability of the resin was determined with the
help of thermogravimetric analysis (Fig. 3b). The temperature was
gradually increased from room temperature to 700 ◦ C at a rate of 10 ◦ C/
min under a nitrogen atmosphere. An initial decrease of 5 % in the mass
at around 100 ◦ C was observed which could be due to the evaporation of
methanol and water [36]. However, the resin remains stable till around
220 ◦ C before a sharp mass loss was observed. This suggested higher
thermal stability of the ICYAN-PA. By employing the salt addition
method, the pH of point zero charge of ICYAN-PA was found to be 9.29
(pHpzc = 9.29, Fig. S1). This suggested that below this pH, ICYAN-PA
will be positively charged whereas above this pH it will become nega­
tively charged.

4
T. Ahmad et al. Journal of Water Process Engineering 53 (2023) 103623

Fig. 3. a) Comparative FT-IR spectra of the ICYAN-PA before and after the adsorption of the BPA, b) TGA of ICYAN-PA.

Fig. 4. pH effect on adsorption of BPA, adsorbent dosage = 0.25 g L− 1, BPA initial concentration = 20 mg L− 1, shaker speed = 275 rpm, T = 298.5 K.

5
T. Ahmad et al.
3.2. Optimization of adsorption parameters
For a better understanding of the adsorption mechanism, optimiza­
tion of adsorption parameters such as pH, dosage, initial dye concen­
tration and contact time is highly desirable. This information is also
important for achieving the optimal performance of adsorbents for real
sample applications.
3.2.1. Effect of pH
Fig. 4 provides information regarding the effect of the pH of the
solution on the adsorption process of BPA, where it varied in the range of
2 and 8. The parameter exerts a great influence on the adsorption since
as the pH rises from 2 to 5 removal increases from 7 % to 116 %, and
from 6 onwards the removal decreases steadily reaching 33 % at pH 8.
This is because the adsorbate species at pH < 8 are molecular BPA,
whereas at 9.6 < pH < 10.4 are BPA− , changing to BPA2− at pH > 10.4
(Fig. S2), this behavior is explained by the speciation graph (Fig. S3).
Therefore, the surface of the adsorbent is charged with negative charges
when the pH is between 5 and 11. The decay behavior of removal close
to pH 5 was also observed in other works that analyzed the adsorption of
BPA [48–50]. The authors indicate that the drop in removal may be
related to electrostatic repulsion and increased hydrophilicity of the
adsorbate at higher pH [51,52]. Therefore, in the following experiments,
pH 5 was fixed.
3.2.2. Dosage of ICYAN-PA
To define the ideal dosage, different amounts of adsorbent dosages
were used, ranging from 0.05 to 0.5 g L− 1, at concentrations of 20, 60,
and 100 mg L− 1 of BPA (Fig. 5). All curves showed similar behavior
regardless of the increase in BPA concentration. Whereas removal
increased from 27 to 100 % at 20 mg L− 1, from 15 to 97 % at 60 mg L-1,
and from 11 to 73 % at 100 mg L− 1, with increasing dosage from 0.05 to
0.5 g L− 1, respectively. In all curves, the most significant increase in
adsorptive removal was at the adsorbent dosage of 0.25 g L− 1, obtaining
Fig. 5. Effect of dosage on % removal of BPA at various concentrations of BPA, adsorbent dosage range = 0.05 to 0.5 g L− 1, pH = 5, shaker speed = 275 rpm, T =
298.5 K.
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Journal of Water Process Engineering 53 (2023) 103623
removals of 100, 80, and 58 % for concentrations of 20, 60, and 100 mg
L− 1, respectively. Therefore, the dosage of 0.25 g L− 1 was selected for
the remaining experiments. When using biochar co-doped with Fe/Mn/
N, the authors also observed a similar behavior in the adsorption of BPA.
An increase in the dosage from 0.05 to 0.4 g L− 1 led to an increase in the
adsorption efficiency from 26 % to 80 % [49]. Moreover, very high
dosage amounts can generate agglomeration of the adsorbent particles,
generating overlap of the adsorption centers, which reduces the effective
contact area and prolongs the migration path of BPA [53].
3.2.3. Effect of ions
The effect of different ions (NaCl and Na2CO3) on the adsorption of
BPA onto ICYAN-PA was evaluated using varying dosages of ions, as
depicted in Fig. 6. As evident, increasing salt dosages tends to decrease
the percentage removal of BPA. Nevertheless, in the absence of salts,
NaCl and Na2CO3, exhibited a fixed removal of around 73 %. The
increasing ion concentration led to competing adsorption on the
adsorbent, which led decreased percent removal.
Moreover, the presence of ions in excessive amount may also affect
the isoelectric point of the adsorbent, depending on the nature of
different ions. Consequently, percent adsorption removal of BPA was
diminished. In general, ions influence on the adsorption represents a
Hofmeister reverse order. In addition, Cl− ions influences less than
CO2−3 [54–56].
3.3. Equilibrium and thermodynamic studies
Isothermal curves were produced by performing adsorption experi­
ments at three different temperatures, in order to assess the effectiveness
of the developed adsorbent (Fig. 7). In addition, these studies elucidate
the mechanisms of interactions that occur between the adsorbent and
the adsorbate and also allow the estimation of thermodynamic param­
eters. The curves are a function of the amount of BPA present on the
surface of ICYAN-PA (qe, mg g− 1), as a function of the adsorbate
T. Ahmad et al.
Fig. 6. Effect of ions on BPA adsorption, time = 240 min, Initial concentration = 20 ppm, rpm = 275, T = 298.5 K, adsorbent dosage = 0.25 g L− 1.
Fig. 7. Study of the adsorption isotherms of the BPA, adsorbent dosage = 0.25
g L− 1, pH = 5; shaker speed = 275 rpm, T = 298.5 K.
concentration in the aqueous medium (Ce). At varied adsorbent con­
centrations, the temperature was ranged from 298 to 318 K. Regardless
of temperature, both curves displayed similar and favorable adsorption
behavior with a propensity to plateau, suggesting that all the BPA
molecules in the solution tended to fit into the spaces available on the
surface of the adsorbent until the equilibrium is attained. With increase
in temperature from 298 to 318 K, the adsorption capacity, at the lowest
concentration of adsorbent used, increase from 136 to 232 mg g− 1
whereas it was increased 151 to 241 mg g− 1 at the highest concentration
studied. The progressive increase in the adsorbent concentration in so­
lution induces the transfer of BPA from the external surface to the pores,
this restarts the absorption process and also increases the chances of
7
Journal of Water Process Engineering 53 (2023) 103623
layered adsorption, facilitated by low energy π-π interaction in the initial
layer of adsorbed BPA, causing more absorption. The favoring of
adsorption at higher temperatures may be related to the increase in
solution viscosity, facilitating the diffusion of adsorbate molecules [57].
Earlier reports have suggested increase in the adsorption of BPA with
increase in temperature [49,58–62].
Isothermal data fit to the Langmuir, Freundlich, Dubinin-
Radushkevich, and Koble-Corrigan models are presented in Table 1.
First, when examining only the statistical adjustments for the co­
efficients R2 and R2adj, we found that the Koble-Corrigan isotherm (>
0.9941), the Langmuir isotherm (> 0.9915), the Dubinin-Radushkevich
(> 0.9784), and the Freundlich (> 0.8872) obtained the highest values.
After further analysis of the ARE and MSR values, it was found that the
Koble-Corrigan model had the lowest values, with ARE <1.4754 and
MSR < 26.86, while the Langmuir model showed values of ARE <3.326
and MSR < 52.35. Likewise, Dubinin-Radushkevich model displayed
least satisfactory fits with ARE <4.094 and MSR < 692, followed by the
Freundlich model with ARE <10.915 and MSR < 692, confirming the
best fit for the Koble-Corrigan model. Furthermore, the adsorption ca­
pacity values of the model are consistent with the values obtained
experimentally. Moreover, the capacity of the Koble-Corrigan model
increased from 240 to 260 mg g− 1 with increasing temperature in the
system. This model incorporates the Langmuir and Freundlich isotherms
to represent equilibrium adsorption data on heterogeneous surfaces
[40]. In addition, the Langmuir monolayer model also showed a good fit
where the capacity obtained by the model was 267 mg g− 1 at the highest
temperature studied.
Table 2 contains a list of the thermodynamic variables examined
during the adsorption of BPA in ICYAN-PA. These variables make it
possible to determine the spontaneity and nature of the adsorption
process. Regarding the Ke values, it was possible to observe that they
increased from 0.4639 × 10− 4 to 1.695 × 10− 4 as the system’s tem­
perature rose from 298 to 318 K, showing that the process was more
favorable at the higher temperature (318 K). The Gibbs energy
decreased from − 26.63 to − 31.84 kJ mol− 1, with the most negative
values at 318 K, showing that the adsorption of BPA was favorable and
T. Ahmad et al. Journal of Water Process Engineering 53 (2023) 103623

Table 1
Equilibrium parameters of BPA adsorption on ICYAN-PA.
Model Temperature (K)

298 308 318

Langmuir
qmL (mg g− 1) 250.7 261.3 267.7
KL (L mg− 1) 0.1981 0.3203 0.7382
R2 0.9957 0.9981 0.9979
R2adj 0.9915 0.9962 0.9959
ARE (%) 3.326 1.985 1.852
MSR (mg g− 1)2 52.35 24.60 27.93

Freundlich
KF ((mg g− 1)(mg L− 1)-1/nF) 144.5 151.9 160.4
1/nF (dimensionless) 0.1136 0.1136 0.1136
R2 0.9436 0.9606 0.9823
R2adj 0.8872 0.9212 0.9645
ARE (%) 10.915 8.933 5.890
MSR (mg g− 1)2 692.0 510.1 240.7

Dubinin-Radushkevich
qmDR (mg g− 1) 232.42 234.05 234.07 Fig. 8. Contact time, adsorbent dosage = 0.25 g L− 1, sample volume = 40 mL,
βx106 (kJ2 mol− 1) 3.5314 1.5579 0.3903 pH = 5, sample collection interval = 0–240 min, shaker speed = 275 rpm, T =
R2 0.9980 0.9952 0.9892
298.5 K.
R2adj 0.9961 0.9904 0.9784
ARE (%) 1.952 2.926 4.094
MSR (mg g− 1)2 24.12 62.05 146.9 of 20 and 100 mg L− 1 in 180 min, the capacity was 80 and 228 mg g− 1,
respectively. This behavior might be explained by the adsorbent’s strong
Koble-Corigan affinity for the BPA molecules. Additionally, the significant amount of
A (mg g− 1) × (L mg− 1)nKC 16.43 53.51 205.2 free space that is quickly occupied by the adsorbate in the first few
KKC (L mg− 1)nKC 0.068 0.216 0.786
minutes corresponds to the quick increase in adsorption capacity. Ad­
nKC (dimensionless) 1.683 1.335 0.807
qKC (mg g− 1) 240.0 247.3 260.9
sorbents with fast kinetics are extremely beneficial and advantageous for
R2 0.9998 0.9994 0.9985 practical applications when considering efficiency and financial gain
R2adj 0.9992 0.9975 0.9941 because they use less energy, maximizing operating time [65,66]. When
ARE (%) 0.5671 0.9803 1.4754 compared to other adsorbents that have been used in the literature, the
MSR (mg g− 1)2 3.674 12.05 26.86
kinetic time of the material studied in this paper exhibits fast kinetics.
When using heat-treated graphene oxides, a kinetic time of 300 min was
observed [67], and 48 h using commercial activated carbon [68].
Table 2 Kinetic data were fitted to Pseudo-first-order, Pseudo-second-order,
Thermodynamic parameters of BPA adsorption on ICYAN-PA. Elovich, and Avrami linear driving force (LDF) models (Table 3). When
T(K) Ke x10− 4
ΔG0 (kJ mol− 1) ΔH0 (kJ mol− 1) ΔS0 (kJ mol− 1
K− 1) analyzing the coefficients of determination (R2; R2adj), we observed that
298 0.4639 − 26.63 50.90 0.2595 the values closest to 1 were obtained by the Elovich model, followed by
308 0.7255 − 28.67 the Pseudo-second order and Pseudo-first order models. Obtaining the
318 1.695 − 31.84 same trend, the lowest values obtained for ARE (%) and MSR (mg g− 1)2
R2 = 0.9622, MSE = 0.0164. were achieved by the Pseudo-first order model, followed by the Avrami,
Pseudo-second order, and Elovich models, respectively. When analyzing
spontaneous. Th According to the isothermal studies, the enthalpy value the values of adsorption capacities, the Pseudo-first order model ob­
(ΔH0) remained positive (50.9 kJ mol− 1), confirming an endothermic tained values closer to those obtained experimentally, where an increase
process. [63]. Strong physical forces, such as electrostatic attraction, are from 81 to 296 mg g− 1 was observed with increasing BPA concentration,
consistent with the magnitude of ΔH0 [64]. Thus, it can be concluded which is in agreement with the experimental values. The best fit may be
that physisorption, which may be reversible and permit desorption, is related to the velocity constant (K1), where it presented a higher value in
the main process in this study. Furthermore, the high affinity for BPA the best fit model when compared to the others. This model assumes that
molecules on the surface of the adsorbent is confirmed by the positive the process is controlled by the diffusion step, which is also in line with
value of ΔS0 (0.2595 kJ mol− 1 K− 1). It is possible to find studies in the other reported studies on the adsorption of phenolic compounds
literature that adsorb endothermic BPA, using a variety of adsorbent [69–72]. The LDF model also showed a good statistical fit to the
materials [49,58–62]. experimental data, where the diffusivity and the model constant
increased with increasing BPA concentration. This is due to the gradient
increase at higher concentrations [73]. Similar behavior was also
3.4. Adsorption kinetics observed in other studies using carbonaceous materials in the adsorption
of emerging contaminants [73–75].
Kinetic studies were carried out with different concentrations of the
adsorbate to evaluate the performance of the ICYAN-PA adsorption 3.5. Adsorption mechanism
process and its equilibrium time. The time (t) was varied from 0 to 240
min for concentrations of 20 and 100 mg L− 1, using the adsorption ca­ There is a possibility of several factors can potentially contribute to
pacity (q). Fig. 8 depicts the kinetic curve profiles. The adsorption ca­ the BPA adsorption onto the ICYAN-PA surface which includes H-
pacity was first seen to rise independently of the adsorbate bonding and BPA hydrophobicity. The presence of two hydroxyl groups
concentration. The adsorption equilibrium was attained at around 180 in BPA and the presence of various hydroxyl groups and triazine rings in
min, regardless of the BPA concentration. As a result, for concentrations the ICYAN-PA makes the H-bonding a facile interaction for the

8
T. Ahmad et al. Journal of Water Process Engineering 53 (2023) 103623

Table 3 adsorption of BPA onto the ICYAN-PA surface. However, BPA remains
Kinetic parameters of BPA adsorption on ICYAN-PA. neutral till pH = 8 and in strongly alkaline conditions it loses both the
Model Bisphenol A initial Concentration (mg L− 1) hydrogens and turns into anionic form. Therefore, the interaction was
highest in the acidic media (pH = 5), but weakens as the pH of the media
20 100
was increased. Many other groups have attributed the adsorption of BPA
Pseudo-first order to H-bonding [76–78]. The adsorption mechanism of BPA is thought to
q1 (mg g− 1) 81.34 296.3
k1 (min− 1) 0.02122 0.007455
occur mainly through H-bonding, hydrophobic interactions, π-π in­
R2 0.9925 0.9889 teractions, and specific surface area, and adsorption could be achieved
R2adj 0.9824 0.9739 through one or more of these mechanisms, the proposal of the adsorp­
ARE (%) 5.924 6.159 tion mechanism is represented by the Fig. 9.
MSR (mg g− 1)2 6.281 79.76

3.6. Desorption and regeneration

Pseudo-second order
q2 (mg g− 1) 100.9 451.9
k2 x104 (g mg− 1 min− 1) 2.1802 11.47
Regeneration of adsorbent is important from a commercialization
R2 0.9875 0.9863 point of view as it reduces the total cost of the adsorption. Desorption
R2adj 0.9707 0.9679 and regeneration of ICYAN-PA were carried out for five consecutive
ARE (%) 5.582 6.244 cycles wherein the desorption was carried out by washing resin with 1 M
MSR (mg g− 1)2 10.44 90.81
NaOH. The adsorbent was then washed with deionized (DI) water and
dried for 3 h at 70 ◦ C. The dried sorbent was reused for another cycle and
Avrami the process was repeated for five cycles. As clear from the graph, the
qAv (mg g− 1) 80.00 232.48
adsorption capacity of ICYAN-PA for BPA was slightly decreased from
kAv10− 2 (min− 1) 2.269 0.2837
nAv (dimensionless) 0.993 1.310 100 % to 94.1 % after the five consecutive cycles (Fig. S4). This indi­
R2 0.9920 0.9861 cated extreme stability and effectiveness of ICYAN-PA toward the
R2adj 0.9794 0.9642 adsorption of BPA.
ARE (%) 5.818 13.68
The maximum adsorption capacity (qmax) of ICYAN-PA was
MSR (mg g− 1)2 7.272 108.9
compared with common functionalized adsorbents as displayed in
Table 4. It is evident, the adsorption capacity of the ICYAN-PA was
LDF-KC
higher or comparable to the most of the commonly applied adsorbent
qe (mg g− 1) 79.74 220.0
kLDF x105 (s− 1) 9.024 17.87 and recently reported adsorbents (Table 4). The high qmax of 260 mg g− 1
DS x1017(cm2 s− 1) 3.813 7.553 (isotherm Koble-Corrigan) and effective reusability of ICYAN-PA
R2 0.9798 0.9738 compared to other reported adsorbents makes it a strong candidate for
R2adj 0.9566 0.9439 practical application.
ARE (%) 17.68 8.815
MSR (mg g− 1)2 15.66 174.3
qexp (mg g− 1) 80.00 232.48

Fig. 9. The proposed mechanism of adsorption of BPA onto ICYAN-PA.

9
T. Ahmad et al. Journal of Water Process Engineering 53 (2023) 103623

Table 4 dipicolylamine (DPA), ChemistrySelect 5 (17) (May 2020) 5300–5305, https://doi.

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