Microporous and Mesoporous Materials 282 (2019) 73–81

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Microporous and Mesoporous Materials

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

Influence of salt on nanozeolite-Y particles size synthesized under organic T

template-free condition
Hanin M. Radmana,b,1, Aasif A. Dabbawalaa,1, Issam Ismaila, Yasser F. Alwahedia,c,∗,
Kyriaki Polychronopoulouc,d, Balasubramanian V. Vaithilingamb, Gnana P. Singaravelb,
Stephane Morinb, Mikael Berthodb, Saeed M. Alhassana,∗
a
Materials and Catalysis Division, Chemical Engineering Department, Khalifa University of Science and Technology-SAN Campus, Abu Dhabi, United Arab Emirates
b
Catalysis Division, ADNOC Refining Research Center, Abu Dhabi, United Arab Emirates
c
Center for Catalysis and Separation, Khalifa University of Science and Technology, Abu Dhabi, P.O. Box 127788, United Arab Emirates
d
Department of Mechanical Engineering, Khalifa University of Science and Technology, Abu Dhabi, P.O. Box 127788, United Arab Emirates

ARTICLE INFO ABSTRACT

Keywords: Zeolite-Y is one of the preferred micro-sized zeolite commonly used as a catalyst and for adsorption and se-
Zeolite-Y paration. The size and shape of zeolite crystals have great influence on their properties therefore the synthesis of
Salt nano-size zeolite-Y has received much attention with straightforward methodology. In the present study, nano-
Crystal growth sized zeolite-Y crystals were synthesized by the clear-solution (CS) and dense-gel (DG) methods in the presence
Clear-solution
of alkali metal chloride salt (i.e. NaCl) under organic template-free condition. The influence of the salt on the
Dense-gel
growth of nano zeolite-Y crystal size and morphology was studied systematically by varying the NaCl con-
centration. Depending on the method selected for synthesis (CS or DG), the growth of nano-size crystals was
affected by the addition of NaCl content. In the CS method, the size of zeolite-Y crystals was found to decrease
from 120 nm to 60 nm with an increase of salt content which signify the influence of salt in hindering diffusion of
nutrients to the crystal nuclei in a homogeneous starting gel. Whereas, the spherical aggregates of well-shaped
nanocrystals were formed with an increase of crystal size in the case of DG method. This is attributed to the
suppression of the rate of crystal dissolution in dense-gel system upon introduction of salt ions. The nano-size
zeolite-Y synthesized by both methods exhibited comparatively higher water adsorption capacity
(15.4 ± 0.38–16.2 ± 0.41 mmol/g) than commercially available micro-size zeolite-Y (12.9 mmol/g) which
can be attributed to the contribution of the meso/macropores arising from the inter-crystal voids. Hence, the
synthesized nano-size zeolite-Y can be considered as promising adsorbents for water adsorption applications.

1. Introduction weakly bounded cations (organic/inorganic). Nevertheless, the cations

Zeolites are well crystalline aluminosilicate materials that possess
three dimensional porous network structure. Due to their unique
structure and properties, the use of zeolite in different applications
related to catalysis, gas separation, adsorption and ion exchange has
been extensively studied [1–11]. In particular, zeolite Y is considered
one of the most widely used zeolites in petrochemical industry as the
main component of fluid catalytic cracking (FCC) catalysts due to its
inherent features such as big cavity, super cage, high surface area and
pore volume, thermal stability and substantial acid sites [12,13]. Zeo-
lite Y has a negative aluminosilicate framework that is balanced by
role is not only limited to charge balance but extends to directing the
course of nucleation and crystallization, hence they are often referred to
as structure directing agents (SDA) or templates [14–16]. It is believed
that the nucleation starts when water molecules begin to surround the
SDAs [15]. Following, the water molecules are gradually replaced by
silicate and aluminate tetrahedra leading to the formation of nucleation
centers [15]. Controlling the batch composition and adjusting the silica
and alumina precursor ratios are essential for synthesizing zeolite with
optimum properties in terms of size, shape and surface properties [16].
The synthesis of nano-size zeolite is one of the most promising ap-
proaches to enhance the properties of conventional micro-size zeolite as

Corresponding author. Materials and Catalysis Division, Chemical Engineering Department, Khalifa University of Science and Technology-SAN Campus, Abu
∗

Dhabi, United Arab Emirates.

E-mail addresses: yasser.alwahedi@ku.ac.ae (Y.F. Alwahedi), saeed.alkhazraji@ku.ac.ae (S.M. Alhassan).
1
Equal contribution.

https://doi.org/10.1016/j.micromeso.2019.03.015
Received 10 December 2018; Received in revised form 6 March 2019; Accepted 11 March 2019
Available online 13 March 2019
1387-1811/ © 2019 Elsevier Inc. All rights reserved.
H.M. Radman, et al.
catalysts or as adsorbents. Considerable work has been done recently to
synthesize nanocrystalline zeolite-Y [16–19]. The most of reported
methodologies involve the use of an organic template, a tetra-
methylammonium cation, such as TMAOH and TMABr [18,19]. How-
ever, the synthesis of nanozeolite-Y with the assistance of such organic
templates suffers from several drawbacks such as, prohibitive costs,
non-recyclability, requirement of calcination to remove the template,
requirement of longer synthesis time and low zeolite yield [20–22].
Hence, the efforts have been directed towards the synthesis of nano-
crystalline zeolite-Y by organic template free approach [20–23]. In the
organic template-free approach, the alkali metal hydroxide (mostly use
NaOH) i.e. sodium cations act as the structure directing agent. The
concentration of NaOH play a significant role in controlling the growth
of nanozeolite-Y crystals [22,23]. Furthermore, the addition of the al-
kali metal salt as a secondary source of alkali metal cations to the
precursor gel solution influences the size, type and surface properties of
zeolite. This was attributed to their structure directing property or the
suppression of the crystals growth [24–26]. Moreover, several groups
observed that alkali metal cation size, charge and amount also affect the
formation or inhibition of specific type of zeolite structures [24–29].
Chaves et al. studied the effect of Na+ cations concentration on the
crystal size of zeolite Y for a system with initial gel composition of 5.5
Na2O: 1.0 Al2O3:10 SiO2:180 H2O: x NaCl, where x was varied between
4 and 6 [26]. The authors reported a proportional increase in the crystal
size upon increasing the salt content compared to the salt-free synthesis
gel [26]. On the other hand, Culfaz and Sand et al. observed a sup-
pression of the crystal growth rate for mordenite as a result of the ad-
dition of NaCl [28]. They attributed this to the increase in viscosity of
the system which slowed down the mobility of ionic species that would
approach the surface of the growing crystals and contribute to their
growth [28]. In addition to alkali metal cation amount, the nature of
the alkali metal cations influences resulting zeolite phase. For instance,
Lowe et al. attempted to synthesize MFI using potassium as a counter
ion instead of sodium [27]. However, in many cases the zeolite phase
Nu 10, was produced at conditions which would normally result with
MFI [27]. G. Zhu et al. reported synthesis of high quality zeolite LTA
and Zeolite-Y crystals and found well-controlled crystal growth and
crystal size reduction in the presence of NaCl salt and TMAOH template
[29].
In view of the above, the inconsistent results on the impact of NaCl
concentration in the initial reactant gel imply that the role of NaCl
requires further systemic investigation. Synthesis of nanozeolite-Y can
be achieved either from a clear-solution (CS) synthesis mixture or by
the conventional dense-gel (DG) approach [30,31]. In the CS approach,
the initial precursor gel suspension is transparent hence suggesting
homogenous distribution of reactive species. The aging of this gel
provides dispersed crystal nuclei leading to monodispersed crystals
[30]. In the DG method, the mixing of initial silica and alumina pre-
cursors form a turbid suspension which upon heating produces ag-
glomerated and intergrown nanoparticles [30,31]. Therefore, each of
the aforementioned methods can result into crystalline zeolite particles
with different characteristics [30–32]. Herein, we studied system-
atically the organic template-free synthesis of nano-size zeolite-Y by the
CS and the DG methods in the presence of alkali metal chloride salt (i.e.
NaCl) as secondary source for Na+ cation (Scheme 1). We present our
findings on the influence of NaCl on zeolite-Y crystals growth. The
growth of nano-size crystals is affected by the introduction of NaCl to
the gel mixture which consequently alter the zeolite-Y particle size
depending on the method selected for nanozeolite-Y synthesis (CS or
DG). As a probing application, the water adsorption behaviors of nano-
size zeolite-Y synthesized by both methods were compared to com-
mercially available microporous zeolite-Y.
2. Materials and method
The organic template-free synthesis of nano-size zeolite-Y either by
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Microporous and Mesoporous Materials 282 (2019) 73–81
CS or DG method were performed in the presence of NaCl following the
procedure of mintova et al. with slight modification [22]. The molar
composition of the gel precursor in both methods was set to 1Al2O3: 15
SiO2: 11 NaOH: 240 H2O: x NaCl, in which x referrers to a salt molar
ratio of 3 or 4.5.
2.1. Synthesis of nano zeolite-Y from clear-solution (CS) method
Nano-sized zeolite-Y was synthesized by the CS method using the
aforementioned molar composition. This was done by preparing two
separate initial solutions of the precursors (alumina and silica) denoted
by solution A and B. Solution A was prepared by dissolving Al(OH)3 and
NaCl in double distilled water while stirring it for 30 min. Solution B
was prepared by adding colloidal silica (Ludox-HS 40, 40 wt%SiO2) to a
NaOH solution under stirring. Both solutions were then kept in ice baths
for 30 min before slowly adding solution A to solution B. The resulting
clear suspension was observed after 1 h of stirring and was kept for
aging for 24 h at room temperature. Following, hydrothermal crystal-
lization at 70 °C was conducted for another 24 h under autogenous
conditions. The final product was washed until the pH reached to 7–8.
The resulting crystals were collected by centrifugation. The recovered
solid was dried at 90 °C for 12 h.
2.2. Synthesis of nano zeolite-Y from dense-gel (DG) method
The synthesis of nano-sized zeolite-Y was performed by the con-
ventional DG method using the aforementioned molar composition.
Similar to the synthesis of CS method, two solutions, A and B were
prepared separately. However, in this case, NaOH was added to solution
A containing Al(OH)3 and NaCl. While solution B was prepared using
colloidal silica (Ludox-HS 40, 40 wt%SiO2) and water. Both solutions
were cooled in ice baths before the drop wise addition of solution A to
B. In this case, the resulting solution turned turbid after 1 h of stirring at
room temperature (Scheme 1). The aging was performed for 24 h at
room temperature followed by crystallization at 70 °C for 24 h. The final
product was separated by centrifugation and dried at 90 °C for 12 h.
2.3. Characterization
X-Ray Diffraction (XRD) patterns of the samples were obtained
using Panalytical X'Pert PRO powder diffractometer with Cu Kα ra-
diation (λ = 1.5406 Å, 45 kV, 40 mA). The samples were mounted on a
zero-background holder. The diffraction patterns were collected in the
range of 3°–50° 2θ using a step size of 0.02°. Scanning electron mi-
croscopy (SEM) was conducted using an FEI Quanta 250 (FEG)
equipped with energy dispersion spectroscopy (EDS) capability. Images
were collected at 3 and 5 kV. N2 adsorption-desorption isotherms were
obtained by a Micromeritics 3Flex (Micromeritics Instruments
Corporation, Norcross, GA, USA) surface area and porosimetry analyzer
using ultra-high purity (99.9999%) N2 gas at 77 K. Prior to sorption
measurements, the samples were degassed overnight at 200 °C after
which the sorption studies were carried out. TEM imaging was con-
ducted on an FEI Tecnai G2 F30 TEM operating at 200 kV. Samples
were prepared for Transmission Electron Microscopy (TEM) by sus-
pending and sonicating the samples in ethanol and then applying a drop
of the resulting suspension onto a copper grid coated with lacey carbon
(Ted Pella Inc.). The water adsorption studies were performed using a
3Flex Micromeritics instrument. For the nano-zeolite samples, the water
adsorption experiments were run three times and the 95% confidence
interval (using t-distribution) for the mean total water capacity was
calculated.
H.M. Radman, et al.
Scheme 1. Synthesis of nanozeolite-Y by clear and dense-gel method in presence of salt.
3. Results and discussion
3.1. Influence of salt in synthesis of nano zeolite-Y by CS method
X-ray diffraction (XRD) patterns of nanozeolite-Y synthesized from
CS method are presented in Fig. 1. XRD of CS samples exhibits all the
characteristic peaks of the pure FAU phase. When compared to the
conventional micro-size zeolite-Y (CBV-400, Fig. S1), the peaks are
broader and less intense hence signifying the formation of nano-sized
zeolite-Y crystals. Upon the successive increase of the salt content (CS
3.0 and CS 4.5), the XRD peaks experience noticeable broadening which
implies a reduction in the crystal size.
FT-IR analysis was carried out for CS samples; CS-SF, CS-3.0 and CS-
4.5 and are presented in Fig. 2. The FT-IR spectra of the studied samples
exhibits identical peaks which signifies similarity in the chemical en-
vironment. The band appearing at 457 cm−1 is assigned to the sym-
metric stretching of Si-O-Al bonds in which Al is in octahedral
Fig. 1. XRD patterns of samples synthesized by CS method; CS-SF (a), CS-3.0 (b)
and CS-4.5 (c).
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Microporous and Mesoporous Materials 282 (2019) 73–81
coordination. The peak at 577 cm−1 arises from the double six-member
rings (D6R) which is attributed to the crystalline structure of zeolite Y
type materials. Clearly there is a slight shift in this peak towards higher
wave numbers upon the addition of salt. The bands at approximately
700 and 1000 cm−1 are assigned to symmetrical and asymmetrical
stretching vibrations corresponding to the Si-O bond in Si-O-Si and Si-
O-Al [33]. The peak around 1650 cm−1 is attributed to the bending
vibration of hydroxyl of water adsorbed in the zeolite. The broad peak
around 3390 cm−1 is assigned to the OH-stretching band in the sodalite
cage which can be associated to Brønsted acid sites [33]. The band at
3608 cm−1 corresponds to acidic bridging hydroxyl in Si-O(H)-Al while
the peak at 3737 cm−1 arises from the internal silanols [33,34].
TEM images of nanozeolite-Y synthesized by the CS method in the
presence of salt NaCl are shown in Fig. 3 while Table 1 presents the
surface properties of the CS samples The sample synthesized without
addition of salt (CS-SF) is comprised of nano intergrown crystals pos-
sessing an average particle size of approximately 120 nm. TEM images
of the samples synthesized in the presence of salt suggests a reduction in
the nanocrystal size upon increasing the salt content. TEM image of the
sample (CS-4.5) shows a clear reduction in the crystal size compared to
the CS-SF sample (60 vs. 120 nm). Furthermore, the resulting mor-
phology of intergrown crystals did not transform and retained octahe-
dral shape even reduction of crystal size in the case of CS-4.5. SEM
images of the CS samples display a clear the reduction in the particle
size upon increasing the salt content following the trend of CS-SF >
CS-3.0 > CS-4.5 (Fig. 3). The reduction in particle size implies that
the crystallization was suppressed as a consequence of NaCl addition in
the CS method. SEM-EDS of all CS samples suggests a similar Si/Al ratio
of 1.7.
The zeolite-Y crystals are grown by the ordered aggregation of ionic
building blocks on the crystal nuclei. In the CS method the starting
synthesis gel is homogeneous as evidenced by the lack of turbidity [15].
A homogeneous starting system is believed to result in a monodispersed
and loosely agglomerated nanosized crystals since the starting nuclei
are dispersed which tends to hinder the interactions between neigh-
boring nuclei during crystal growth [21,22]. The addition of salt in the
CS method creates hydrated spheres comprised of the ions (Na+ and
Cl−) surrounded by water molecules. These hydrated spheres hinder
the diffusion of the ionic blocks (aluminate and silicate) to the crystals
which in turn suppresses their growth. As a result, a decrease in the
H.M. Radman, et al. Microporous and Mesoporous Materials 282 (2019) 73–81

Fig. 2. FT-IR spectra of samples CS-SF, CS-3.0 and CS-4.5 (A), a zoomed section in the range of 1500-400 cm−1 (B).

average crystal size is observed. Hence, increasing NaCl concentration
suppresses crystal growth when following CS method, which supports
the conclusions from Zhu et al. study using TMAOH [29].
The N2 sorption isotherms and pore size distributions curve of
samples CS-SF, CS-3.0 and CS-4.5 are presented in Fig. 4. From the N2
adsorption-desorption isotherm, all the samples displays a combination
of type I and type IV isotherm possessing a hysteresis loop extending
over a wide relative pressure range (0.5–1.0). The presence of the
hysteresis loop at elevated P/Po (H4 type) suggests the presence of
meso-macropores arising probably from the inter-crystals voids gener-
ated by the stacking of the nano-size zeolite-Y crystals [22,35]. The
hysteresis loop of samples CS-3.0 and CS-4.5 exhibits a wider dis-
crepancy between adsorption and desorption isotherms (wider opening
between the two isotherms) which reflects a wider pore size distribu-
tion. In addition, the samples (CS-3.0 and CS-4.5) possess higher total
pore volume upon increasing the salt concentration (Table 1). The total
pore volume of CS-SF sample is 0.40 cm3/g which increases to
0.58 cm3/g of the CS-4.5. All aforementioned results indicate the im-
provement in porosity upon salt addition following CS method. The
assemblies of smaller crystals create larger number of inter-crystal va-
cancies which lead to higher count of mesopores and hence higher total
pore volume. Worth to notice herein that the BJH pore size distribution
suggests that the pore size is centered at 50 nm for all CS based samples.
3.2. Influence of salt in synthesis of nanozeolite-Y by DG method
X-ray diffraction (XRD) patterns of the nano zeolite-Y samples
synthesized using the dense gel method at no salt free condition (DG-
SF), NaCl/Al2O3 of 3 and 4.5 (DG-3.0 and DG-4.5) are presented in
Fig. 5. It is clear from the XRD patterns that all the samples exhibits all

Fig. 3. TEM images of CS-SF (a,b), CS-3.0 (c,d), CS-4.5 (e–g) and SEM images of CS-SF (h), CS-3.0 (i) and CS-4.5 (j).

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H.M. Radman, et al. Microporous and Mesoporous Materials 282 (2019) 73–81

Table 1
Surface properties of nanozeolite-Y synthesized by clear-solution method.
Sample SABET (m2/g) PVtotal (cm³/g) PVmicro (cm³/g) PVmeso/macro (cm³/g) SExt (m2/g) DExta (nm) CXRDb (%) DTEM (nm)

CS-SF 639 0.40 0.24 0.16 46 88 64 120

CS-3.0 626 0.48 0.22 0.26 65 62 37 80
CS-4.5 636 0.58 0.22 0.36 81 50 24 60

a
Calculated using equation, DExt = 4061/SExt [21].
b
Crystallinity calculated by XRD.

characteristic peaks of FAU structure. The salt free sample (DG-SF)

displays less intense and broader characteristic diffraction peaks. The
broadening of the peaks suggests the formation of smaller zeolite na-
nocrystals. Upon increasing the salt content, the intensity and sharpness
of the peaks increases which indicates an increase in the crystallinity
accompanied with an increase in the crystal size.
SEM images of nanozeolite-Y synthesized following DG method are
presented in Fig. 6. From the SEM images, it can be see that the DG-SF
sample synthesized without addition of salt are comprised of aggregates
primary nanoparticles possessing spherical morphology. However, the
size of the aggregates are not uniform. SEM images of the samples
produced with addition of salt (DG-3.0 and DG-4.5) displays aggregates
of larger nano crystals possessing well-developed crystal faces (Fig. 6).
The Si/Al computed from the SEM-EDS analysis of all the DG samples is
around 1.7 which confirms the formation of FAU-Y phase.
TEM images of DG-SF sample displays polycrystalline spherical
aggregates of nanocrystals with different cluster sizes (Fig. 7). The
HRTEM image reveals that each aggregate is comprised of many closely
packed primary nanocrystals possessing an average size of around
50 nm. This observation corroborates the SEM and XRD results hinting Fig. 5. XRD patterns of samples synthesized by dense-gel method; DG-SF (a),
a surface roughness and complex intergrowth. TEM images of the DG-3.0 (b) and DG-4.5 (c).
samples (DG-3.0 and DG-4.5) clearly display the change in the ag-
gregate size as well as primary crystals size and morphology upon salt
the gel precursor solution boosts condensation of reactants on the
addition. Contrary to the CS method, the most of particles produced by
surface of the particles, which in turn enhance the growth of crystals
the DG method are comprised of intergrown primary nanocrystals
[26]. In the present study using DG approach, the crystal nuclei exist in
which is influenced by the salt content. (Fig. 7). The polycrystalline
close proximity to one another due to the high density of the gel. In
aggregate size decreases upon increasing the salt content however the
such environments, rate of diffusion of the ionic building blocks is not
primary crystal size increases (60–90 nm) in the case of samples, DG-3.0
limiting the crystal growth. Furthermore, the rate of crystal dissolution
and DG-4.5. Bosnar et al. studied the crystallization of zeolite NaA and
and growth are accelerated which explains the asymmetrical mor-
found that the kinetic rate constants of growth increases with increasing
phology and increase in crystal size. The addition of salt seems to
Na+ content [36,37]. Chaves et al. investigated the influence of Na+
suppress the rate of dissolution to a higher extent compared to the
cation on crystal size by adding salt NaCl with varying molar content.
growth rate which at the end leads to formation of larger crystals. In the
They observed asymmetrical growth patterns of zeolite-Y crystals ac-
absence of salt, the hydrothermal treatment of the precursor gel pro-
companied with an increase of crystals size upon increasing the salt
duces spherical clusters of inter-grown nanocrystals with surface
content [26]. They suggested that the higher sodium concentration in

Fig. 4. N2 adsorption-desorption isotherms (A) and BJH pore size distributions (B) for the samples, CS-eSF (a), CS-3.0 (b) and CS-4.5 (c).

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H.M. Radman, et al. Microporous and Mesoporous Materials 282 (2019) 73–81

Fig. 6. SEM images of DG-SF (a, b), DG-3.0 (c,d) and DG-4.5 (e,f).

roughness and complex intergrowth. While in presence of salt, the
condensation of amorphous mass improves on the surface of nuclei
centers which helps the growth of well-shaped nanocrystals at a lesser
degree of intergrowth.
FT-IR spectra of DG samples are presented in Fig. S2. The peaks
positions of all the samples appear to be identical. The band appearing
at 577 cm−1 seems to become more intense upon salt addition sug-
gesting an increase in the crystallinity. One can also note the decrease
of peak broadening upon NaCl addition in both samples (DG-3.0 and
DG-4.5) which signifies a more uniform distribution of Si and Al in the
framework [38]. Fig. 8 depicts the N2 adsorption-desorption isotherm
and pore size distribution for samples synthesized following DG ap-
proach. The N2 adsorption-desorption isotherm of all DG samples ex-
hibits type IV isotherm accompanied with a hysteresis loop which is
usually characteristic of materials possessing meso and macropores
[35]. The H4 type hysteresis loop indicates the presence of inter-crys-
talline mesopores arising from the packing of the nanocrystals [35,39].
The samples synthesized in the presence of salt (DG-3.0 and DG-4.5)
showed comparatively higher BET surface area and higher total pore
volume (Table 2). Both samples (DG-3.0 and DG-4.5) exhibits steeper
nitrogen uptake at low relative pressures (P/P0 = 0.02) attributed to
the micropores filling. The N2 adsorption uptake for the samples (DG-
3.0 and DG-4.5) was comparative higher than sample DG-SF at low
pressures which further support the larger size of the primary crystals.
The steep increase in N2 uptake and the presence of the hysteresis loop
(from 0.40 to 0.85) for both samples signified the presence inter-crystal
mesopores [39]. Pore size distributions of DG samples are shown in
Fig. 8. The multimodal pore size distribution observed in the salt con-
taining samples suggests their hierarchical porous nature. The samples
(DG-3.0 and DG-4.5) showed higher total pore volume than that of the

Fig. 7. TEM images of DG-SF (a, b), DG-3.0 (c,d) and DG-4.5 (e,f).

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H.M. Radman, et al. Microporous and Mesoporous Materials 282 (2019) 73–81

Fig. 8. N2 adsorption isotherm (A) and BJH pore size distributions (B) for the samples, DG-SF (a), DG-3.0 (b) and DG-4.5 (c).

Table 2
Surface properties of nanozeolite-Y synthesized by dense-gel method.
Sample SABET (m2/g) PVtotal (cm³/g) PVmicro (cm³/g) PVmeso/macro (cm³/g) SExt (m2/g) DExta (nm) CXRDb (%) DTEM (nm)

DG-SF 600 0.45 0.23 0.22 71 57 32 50

DG-3.0 658 0.49 0.24 0.25 64 63 51 70
DG-4.5 663 0.48 0.24 0.24 60 68 58 80

a
Calculated using equation, DExt = 4061/SExt [21].
b
Crystallinity calculated by XRD.

sample DG-SF. The hierarchical porous structures were formed by the

intergrowth of well-developed crystals which improve mesoporosity
and overall total pore volume of salt added samples.

3.3. Water adsorption study

Synthesis of the nanozeolite-Y by following two different methods

resulted into zeolite-Y crystals with different growth and size of parti-
cles. The differences in the properties of nanozeolite-Y crystals were
profound after the addition of sodium chloride salt. Such variation in
the size and the morphology of synthesized nanozeolite-Y results into
diverse porous features as suggested by N2 sorption analysis. To eluci-
date the impact of the porous structure on the efficacy of the samples as
drying agents, all the synthesized samples were then studied for their
water adsorption behavior at 30 °C. The water adsorption isotherms of
nano-size zeolite-Y samples synthesized by CS method (CS-SF, CS-3.0,
CS-4.5) are presented in Fig. 9. In order to compare performance of
nano-size zeolite-Y, the water uptake capacity of micro-size commercial
zeolite-Y (CBV-400) was also measured at the same conditions. Due to
its high affinity toward water, the sample CBV-400 exhibited Type I
isotherm and steep water uptake at low relative pressure (P/Po < 0.2)
which is characteristic of hydrophilic microporous material possessing
of hydrophilic surface [40]. From Fig. 9, it can be seen that all CS based
nano-zeolite-Y samples displays a higher water uptake than micro-
porous zeolite CBV-400 through the entirety of the studied relative
pressure range (0.05–0.82 P/Po). The sample (CS-SF) showed water
uptake trend similar to CBV-400 (hydrophilic nature). The water uptake
capacities of samples (CS-3.0 and CS-4.5) at low relative pressure (P/ Fig. 9. (A) Water adsorption uptake of samples, CBV-400 (a), CS-SF (b), CS-3.0
Po < 0.4) are lower in comparison to the sample (CS-SF). But, the (c), CS-4.5 (d); (B) Total water uptake at pressure range of 0.0–0.8 P/Po; the
samples (CS-4.5 and CS 3.0) displays considerable enhancement in error bars represents the 95% confidence interval (using t-distribution) for the
water adsorption capacity at higher relative pressure (P/Po > 0.4). mean total capacity.
The maximum water uptake increases in the following order CS-SF <
CS-3.0 < CS-4.5. Interestingly, the sample (CS-4.5) exhibited the
shape) in the case of sample (CS-4.5) indicates the presence of multi-
highest water uptake reaching to 16.2 mmol/g at P/Po = 0.82 which is
porous domains (micro-meso and macro porosity) and is indicative of
considerably higher than that of commercial zeolite CBV-400
multilayer adsorption [41,42]. At low relative pressures, the water
(12.9 mmol/g) and other CS samples. The clear Type IV isotherm (S

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H.M. Radman, et al.
uptake is likely to occur in the micropores of zeolitic channels while at
high relative pressures water adsorption preferably occurs in the meso-
macropores which are created by inter-crystal voids due to random
aggregation of the small crystallites. The CS-SF sample possesses the
highest micropore volume. Therefore, it displays the highest water
uptake at low relative pressure where adsorption is dominated by mi-
cropore filling [40–42]. The sample CS-4.5 possesses higher total pore
volume as well as mesopores volume (Table 1) than all the other CS
samples which explains the higher water capacity observed at P/
Po = 0.82. Moreover, the shape of the water adsorption isotherm of
samples CS-4.5 suggests the existence of hierarchy in the pore structure
[41–43]. Both effects contributes to the higher observed water capacity
as water adsorption capacity is mainly influenced by pore volume, pore
size and nature of the pores surface in the sample.
The nanozeolite-Y samples synthesized by following the DG method
also exhibits higher water uptake capacity when compared to the
commercial zeolite-Y (CBV-400) across the entirety of the studied re-
lative pressure range (Fig. 10). The water uptake increases in the fol-
lowing order DG-SF < DG-4.5 < DG-3.0 throughout the studied re-
lative pressure range in a trend which follows their corresponding total
pore volumes. At high relative pressures (P/Po > 0.4), the sample (DG-
3.0) displayed the maximum water adsorption capacity reaching to
15.4 mmol/g at P/Po = 0.82. The DG-3.0 showed also significantly
higher water adsorption performance than commercial zeolite CBV-400
(12.9 mmol/g). The water adsorption capacities of nanozeolite-Y sam-
ples (CS-4.5 and DG-3.0) synthesized by both methods are also com-
pared with reported adsorbents studied for water adsorption (Table S1).
It can be seen that the nano-size zeolite-Y samples (CS-4.5 and DG-3.0)
possess higher water capacities when compared to alkali metal cation
Fig. 10. (A) Water adsorption uptake of samples, CBV-400 (a), DG-SF (b), DG-
3.0 (c), DG-4.5 (d); (B) Total water uptake at pressure range of 0.0–0.8 P/Po;
the error bars represents the 95% confidence interval (using t-distribution) for
the mean total capacity.
80
Microporous and Mesoporous Materials 282 (2019) 73–81
exchanged Zeolite-X, Zeolite P (GIS), LTA, mordenite, erionite, AlPO-5
and SAPO-5 [40–42] indicating the efficacy of nano-sized hierarchical
zeolite-Y for water adsorption application. Overall, the present study
reveals the potential use of nano-sized zeolite-Y as excellent adsorbents
for thermochemical energy storage systems [44] and humidity con-
trollers particularly for cooling systems including refrigerators and air
conditioners [45,46].
4. Conclusion
In conclusion, we examined the influence of NaCl salt on crystal size
and morphology of nano-size zeolite-Y synthesized under organic
template free condition. Two different methodologies were selected (CS
and conventional DG method) to investigate the growth of the nano-
crystals by introducing varied amount of salt in initial gel. A decrease in
the nanocrystals size and crystallinity were observed when adding salt
following the CS method. This was attributed to suppression of ionic
building blocks diffusion towards the surface of the crystals which tends
to be the rate limiting step in the CS method. On the other hand, the
spherical aggregates of larger primary nanocrystals were formed in the
case of DG method. Due to the difference in size and morphological
arrangement of the nanocrystals, all synthesized nano-size zeolite-Y
samples in presence of salt showed diverse porous features which
played a crucial role in improving water adsorption capacity. The
highest water adsorption capacity was achieved by the sample CS-4.5
which is due to its higher total pore volume. The increase of total pore
volume is attributed to the hierarchical pore structure exhibiting pores
in the meso and macro range in addition to the native micropores of
zeolite-Y. The higher observed water adsorption capacity
(16.2 ± 0.41 mmol/g) in comparison to commercial zeolite-Y clearly
displays the potential of nano-size zeolite-Y in drying applications.
Acknowledgement
We greatly acknowledge ADNOC refining, ADNOC, Abu Dhabi, UAE
for funding and technical support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.micromeso.2019.03.015.
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