Microporous and Mesoporous Materials 347 (2023) 112341

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Microporous and Mesoporous Materials

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

A facile strategy of preparing nanosized NaY zeolite by stimulating negative

crystals to accelerate the formation of D6R units
Peng Liu a, *, Chengqu Yu a, Weixue Li a, c, ***, Baojian Shen b, **
a
School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, 453007,
Xinxiang, Henan, China
b
State Key Laboratory of Heavy Oil Processing, The Key Laboratory of Catalysis of CNPC, College of Chemical Engineering and Environment, China University of
Petroleum, Beijing, 102249, China
c
School of Chemistry and Chemical Engineering, National Chemistry Experimental Teaching Demonstration Center, Henan Normal University, 453007, Xinxiang, Henan,
China

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

Keywords: Nanosized Y zeolite has excellent potential as a catalyst or adsorbent to boost the chemical industry. However,
Nanosized NaY zeolite the synthesis of nanosized Y zeolite under traditional industrial conditions still faces many huge challenges.
Sodium halides Herein, we report a facile strategy of preparing nanosized NaY zeolite by applying sodium halides (NaCl or NaBr)
Negative crystal
to regulate amorphous gel. Sodium halides regulate the micro-structural transformation of the initial amorphous
D6R units
gel during the induction period and promote the polymerization between silicate ions and aluminosilicate. Thus,
many more negative crystals are stimulated to form and the emergence of double six-ring (D6R) building units is
accelerated. In a short 12 h, nanosized NaY zeolite with small crystal size (about 100 nm), large pore volume
(0.476 cm3 g− 1), and rich mesoporous volume (0.165 cm3 g− 1) is synthesized. These synthesized nanosized NaY
zeolites are expected to be better precursors to exert their advantages.

1. Introduction
Zeolite Y is a kind of aluminosilicate material that belongs to FAU
topology and possesses a three-dimensional 12-ring supercage with a
7.4 Å aperture and 13 Å diameter. It is widely applied to the field of
heterogeneous catalysis, adsorption, and separation process due to its
abundant active sites and tunable pore structure [1–4]. In particular, the
development of Y zeolite boosted the catalytic cracking technology
[5–7]. However, the conventional micron-sized Y zeolite needs further
structual optimization to meet the needs of heavy oil cracing due to the
limitation of pore diffusion. Mesopore architecture introduced into Y
zeolite by the top-down method is one of the effective strategies to
overcome the severe mass transfer limitations [8–10]. Structural dam­
age and acid site loss are inevitable in the process of introducing mes­
opores [11]. Another effective method is to prepare nanosized Y zeolite,
which is expected to greatly lower the transport resistances of heavy oil
and improve the full use of acid sites [1].
Previously, the nanosized Y zeolite has been prepared with the
assistance of organic compounds, such as tetramethylammonium cation
[12–14]. However, the application of organic compounds to the syn­
thesis of nanosized Y zeolite suffers from some drawbacks, such as in­
cremental cost, non-environmentally friendly, non-recyclable, longer
synthesis time, and lower zeolite crystal yield [15–17]. Therefore, the
organic template-free method to direct the synthesis of nanosized zeolite
was generally considered [18]. During the synthesis method of Y zeolite,
sodium cation (Na+) was considered the first type of structure direction
agent (SDA) [19]. The Na+ here was mainly added to the zeolite gel in
the form of sodium hydroxide where hydroxyl ions (OH− ) act as min­
eralizers to promote the dissolution and polymerization of silicate and
aluminate. The concentration of hydroxyl ions was adjusted to control
the alkalinity of gel thus causing a decrease in the size of Y zeolite [20,
21]. Although the size of Y zeolite was decreased by adjusting alkalinity,
the zeolite crystal surface was damaged due to the higher solubility of
silicates and aluminates in the higher OH− concentration and the lower

* Corresponding author.
** Corresponding author.
*** Corresponding author. School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan
Normal University, 453007, Xinxiang, Henan, China.
E-mail addresses: liupeng@htu.edu.cn (P. Liu), liweixue@htu.edu.cn (W. Li), baojian@cup.edu.cn (B. Shen).

https://doi.org/10.1016/j.micromeso.2022.112341
Received 6 September 2022; Received in revised form 16 October 2022; Accepted 9 November 2022
Available online 15 November 2022
1387-1811/© 2022 Elsevier Inc. All rights reserved.
P. Liu et al.
framework SiO2/Al2O3 mole ratio was obtained [20–24]. Additionally,
sodium halides were used to be a secondary Na+ source to influence the
synthesis of Y zeolite [16,25–27]. Sodium halides supplied structure
directing agent of Na+ and regulated the cystal size of Y zeolite [16,20,
27,28]. The addition of sodium halides to the synthesis gel restrained the
growth rate of Y zeolite and lowered the crystal size of Y zeolite [28]. On
the contrary, the crystal size of Y zeolite was increased by using the
sodium halides in the different methods from Dilson Cardoso [20],
Shilun Qiu [27], and their co-workers. Radman and Alhassan et al. found
that the different effects of sodium halides on the crystal size of Y zeolite
were obtained in different gel environments. In the clear-solution gel,
sodium halides hydrated spheres hindered the diffusion of nutrients to
the crystals, resulting in the decrease of Y zeolite crystal size. Whereas,
in the dense gel, the Y zeolite crystal dissolution process was hindered
upon the introduction of sodium halides. The larger-sized Y zeolite
crystal was formed [16]. Hence, it is difficult to achieve nanosized Y
zeolite synthesis by tuning a single parameter. The crystallization pro­
cess of Y zeolite follows many complex routes.
Even though, promoting zeolite nucleation is still an efficient way to
prepare nanosized Y zeolites [1,5]. In the crystallization process of Y
zeolite, the induction period was the critical stage for the formation of
crystal nuclei, and negative crystals were the key sites for the formation
of nuclei [5,29]. Negative crystals were determined to be the faced gel
cavities containing highly hydrated silica where the Si/Al ratio of gel
was much more significant than one [29,30]. In addition, our previous
findings indicated that the formation of negative crystals was promoted
by cationic polyacrylamide, which accelerated the formation of double
six-ring (D6R) units and thus led to the rapid nucleation [5]. Therefore,
it can be deduced that the D6R units prefer to be formed in the gel
containing negative crystals and the formation of Y zeolite nuclei is
directly related to the D6R units. Na+ cations in the amorphous gel were
determined to be capable of stabilizing the double six-ring (D6R) units
and sodalite cages, that was to say, the formation of D6R units and so­
dalite cages could be promoted by Na+ [31]. During the nucleation and
crystallization of Y zeolite, the formation and evolution of D6R units act
as an essential role, in determining the crystallization efficiency and the
size of their crystals [32]. According to the recent research results from
Jihong Yu and co-workers [33], halides anions could promote the for­
mation of Si–O–Si by the hydrogen bonds between Si(OH)4 and halides
anions. Therefore, it is expected that the introduction of sodium halides
into Y zeolite gel will regulate the evolution of silicate and aluminate
sources, thereby promoting the formation of negative crystals, and
exciting the formation of D6R units and accelerating Y zeolite nucle­
ation, and finally realizing the synthesis of nanosized Y zeolite.
Herein, we demonstrated a facile strategy of stimulating negative
crystals to accelerate the formation of D6R units to prepare nanosized Y
zeolite by using sodium halides such as NaCl or NaBr. In this way, the
silicate sources were assembled by NaCl or NaBr to stimulate the for­
mation of negative crystals. Meanwhile, the polymerization between
silicate sources and aluminosilicate was promoted by NaCl or NaBr,
which resulted in the formation of D6R building units. The formation of
FAU zeolite nuclei was promoted and the induction period was short­
ened by 5 h. Nanosized Y zeolite with a size about 100 nm was prepared
in 12 h. Such a facile strategy provides a new route for efficiently syn­
thesizing nanosized Y zeolite.
2. Experimental
2.1. Synthesis of zeolite samples
2.1.1. Nanosized NaY zeolite
The nanosized NaYzeolite was synthesized by a similar method our
previously reported [5]. The detailed process is as follows: Firstly, 1.57 g
of water glass (Na2O, 9.0 wt%, SiO2, 27.8 wt%) was mixed with 0.39 g
sodium hydroxide (NaOH, 99.0 wt%, Aladdin), 0.11 g sodium aluminate
(Na2O, 47.7 wt%, Al2O3, 44.6 wt%), 1.69 g deionized water, and sodium
2
Microporous and Mesoporous Materials 347 (2023) 112341
halides. Then the mixture was aged at 33 ◦ C for 12 h. The mixture so­
lution was named solution A. The feeding concentration of sodium ha­
lides was defined as the mass percentage of sodium halides in solution A.
Secondly, solution A was transferred into a 5.79 g water glass at 50 ◦ C in
the condition of stirring, followed by the addition of 0.10 g sodium
hydroxide, 0.93 g deionized water, and 0.11 g sodium aluminate in
sequence. Then 4.15 g aluminum sulfate aqueous solution (Al2O3, 7.6 wt
%) was added slowly to form gel suspension. The formed gel suspension
followed chemical mole composition: 2.8 Na2O: 1 Al2O3: 8.5 SiO2:
179.1H2O: (0.85–2.17) sodium halides (NaCl, NaBr, or NaI). Then the
resulting gel suspension was transferred into a polypropylene bottle and
placed in the 96 ◦ C oven. After crystallization, the solid products were
filtered and washed using deionized water and then dried at 120 ◦ C
overnight. The obtained samples were named NaY–NaCl-x, NaY–NaBr-x,
and NaY–NaI-x, where x represented the feeding concentration of so­
dium halides (NaCl, NaBr, or NaI).
2.1.2. The contrast NaY zeolite
The contrast NaY zeolite was prepared as follows: Firstly, solution A
was prepared in the same way as for the nanosized NaY zeolite except
that the sodium halides was not added. Secondly, the synthesis steps of
gel suspension followed the ones of nanosized NaY zeolite. The formed
gel suspension was following chemical mole composition: 2.8 Na2O: 1
Al2O3: 8.5 SiO2: 179.1H2O. Then the gel suspension was transferred into
a polypropylene bottle and placed in the 96 ◦ C oven for 24 h. The solid
products were filtered and washed using deionized water and then dried
at 120 ◦ C overnight. The obtained sample was named NaY-Contrast.
2.1.3. The HY zeolites
The HY zeolites were prepared as follows: Firstly, NaY-Contrast,
NaY–NaCl-x, NaY–NaBr-x, and NaY–NaI-x zeolites were converted to
the NH+4 -type zeolites by ion-exchange in 10 wt% NH4Cl solutions with
3.3 pH at 90 ◦ C for 1 h. Then obtained solid samples were washed
thoroughly and dried at 120 ◦ C overnight. Secondly, the dried samples
were carried on calcination in the 500 ◦ C muffle for 4 h. The resulting
samples were named as HY-Contrast, HY-NaCl-x, HY-NaBr-x, and HY-
NaI-x respectively.
2.2. Characterization
X-ray diffraction (XRD) was applied to characterize the crystalline
phase of synthesized zeolite samples and calculate the relative crystal­
linity, unit cell, and framework SiO2/Al2O3 mole ratio according to our
previous reports [34]. The crystallization process of nanosized zeolites
was investigated by XRD. XRD patterns of all samples were recorded on
a Bruker D8-advance X-ray diffractometer with Cu Kα radiation at 35 kV
and 25 mA. The specific domain size of zeolite crystals using Scherrer’s
equation. The full-width at half maximum (FWHM) was determined at
the peaks 2θ of 15◦ (311), 23◦ (533), and 26◦ (642), using Si as the
reference to correct peak width [20]. Commercial NaY zeolite of
NKF-7FJ (Tianjin Nanhua Catalyst Co., LTD) was used as a standard
sample and its relative crystallinity was 93%. Fourier transform infrared
spectrometry (FT-IR) was used to characterize structure sensitive vi­
brations of zeolite samples and trace the evolution of D6R units in the
whole crystallization process of nanosized zeolites. FT-IR spectra were
recorded on a Nexus series intelligent Fourier infrared spectrometer. The
scanning range was 400–4000 cm− 1 with 32 scans and a 4 cm− 1 reso­
lution ratio. The synthesized zeolite samples were fully ground with KBr
in a mass ratio range from 1:50 to 1:100. Then the mixture was pressed
into a transparent self-supporting wafer. Transmission electron micro­
scopy (TEM) was used to study the evolution of the nanosized zeolite gel.
TEM was carried out on an FEI Tecnai F20 field emission transmission
electron microscope. The element mapping analysis was carried out by
TEM equipped with an energy-dispersive X-ray spectrometry system.
Besides, the morphology and microstructure were observed by TEM and
scanning electron microscope (SEM). SEM was carried out using a
P. Liu et al.
SU8010 field emission scanning electron microscope equipped with a
tungsten filament. The texture properties of synthesized zeolites were
determined by N2 physical adsorption and desorption on a Micro­
meritics TriStar 2020 apparatus. The total surface area, micropore sur­
face area, and pore size distribution were determined by
Brunauer–Emmett–Teller (BET) method, t-plot method, and Bar­
rett–Joyner–Halenda (BJH) method respectively. The elemental analysis
of synthesized zeolite samples was carried out using X-ray fluorescence
(XRF) on a PANalytical Axios instrument. The differential scanning
calorimetry (DSC) of synthesized zeolite samples was determined on an
HCT-1/2/3/4 comprehensive thermal analyzer. The samples were
heated in a crucible at a heating rate of 10 C/min in an air atmosphere
◦
from 25 C to 1000 C. The acid properties of the H-formed Y zeolite
◦ ◦
were determined by a Thermo Fisher Nicolet iS50 spectrometer. The 20
mg dehydrated zeolite sample was pressed into a self-supporting wafer
under 5 MPa pressure and placed in an infrared vacuum cell equipped
with a CaCl2 window, and then degassed at 400 ◦ C and 10− 5 Pa for 2 h.
After cooling down to room temperature, the sample was adsorbed in
contact with pyridine vapor for 3 min and equilibrated for 15 min to
achieve adsorption saturation. Afterward, the sample adsorbed pyridine
was evacuated at 200 ◦ C and 350 ◦ C for measuring the total acid and
strong acid, respectively. The Py-IR spectra were collected in the range
from 1300 to 1800 cm− 1 with 32 scans and a 4 cm− 1 resolution ratio at
room temperature. The concentration of Brønsted and Lewis acids was
calculated in the areas at 1545 cm− 1 and 1450 cm− 1, respectively [35].
2.3. Catalytic test
The catalytic behaviors of the H-formed Y zeolite here in the catalytic
cracking of 1,3,5-triisopropylbenzene (TIPBz, Sigma-Aldrich, 95 wt%)
were carried out in a fixed bed reactor. Prior to reaction, 100 mg of the
catalyst with 40–60 mesh was loaded in the reactor and enclosed be­
tween two layers of quartz wool, and then activated at 400 ◦ C in an Ar
flow of 40 mL min− 1 for 1 h. After that, the reactor was cooled down to
the reaction temperature of 200 ◦ C. The TIPBz was vaporized and added
to the Ar carrier of 100 mL min− 1, and then passed through the catalyst
bed. The volume flow ratio of TIPB (FTIPBz) was controlled as 10 μl
min− 1 by a serriesII liquid pump. The reaction products were analyzed
Fig. 1. XRD patterns (A), N2 adsorption/desorption isotherms (B), and pore-size distribution (adsorption branch (C) and desorption branch (D)) of NaY-Contrast,
NaY–NaCl-13.3, NaY–NaBr-10.0, and NaY–NaI-10.0 zeolite samples.
3
Microporous and Mesoporous Materials 347 (2023) 112341
online using a gas chromatograph (GC) with a flame ionization detector
(FID).
3. Results and discussion
3.1. Properties of nanosized NaY zeolite
3.1.1. Structure characteristics of nanosized zeolite
The structure characteristics and morphology of nanosized NaY
zeolite under the stimulation of sodium halides (NaCl, NaBr, or NaI)
were explored by XRD, N2 physical adsorption-desorption, and SEM.
The corresponding XRD results are listed in Fig. 1 A, Table 1, Fig. S1, and
Table S1 respectively. It is can be seen that the synthesized zeolite
samples under the introduction of sodium halides exhibit typical FAU-
type peaks. The relative crystallinity of NaY–NaCl-13.3, NaY–NaBr-
10.0, and NaY–NaI-10.0 zeolites show lower than NaY-Contrast zeolite.
It is evidenced that the crystallization process of Y zeolite should be
interfered with due to the introduction of sodium halides. Moreover,
there are different crystallization performances for different kinds of
sodium halides. Among three sodium halides, the relative crystallinity of
NaY–NaCl-x and NaY–NaBr-x zeolite samples show a downtrend with
the increased concentration of NaCl, NaBr, and NaI. And the relative
crystallinity of zeolite samples by introducing NaCl and NaBr is lower
than the one of introducing NaI. The unit cell size of NaY–NaCl-x,
NaY–NaBr-x, and NaY–NaI-x zeolite samples is more shrunken than the
one of NaY-Contrast zeolite. It is shown that more framework silicon was
formed under the facilitation of sodium halides. Because the bond length
of Si–O (1.62 Å) is lower than the one of Al–O (1.75 Å). Therefore, the
higher framework SiO2/Al2O3 mole ratios for NaY–NaCl-x, NaY–NaBr-x,
and NaY–NaI-x zeolites than NaY-Contrast zeolite are shown in Table 1
and Table S1. This is consistent with the results reported by Sun and Yu.
They found that halides anion facilitated the formation of Si–O–Si bonds
in zeolite thus increasing the SiO2/Al2O3 mole ratio of MOR zeolite [33].
The results here show that sodium halides (NaCl, NaBr, and NaI) should
have the same effect on increasing the framework SiO2/Al2O3 mole ratio
of zeolite. In addition, from Table 1, it is can be seen that the framework
SiO2/Al2O3 mole ratio is lower than the bulk SiO2/Al2O3 mole ratio for
the synthesized zeolite samples. It is indicated that the absence of
P. Liu et al. Microporous and Mesoporous Materials 347 (2023) 112341

Table 1
SiO2/Al2O3 mole ratio and textural properties of NaY-Contrast, NaY–NaCl-13.3, NaY–NaBr-10.0, and NaY–NaI-10.0 zeolite samples determined by XRD, XRF, and N2
physical adsorption-desorption, respectively.
Samples SiO2/Al2O3 mole ratioa SiO2/Al2O3 mole ratiob SBETc m2⋅g− 1
SMicrod m2⋅g− 1
SExternale m2⋅g− 1
Vtotalf cm3⋅g− 1
Vmicrog cm3⋅g− 1
Vmesoh cm3⋅g− 1

NaY-Contrast 5.05 5.20 746 713 33 0.381 0.349 0.032

NaY–NaCl-13.3 5.16 5.20 675 606 69 0.456 0.318 0.138
NaY–NaBr- 5.12 5.22 661 592 69 0.476 0.311 0.165
10.0
NaY–NaI-10.0 5.14 5.33 647 606 41 0.387 0.318 0.069
a
XRD.
b
XRF.
c
BET method.
d
t-plot method.
e
SExternal = SBET - SMicro.
f
Volume absorbed at p/p0 = 0.9944.
g
t-plot method.
h
Vmeso = Vpore - Vmicro.

extra-framework aluminum is formed in the synthesized zeolites.
3.1.2. Morphology of nanosized zeolite
The morphologies of the synthesized zeolite samples are shown in
Fig. 2 and Figs. S2–S4. From Figs. S2–S4 in Supporting Information, it is
exhibited that the zeolites crystal size decreases first and then increases
with the increasing concentration of sodium halides. However, NaCl,
NaBr, and NaI have different degrees of influence on the zeolite crystal
size. Among the three kinds of sodium halides, NaCl and NaBr are more
conducive to the synthesis of nanosized NaY zeolite crystal. In addition,
it can be seen from Table S2 in Supporting Information that the average
crystallite size calculated by Scherrer’s equation is significantly smaller
than the mean crystal size of zeolite obtained by SEM. It should be
ascribed to the fact that there are crystal cluster environments [20].
Although there are differential results between XRD and SEM in the size
of zeolite samples, both results show that the crystallite size of the
synthesized Y zeolite can be reduced by the introduction of sodium
halides.
3.1.3. Texture properties of nanosized zeolite
The texture properties of the synthesized zeolite samples are listed in
Fig. 1 and Table 1. From Fig. 1B, it is can be seen that the NaY-Contrast
zeolite sample shows a typical I isotherm curve of microporous Y zeolite
materials. Compared to NaY-Contrast zeolite, both NaY–NaCl-13.3 and
NaY–NaBr-10.0 zeolite samples show an uptake trend at the range of
0.2–0.8 relative pressure. Upon the relative pressure excessing 0.8, the
isotherm curves for NaY–NaCl-13.3 and NaY–NaBr-10.0 zeolites display
a sharp uptake. Both exhibit a mix of type I and type II isotherm curves,
determining that the aggregated small-sized zeolite crystals are formed
for NaY–NaCl-13.3 and NaY–NaBr-10.0 zeolites [36]. It is consistent
with the formed nanosized zeolite crystal for NaY–NaCl-13.3 and
NaY–NaBr-10.0 zeolites, which result in the formation of higher meso­
porous volume in Table 1 for NaY–NaCl-13.3 and NaY–NaBr-10.0 zeo­
lites than NaY-Contrast zeolite. Though a sharp uptake isotherm curve is
shown in NaY–NaI-10.0 zeolite at higher relative pressure, the meso­
porous volume is not formed. From the results of pore size distribution in
Fig. 1 C-D and Fig. S5 in Supporting Information, NaY–NaBr-10.0 and
NaY–NaCl-13.3 zeolites display obviously mesoporous and macroporous
size distribution, which shows that the close packing of smaller zeolite
crystals is formed for NaY–NaBr-10.0 and NaY–NaCl-13.3 zeolites. This
is consistent with the results we reported earlier [5]. Unfortunately, the
micropore areas for NaY–NaCl-13.3 and NaY–NaBr-10.0 zeolites are
lower than the ones for NaY-Contrast zeolite. It should be related to the
lower relative crystallinity for NaY–NaCl-13.3 and NaY–NaBr-10.0
zeolites.
3.1.4. Thermal stability of nanosized zeolite
The thermal stabilities of the synthesized zeolite samples are shown
in Fig. S6, Supporting Information. The structural collapse temperatures
of the synthesized zeolite samples exhibit an order of NaY–NaCl-13.3 ≈
NaY–NaBr-10.0 < NaY–NaI-10.0 < NaY-Contrast. Because the thermal
stability of zeolites is not only related to the framework SiO2/Al2O3 mole

Fig. 2. SEM images and crystal size distribution of (A, a) NaY-Contast, (B, b) NaY–NaCl-13.3, (C, c) NaY–NaBr-10.0, and (D, d) NaY–NaI-10.0 zeolite samples,
respectively.

4
P. Liu et al.
ratio, but also to its crystal size. The thermal stability of zeolite decreases
with the decrease of zeolite crystal size [37,38]. It is also indicated that
the NaY zeolite crystal size can be significantly reduced by introducing
NaCl and NaBr.
3.2. Crystallization investigation of nanosized zeolite
According to the above results, it was clear that NaCl and NaBr can
significantly reduce the crystal size of Y zeolite, and obtain nanosized Y
zeolite. How does the sodium halides reduce the crystal size of Y zeolite?
And what is the relationship between sodium halides and the formation
of Y zeolite nuclei? Next, the crystallization process of nanosized Y
zeolite under the introduction of NaCl and NaBr is investigated in detail
by XRD, TEM, and FT-IR.
The evolution and transformation of the amorphous gel micro­
structure are firstly analyzed by XRD. The XRD patterns of the aliquots
taken from the gel at different crystallization times are listed in Fig. 3
and Fig. S7 (Supporting Information). The relative crystallization of the
samples taken from the gel at different crystallization times is shown in
Table S3. From Fig. 3 A-D, it is shown that none of the gels before the
crystallization time of 4 h show obvious XRD characteristic peaks. Until
the crystallization time reaches 6 h, the gel with the addition of NaCl
(Fig. 3 B and E) and NaBr (Fig. 3C and E) begins to appear at the (111)
crystal plane peak. And, in addition to the (111) crystal plane peak, the
former also shows other characteristic peaks of (331), (533), and (642)
belonging to FAU zeolite. The relative crystallinities at 6 h for
NaY–NaCl-13.3 and NaY–NaBr-10.0 are 2% and 0%, respectively, in
Table S3. It is indicated that FAU zeolite crystals begin to appear in the
gel with NaCl at 6 h, while FAU zeolite crystals have not yet appeared in
the gel with NaBr. Instead, for the gel of NaY-Contrast (Fig. 3 A and E)
and NaY–NaI-10.0 (Fig. 3 D and E) samples, the crystallization time
needs to be extended to 11 h and 9 h, respectively, before the charac­
teristic peak of (111) begins to appear. Although the (111) crystal plane
peaks have appeared (Fig. 3 E), the relative crystallinities of the gel
samples are still zero (Table S3). It is indicated that the gels at 6 h for
NaY–NaBr-10.0, 9 h for NaY–NaI-10.0, and 11 h for NaY-Contrast are
still in the induction period. After that, some of the XRD characteristic
peaks belonging to FAU zeolite are shown in Fig. 3 A-D and Fig. S7, and
their relative crystallinities are increased gradually (Table S3), which
Fig. 3. (A–D) XRD patterns of samples taken from the gel of (A) NaY-Contrast at 4–14 h, (B) NaY–NaCl-13.3 at 2–8 h, (C) NaY–NaBr-10.0 at 2–8 h, and (D) NaY–NaI-
10.0 at 2–11 h. (E) The enlarged view of 5–10 (2 Theta (Deg.)) XRD patterns from NaY-Contrast-11 h, NaY–NaCl-13.3–6 h, NaY–NaBr-10.0–6 h, and NaY–NaI-9h. (G)
Crystallization curves of NaY-Contrast, NaY–NaCl-13.3, NaY–NaBr-10.0, and NaY–NaI-10.0 zeolites.
5
Microporous and Mesoporous Materials 347 (2023) 112341
represent the formation and growth of FAU zeolite crystal. When the
relative crystallinity of the samples reaches more than 90%, the crys­
talization process of these zeolites is complete basically. The crystali­
zation time of NaY–NaCl-13.3 (12 h) and NaY–NaBr-10.0 (12 h) is
significantly shorter than NaY-Contrast (23 h). The crystallization
curves of these zeolite samples are shown in Fig. 3 G. It can be obtained
that the induction period and zeolite crystal growth for NaY–NaCl-13.3
and NaY–NaBr-10.0 are shorter and more rapid than NaY-Contrast.
Zeolite nucleation is a prerequisite for its crystal growth. The induc­
tion period is the crucial stage of nucleation. And the formation of a
large number of FAU nuclei is directly related to the nanosized Y zeolite
crystal. Therefore, from the crystallization curves in Fig. 3 G, it can be
deduced that more FAU zeolite nuclei should be formed in the shorter
induction period by the introduction of NaCl and NaBr into the gel.
Regarding Y zeolite nucleation, the place where the zeolite nucle­
ation takes place is the key point during amorphous gel transformation.
The negative crystal regions were recognized to be the key place for FAU
zeolite nucleation [5,29,30]. Does it mean that the more negative crystal
regions, the more FAU zeolite nuclei? Transmission electron microscopy
technology is a widely used and better characterization method to study
the formation and evolution of negative crystal and zeolite gel [5,12,29,
30]. Hence, the evolution of amorphous gel under the function of NaCl
and NaBr is investigated by TEM to uncover the relationship between
sodium halides (NaCl and NaBr) and the formation of nanosized Y
zeolite.
TEM images of initial gel at 6 h for NaY-Contrast, NaY–NaCl-13.3,
and NaY–NaBr-10.0 are shown in Fig. 4. There are three kinds of the
amorphous gel shown in Fig. 5: (1) bulk gel with fewer bright spot
particles for NaY-Contrast, as shown in Fig. 4 A, which is consistent with
the conventional NaY zeolite gel [29], and (2) small gel containing many
bright spot particles as shown in Fig. 4 B, (3) small gel with higher
numbers of bright spot particles that are more homogeneously distrib­
uted as shown in Fig. 4C. The bright spot particles are measured to be a
size ranging from 5 nm to 20 nm. The bright spot particles in
NaY-Contrast gel are fewer and mainly distributed in the periphery of
the gel as shown in Fig. 4a white arrow. On the contrary, the bright spot
particles in NaY–NaCl-13.3 and NaY–NaY–NaBr-10.0 gel are much more
distributed uniformly in the gel. It is indicated that the formation of
bright spot particles is promoted due to the introduction of NaCl and
P. Liu et al.
Fig. 4. TEM images of the gel material without sodium halides (A, a) and with NaCl (B, b) and NaBr (C, c) during the initial crystallization stages at 6 h.
NaBr. Meanwhile, at high magnifications, it can be seen from the gel of
NaY–NaCl-13.3 and NaY–NaBr-10.0 that the outlines of some bright spot
particles are straight and faceted, resembling crystal faces, and some
bright spot particles still show curves outlines. The change of the shape
of the bright spot particles from curved to faceted was recognized to be
direct proof that some reorganization has taken place at the interface of
dense gel and bright spot particles [30]. Also, these faceted bright spot
particles with a highly hydrated silica phase were identified to be
negative crystals by Bonev, Viti, and Valtchev [30,39,40]. Therefore, it
is indicated that the crystal phase transformation of gel particles for
NaY–NaCl-13.3 and NaY–NaBr-10.0 is earlier than the one for
NaY-Contrast, and structure units required for the Y zeolite crystal
growth should be formed. Meanwhile, the elemental compositions of
these gel regions are obtained by EDS, as shown in Table 2. The EDS
6
Microporous and Mesoporous Materials 347 (2023) 112341
results show that the Si/Al ratios of these three gel regions exhibit an
order of NaY–NaBr-10.0 > NaY–NaCl-13.3 > NaY-Contrast. It is indi­
cated that more silicon sources were concentrated in gel with rich bright
spot particles. In addition, the Na elemental compositions for
NaY–NaCl-13.3 and NaY–NaBr-10.0 are more than NaY-Contrast. It is
ascribed to the introduction of NaCl and NaBr into the gel. The element
mapping of the corresponding gels for NaY–NaCl-13.3 (Fig. S8) and
NaY–NaBr-10.0 (Fig. S9) indicate that a few of Cl− and Br− are dispersed
around the gel due to the electrostatic repulsion force of anions in the
gel. Na+, and most of Cl− and Br− are distributed in the bright spot
particle regions. Therefore, it can be obtained that the formation of
negative crystals is promoted in induction period by NaCl or NaBr. Does
this mean that more FAU zeolite nuclei can able to be incubated by the
introduction of NaCl and NaBr into Y zeolite gel? Next, the growth
P. Liu et al. Microporous and Mesoporous Materials 347 (2023) 112341

Fig. 5. (A–C) Low magnification TEM images of the gel material crystalized at 14 h without sodium halides (A), crystalized at 8 h with NaCl (B) and NaBr (C). (b–c)
High-magnification TEM images of gel with NaCl (b) and NaBr (c) shown in B (blue square region) and C (green square region). (For interpretation of the references
to colour in this figure legend, the reader is referred to the Web version of this article.)

with the size ranging from 200 nm to 300 nm are formed. In addition,
Table 2
there are still some bulk amorphous gels that have not been transformed
Elemental analysis of different gel samples taken from NaY-Contrast, NaY–NaCl-
to form Y zeolite crystals. It is consistent with the relative crystallinity of
13.3, and NaY–NaBr-10.0, respectively, determined by EDS.
53% (Table S3). For the other two gels with NaCl (Fig. 5B) and NaBr
Samples Elemental composition in the gel for 6 h Si/Al (Fig. 5C), some smaller Y zeolite crystals with a size of about 100 nm are
Na, % Si, % Al, % Cl, % Br, % formed, though some small amorphous gel particles are still present.
NaY-Contrast 3.60 27.99 11.45 – – 2.44 This can also be consistent with the relative crystallinity of 52% and
NaY–NaCl-13.3 4.56 24.39 7.71 0.58 – 3.16 37% for NaY–NaCl-13.3 and NaY–NaBr-10.0 (Table S3), respectively.
NaY–NaBr-10.0 5.67 24.80 3.93 – 0.69 6.31 The amorphous gel regions for NaY–NaCl-13.3 and NaY–NaBr-10.0
corresponding to blue square (Fig. 5B) and green square (Fig. 5C) are
further studied in detail by high-magnification TEM, as shown in Fig. 5b-
process of zeolite crystals continues to be investigated, aiming to further
c, respectively. It can be seen from Fig. 5b-c that in addition to Y zeolite
clarify the relationship between negative crystals and FAU zeolite nuclei
crystals, the gels of NaY–NaCl-13.3 and NaY–NaBr-10.0 present more
and the reason for the formation of nanosized Y zeolite in the gel con­
negative crystals than NaY-Contrast (Fig. S10). HRTEM images show
taining NaCl and NaBr.
that some negative crystals are disappeared, which is due to the
With the extension of crystallization time to 14 h and 8 h for NaY-
extremely unstable property and collapse of these negative crystals
Contrast, NaY–NaCl-13.3, and NaY–NaBr-10.0, respectively, the TEM
under the high-intensity electron beam [29]. Moreover, it is worth
images of their gel are shown in Fig. 5 and Fig. S10. For the gel of NaY-
mentioning that, in some gel with rich negative crystals as shown in
Contrast (Fig. 5A and Fig. S10), some well-shaped NaY zeolite crystals

7
P. Liu et al. Microporous and Mesoporous Materials 347 (2023) 112341

Fig. 5c, some crystal structures with lattice fringes attributed to the
(111) reflections of Y zeolite begin to be formed. And the formed zeolite
crystals show aggregates of randomly intergrown crystallites. Such re­
veals that the negative crystal regions should be the crystallization
centers of Y zeolite. During the growth stage of zeolite crystals, the
synthesized gels maintain the mixture of amorphous gel and zeolite
crystal aggregates. With the crystallization time extension, the Y zeolite
crystals continue to grow and the amorphous gel particles are gradually
consumed. Until the crystallization time reaches 12 h for NaY–NaCl-13.3
(Fig. S11), and NaY–NaBr-10.0 (Fig. S12), the amorphous gels are
consumed completely, and the growth of Y zeolite crystals maintain in
equilibrium. It is consistent with the 92% relative crystallinity of
NaY–NaCl-13.3 and NaY–NaBr-10.0 (Table S3). In view of this obser­
vation, a crystallization mechanism of Y zeolite follows the progressive
transformation of the amorphous gel phase. Therefore, it can be deduced
that the formation of more negative crystals can be promoted by the
introduction of NaCl and NaBr into the gel, resulting in the formation of
more FAU nuclei, thus effectively preparing nanosized Y zeolite.

Fig. 6. FT-IR spectra of samples taken from the gel at some typical crystallization time in the synthesis of (A, a) NaY-Contrast, (B, b) NaY–NaCl-13.3, (C, c)
NaY–NaBr-10.0, and (D, c) NaY–NaI-10.0, respectively. FT-IR spectra in different wavenumber ranges from (A–D) 400-4000 cm− 1 and (a–d) 500-600 cm− 1,
respectively.

8
P. Liu et al.
In the following study, FT-IR is used to further investigate the
microstructure transformation during the crystallization process of
zeolite gel.
FT-IR spectra of samples taken from the gel at some typical crystal­
lization time in the preparation of NaY-Contrast, NaY–NaCl-13.3,
NaY–NaBr-10.0, and NaY–NaI-10.0 are shown in Fig. 6. Structure-
sensitive vibrations near 580 cm− 1, 722 cm− 1, and 792 cm− 1 belong
to the double six-ring (D6R), [T (Si or Al)O4] symmetric stretching vi­
bration in the inner framework, TO4 symmetric stretching vibration in
the outer framework, respectively, of Y zeolite [38,41]. Before crystal­
lization for 2 h, the above three structure vibrations, especially double
six-ring at 580 cm− 1, have not been established obviously in the gel of
NaY-Contrast, NaY–NaCl-13.3, NaY–NaBr-10.0, and NaY–NaI-10.0. It is
indicated that the gels before 2 h undergo a simple structural rear­
rangement, which is not enough to form more structural units belonging
to Y zeolite that can be detected by FT-IR. This is consistent with the
XRD results (Fig. 3, Fig. S7, and Table S3). There are none of the XRD
characteristic peaks of Y zeolite before 2 h. With the extension of crys­
tallization time to 6 h, only the gels of NaY–NaCl-13.3 and
NaY–NaBr-10.0 show the stronger structure vibration of D6R at 580
cm− 1 (Fig. 6b-c). For the gel without sodium halides, the emergence
time of the D6R band is delayed by at least 11 h (Fig. 6a). Furthermore,
the gels at 5 h in NaCl and NaBr systems are detailed studied by XRD and
FT-IR. The XRD and FT-IR results of the gel at 5 h in the NaCl and NaBr
systems are listed in Fig. S13 (Supporting Information). Fig. S13 A-B
shows no XRD characteristic peaks in the gel for NaY–NaCl-13.3 and
NaY–NaBr-10.0 at 5 h. It is indicated that there is no zeolite crystallite
being formed in the two gels. Interestingly, Fig. S13 C–F shows that the
D6R peak at about 580 cm− 1 has been developed in the gel for
NaY–NaCl-13.3 and NaY–NaBr-10.0 at 5 h. It shows that D6R structure
units have been formed before forming FAU zeolite crystallite. This
result proves that the addition of NaCl and NaBr to the gel accelerates
the formation of D6R in the amorphous aluminosilicate prior to the
nucleation.
Negative crystals provide the key place for the formation of FAU
nuclei. And D6R structure units play an essential role during FAU zeolite
nucleation. Therefore, FAU zeolite nucleation can be promoted through
the facile method for stimulating the formation of negative crystals by
NaCl or NaBr, thus effectively prepare smaller-sized Y zeolite crystals.
After a crystallization time of 6 h, the intensity of the D6R band for
NaY–NaCl-13.3 and NaY–NaBr-10.0 becomes sharper and other struc­
ture vibrations also become clear and can be distinguished. It is also
indicated that the induction period is finished and the Y zeolite crystals
begin to be formed. These results are consistent with the XRD and TEM
results of the emergence of Y zeolite characteristic diffraction peaks and
Y zeolite crystals after 6 h.
Moreover, the increase in the intensity of the structure-sensitive
bands at 580 cm− 1, 722 cm− 1, and 792 cm− 1 is accompanied by the
decrease of the band at about 885 cm− 1. The band at about 885 cm− 1
was assigned to a Si–OH bending vibration, and the decrease of this band
suggested that the number of framework atoms connected via oxygen
bridges increased with time [29]. Here, during the whole crystallization
process of NaY–NaCl-13.3 and NaY–NaBr-10.0 zeolite, the band at 885
cm− 1 shows a gradual decrease. This band does not disappear
completely until the crystallization process reaches equilibrium (Fig. 6B
and C). On the contrary, the band intensity at 885 cm− 1 for the gel of
NaY-Contrast shows a significant decrease in the early crystallization
stage. In addition, from the analysis of TEM and XRD results, the Si/Al
ratio of amorphous gels with NaCl or NaBr was significantly improved.
And the zeolite framework SiO2/Al2O3 mole ratio was increased by NaCl
or NaBr. Therefore, it means that more gel particles with Si–OH need to
be transformed into zeolite stuctural units during the crystallization
process, such as D6R units or sodalite cage units, due to the introduction
of NaCl or NaBr, which is also an essential factor the formation of FAU
zeolite nuclei.
According to the above-detailed characterization and discussion of
9
Microporous and Mesoporous Materials 347 (2023) 112341
the crystallization process of NaY–NaCl-13.3 and NaY–NaBr-10.0, it is
revealed that NaCl and NaBr play a key role in the synthesis of nanosized
NaY zeolite, which is mainly reflected in the stimulation of negative
crystals to accelerate the formation of D6R building units. Therefore, the
crystallization mechanism of nanosized NaY–NaCl-13.3 and NaY–NaBr-
10.0 zeolites is speculated as follows (Fig. 7). The amorphous gel crys­
tallization process of nanosized NaY–NaCl-13.3 and NaY–NaBr-10.0
zeolites is divided into three stages, including the induction period,
crystal growth, and Ostwald ripening stage. Firstly, the induction period
includes chemical evolution coupled with the microstructural trans­
formation of the initial gel and the formation of FAU nuclei with D6R
building units. NaCl or NaBr attract more silicate ions and promote the
polymerization between silicate ions and aluminosilicate, which stim­
ulates the negative crystals to accelerate the formation of FAU nuclei
contained in D6R building units. This process, where evolution by
propagation in the interface between dense-gel and negative crystals
dominates, takes about 6 h. Secondly, the FAU nuclei gradually grow up
by consuming the nutrients in the dense-gel phase and begin to form the
FAU crystal structure at the interface between the negative crystals and
the dense gel. Once the FAU crystal structure is formed, the dense-gel
aggregates collapse, and fast crystallization takes place around the
FAU nuclei center. Due to the formation of abundant negative crystals
and FAU nuclei, in the gel system with the same nutrient content as the
conventional synthesized method, each FAU nucleus consumes limited
nutrients and grows into a Y zeolite crystal with a smaller size. This
process, where propagation of the amorphous gel and aggregation of
crystal particles take place simultaneously, takes about 6 h. Thirdly, as
the amorphous gel is totally exhausted, the crystallization process enters
the Ostwald ripening stage. At this stage, the smaller Y zeolite crystals
continue to grow and the nutrients are provided by the dissolution of the
less stable zeolite crystals.
3.3. Catalysis performance
These results highlight that nanosized Y zeolites can be prepared
efficiently by the facile method of applying NaCl or NaBr in a very short
time of 12 h. As the Y zeolite crystal size decreases, amounts of acid
centers are exposed on the outer surface, which will significantly
enhance the conversion capacity of heavy oil. As far as catalytic appli­
cations of the nanosized Y zeolite are concerned, the dealkylation of a
bulky molecule, 1,3,5-triisopropylbenzene (TiPBz), is often considered
to evaluate the external surface properties of the nanosized Y zeolite [1,
42,43]. Therefore, the four kinds of H-formed Y zeolite of HY-Contrast,
HY-NaCl-13.3, HY-NaBr-10.0, and HY-NaI-10.0 zeolites were prepared
by NH+ 4 ion-exchange and calcination.
The TIPBz conversions and the associated selectivities for HY-
Contrast, HY-NaCl-13.3, HY-NaBr-10.0, and HY-NaI-10.0 zeolites are
reported in Fig. 8. Fig. 8A shows that among the synthesized nanosized
Fig. 7. Schematic illustration of the crystallization mechanism of NaY zeolite
with the stimulation of NaCl or NaBr.
P. Liu et al.
Fig. 8. Catalytic cracking of TIPBz on HY-Contrast, HY-NaCl-13.3, HY-NaBr-10.0, and HY-NaI-10.0 catalysts. (A) TIPBz cracking conversion versus time on stream
plotted with the error bar. (B) Selectivity on these catalysts during the TIPBz conversion for propylene, benzene, cumene, and DIPB under identical conditions.
Reaction conditions: Temperature = 200 ◦ C, FTIPBz = 10 μL min− 1. FTIPBz is defined as the volume flow ratio of TIPBz.
zeolites, only HY-NaBr-10.0 zeolite exhibits higher initial TIPBz con­
version than HY-Contrast zeolite. Fig. 8B indicates that the cracking
depth increase with the decrease in zeolite crystal size, except for
nanosized HY-NaCl-13.3. It is implied that the activity and selectivity of
these catalysts are not only related to the crystal size but also impor­
tantly determined by structural and acid properties. On the one hand,
these three nanosized zeolite catalysts for HY-NaCl-13.3, HY-NaBr-10.0,
and HY-NaI-10.0 show closing relative crystallinity and elemental
composition, including framework and bulk SiO2/Al2O3 mole ratio, and
NaO2 content (Fig. S14 and Table S4). Besides, their surface areas show
obviously lower than HY-Contrast (Fig. S15 A and Table S5). Fortu­
nately, these three nanosized zeolites show superior pore structure than
that of HY-Contrast (Fig. S15 B–C and Table S5), which provides ad­
vantageous reaction space for TIPBz conversion. On the other hand, the
Py-IR results indicate that HY-NaBr-10.0 zeolite shows higher total
Brønsted acid concentrations (210 μmol g− 1) and strong Brønsted acid
concentrations (102 μmol g− 1) than HY-Contrast zeolite in Supplemen­
tary Fig. S16 and Table S6, which promote the deep cracking of TIPBz to
form much more propylene. Though the same crystal size as for HY-
NaCl-13.3 and HY-NaBr-10.0, the Brønsted acid concentrations in HY-
NaCl-13.3 zeolite are extremely lower than HY-Contrast zeolite, which
results in the poor catalytic cracking properties. This should be related to
the different local environments of silicon and aluminum in the frame­
work and extra-framework of these zeolites.
In addition, at the initial reaction period from 15 min to 30 min
(Fig. 8A), the conversion on HY-Contrast zeolite decreases by 35.5%,
while HY-NaBr-10.0 and HY-NaI-10.0 decrease by 21.1% and 21.8%,
respectively. It is indicated that HY-NaBr-10.0 and HY-NaI-10.0 zeolites
show higher initial stability than HY-Contrast zeolite. It is ascribed to the
higher mesoporosity and acidity for the first two zeolites than that for
HY-Contrast zeolite. The conversion on HY-Contrast zeolite is reduced to
below 10% after a 75 min process time and the loss of conversion rea­
ches 83.8%. Among the other three zeolites, only the conversion on HY-
NaBr-10.0 remains above 40% at 75min, and its loss of conversion is
56.7%. Therefore, the stability of HY-NaBr-10.0 zeolite is best than that
of the other three zeolites. Meanwhile, HY-NaBr-10.0 and HY-NaI-10.0
show higher overall selectivity of propylene, benzene, and cumene
than HY-Contrast (Fig. 8B), suggesting that the larger mesoporosity in
the two zeolite crystallites improves the accessibility to and diffusion in
their crystallites. Though the larger mesoporosity is also presented in
HY-NaCl-13.3 zeolite crystallite, its poor acidity is insufficient to support
further cracking of dipropylbenzene (DIPBz), which leads to lower
overall selectivity of propylene, benzene, and cumene than others zeo­
lites. Therefore, the nanosized HY-NaBr-10.0 zeolite show superior
catalytic cracking properties of the heavy oil molecule.
4. Conclusions
In conclusion, the synthesis strategy in this work opens a facile way
10
Microporous and Mesoporous Materials 347 (2023) 112341
for the rapid preparation of template-free nanosized Y zeolite under the
traditional preparation conditions of NaY zeolite. It is found that NaCl or
NaBr was used here to regulate the micro-structural transformation of
the initial amorphous gel in the synthesis induction period of NaY
zeolite, which involved the promotion of the polymerization between
silicate ions and aluminosilicate and stimulation of many more negative
crystals to accelerate the formation of D6R building units, thus realizing
the efficient synthesis of nanosized NaY zeolite. As a result, the crys­
tallization time was significantly shortened by nearly 11 h. The syn­
thesized nanosized Y zeolite showed exceptional properties, including
small crystal size about 100 nm, large pore volume (0.476 cm3 g− 1), and
rich mesoporous volume (0.165 cm3 g− 1). The nanosized HY-NaBr-10.0
zeolite showed superior catalytic cracking properties of the heavy oil
molecule. Moreover, these nanosized NaY zeolites here deserve further
research in the future to develop their performance in adsorption,
catalysis, and biomedicine et al.
Supporting information
XRD patterns, relative crystallinity, SiO2/Al2O3 mole ratio, and unit
cell of zeolite samples prepared by introduction of sodium halides into
the liquid structure-directing agent. SEM images and crystal size dis­
tribution of NaY-Contrast, NaY–NaCl-x, NaY–NaBr-x, and NaY–NaI-x
zeolites. TG and DSC curves of NaY-Contrast, NaY–NaCl-13.3,
NaY–NaBr-10.0, and NaY–NaI-10.0 zeolites. XRD patterns and relative
crystallinity of samples taken from gel at different crystallization time in
the synthesis of NaY-Contrast, NaY–NaCl-13.3, NaY–NaBr-10.0, and
NaY–NaI-10.0, respectively. Element mapping of the corresponding
amorphous gel for NaY–NaCl-13.3 and NaY–NaBr-10.0. TEM images of
the gel material crystalized at 14 h without sodium halides. TEM images
of the gel crystalized at 12 h under the introduction of NaCl and NaBr
into the gel, respectively. The characterization of HY-Contrast, HY-NaCl-
13.3, HY-NaBr-10.0, and HY-NaI-10.0 zeolites by XRD, XRF, N2
adsorption-desorption, and Py-IR.
CRediT authorship contribution statement
Peng Liu: Writing – review & editing, Writing – original draft,
Visualization, Validation, Supervision, Software, Resources, Project
administration, Methodology, Investigation, Funding acquisition,
Formal analysis, Data curation, Conceptualization. Chengqu Yu:
Investigation, Funding acquisition, Formal analysis, Data curation.
Weixue Li: Writing – review & editing, Writing – original draft, Funding
acquisition, Formal analysis. Baojian Shen: Writing – review & editing,
Investigation, Formal analysis.
Declaration of competing interest
The authors declare that they have no known competing financial
P. Liu et al.
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
We acknowledge the financial support provided for this project by
Doctoral Scientific Research Start-up Foundation from Henan Normal
University (5101039170345 and 5101039170342).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.micromeso.2022.112341.
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