Microporous and Mesoporous Materials 323 (2021) 111248

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Microporous and Mesoporous Materials

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A facile organic-free synthesis of high silica zeolite Y with small crystal in

the presence of Co2+
Bo Meng a, 1, Shenyong Ren a, *, 1, Zhi Li b, Suofu Nie a, Xinyue Zhang a, Weiyu Song b,
Qiaoxia Guo b, Baojian Shen a, **
a
State Key Laboratory of Heavy Oil Processing, The Key Laboratory of Catalysis of CNPC, College of Chemical Engineering and Environment, China University of
Petroleum, No. 18 Fuxue Road, Changping, Beijing, 102249, China
b
College of Sciences, China University of Petroleum, No. 18 Fuxue Road, Changping, Beijing, 102249, China

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

Keywords: The direct synthesis of zeolite Y with high SiO2/Al2O3 (SAR > 6.0) and small crystal size is a great challenge. The
Small crystal conventional production of high silica Y usually involves organic template into the synthesis system, which takes
High SiO2/Al2O3 high cost. Here, zeolite Y with SAR of 6.15 and small crystal size via introducing Co2+ in a facile one-step hy­
Zeolite Y
drothermal method without organic template was achieved. The SAR increased from 5.2 to 6.15 compared to
Co
normal NaY, and the crystal size decreased to 50%. The introduction of Co2+ in synthesis system affects the
Crystallization process
formation of 5-coordination intermediate (M-O-Si)* around Co2+ during crystallization process which is the
critical factor to nucleation. The stability of (Co–O–Si)* is weaker than that of (Al–O–Si)*, which leads to the
increase of SAR around Co2+. The microcrystals of Co(OH)2 provide adhesive surface for the amorphous material
and promote nucleation. The zeolite Y shows good performance in the cracking of 1,3,5-triisopropylbenzene
because of larger surface area and more active sites being exposed. This is a new strategy for industrial syn­
thesis of high SiO2/Al2O3 and small crystal size zeolite Y.

1. Introduction
Due to the acidity and structural properties of Y zeolite, it is often
used as catalytic material in the FCC of petroleum refining industry
[1–9]. The SiO2/Al2O3 (SAR) is an important property of zeolite Y,
which determines the acidity, thus affects its reactivity. It is difficult to
improve the SAR of Y zeolite due to the apparent activation energy in­
creases (the activation energy of polycondensation reaction between
polysilicate and aluminate is high and the rate constant k is small) when
the increase of SAR [10]. So great efforts have been made to improve the
SAR, which can be divided into direct synthesis and post treatment. The
use of organic structure directing agent (OSDA) (crown ethers) [11–13],
tetraethylammonium hydroxide (TEAOH) [14], Imidazolium-based
ionic liquids [15], inositol [16], poly (ethylene oxides) [17], and
N-methylpyridinium iodide [18]) can be used to synthesize directly
zeolite Y of high SAR. The application of template has great significance
in the synthesis of high silica zeolite. In recent years, with the
increasingly stringent environmental policy and tight cost, higher re­
quirements for the synthesis of high silica Y zeolite have been put for­
ward. Zhu et al. Has proposed a high silicon Y zeolite in organic
structure directing agent (OSDA) and low alkalinity gel system (named
NOA-co strategy), of which silicon aluminum ratio can reach 15.6 [19].
The synthesis of low basicity system can greatly reduce the cost of
zeolite Y, but the use of structure directing agent also increases the cost
of its application, which limits its industrial application. There are also
other methods to synthesize high SAR NaY. For example, the introduc­
tion of hydroxyl radicals (•OH) in the synthesis system can significantly
enhance the formation of Si–O–Si bond in the nucleation stage, so as to
synthesize NaY zeolite with SAR of 6.35 [20–23]. Another method to
improve SAR is post-treatment, such as treating zeolite Y under steam or
acidic conditions to remove Al [24–28]. Zeolite Y was treated with alkali
or introduced heteroatoms into the framework before steam treatment
to improve the SAR [29–31]. This is because the introduction of va­
cancies or unstable site into the framework of zeolite can promote the

* Corresponding author.
** Corresponding author.
E-mail addresses: shenyong@cup.edu.cn (S. Ren), baojian@cup.edu.cn (B. Shen).
1
Bo Meng and Shenyong Ren contributed equally to this work.

https://doi.org/10.1016/j.micromeso.2021.111248
Received 7 February 2021; Received in revised form 11 June 2021; Accepted 14 June 2021
Available online 19 June 2021
1387-1811/© 2021 Elsevier Inc. All rights reserved.
B. Meng et al.
removal Al. The methods mentioned above are either expensive or
cumbersome to operate. Therefore, it is necessary and urgent to find a
simple and facile method to synthesize zeolite Y of high SAR for labo­
ratories and factories.
The microporous properties of Y zeolite also lead to many mass
transfer problems. In recent years, small crystal zeolite Y (typical crystal
size: 100–300 nm) has become a research hotspot [32–36]. When the
crystal size is reduced, more externally exposed surface area and active
sites are exposed on the surface, which facilitates the diffusion of re­
actants and products and suppresses carbon deposition [37–42]. How­
ever, the synthesis of small crystal zeolite Y is complicated, such as
OSDA (tetramethylammonium cation) [43–45], microwave [46–48],
lower synthesis temperature [49], higher alkalinity [50], and ultrapure
water [51]. Although the lower temperature is conducive to the nucle­
ation process, the crystallization time is greatly prolonged. The crys­
tallization time of zeolite Y in industry is generally less than 24 h, so this
method is difficult to use in subsequent industry. In comparison, intro­
ducing heteroatoms in the synthesis of zeolites can effectively control
the zeolite size. In 1973, Albers et al. observed a reduced crystal size in
zeolite NaY synthesized using raw materials containing a small amount
of impurities (B, V, P, or other elements) [52]. Inui et al. added Fe3+ into
the hydrothermal system for synthesizing zeolite ZSM-5, and found that
the Fe3+ was introduced into the framework and changed the size and
shape of the grains [53]. However, the underlying mechanism has not
been explained [54], even though it is crucial for guiding the synthesis of
small crystal zeolites in the future.
It seems that NaY zeolite with high SAR and small crystal size can
only be synthesized in the presence of organic template. To the best of
our knowledge the direct synthesis of high silica zeolite Y has not been
reported yet in the organic-free system. In this paper, we introduce
heteroatoms into the organic-free synthesis system to prepare zeolite Y
with high SAR and small crystal size. Co2+ was selected as a competition
with Al3+ further increases the amount of crystallization intermediate
product 5-coordination intermediate (Al–O–Si)*, and the resulting SAR
of zeolite Y is 6.15. Because of the existence of Co–O–Si bond and
microcrystalline Co(OH)2, which can provide a good attachment surface
for nucleation, reduce the nucleation free energy, and promote the
nucleation, thus reducing the grain size by 50%. The cracking properties
of zeolite Y were further tested for 1,3,5-triisopropylbenzene (TIPB).
2. Experimental
2.1. Preparation
NaY and [Co, Al]-NaY zeolites were synthesized without using
organic templates. For NaY, a colloidal directing agent was prepared by
mixing a solution of NaAlO2 (20.60 g, 21.11 wt% Na2O, 3.16 wt%
Al2O3), water glass (20.85 g, 28.45 wt% SiO2, 8.89 wt% Na2O), and
deionized water (8.56 g), then stirring the mixture at 33 ◦ C for 1 h prior
to aging for 16 h. To prepare the gel, water glass (75.86 g), the colloidal
directing agent (50 g), NaAlO2 solution (16.88 g), and deionized water
(25 g) were mixed and stirred for 5 h. Afterwards, an Al2(SO4)3 solution
(51.05 g, 7.60 wt% Al2O3) was poured slowly into the uniform gel and
stirred for 1 h. The above operations were carried out at 50 ◦ C. The
resulting gel was then transferred into a polytef kettle, and hydrother­
mal crystallization was carried out at 98 ◦ C for 18 h. For the [Co, Al]-
NaY-x (x = 1–5) zeolites, Co2+ was introduced into the gel as five
mixed solutions of CoSO4 and Al2(SO4)3: (1) 51.03 g, 7.53 wt% Al2O3,
0.15 wt% CoO, (2) 50.98 g, 7.38 wt% Al2O3, 0.44 wt% CoO, (3) 50.92 g,
7.24 wt% Al2O3, 0.73 wt% CoO), (4) 50.88 g, 7.09 wt% Al2O3, 1.02 wt%
CoO, and (5) 50.83 g, 6.95 wt% Al2O3, 1.32 wt% CoO, respectively. And
the crystallization time of [Co, Al]-NaY-x (x = 1–5) zeolites is 18 h, 18 h,
19 h, 21 h and 24 h, respectively. All reagents were A.R. grade and
purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. All
solutions were prepared in deionized water.
The [Co, Al]-NH4Y-x and NH4Y zeolites were prepared from the [Co,
2
Microporous and Mesoporous Materials 323 (2021) 111248
Al]-NaY-x and NaY zeolites, respectively. For the synthesis of the NH4Y
zeolite, a 10 mL g− 1 solution-to-zeolite ratio was used to exchange the
NH4Cl solution with the NaY zeolite over 1 h at 90 ◦ C, and the pH value
of the NH4Cl solution was adjusted to 3.3–3.5 using a 1 mol L− 1 hy­
drochloric acid solution during the exchange process. After ion-
exchange, the zeolite was washed to give a neutral pH, and then dried
at 120 ◦ C for 12 h.
2.2. Characterization
X-ray diffraction (XRD) patterns of the zeolites were obtained using a
PANalytical X’Pert Power diffractometer (Holland) with Ni-filtered Cu
Kα radiation (40 kV, 40 mA). The relative crystallinity was estimated by
comparing the total integrated intensities of the eight peaks of (331),
(511), (440), (533), (642), (822), (555), and (664) belonging to zeolite
Y. The scan range was from 5◦ to 35◦ , and the scan rate was 2◦ /min with
a step width of 0.02◦ . The unit cell parameter (a0) is based on pure sil­
icon as the internal standard according to SH/T 0339–92, and the scan
range was 28–32◦ . The SAR of the zeolites were determined using the a0
value according to Breck’s equation. X-ray photoelectron spectroscopy
(XPS) measurements were performed using a Thermo Fisher K-Alpha
spectrometer (USA) with Al Kα radiation (hν = 1486.6 eV). All binding
energies were calibrated using the carbon C 1s peak (284.6 eV) as a
reference. Fourier-transform infrared (FTIR) spectra were collected
using a Thermo Fisher Nicolet IS10 (USA) spectrometer in the wave­
number range of 1250–400 cm− 1. UV–Vis diffuse reflectance (DRS)
spectra were collected on a Shimadzu UV-2600 (Japan) instrument with
the spectral resolution of 0.1 nm N2 physisorption measurements were
performed on a Micrometrics ASAP 2010 (USA) system at 77 K, after
first vacuum-degassing the sample at 350 ◦ C for 8 h. The apparent
specific surface area and pore volume were obtained using the Brunauer-
Emmet-Teller (BET) and the t-plot methods, respectively. The surface
morphology of the samples was analyzed using scanning electron mi­
croscopy (SEM) on an FEI Quanta 200 F (Holland) at an accelerating
voltage of 5–20 kV. Transmission electron microscopy (TEM) analysis
was performed using a JEOL JEM-2100 (Japan) operating at a voltage of
200 kV. The elemental contents in the samples were measured using X-
ray fluorescence spectrometry (XRF) on an AxiosmAX (Holland), after
pressing 1 g of sample powder into a self-supporting disk at 20 MPa for
20 s.
2.3. Catalytic activity assessment
The catalytic activities of the prepared zeolites in the cracking of
TIPB were investigated using a microreactor, whereby the in situ-
activated zeolite (NH4Y, 100 mg) was initially heated at 773 K for 1 h
under a nitrogen flow rate of 40 mL min− 1. Subsequently, TIPB was
added to the nitrogen carrier gas (flow rate 200 mL min− 1) via a ram
pump (60 μL min− 1) and fed into the reactor at 523 K. The reaction was
monitored using an online Agilent 6890 A gas chromatograph.
3. Results and discussion
3.1. Structural characterization of zeolites
The XRD patterns of NaY and [Co, Al]-NaY-x zeolites are shown in
Fig. 1a. All samples display the characteristic diffraction peaks of
faujasite-type structure (FAU) such as (111), (220), (311), (331), (511),
(440), (533), (642), (555), (840), and (664) [55–57]. Moreover, no
diffraction peaks of CoO were observed on the [Co, Al]-NaY-x zeolites
even when the Co content was high. These observations indicate that the
Co2+ either might be introduced into the zeolite Y or be simply highly
dispersed. The SAR and cell constant of NaY zeolite and [Co, Al]-NaY-x
were determined by XRD. As shown in Table 1, it is found that the SAR
increases, while the cell constant is opposite. In the previous literature, it
is often believed that when heteroatoms are introduced in the zeolite
B. Meng et al.
Fig. 1. (a) XRD patterns, (b) N2 adsorption-desorption isotherms, (c) pore size distribution, (d) FTIR, (e, f) UV–Vis DRS, and (g, h) XPS data of different
zeolite samples.
framework, the unit cell becomes larger [58]. However, the SAR of [Co,
Al]-NaY-x zeolites is higher than that of ordinary NaY zeolite, especially
the maximum SAR can reach 6.15. In fact, it is difficult to prepare high
silicon NaY by the hydrothermal synthesis method without template for
NaY of SAR over 6.0, which is the highest SAR of zeolite Y synthesized by
in situ one-step organic-free route [59]. The direct preparation of high
3
Microporous and Mesoporous Materials 323 (2021) 111248
silicon NaY by hydrothermal method is mainly through template, such
as 15-crown-5. And its synthesis temperature is high and crystallization
time is long. From the XRD spectrum, we can see that the peak height
difference between (111) and (220) diffraction peaks of each sample is
decreasing, which indicates that there is a large interaction between Co
species and zeolite, which may have some influence on the
B. Meng et al. Microporous and Mesoporous Materials 323 (2021) 111248

Table 1 replaces a lighter one, the vibration frequency decreases, and this is
Properties of the NaY and [Co, Al]-NaY zeolites. expected when the heavy atom Co could enters the framework of zeolite
Samples SiO2/Al2O3a a0a/nm Cob/wt% Nab/wt% Y (Co interact with the Si in the zeolite Y).
The chemical environment in [Co, Al]-NaY zeolites can be probed
NaY 5.20 2.464 – 13.13
[Co, Al]-NaY-1 5.64 2.463 0.23 12.79 using UV–Vis DRS. The spectra of NaY and [Co, Al]-NaY-x are shown in
[Co, Al]-NaY-2 6.15 2.460 0.69 12.68 Fig. 1e and f. All samples have distinct absorption bands at ~220 nm.
[Co, Al]-NaY-3 5.80 2.462 1.15 12.63 However, additional strong absorption bands appeared in [Co, Al]-NaY-
[Co, Al]-NaY-4 5.64 2.463 1.62 12.65 x at about 200 nm, and their intensity increased with increasing Co2+
[Co, Al]-NaY-5 5.47 2.464 2.02 12.71
content. There were also obvious spectral differences at 450–700 nm.
a
Derived from XRD analysis. Compared with NaY, [Co, Al]-NaY-x zeolites have an obvious absorption
b
Derived from XRF analysis. band there, and its peak area increases with increasing Co2+ content.
When examined by peak-differentiating analysis, this peak can be
crystallization process. Therefore, we can speculate that the introduc­ separated into three bands at 580, 638, and 520 nm. The former two is
tion of Co2+ in the synthesis of zeolite Y may have effect on its crys­ due to the pseudo-tetrahedral Co2+ and attributed to the 4A2–4T1(4 F)
tallization process. Whether Co2+ interacted with the zeolite needs and 4A2–4T2 transitions, respectively [69], while the band at 520 nm
further characterization. may indicate multinuclear Co2+ species in an octahedral environment
From the results of N2 adsorption, the NaY zeolite exhibited typical [70]. As the Co2+ content increases, the peak area of the band at 520 nm
type I isotherm and no significant hysteresis loop, indicating the zeolite gradually increases.
is a typical microporous material [60–62]. [Co, Al]-NaY-x displayed XPS was used to determine the valence and coordination forms of Co
similar isotherms, but their maximum N2 adsorption capacities were species in the [Co, Al]-NaY zeolites, using bulk CoO as reference. In
higher than that of NaY (Fig. 1b). The pore size distribution of NaY and Fig. 1g, the Co 2p3/2 and 2p1/2 electron binding energies of bulk CoO are
[Co, Al]-NaY zeolites suggests that they were all microporous (HK model 779.6 and 795.1 eV, respectively, whereas those in the [Co, Al]-NaY-x
to treat the nitrogen sorption isotherms and get the micropore size dis­ zeolites are much higher in comparison. This change in the electron
tribution in Fig. S1) instead of mesoporous materials. As the Co2+ con­ binding energy indicates a change in the Co2+ coordination structure
tent increased, there was no significant change in the pore volume from octa-to tetra-coordination, which is similar to the change in other
(Table 2), and no obvious mesopores were observed in the sample heteroatomic zeolites [71–73]. In order to further study the valence
(Fig. 1c). If Co did not interact with NaY (could not be introduced into state and coordination structure of Co2+, the Co orbitals of [Co, Al]-NaY
the zeolite Y), but exists in the form of oxide, its apparent specific surface zeolites were subjected to peak-saturation fitting. For [Co, Al]-NaY-x,
area will decrease greatly [63]. This is further evidence for the inter­ the core levels of Co 2p3/2 and 2p1/2 are at approximately 781.6 and
action between Co2+ and zeolite Y. With the increase of Co2+ content, 797.5 eV (Fig. 1h). These primary signals can be attributed to highly
Sexter increased gradually from 40 m2 g− 1 in NaY up to 79 m2 g− 1. dispersed Co species, most likely in the form of pseudo-tetrahedral Co2+
Therefore, zeolite Y greatly reduced the crystal size in the presence of in the zeolite [74]. Those values are also very close to the electron
Co2+. binding energies of highly dispersed Co2+ ions and Co-containing het­
The infrared spectra of NaY and [Co, Al]-NaY-x zeolites (Fig. 1d) all eroatomic zeolites reported in the literatures [75]. Besides the
showed the typical vibration of standard zeolite Y reported in the spin-orbital peak of Co 2p, satellite peaks corresponding to 2p3/2 and
literature: the peak of Si–O bending vibration at about 460 cm− 1, and the 2p1/2 were also observed at ~787.7 and ~804.5 eV, respectively, indi­
absorption peaks at around 790 and 1220 cm− 1 due to the symmetric cating that the oxidation state of Co in the sample is divalent [76]. The
and asymmetric stretching vibrations of Si–O–M (M = Al or other het­ presence of a second peak for Co 2p3/2 and 2p1/2 (~784.3 and ~801.9
eroatoms). There was also a vibration peak for the double six-membered eV) revealed the presence of a different Co2+ species in the sample,
ring (D6R) at about 580 cm− 1 that is peculiar to zeolite Y [64–66]. This possibly octahedral Co2+ [77]. Thus, XPS results show that the intro­
result is consistent with that of XRD, and no absorption peak of Co duced Co existed in the divalent state and acted as pseudo-tetrahedral
species was observed. A closer examination of the FTIR spectra shows Co2+ in the zeolite Y. Although the content of octahedral cobalt spe­
shifts in the peaks for Si–O–M bond [67]. For example, the symmetric cies increased with the Co content in the gel, most of the Co2+ existed as
and asymmetric stretching vibrations of Si–O-M in NaY are at 1027.4 the pseudo-tetrahedral cobalt species depending on the area of each
and 793.4 cm− 1, respectively, while in [Co, Al]-NaY-5 they are at 1023.3 peak.
and 791.0 cm− 1. According to Hooke’s Law [68], when a heavier atom The TEM images of different samples (Fig. 2) confirm that there were
no mesopores in NaY. In the [Co, Al]-NaY-x zeolites, no oxide particles
similar to impregnation were observed on the sample surface. The above
Table 2 results are consistent with the results of XRD analysis and N2 physical
Texture properties and Co content of the zeolites.
sorption.
Samples Apparent Sextera Vporeb Vmicroc Vmesod
specific surfacea (m2 g− 1) (cm3 (cm3 g− 1) (cm3 g− 1)
3.2. SEM results and reaction mechanism of [Co, Al]-NaY-x zeolites
(m2 g− 1) g− 1)

NaY 714 46 0.38 0.33 0.05 The morphology and structure of synthetic zeolites are important
[Co, Al]- 758 60 0.39 0.34 0.05
NaY-1
and usually studied by SEM. The SEM images in Fig. 3 indicate that the
[Co, Al]- 750 57 0.38 0.34 0.04 NaY and [Co, Al]-NaY-5 zeolites have a typical FAU zeolite morphology,
NaY-2 i.e., chamfered octahedron, and the crystal sizes in each sample fall
[Co, Al]- 756 64 0.39 0.34 0.05 within a normal distribution. However, when the Co2+ is introduced into
NaY-3
the gel, the average crystal size of [Co, Al]-NaY-x decrease, and the
[Co, Al]- 763 79 0.40 0.33 0.07
NaY-4 minimum can be reduced to 50% of the ordinary NaY. (Figs. 3 and S2).
[Co, Al]- 758 73 0.40 0.34 0.06 Whether it occurs by the liquid-phase or solid-phase crystallization
NaY-5 mechanism, the entire crystallization process of zeolite can be divided
a
Derived from the BET method. into four steps: polycondensation of polysilicates and aluminates,
b
Volume of N2 adsorbed at P/P0 = 0.99. nucleation of zeolites, growth of zeolite crystals, and metastable phase
c
t-plot method. transition [78,79]. When some Al(III) in the gel are replaced by Co2+
d
Vpore-Vmicro. during synthesis, the polycondensation reaction of [Si(OH)3O]- and

4
B. Meng et al. Microporous and Mesoporous Materials 323 (2021) 111248

Fig. 2. TEM images for (a) NaY and (b–f) [Co, Al]-NaY-x (x = 1–5) zeolites.

oxometallate [M(OH)x]y-x (y is valence states of metal ion) is affected,

Fig. 3. SEM images and crystal size statistics for (a) NaY (a) and (b) [Co, Al]-
NaY-5 zeolites.
which will in turn affect the nucleation process.
According to the 5-coordinated intermediate mechanism (Fig. 4a) for
the solution-phase polymerization of silicate and aluminate ions pro­
posed by Dent Glasser [80], in the initial synthesis stage of NaY, [Al
(OH)4]- undergoes a slower and reversible reaction with [SiO(OH)3]- to
form the 5-coordinated intermediate (Al–O–Si)* Subsequently, the
(Al–O–Si)* is adsorbed by Na+ and undergoes a polycondensation re­
action around Na+ to form a complex silicate ion, followed by the for­
mation of a crystal nucleus. However, the introduced Co2+ exists mainly
as Co(OH)2 and [Co(OH)4]2-, and [Co(OH)4]2- forms another 5-coordi­
nated intermediate (Co–O–Si)* with the silicon species. Herein, we use
density functional theory calculations (DFT) to gain insight into the
mechanism of condensation of SiO4 units with either AlO4 or CoO4
units to form Si–O–Al or Si–O–Co dimers respectively, which constitute
the initial steps of zeolite growth. After depolymerization of the silica
gel, the soluble silicate, aluminate and cobaltate species present in the
synthesis media can be modeled by Si(OH)3ONa, Al(OH)4Na and Co
(OH)4Na2 monomers, and the models are similar to those used in pre­
vious studies [20]. Therefore, we studied the condensation of Si
(OH)3ONa monomers with Al(OH)4Na and Co(OH)4Na2 monomers to
form NaSi(OH)3–O–Al(OH)4Na and NaSi(OH)3–O–Co(OH)4Na2 dimers,
shown in Fig. 5. In both cases, the two monomers interact initially

Fig. 4. (a) The 5-coordinated intermediate mechanism (Schemes 1 and 2 in Fig. 4a). (b) UV–Vis DRS patterns during the synthesis of [Co, Al]-NaY-2 zeolite.

5
B. Meng et al. Microporous and Mesoporous Materials 323 (2021) 111248

may indicate the existence of multinuclear Co2+ species in the octahe­

dral environment) and that for the Co–O–Si bonds in the pseudo-
tetrahedral Co2+ already exist in the initial stage of crystallization.
This is consistent with the previously mentioned 5-coordinated inter­
mediate (Co–O–Si)* formed during the nucleation stage, and this inter­
mediate will further disperse and disappear as the crystallization time
increases because (Al–O–Si)* is more stable. Therefore, introducing even
a small amount of Co2+ into the gel can affect the formation of crystal
nuclei. In addition, the peak intensities of pseudo-tetrahedral Co2+
decreased significantly. Co(OH)2 microcrystals may be produced during
the crystallization, and as a typical amphoteric hydroxide it can be
dissolved in hot alkali salt. Thus, the Co(OH)2 will further react with
OH− to form Co(OH)2− 4 , and the resultant dispersal of Co species in the
gel explains the reduced peak intensities of pseudo-tetrahedral Co2+.

3.3. Synthesis process of [Co, Al]-NaY zeolite

The synthesis process of zeolite was analyzed in order to verify the

above conjecture that the added Co promotes nucleation. Ex situ XRD
Fig. 5. Gibbs free energy profiles including the solvent correction and opti­
patterns of [Co, Al]-NaY-2 (Fig. 6a) show that the materials did not
mized structures for condensation of Si(OH)3ONa with Al(OH)4Na and
Co(OH)4Na2. crystallize prior to 9 h. After 9 h, a weak peak at 2θ = 6.28◦ (corre­
sponding to the (111) crystal plane of FAU) became the strongest
reflection in the XRD pattern. From 12 to 21 h, the crystallinity gradu­
through electrostatics and hydrogen bonds, forming stable reactant
ally increased, but afterwards the crystallinity of the FAU zeolite did not
structures 1. Then, one of the O atoms of the Si unit attacks either the Al
increase any further. The trend of apparent specific surface against
or Co atom in the other unit to form a new Si–O–Al or Si–O–Co bond with
crystallization time (Fig. S3) is similar to that of the crystallinity, namely
a pentacoordinated Al or Co center structures 2, respectively. The
increasing rapidly after 9 h and reaching saturation at 18 h.
calculated Gibbs free energies including the solvent correction indicate
A series of samples synthesized for 0–18 h were examined by infrared
that the formation of Si–O–Al bonds is a more thermodynamic favor­
spectroscopy (Fig. 6b). Before crystallization, the solid product had a
ability which is endothermic by 0.16 eV with a barrier of 0.08 eV, as
relatively simple IR spectrum, with only two distinct absorption peaks
compared to the formation of a Si–O–Co bridge endothermic by 0.54 eV.
(1038 and 463 cm− 1) assignable respectively to the asymmetric Si–O–T
Our DFT study clearly illustrates that Si–O–Al bonds with high SAR are
stretching vibration of the external tetrahedron, and the internal T-O
more favorable to formation than Si–O–Co bonds. This causes a reverse
bending vibration of TO4 which is structurally insensitive [81]. This is
shift in the reaction Scheme 1 in Fig. 4a, which increases the [SiO
consistent with the XRD results and further confirms that the sample was
(OH)3]-/[Al(OH)4]- ratio and shifts the reaction in Scheme 2 in Fig. 4a
amorphous. With the progress of crystallization, three new absorption
the positive direction, resulting in more 5-coordinated intermediates
peaks appeared at 720, 792, and 580 cm− 1, indicating a change in the
(Al–O–Si)* to affect the nucleation, and which may lead to a further
structure of the silica-alumina gel and rearrangement of structural units
increase SiO2/Al2O3 around Co2+.
constituting the zeolite Y. The former two absorption peaks could be
To verify this idea, UV–Vis DRS was used to characterize the gelation
matched to the stretching vibration of internal and external TO4 in the
samples after different crystallization times. In Fig. 4b, when the crys­
framework, and that at 580 cm− 1 is the characteristic D6R absorption
tallization time was increased from 0 to 3 h, the shoulder peak at
peak of zeolite Y. These results support a gradual formation of the
320–430 nm (characteristic of cobalt oxide in larger particles, enclosed
characteristic framework structure for zeolite Y. At the same time, the
by the rectangle) visibly decreased. At each stage of crystallization,
stretching vibration of the internal tetrahedron moved from 1038 to
absorption peaks at 580, 638, and 520 nm can be observed in the UV–Vis
1023 cm− 1, due to the change in the T-O-T stretching mode, the atomic
DRS data. The peaks at 580 and 638 nm are known to be due to pseudo-
weights of Si and Al are not very different (28.08 vs. 26.98), but the Si–O
tetrahedral Co2+ in the zeolite. Meanwhile, the band at 520 nm (which
bond is significantly shorter than the Al–O bond (0.161 vs. 0.175 nm),

Fig. 6. (a) XRD and (b) FTIR patterns obtained during the synthesis of [Co, Al]-NaY-2 zeolite.

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B. Meng et al. Microporous and Mesoporous Materials 323 (2021) 111248

and Si is more electronegative than Al (1.90 vs. 1.61). Therefore, the

Al–O bond is weaker than the Si–O bond, and its force constant must be
smaller. According to Hooke’s Law, the vibration frequency is reduced
(i.e., moving to a lower wavenumber).
Compared to the crystallization process of ordinary NaY, the crys­
tallization curve of [Co, Al]-NaY-2 zeolite also shows characteristics of
self-catalyzed crystallization (Fig. 7). There was a considerable induc­
tion period at the beginning, during which no zeolite XRD patterns were
detected. After this period, the crystallization started, and its speed
increased sharply at first and then slowed down gradually. However,
compared to conventional NaY, the induction period required for the
synthesis of [Co, Al]-NaY-2 was longer (about 6 and 9 h, respectively).
For [Co, Al]-NaY-2, crystallization occurred from 9 to 18 h (taking 9 h to
reach equilibrium), while for NaY it occurred from 6 to 18 h (taking
about 12 h to reach equilibrium). From this, we infer that during the
synthesis of conventional NaY, the crystal growth is a slow process and
the crystals are larger, while the crystal growth is very fast in [Co, Al]-
NaY-2. After a period of nuclei combination and conversion, large-scale
and rapid nucleation is followed by a rapid nuclei growth process, and
thus the size of the formed crystals is small.
The above characterization results did not include any information
about Co, possibly because of its low content (about 0.7 wt%). There­
fore, gel solid products after different crystallization times were taken
out and further characterized by SEM and TEM (Figs. S4–S5). When not
crystallized, the gel had a low silicon content compared with the initial
stage of crystallization (see Table S1 for the XRF results). The solid phase
products contained mainly amorphous sheet structures of different sizes,
and the surface was rough. At the same time, TEM images (Fig. 8a and b)
revealed that the sheet structures were wrapped in a large number of
spherical particles, most of which had a size of 1–2 nm although some
can reach about 10 nm. This is consistent with the UV–Vis DRS results
that there were some large CoxOy aggregates in the gel. When the
crystallization time reached 3 h, some changes occurred in the sheet
Fig. 8. TEM images during the synthesis of [Co, Al]-NaY-2 zeolite at 0 h (a, b),
structure of the gel (Fig. S4b), the surface became smooth, and a series of
3 h (c, d), 9 h (e, f), and NaY zeolite at 6 h (g, h).
aggregates appeared on the surface. It can be seen in the TEM image
(Fig. 8b) that the sheet structure became branched and more broken,
and the size was mainly concentrated between 30 and 50 nm. In the microcrystals provided a good attachment surface for the nucleation of
high-resolution images for certain areas, some lattice fringes were zeolites, thereby reducing the surface free energy to make nucleation
wrapped in an amorphous substance (inside the red rectangles in Fig. 8c more favorable due to nucleation theory (Eqs. S1–S3) [82]. So, there is a
and d). The spacing of these lattice fringes was measured to be about longer induction period in the [Co, Al]-NaY zeolite (from 6 h to 9 h).
2.37 Å and can be attributed to the (101) plane of the Co(OH)2 structure. With the crystallization time reaching 9 h, some small particles with
At the same time, compared with the initial gel (0 h), the number of sharp edges (Fig. S4c) and a size less than about 200 nm could be seen on
spherical particles was greatly reduced, which illustrates the formation the surface of the lamellar structure by SEM. Inside these lamellar
of Co(OH)2 crystallites and the further dispersion of Co species. These structures there were small circular channels about 20 nm in size (Fig. 8e
and f). It is known that the growth of zeolites likely occurs at the
interface of solid and liquid phases. It has been reported that these
channels are the key to the nucleation [83]. We compared the inflection
points of crystallization curves of ordinary NaY and [Co, Al]-NaY-2
zeolite (i.e. the samples corresponding to 6 h and 9 h). The compari­
son shows that these channels almost cover the whole surface on gel of
[Co, Al]-NaY-2 zeolite, while less channels are produced on ordinary
NaY zeolite (Fig. 8g and h). These results indicate that at the end of the
induction period of crystallization curve, [Co, Al]-NaY-2 zeolite will
produce more nuclei. Some particles with a regular shape, the (111)
crystal surface of FAU structure, and a lattice fringe spacing of about
14.0 Å were observed at the edge of these holes, indicating that the NaY
crystals began to form there (Fig. S5a). From 9 to 12 h, zeolite Y crystals
grew massively on the amorphous lamella structure and basically
covered the latter (Fig. S4d). At the same time, the TEM images
(Fig. S5b) revealed that the pores of the lamellar structure were mostly
covered. When the crystallization time reached 15 h, only a small
amount of lamellar structure was visible in the SEM image (Fig. S4e),
and at the same time the (111) crystal plane of a clear FAU structure
appeared on the edge of the circular channels (Fig. S5c). This further
shows that the crystal grew from the solid-liquid phase boundary in the
channel. In the late stage of crystallization (18–30 h), the NaY crystals
Fig. 7. Crystallization curves of NaY and [Co, Al]-NaY-2 zeolite.

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B. Meng et al. Microporous and Mesoporous Materials 323 (2021) 111248

were completely formed, and the amorphous content was low.

During the crystallization process (3–30 h), the Si and Al contents
changed to a certain extent: the silicon content in the gel gradually
decreased while the aluminum content gradually increased. This may be
attributed to the dissolution rearrangement of colloids at the solid-liquid
phase boundary to form structural units such as the six-membered ring.
These units are the precursors that form firstly the zeolite nuclei and
then the zeolite, which is consistent with the results of XRD, FTIR, and
TEM.

3.4. Cracking of TIPB

In order to test the activity of the synthesized zeolites, especially the

effect of the crystal size on the catalytic activity, the cracking reaction of
the macromolecular TIPB was demonstrated. TIPB is usually used to
study the outer surface properties of microporous zeolite. Because its
kinetic diameter is 0.95 nm, which is much higher than pore size of
zeolite Y (0.74 nm). NH4Y, [Co, Al]-NH4Y-2 and [Co, Al]-NH4Y-5 zeo­
lites were obtained by ammonium exchange of zeolite Y, the NH4Y, [Co,
Al]-NH4Y-2 and [Co, Al]-NH4Y-5 zeolites were characterized by XRF
and XPS. According to XRF, the Co2+ contents of [Co, Al]-NH4Y-2 and
[Co, Al]-NH4Y-5 zeolites are 0.61% and 1.92% respectively. The binding
energy of Co 2p3/2 and 2p1/2 of [Co, Al]-NH4Y-x zeolites are 781.6 and
797.5 eV, respectively (Fig. S6). However, the binding energy of CoO
sample is much lower than these values. These data suggested Co species
have not changed according to the previous analysis of [Co, Al]-NaY. It
shows that the modification of ammonium exchange has no effect on the
distribution of Co species in zeolite. The TIPB transformation is reported
in Fig. 9, which shows that all the small crystal zeolites ([Co, Al]-NH4Y-
x) are more active than the NH4Y. In particular, the initial conversion of
TIPB on [Co, Al]-NH4Y-5 zeolite with the smallest crystal size is 76%
higher than that of the conventional NH4Y zeolite due to its smaller
crystal size. Moreover, the instantaneous yield of isopropylbenzene
(IPB) was increased by about 80%, which indicated that the crystal size
had a great influence on the reaction.
4. Conclusions
Zeolite Y samples with high SAR and small crystal were synthesized
via introducing Co2+ facilely, and their structural properties were
characterized in detail to confirm the interaction between Co2+ and
zeolite Y. The presence of Co2+ had a significant effect on the zeolite
crystallization process, in particular to increase SAR and decrease crystal
size. The Co–O–Si bond persisted throughout the entire crystallization
process, indicating that the five-coordinated species (Co–O–Si)* was
formed during the gelation process, DFT calculation shows that the
Gibbs free energy of (Co–O–Si)* is higher than that of (Al–O–Si)*, the Si
species around Co are more likely to combine with (Al–O–Si)* in­
termediates, and the existence of this intermediate species increased the
SAR around Co, which made the synthesized zeolite Y have a higher SAR
of 6.15 (vs NaY zeolite is 5.20). Compared with ordinary zeolite Y, the
crystallization of [Co, Al]-NaY zeolite had a longer induction period and
the growth time was shorter, which are responsible for the smaller
crystal size, in particular, the particle size decreased to 50% of the or­
dinary NaY zeolite. During the initial stage of crystallization, in addition
to Co–O–Si bonds, Co species can also form microcrystalline Co(OH)2 for
the adhesion of amorphous substances to reduce the nucleation free
energy, thereby promoting the nucleation process and extending the
induction period for [Co, Al]-NaY zeolites. And compared with the or­
dinary NaY, the inflection point of the crystallization curve found that
there were more channels (the key to the nucleation) in the gel of [Co,
Al]-NaY zeolite. The reason for the high SAR and smaller crystal size of
zeolite Y in the presence of heteroatoms is revealed, and the synthesis
method is simpler than other reported ones for preparing small crystal
and high SAR zeolite Y. The cracking results of TIPB shows that the
catalytic performance of this sample is significantly higher than that of
Fig. 9. Conversion of TIPB over NH4Y and [Co, Al]-NH4Y-x zeolites.
ordinary NaY. Therefore, we hope that this approach can inspire further
development of small crystal and high SAR zeolites.
CRediT authorship contribution statement
Bo Meng: Synthesis, Characterization, Catalyst test. Shenyong Ren:
Supervision. Zhi Li: DFT Calculation. Suofu Nie: Suggestions to
manuscript. Xinyue Zhang: Suggestions to manuscript. Weiyu Song:
DFT Calculation. Qiaoxia Guo: Suggestions to manuscript. Baojian
Shen: Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.micromeso.2021.111248.
Appendix B. Supplementary data
Supplementary data to this article can be found online at …
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