Materials Chemistry and Physics 238 (2019) 121824

Contents lists available at ScienceDirect

Materials Chemistry and Physics

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

Paraquat adsorption on NaY zeolite at various Si/Al ratios: A combined

experimental and computational study
Chalermpan Keawkumay a, Wina Rongchapo a, b, Narongrit Sosa a, Suwit Suthirakun a,
Iskra Z. Koleva c, Hristiyan A. Aleksandrov c, **, Georgi N. Vayssilov c, Jatuporn Wittayakun a, *
a
School of Chemistry, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima, 30000, Thailand
b
School of Environmental Health, Institute of Public Health, Suranaree University of Technology, Nakhon Ratchasima, 30000, Thailand
c
Faculty of Chemistry and Pharmacy, University of Sofia, Blvd. J. Bauchier 1, 1126, Sofia, Bulgaria

H I G H L I G H T S G R A P H I C A L A B S T R A C T

� NaY zeolites with Si/Al ratios from 2.15

to 2.40 were synthesized.
� The zeolites had paraquat adsorption
capacity from 210 to 240 mg/g-
adsorbent.
� NaY zeolite with the highest crystal­
linity had the highest adsorption
capacity.
� Interaction between paraquat and the
zeolite is investigated by DFT
calculations.
� Paraquat located close to the negatively
charged of the zeolite framework.

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

Keywords: NaY samples in the crystalline form with Si/Al ratios from 2.15 to 2.40 were synthesized as adsorbents for
NaY zeolite paraquat. Their surface areas, particle size, concentration of basic sites decreased with an increase of Al content
Si/Al ratio in the synthesis gel. The interaction between paraquat molecule and NaY zeolite was investigated by periodic
Paraquat adsorption
DFT calculations to understand the adsorption behavior. Paraquat adsorption by all samples fit with Langmuir
DFT calculations
model. The capacity of the adsorbents was in the range of 210–240 mg/g-adsorbent, higher than NaY in the
previous reports. After paraquat adsorption, the surface areas of the samples decreased from around 800 to
30 m2/g indicating that paraquat adsorbed inside the zeolite pores. FAU samples with the highest Si/Al ratio
(2.40) had the highest adsorption capacity in line with the results from the DFT calculations. The paraquat
molecules located close to the negatively charged fragments of the zeolite framework, due to the electrostatic
interaction with the positively charged ammonia groups of the organic molecule.

1. Introduction Nakhon Ratchasima province which has the largest agricultural area in
the country [1]. Paraquat is toxic [2] and could easily contaminate
A herbicide paraquat has been widely used in Thailand including water due to its high solubility. Thus, it is necessary to investigate

* Corresponding author.
** Corresponding author.
E-mail addresses: haa@chem.uni-sofia.bg (H.A. Aleksandrov), jatuporn@sut.ac.th (J. Wittayakun).

https://doi.org/10.1016/j.matchemphys.2019.121824
Received 5 October 2018; Received in revised form 29 April 2019; Accepted 7 July 2019
Available online 10 July 2019
0254-0584/© 2019 Elsevier B.V. All rights reserved.
C. Keawkumay et al.
paraquat removal from aqueous solution as a proposed method for
environmental management.
Various sorbents have been studied for paraquat adsorption
including clay, activated carbon, ordered mesoporous materials and
zeolites [3–10]. Those materials are different in pore structure, surface
area and Si/Al ratio. From our previous works on silica-based adsor­
bents, the adsorption capacity depends on Al content to some extent.
The capacity is ranked in the following order: NaY > NaY/SBA-15
composite > NaBEA > NaX > Al-MCM-41 > MCM-41 > rice husk silica
[5,7,8,10]. The presence of Al in the mesoporous Al-MCM-41 leads to
increase of the adsorption capacity compared to the silicate MCM-41
sample [5,7]. NaY has larger Al content thus larger adsorption capac­
ity than NaBEA [5]. In contrast, NaX which has the same faujasite
structure and more Al content than NaY has the smaller adsorption ca­
pacity. The interaction of sodium ions with the AlO‾4 tetrahedra in the
cavity of NaX is stronger than that in NaY, thus, making them less
exchangeable with paraquat [10].
From the previous works mentioned above, one can conclude that
NaY is the best adsorbent for paraquat among the studied ones. Thus,
our main goal in the current study is to improve its adsorption capacity.
Two strategies are employed: changing the Si/Al ratio and modifying the
synthesis method to produce NaY with a smaller crystal size. Periodic
calculations based on Density Functional Theory (DFT) were also per­
formed to achieve a better understanding on the interaction between
NaY zeolite and the paraquat molecule. Hence, we modeled various
structures with different Si/Al ratios loaded with up to four paraquat
molecules in one unit cell.
Changing aluminum content in the framework of zeolite Y provides a
way of controlling the properties and the sorption capacity [11]. Zeolite
Y can be synthesized with lower and higher critical point of Si/Al value
[12]. Ferchiche et al. [13] synthesized zeolite Y with Si/Al ratios from
1.7 to 2.1 using different amounts of silica. The lattice parameter
decreased with the increasing of silica content indicating the less
incorporation of Al atoms in the faujasite framework due to the longer
Al-O bond length in tetrahedral units than the Si-O [13]. Qiang et al.
[14] also studied the effect of Si/Al ratio in the range of 2.6–3.1 on the
crystallinity of NaY zeolite. The crystallinity remained constant at the
Si/Al ratio of 2.6–2.8 but decreased significantly with increasing of the
water content in the reaction mixture at Si/Al ratio of 2.8–3.0. In this
work, NaY samples will be synthesized with Si/Al ratio between 1.8 and
2.4.
Another approach to improve the adsorption capacity is changing the
zeolite synthesis gel composition. Variation of water content in the
synthesis gel could lead to zeolites with different crystal size, surface
charge, hydrophilicity and external surface activity [15,16]. In this work
NaY samples will be synthesized with a smaller amount of water than
that reported by Rongchapo et al. [5,10].
Besides the main goal to improve the adsorption capacity, the in­
teractions between paraquat and zeolite Y with different Si/Al ratios are
studied to understand the adsorption behavior. DFT method is an
effective and reliable tool to complement experimental results. For
instance, there are several examples showing that DFT can be used for
modeling of zeolite systems and clarifying various experimental data
related to the interaction of zeolites with organic molecules [17–20].
2. Experimental
2.1. Materials
Chemicals for NaY synthesis were rice husk silica, sodium aluminate
Riedel-de Ha€en®, 41.383% Na2O, 58.604% Al2O3), sodium hydroxide
(97%wt NaOH, Carlo-Erba). Commercial grade paraquat solution (27.6
%w/v, Masda) was employed in the adsorption study and the solid
chemical grade (99.9 %w/w, Fluka) was used to verify the actual
concentration.
2
Materials Chemistry and Physics 238 (2019) 121824
2.2. Synthesis and characterization of NaY zeolites
NaY zeolite samples with Si/Al ratio from 1.8 to 2.4 were synthesized
with a procedure modified from that by Wittayakun [21]. Sodium sili­
cate solution was prepared by dissolving 57.40 g of rice husk silica in
NaOH solution prepared from dissolving 23.00 g of NaOH in 119.60 g of
deionized (DI) water. A seed gel with a molar ratio of 10.67Na2O:1A­
l2O3:10SiO2:180H2O was prepared by dissolving 4.09 g of NaOH in
20.00 g of DI water in a polyethylene (PE) bottle followed by and
addition of a desired amount of anhydrous NaAlO2 to the NaOH solu­
tion. The mixture was stirred for 10 min until the solution became clear.
After that 22.72 g of the Na2SiO3 solution was added and the mixture
was stirred for 10 min, capped, and aged at room temperature for 24 h.
A feedstock gel with molar ratio 4.3Na2O:1Al2O3:10SiO2:180H2O
was prepared with the procedure similar to that of the seed gel except
that it was used immediately without aging. In brief, 0.14 g of NaOH was
dissolved in 131.97 g of DI water in a PE bottle, then, a desired amount
of sodium aluminate was added, stirred for 10 min and at the end
143.43 g of sodium silicate solution was added. The overall gel com­
positions and names of the synthesized NaY samples from various gel
ratios are summarized in Table S1 (Supplementary data). Note that the
gel composition used in this work was different from the one in the work
of Rongchapo et al. [5,10]. The main difference is that their gel
composition contains a larger amount of water.
The Si/Al ratios of the products were determined by X-ray fluores­
cence spectroscopy (ED-XRF, Horiba 5200). Morphologies of the NaY
were studied by scanning electron microscopy (SEM, CARL ZEISS-
AURIGA). The zeolite basicity was determined by temperature-
programmed desorption of carbon dioxide (CO2-TPD) in a Belcat-B
equipped with a thermal conductivity detector.
Bare and paraquat containing NaY zeolite samples were character­
ized by X-ray diffraction (XRD, Bruker D8 ADVANCE) with a Cu Kα
radiation. N2 adsorption-desorption isotherms were obtained at a liquid
nitrogen temperature from a Bel Sorp mini II. The surface area was
calculated using a Brunauer–Emmett–Teller (BET) method. Functional
groups of all adsorbents before and after adsorption of paraquat
(500 mg/L) were determined by a Fourier transform infrared spectros­
copy (FTIR, Perkin Elmer Spectrum GX) using KBr pellet technique with
2 cm 1 resolution.
2.3. Adsorption of paraquat
The adsorption procedure was done as described in the literature [5].
Each adsorbent (0.05 g) was added into 20 mL of paraquat solution with
a concentration ranging from 100 to 1500 mg/L in a 125-mL poly­
propylene bottle. The mixture was stirred for 60 min with mixing speed
of 400 rpm at room temperature (25 � C). As shown in Fig. S1 (Supple­
mentary data), paraquat adsorbed rapidly on NaY samples and equi­
librium was reached in 5 min. The adsorption time of 60 min was used in
the study to ensure that the system was in equilibrium. The solution was
collected using a 0.45 μm syringe filter. The remaining paraquat con­
centration was determined using a UV–Vis spectrophotometer (Varian
CARY 300) at 257 nm. The effect of pH was investigated with the same
procedure using 500 mg/L of paraquat solution at various pH (1, 3, 5
(as-prepared), 7, 9). The amount of paraquat adsorbed at equilibrium
(qe) was calculated by the equation below [22,23].
ðC0 Ce Þ � V
qe ¼
w
C0 and Ce are the initial and equilibrium concentration of paraquat (mg/
L), respectively. V is the volume of paraquat solution (L) and w is the
amount of adsorbent (g).
Maximum adsorption capacity of paraquat on NaY samples was
determined based on Langmuir isotherm shown below [22,23].
C. Keawkumay et al. Materials Chemistry and Physics 238 (2019) 121824

Ce 1 Ce 3.2. Properties of NaY zeolite before and after paraquat adsorption

¼ þ
qe KL qm qm
KL is the Langmuir constant related to the affinity of binding site (L/mg)
and qm is the maximum adsorption capacity (mg/g). Both KL and qm can
be determined from the linear plot of Ce/qe versus Ce.
2.4. Computational model
The interaction between paraquat molecule and NaY zeolite struc­
ture was performed by periodic DFT calculations with the PW91
exchange-correlation functional [24] using Vienna ab initio simulation
package, VASP [25,26]. Ultrasoft pseudopotentials [27,28] were used as
implemented in the VASP package. Due to the large unit cell (see below)
the Brillouin zone was sampled using only the Γ point [29]. The valence
wave functions were expanded in a plane-wave basis with a cutoff en­
ergy of 400 eV.
The rhombic unit cell of the FAU-type zeolite framework [30] was
optimized for the pure silicate structure containing 48 crystallographi­
cally equivalent T atoms with dimensions a ¼ b ¼ c ¼ 17.34 Å and
α ¼ β ¼ γ ¼ 60� .
3. Results and discussion
3.1. Si/Al ratio, morphology and basicity of NaY zeolites
The Si/Al ratios of the synthesized NaY samples are shown in
Table 1, in the range of FAU-type zeolite NaY [12]. The morphologies of
NaY zeolite samples obtained by SEM are shown in Fig. 1. All samples
composed of small particles with uniform size lower than 1 μm. The size
of individual crystals, of which each particle is composed, is approxi­
mately 100–200 nm. However, the particle size of NaY samples with a
higher Al content becomes smaller, due to the higher alkalinity of the
synthesis gel. Similarly, there are several reports for the synthesis of
nanozeolites with small crystal sizes (10–100 nm) [15,31,32]. These
results are compared with NaY with the Si/Al ratio of 2.2 synthesized
with a larger amount of water (256H2O) in the gel [10]. In this study the
gel with less amount of water (180H2O) produces the zeolite with
smaller crystals which might improve the zeolite textural properties
leading to increased adsorption capacity.
The CO2-TPD profiles of NaY samples are shown in Fig. S2 in Supple­
mentary data. All NaY samples showed one peak between 190 and 370 � C
contributing to a weak basicity [33]. As shown in Table 1, the amount of
total basic sites decreased as the Al content increased. Typically, oxygen
atoms in the framework of zeolites are intrinsic Lewis basic sites which
form acid-base pairs with the charge compensating cations [34].
XRD patterns of all NaY zeolite samples before and after paraquat
adsorption (Fig. 2a and b, respectively) were similar to those of the
standard NaY zeolite [35]. Sharp peaks indicated that all samples were
in a crystalline form. Other zeolite phases were not observed. After
paraquat adsorption, all peak positions remained the same. However,
intensity ratio of the plane (220) and (311), I(220)/I(311) decreased
significantly indicating an incorporation of paraquat in the zeolite
supercages which changes the distribution of sodium ions (Naþ) [36,
37]. Such change is an evidence of ion exchange. Similar results are
reported on NaY and NaX zeolites [5,10]. As shown in Table 1, the
crystal size and the crystallinity of NaY zeolite decreased with increasing
Al content because amorphous phase occurred. This effect led to less
adsorption sites in the zeolite sample.
Nitrogen adsorption-desorption isotherms of all NaY samples are
shown in Fig. 3a–e. All samples possessed a type I isotherm. A high
nitrogen uptake at low relative pressure (P/P0 ¼ 0.0–0.1) indicated that
a monolayer adsorption was achieved at low relative pressure. After a
nearly constant uptake, a steep adsorption step appears at
P/P0 ¼ 0.9–1.0, related to the narrow pore size distributions [38]. The
BET surface area (SBET) of NaY zeolite samples increased with increasing
of the Al content (Table 1). The external surface area (SEXT) increased
with Al content probably due to the decrease in crystallinity and crystal
size. All samples have similarly micropore volume (VMicro).
The isotherm of all paraquat containing NaY samples are shown in
Fig. 3a–e. The nitrogen uptake at low P/P0, BET surface area and
micropore volume decreased significantly (Table 1) confirming that
paraquat occupied micropores of NaY. These results are consistent with
the previous report [10] but the percent decrease of surface area in this
study is higher. Thus, NaY zeolite synthesized with the less amount of
water had the higher paraquat adsorption capacity.
Fig. 4a and b shows FTIR spectra of the pristine NaY samples and the
samples with adsorbed paraquat. The assignments are summarized in
Table S2 in the Supplementary data. All samples showed typical peaks of
NaY zeolite. After adsorption, the measurement by KBr method at an
ambient condition did not show clear evidence of the interaction be­
tween paraquat and NaY zeolite samples. The paraquat peaks around
2990-2850 cm 1 were also observed in some samples (NaY1-PQ and
NaY3-PQ) and seemed to shift to higher wavenumber. The strongest
peak of paraquat at 1645 cm 1 overlapped with the hydroxyl of water.
The peaks at 1639, 1504, and 1459 cm 1 were observed on some sam­
ples and did not shift [39]. The paraquat peak at 815 cm 1 was not
observed from all paraquat-containing NaY samples.

Table 1
Properties of pristine zeolite samples including Si/Al ratio, crystal size, relative crystallinity, BET surface area (SBET), micropore volume (VMicro), external surface area
(SExt); porosity of NaY samples with adsorbed paraquat; Langmuir parameters of paraquat adsorption on NaY samples with various Si/Al ratios compared to NaYa
sample obtained from Rongchapo et al. [5,10].
Sample Si/Al Total Crystal % Relative NaY Paraquat-adsorbed NaY Langmuir parameters
ratioa basicity size (nm)b crystallinityc
SBET VMicro Sext SBET VMicro Sext qm (mg/g) KL (L/ R2
(mmol/g)
(m2/g) (cm3/g) (m2/ (m2/g) (cm3/g) (m2/ mg)
g) g)

NaY1 2.40 0.274 42.16 100.00 789 0.29 47 21 0.01 10 234.40 � 1.36 0.0462 0.9771
NaY2 2.31 0.252 41.43 98.93 804 0.30 51 24 0.01 11 228.30 � 1.35 0.0445 0.9760
NaY3 2.25 0.222 38.81 97.53 844 0.31 56 27 0.01 12 222.83 � 1.68 0.0435 0.9721
NaY4 2.19 0.212 37.83 93.30 849 0.31 61 29 0.02 14 214.35 � 1.46 0.0438 0.9724
NaY5 2.15 0.192 36.24 89.50 856 0.31 63 39 0.02 15 208.23 � 1.46 0.0423 0.9696
NaYd 2.20 N/Ae N/Ae N/Ae 870 N/Ae N/Ae 92 N/Ae N/Ae 185 N/Ae 0.9997
a
From XRF.
b
From XRD using Scherrer equation.
c
From XRD.
d
From Rongchapo et al. [5,10].
e
Not Reported.

3
C. Keawkumay et al.
Fig. 1. SEM images of NaY zeolite samples with various Si/Al ratios, i.e., 2.40 (NaY1), 2.31 (NaY2), 2.25 (NaY3), 2.19 (NaY4) and 2.15 (NaY5).
Fig. 2. XRD pattern of (a) NaY zeolite samples with various Si/Al ratios, i.e.,
2.40 (NaY1), 2.31 (NaY2), 2.25 (NaY3), 2.19 (NaY4) and 2.15 (NaY5) and (b)
NaY zeolite samples after paraquat adsorption.
4
Materials Chemistry and Physics 238 (2019) 121824
3.3. Adsorption capacity of paraquat
The amount of paraquat adsorbed on all NaY samples at various
equilibrium concentrations is shown in Fig. 5. The adsorbed amount on
all NaY adsorbents increased rapidly at low equilibrium concentrations
indicating that the interaction was chemisorption. The isotherms of
paraquat adsorbed on NaY samples based on Giles classification were
class H (high affinity) sub-group 2 which is a strong adsorption [40]. The
adsorption curve tended to be a plateau, which for adsorption on surface
indicates formation of a monolayer, while in paraquat sorption in the
zeolite pores indicates occupations of sorption positions with similar
binding affinity. The similar adsorption behavior is reported on NaY and
NaX zeolites [5,7].
We noticed that the amount of paraquat adsorbed in the various
samples is different at high paraquat concentrations (>100 mg/L). A
possible explanation is that paraquat adsorbs on NaY by ion exchange
with Naþ ions, according to the XRD results [10]. Osakoo et al. [9]
proposed that C and N atoms in the paraquat molecules interacted with
oxygen centers from NaY-SBA-15 composite.
Paraquat adsorption on NaY samples followed Langmuir isotherms
indicating a sorption at sites with uniform binding affinity. The Lang­
muir parameters are summarized in Table 1. The sample with a higher
Si/Al ratio has a higher maximum adsorption capacity (qm) and KL value
indicating a higher affinity of paraquat to the binding sites [40]. This
trend is opposite to the trend of surface area indicating that changing
Si/Al ratio is the main key to improve the adsorption capacity.
The pH influences on the adsorption of paraquat (Fig. S3 in supple­
mentary data). We found that the lowest pH of 3 correspond to the
lowest adsorption capasicty due to the competition between Hþ cations
and paraquat to the adsorption sites. Increasing of pH from 3 to 9 leads
to increasing of the adsorption capacity of NaY samples towards para­
quat due to the loss of Brønsted acidic sites in the zeolite samples. A
similar effect is reported on adsorption of paraquat on silica [39].
In comparison with the previous work [5] that the NaY with the Si/Al
ratio of 2.20 shows the qm value of 185 mg/g-adsorbent. In this work,
the NaY with the Si/Al ratio of 2.19 gave the qm value of 214
mg/g-adsorbent. Both samples were synthesized with different amount
of water in gel composition [5] and had different crystal size. Hence, we
can conclude that the modification of zeolite synthesis is another way to
increase the adsorption capacity.
According to the number of supercages per gram in NaY zeolite and
the computational result (see below) that two paraquat molecules can be
accommodated in one supercage, we may estimate that 7.26 � 1020
C. Keawkumay et al.
Fig. 3. Nitrogen sorption isotherms of pristine NaY zeolite samples with various Si/Al ratios, i.e., 2.40 (NaY1), 2.31 (NaY2), 2.25 (NaY3), 2.19 (NaY4) and 2.15
(NaY5) and NaY zeolite samples with adsorbed paraquat: (a) NaY1 and NaY1-PQ, (b) NaY2 and NaY2-PQ, (c) NaY3 and NaY3-PQ, (d) NaY4 and NaY4-PQ, and (e)
NaY5 and NaY5-PQ.
paraquat molecules can be sorbed per gram zeolite. For the sample with
the highest sorption the amount of paraquat is 5.45 � 1020 molecules, i.
e. by about 25% lower than the maximal amount. As discussed above,
the maximal sorption capacity of the five samples decreases in the order
NaY1 to NaY5, which is also in line with decreasing percentage of
crystallinity, as shown in Table 1.
3.4. Computational results of paraquat adsorption in supercage of NaY
zeolite
FAU structure was modeled by insertion 8, 12, 14, 16, and 22 Al
centers in the unit cell, which corresponds to Si/Al ratio of 5.0, 3.0, 2.4,
2.0, and 1.2, respectively. The charge compensation of the negative
charge around Al centers in the framework is accomplished by sodium
cations. For all structures ion exchange with 1, 2, and 4 paraquat dica­
tions was considered as in each case one paraquat dication replaced two
Naþ cations located in the corresponding region. Note that one may not
expect quantitative agreement between experiment and the modeling
due to various possible factors that may influence the experimental
measurements, which cannot be adequately accounted by the
5
Materials Chemistry and Physics 238 (2019) 121824
computational modeling.
To estimate the preference for the process of exchange of Naþ cations
in NaY structures with different Si/Al ratios by one or more paraquat
dications we used the structure with the Si/Al of 5 (with eight aluminum
ions per unit cell, denoted as NaY-5.0-6Na-PQ) as a reference. For the
equilibria with one paraquat, the energies are calculated as follow:
ΔE1 ¼ E(NaY-5.0-6Na-PQ) þ 2 � E(Naþ) – E(NaY-5.0-8Na) – E(PQ)
ΔE2 ¼ E(NaY-3.0-10Na-PQ) þ 2 � E(Naþ) – E(NaY-3.0-12Na) – E(PQ)
Erel(1PQ) ¼ ΔE2 – ΔE1
In this way the energy contributions of the solvated sodium and
paraquat ions are canceled and Erel is an estimate for the preference for
exchange of sodium ions by paraquat compared to NaY zeolite with the
Si/Al ratio of 5.0. A negative value suggests higher preference for
incorporation of paraquat. Negative energy values were obtained for the
zeolites with Si/Al ratio from 1.2 to 3 (Table 2). These results suggested
that the structure with higher Al content will have a higher preference to
exchange sodium by paraquat as the maximal preference, 0.64 eV,
corresponding to the model with the Si/Al ratio of 2.0. This is consistent
C. Keawkumay et al.
Fig. 4. FTIR spectra of (a) the pristine NaY zeolite samples with various Si/Al
ratios, i.e., 2.40 (NaY1), 2.31 (NaY2), 2.25 (NaY3), 2.19 (NaY4) and 2.15
(NaY5) and (b) NaY samples with adsorbed paraquat.
Fig. 5. Adsorption isotherms of paraquat in NaY zeolite samples with various
Si/Al ratios i.e., 2.40 (NaY1), 2.31 (NaY2), 2.25 (NaY3), 2.19 (NaY4) and
2.15 (NaY5).
6
Materials Chemistry and Physics 238 (2019) 121824
with the experimental results from this work and previous works [5,7,
10] that adsorption occurs quickly at a low paraquat concentration.
For the equilibria with two paraquat molecules, the energies are
calculated in a similar way:
ΔE3 ¼ E(NaY-5.0-4Na-2PQ) þ 4 � E(Naþ) – E(NaY-5.0-8Na) – 2 � E(PQ)
ΔE4 ¼ E(NaY-3.0-8Na-2PQ) þ 4 � E(Naþ) – E(NaY-3.0-12Na) – 2 � E(PQ)
Erel(2PQ) ¼ ΔE4 – ΔE3
In all cases positive relative energy (Erel(2PQ)) is obtained (Table 2),
as it is particularly high for the zeolite structures with lowest Si/Al ratio,
2.0 and 1.2. These results agree with the previous experimental results
[7,10] that the adsorption capacity on NaY is higher than that on NaX, as
well as with the results reported here.
In the modeled complexes with four paraquat ions per unit cell
additional interactions between the sorbed molecules occur and the
analysis of the energy trends becomes very complicated and is not dis­
cussed. Such paraquat loading, however, correspond to the results re­
ported by Rongchapo et al. [10] that the number of paraquat cations per
supercage of NaX and NaY were 1 and 2 ions, respectively, meaning that
the number of cations per unit cell were 2 and 4, respectively.
As expected, in the optimized structures of the paraquat in the zeolite
pores the positively charged parts of the paraquat are located close to the
negatively charged fragments of the zeolite framework as in this way the
electrostatic interaction is maximized (Fig. 6). The calculated distances
between nitrogen centers of the paraquat and the aluminum centers of
the framework for most of the structures with one sorbed paraquat
molecule are in the range 450–520 pm. The shortest distances between
the carbon centers of the methyl groups and the aluminum centers of the
framework are in the range 390–450 pm. In all structures weak
hydrogen bonds between the paraquat hydrogen atoms and zeolite ox­
ygen centers around Al in the framework are formed (see Fig. 6b–d).
The shape of the paraquat molecules in the zeolite pores depends on
the loading. For models with one or two sorbed molecules per unit cell
both carbon atoms connecting the pyridine rings and the nitrogen cen­
ters in each ring are located essentially on one line. In the structures with
higher loading, four molecules per unit cell, this line is distorted and the
molecules are bent due to too close location of the neighboring
molecules.
4. Conclusions
Zeolites NaY with Si/Al ratios in the range of 2.1–2.4 were synthe­
sized by hydrothermal method. All samples were in crystalline form with
particle sizes in the range of 100–300 nm. Zeolite samples had smaller
crystal sizes than those in previous works due to the lower amount of
water in the synthesis gel. The surface areas of NaY zeolite samples
prepared in the current study were in the range 789–856 m2/g. The
surface area increased with increasing of the Al content. The sample
with the highest Si/Al ratio (lowest Al content) had the highest basicity
(0.274 mmoL/g). The adsorption of paraquat on NaY samples followed
the Langmuir model. The capacity of the adsorbents was in the range of
210–240 mg/g-adsorbent. NaY sample with the highest investigated Si/
Al ratio 2.4 had the highest adsorption capacity. When paraquat was
introduced in the zeolite cavities, the surface area of the samples
Table 2
Relative energy, Erel (in eV), calculated as described in the text for exchange of
Naþ by paraquat in zeolite structures with various Si/Al ratios containing
different amount of paraquat in supercage.
Si/Al Erel (1PQ) Erel (2PQ)
3.0 0.02 0.43
2.4 0.41 0.10
2.0 0.64 2.25
1.2 0.52 2.57
C. Keawkumay et al.
Fig. 6. Structures of pristine NaY zeolite (a) and zeolite with one (b), two (c) and four (d) sorbed paraquat molecules per unit cell. Color coding of different centers is
shown in panel b: Al – green, Na – yellow, C – black, N – blue, H – light pink; Si and O centers are not shown. (For interpretation of the references to colour in this
figure legend, the reader is referred to the Web version of this article.)
decreased significantly from about 800 to about 30 m2/g. In addition,
the interaction between paraquat molecule and NaY zeolite structure
was studied by periodic DFT calculations to understand the adsorption
behavior. Our results showed that in case of one paraquat dication, the
structures with higher Al contents are more prone to exchange sodium.
For instance, NaY with Si/Al ratio 2.4 is the most favorable to exchange
sodium by paraquat. Our finding that the paraquat molecules prefer to
be located close to the negatively charged fragments of the zeolite
framework is consistent to the electrostatic interaction between the
organic molecule and the zeolite framework.
Acknowledgement
Chalermpan Keawkumay is supported by Suranaree University of
Technology (SUT-PhD Scholarship and Full-Time Doctoral Researcher
Grants). Narongrit Sosa is supported by the Science Achievement
Scholarship of Thailand (SAST). .Iskra Z. Koleva, Hristiyan A. Aleksan­
drov and Georgi N. Vayssilov acknowledge the support by European
Union’s Horizon 2020 programme (“Materials Networking” project,
grant agreement No 692146) for networking with the partner team and
the COST Action MP1306. Iskra Z. Koleva and Hristiyan A. Aleksandrov
also acknowledge the financial support by the Bulgarian Science Fund
(project DCOST01/18).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.matchemphys.2019.121824.
References
[1] Office of Agricultural Economics, Agricultural Statistics of Thailand 2016, Ministry
of Agriculture and Cooperatives, 2017. http://www.oae.go.th/download/downloa
d_journal/2560/yearbook59.pdf. (Accessed 4 May 2018).
[2] Z.E. Suntres, Role of antioxidants in paraquat toxicity, Toxicology 180 (2002)
65–77.
7
Materials Chemistry and Physics 238 (2019) 121824
[3] N.K. Hamadi, S. Swaminathan, X.D. Chen, Adsorption of Paraquat dichloride from
aqueous solution by activated carbon derived from used tires, J. Hazard Mater. 112
(2004) 133–141.
[4] Y. Seki, K. Yurdakoç, Paraquat adsorption onto clays and organoclays from
aqueous solution, J. Colloid Interface Sci. 287 (2005) 1–5.
[5] W. Rongchapo, O. Sophiphun, K. Rintramee, S. Prayoonpokarach, J. Wittayakun,
Paraquat adsorption on porous materials synthesized from rice husk silica, Water
Sci. Technol. 68 (2013) 863–869.
[6] J.M. Sieliechi, P.S. Thue, Removal of paraquat from drinking water by activated
carbon prepared from waste wood, Desalin. Water. Treat. 55 (2015) 986–998.
[7] W. Rongchapo, K. Deekamwong, S. Loiha, S. Prayoonpokarach, J. Wittayakun,
Paraquat adsorption on NaX and Al-MCM-41, Water Sci. Technol. 71 (2015)
1347–1353.
[8] C. Keawkumay, S. Rakmae, W. Rongchapo, N. Suppakarn, S. Prayoonpokarach,
J. Wittayakun, Adsorption of paraquat and pirimiphos-methyl by montmorillonite
modified with tetradecylammonium chloride and intragallery templating method,
Adsorpt. Sci. Technol. 35 (2017) 357–371.
[9] N. Osakoo, C. Pansakdanon, N. Sosa, K. Deekamwong, C. Keawkumay,
W. Rongchapo, S. Prayoonpokarach, J. Wittayakun, Characterization and
comprehension of zeolite NaY/mesoporous SBA-15 composite as adsorbent for
paraquat, Mater. Chem. Phys. 193 (2017) 470–476.
[10] W. Rongchapo, C. Keawkumay, N. Osakoo, K. Deekamwong, N. Chanlek,
S. Prayoonpokarach, J. Wittayakun, Comprehension of paraquat adsorption on
faujasite zeolite X and Y in sodium form, Adsorpt. Sci. Technol. 36 (2018)
684–693.
[11] J. Kaduk, J. Faber, Crystal structure of zeolite y as a function of ion exchange,
Rigaku J 12 (1995) 14–34.
[12] W. Lutz, Zeolite Y: synthesis, modification, and properties-A case revisited, Ann.
Mater. Sci. Eng. 2014 (2014) 1–20.
[13] S. Ferchiche, J. Warzywoda, A. Sacco Jr., Direct synthesis of zeolite Y with large
particle size, Int. J. Inorg. Mater. 3 (2001) 773–780.
[14] L. Qiang, Z. Ying, C. Zhijun, G. Wei, C. Lishan, Influence of synthesis parameters on
the crystallinity and Si/Al ratio of NaY zeolite synthesized from kaolin, Pet. Sci. 7
(2010) 403–409.
[15] S. Mintova, J. Grand, V. Valtchev, Nanosized zeolites: quo Vadis? C. R. Chim. 19
(2016) 183–191.
[16] R. Tekin, N. Bac, J. Warzywoda, A. Sacco Jr., Encapsulation of a fragrance
molecule in zeolite X, Micropor. Mesopor. Mater. 215 (2015) 51–57.
[17] Y. Wang, Q. Wu, X. Meng, F.S. Xiao, Insights into the organotemplate-free synthesis
of zeolite catalysts, Eng. Times 3 (2017) 567–574.
[18] M. Popova, I. Trendafilova, A. Szegedi, J. Mihaly, P. Nemeth, S.G. Marinova, H.
A. Aleksandrov, G.N. Vayssilov, Experimental and theoretical study of quercetin
complexes formed on pure silica and Zn-modified mesoporous MCM-41 and SBA-
16 materials, Micropor. Mesopor. Mater. 228 (2016) 256–265.
[19] K.-H. Tan, H. Awala, R.R. Mukti, K.-L. Wong, B. Rigaud, T.C. Ling, H.
A. Aleksandrov, I.Z. Koleva, G.N. Vayssilov, S. Mintova, E.-P. Ng, Inhibition of
palm oil oxidation by zeolite nanocrystals, J. Agric. Food Chem. 63 (2015)
4655–4663.
C. Keawkumay et al.
[20] H.A. Aleksandrov, P.St Petkov, G.N. Vayssilov, Computational modeling of
coordination chemistry of transition metal cations in zeolites and in metal-organic
frameworks, Curr. Phys. Chem. 2 (2012) 189–199.
[21] J. Wittayakun, P. Khemthong, S. Prayoonpokarach, Synthesis and characterization
of zeolite NaY from rice husk silica, Korean J. Chem. Eng. 25 (2008) 861–864.
[22] W.J. Thomas, B. Crittenden, Adsorption Technology and Design, Butterwort-
Heinemann, Boston, 1998, pp. 38–50.
[23] N. Singh, Adsorption of herbicides on coal fly ash from aqueous solutions,
J. Hazard Mater. 168 (2009) 233–237.
[24] J.P. Perdew, Y. Wang, Accurate and simple analytic representation of the electron-
gas correlation energy, Phys. Rev. B 45 (1992) 13244–13249.
[25] G. Kresse, J. Hafner, Ab initio molecular-dynamics simulation of the liquid-metal-
amorphous-semiconductor transition in germanium, Phys. Rev. B 49 (1994)
14251–14269.
[26] G. Kresse, J. Furthmüller, Efficiency of ab-initio total energy calculations for metals
and semiconductors using a plane-wave basis set, J. Comput. Mater. Sci. 6 (1996)
15–50.
[27] D. Vanderbilt, Soft self-consistent pseudopotentials in a generalized eigenvalue
formalism, Phys. Rev. B 41 (1990) 7892–7895.
[28] G. Kresse, J. Hafner, Norm-conserving and ultrasoft pseudopotentials for first-row
and transition elements, J. Phys. Condens. Matter 6 (1994) 8245–8257.
[29] Y. Jeanvoine, J. Angyan, G. Kresse, J. Hafner, Brønsted Acid Sites in HSAPO-34 and
Chabazite: an ab initio structural study, J. Phys. Chem. B 102 (1998) 5573–5580.
[30] C. Baerlocher, L.B. McCusker, Database of Zeolite Structures. http://www.iza-struc
ture.org/databases/.
[31] Q. Li, D. Creaser, J. Sterte, An investigation of the nucleation/crystallization
kinetics of nanosized colloidal faujasite zeolites, Chem. Mater. 14 (2002)
1319–1324.
Materials Chemistry and Physics 238 (2019) 121824
[32] H. Awala, J.-P. Gilson, R. Retoux, P. Boullay, J.-M. Goupil, V. Valtchev, S. Mintova,
Template-free nanosized faujasite-type zeolites, Nat. Mater. 14 (2015) 447–451.
[33] S. Rakmae, C. Keawkumay, N. Osakoo, K.D. Montalbode, R.L. Leon,
P. Kidkhunthod, N. Chanlek, F. Roessner, S. Prayoonpokarach, J. Wittayakun,
Realization of active species in potassium catalysts on zeolite NaY prepared by
ultrasound-assisted impregnation with acetate buffer and improved performance in
transesterification of palm oil, Fuel 184 (2016) 512–517.
[34] D. Barthomeuf, Basic zeolites: characterization and uses in adsorption and
catalysis, Catal. Rev. Sci. Eng. 38 (1996) 521–612.
[35] M.M.J. Treacy, J.B. Higgins, Collection of Simulated XRD Powder Patterns for
Zeolites, fifth ed., IZA, Elsevier, Amsterdam, 2007, ISBN 0444530673.
[36] A. Kozlov, K. Asakura, Y. Iwasawa, Synthesis and characterization of vanadium
(IV) complexes in NaY zeolite supercages, Micropor. Mesopor. Mater. 21 (1998)
571–579.
[37] M. Nakayama, J. Yano, K. Nakaoka, K. Ogura, Spectroscopic studies on the
incorporation of polypyrrole into zeolite channels, Synth. Met. 138 (2003)
419–422.
[38] P. Khemthong, W. Klysubun, S. Prayoonpokarach, J. Wittayakun, Reducibility of
cobalt species impregnated on NaY and HY zeolites, Mater. Chem. Phys. 121
(2010) 131–137.
[39] M. Brigante, M. Avena, Synthesis, characterization and application of a hexagonal
mesoporous silica for pesticide removal from aqueous solution, Micropor. Mesopor.
Mater. 191 (2014) 1–9.
[40] C.H. Giles, T.H. Macewan, S.N. Nakhwa, D. Smith, Study in adsorption Part XI. A
system of classification of solution adsorption isotherm, and its use in diagnosis of
adsorption mechanism and in measurement of specific surface areas of solids,
J. Chem. Soc. 4 (1960) 3973–3993.