A Cationic Oligomer as an Organic Template for Direct Synthesis of Aluminosilicate ITH Zeolite

Article abstract of DOI:10.1002/anie.202003282

There are a large number of zeolites, such as ITH, that cannot be prepared in the aluminosilicate form. Now, the successful synthesis of aluminosilicate ITH zeolite using a simple cationic oligomer as an organic template is presented. Key to the success is that the cationic oligomer has a strong complexation ability with aluminum species combined with a structural directing ability for the ITH structure similar to that of the conventional organic template. The aluminosilicate ITH zeolite has very high crystallinity, nanosheet-like crystal morphology, large surface area, fully four-coordinated Al species, and abundant acidic sites. Methanol-to-propylene (MTP) tests reveal that the Al-ITH zeolite shows much higher selectivity for propylene and longer lifetime than commercial ZSM-5. FCC tests show that Al-ITH zeolite is a good candidate as a shape-selective FCC additive for enhancing propylene and butylene selectivity.

Full text of DOI:10.1002/anie.202003282

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
www.angewandte.org
Accepted Article
Title: Cationic Oligomer as an Organic Template for Direct Synthesis of
Aluminosilicate ITH Zeolite
Authors: Feng-shou Xiao, Chi Lei, Zhuoya Dong, Cristina Martínez,
Joaquín Martínez-Triguero, Wei Chen, Qinming Wu, Xiangju
Meng, Andrei-Nicolae Parvulescu, Trees De Baerdemaeker,
Ulrich Mueller, Anmin Zheng, Yanhang Ma, Weiping Zhang,
Toshiyuki Yokoi, Bernd Marler, Dirk De Vos, Ute Kolb, and
Avelino Corma
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content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202003282
Link to VoR: https://doi.org/10.1002/anie.202003282

10.1002/anie.202003282
Angewandte Chemie International Edition
RESEARCH ARTICLE
Cationic Oligomer as an Organic Template for Direct Synthesis of
Aluminosilicate ITH Zeolite
Chi Lei,+, [a] Zhuoya Dong,+, [b] Cristina Martínez,[c] Joaquín Martínez-Triguero,[c] Wei Chen,[d] Qinming
Wu,*[a] Xiangju Meng,[a] Andrei-Nicolae Parvulescu,*[e] Trees De Baerdemaeker,[e] Ulrich Müller,[e]
Anmin Zheng,[d] Yanhang Ma,*[b] Weiping Zhang,[f] Toshiyuki Yokoi,[g] Bernd Marler,[h] Dirk E. De Vos,[i]
Ute Kolb,[j] Avelino Corma*[c] and Feng-Shou Xiao*[a]
[a]
[b]
[c]
C. Lei, Dr. Q. Wu, Dr. X. Meng, Prof. F.-S. Xiao
Key Laboratory of Applied Chemistry of Zhejiang Province
Zhejiang University
Hangzhou 310007, P. R. China
E-mail: qinmingwu@zju.edu.cn; fsxiao@zju.edu.cn
Z. Dong, Dr. Y. Ma
School of Physical Science and Technology
ShanghaiTech University
Shanghai 201210, P. R. China
E-mail: mayh2@shanghaitech.edu.cn
Dr. C. Martínez, Dr. J. Martínez-Triguero, Prof. A. Corma
Instituto de Tecnología Química
Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas
Avenida de los Naranjos s/n, 46022 València, Spain
E-mail: acorma@itq.upv.es
[d]
[e]
Dr. W. Chen, Prof. A. Zheng
Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences
Wuhan 430071, P. R. China.
Dr. A.-N. Parvulescu, Dr. De Baerdemaeker, Dr. U. Müller
BASF SE, GCC/PZ-M311
Ludwigshafen 67056, Germany
E-mail: andrei-nicolae.parvulescu@basf.com
Prof. W. Zhang
[f]
State Key Laboratory of Fine Chemicals
Dalian University of Technology
Dalian 116012, P. R. China
[g]
[h]
[i]
Prof. T. Yokoi
Chemical Resources Laboratory
Tokyo Institute of Technology
Yokohama 226-8503, Japan
Prof. B. Marler
Department of Geology, Mineralogy and Geophysics
Ruhr University Bochum
Bochum 44780, Germany
Prof. D. E. De Vos
Centre for Surface Chemistry and Catalysis
KU Leuven
Kasteelpark Arenberg 23, Leuven 3001, Belgium
Prof. U. Kolb
[j]
Institute of Inorganic Chemistry and Analytical Chemistry
Johannes Gutenberg University Mainz
Mainz 555128, Germany
[+]
These authors contributed equally to this work
Supporting information for this article is given via a link at the end of the document.((Please delete this text if not appropriate))
Abstract: Despite great progress in the synthesis of aluminosilicate
zeolites, there are still a large number of zeolites that could not be
prepared in the aluminosilicate form. One of typical examples is ITH
zeolite, where direct synthesis of aluminosilicate ITH is currently still
challenging. Herein, for the first time we demonstrate the successful
synthesis of aluminosilicate ITH zeolite using a simple cationic
oligomer as an organic template. The key to this success is that the
cationic oligomer has a strong complexation ability with aluminum
species combined with a structural directing ability for the ITH
structure similar to that of the conventional organic template.
Physicochemical analysis shows that the aluminosilicate ITH zeolite
has very high crystallinity, nanosheet-like crystal morphology, large
surface area, fully four-coordinated Al species, and abundant acidic
sites. More importantly, methanol-to-propylene (MTP) tests reveal
that the Al-ITH zeolite shows much higher selectivity for propylene
and longer lifetime than commercial ZSM-5. FCC tests show that Al-
ITH zeolite is a good candidate as a shape selective FCC additive
for enhancing propylene and butylene selectivity.
Introduction
Zeolites, as a typical family of microporous materials, have
shown important roles in the process of oil refining and fine
chemicals production because of their uniform channel
1
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10.1002/anie.202003282
Angewandte Chemie International Edition
RESEARCH ARTICLE
distribution, high surface area, and large micropore volume.[1–22]
As an important type of zeolites, germanosilicate-based zeolites
provide many new structures, exhibiting excellent performance
in various catalytic reactions.[23–34] For example, BEC zeolite
displays good catalytic performance in the isomerization of
glucose to fructose;[24] ECNU-21 zeolite is an efficient shape
selective catalyst for ethylene oxide hydration;[25] ITH zeolite
shows excellent performance in the catalytic cracking and
methanol-to-propylene (MTP) reaction.[26–29]
it is suggested that the use of novel cationic oligomer as an
efficient organic template might be favourable for direct
synthesis of the aluminosilicate ITH zeolite.
In this work, using a simple cationic oligomer as an organic
template, the direct synthesis of an aluminosilicate ITH zeolite
(Al-ITH) was shown to be successful. The obtained Al-ITH
zeolite has a Si/Al ratio as low as 57. More interestingly, the Al-
ITH shows excellent hydrothermal stability and good
performance in both methanol-to-propylene (MTP) and FCC
reactions.
ITH zeolite, firstly discovered by Corma’s group,[30] has a
special framework structure (three dimensional 91010-
membered ring channels; aperture size of 4.04.8, 4.85.1, and
4.85.3 Å). It could be prepared in the form of silicate and
borosilicate but it was tough to synthesize the aluminosilicate
form due to competitive growth of EUO when aluminum is
present in the synthesis gel.[27,31–33] In order to incorporate
aluminum in the structure of ITH zeolite to extend the catalytic
applications, the addition of germanium species in the ITH
zeolite synthesis was always required.[26–29] This addition not
only greatly increases the synthetic cost, but also significantly
reduces the hydrothermal and thermal stabilities of the ITH
zeolite.[34] The drawbacks mentioned above strongly limit its
catalytic application. To avoid the use of germanium, a post-
synthesis route was developed through alumination of
borosilicate ITH zeolite into aluminosilicate ITH zeolite.[30] Up to
now, it was still a challenge to directly synthesize aluminosilicate
ITH zeolite.
Recently, it has been reported that many zeolites such as
RHO, Beta, and GME could be successfully synthesized using
cationic polymers/oligomers as novel organic templates.[35–37] In
these cases, it is worth noting that the zeolite products have
more Al species in the framework than those synthesized from
conventional organic templates. One possibility is that the
cationic polymers/oligomers have a stronger complexation ability
with aluminum species than conventional templates. Therefore,
Results and Discussion
In order to search for a suitable cationic oligomer for
directing the ITH zeolite structure, theoretical simulations were
performed, as presented in Figure 1 and Table S1. Notably, the
interaction stability energy between the pure silica ITH zeolite
framework and the structure of the cationic oligomer (Figure 1,
OSDA1) is very similar to that of the conventional organic
template (Figure 1, OSDA2), suggesting the possibility of the
cationic oligomer for directing the ITH zeolite. In order to
compare the complexation ability of the organic templates with
aluminum species, both OSDA1 and OSDA2 solutions were
mixed with a certain amount of AlF3. ICP analysis shows that the
concentration of aluminum species in the solution of OSDA1 is
much higher than that of the OSDA2, as presented in Table S2.
These results indicate that the OSDA1 has indeed stronger
complexation ability with aluminum species than the OSDA2. To
measure the importance of Al complexation ability for OSDA1,
we performed additional experiments for addition of aluminum
source (AlF3) in the final gel (H2O/SiO2 at 3) by partial removal of
water from the starting gel (H2O/SiO2 > 30). In the final gel, the
a
b
Figure 1 Structures of the cationic oligomer (OSDA1, a) and traditional template (OSDA2, b), and their positions within the all silica ITH zeolite framework.
2
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10.1002/anie.202003282
Angewandte Chemie International Edition
RESEARCH ARTICLE
complexation ability between OSDA1 with aluminum species
should be weak due to shortage of water solution, compared
with the starting gel. As a result, the addition of aluminum
species in the final gel leads to the formation of amorphous
product rather than the Al-ITH zeolite (Figure S1), confirming the
importance of the complexation of Al with OSDA1. Therefore,
both structural directing ability and strong complexation ability
with aluminum species of the OSDA are very important for the
successful synthesis of Al-ITH zeolite.
Figure 2A shows X-ray diffraction (XRD) pattern of as-made
Al-ITH zeolite from the initial gel with Si/Al ratio at 100, exhibiting
a series of characteristic peaks associated with ITH structure
(Si/Al ratio of 70), in good agreement with the simulated XRD
pattern (Figure S2). The scanning electron microscopy (SEM)
images in Figure 2B and Figure S3 show that the as-made Al-
ITH zeolite has a nanosheet-like morphology with a thickness of
about 30 nm. Figure 2C displays nitrogen sorption isotherm of
calcined Al-ITH zeolite, giving BET surface area and micropore
volume of about 400 m2/g and 0.15 cm3/g, respectively. In
addition, the measured external surface area of 64 m2/g and
mesopore volume of 0.22 cm3/g, might be related to the
nanosheet-like morphology of Al-ITH zeolite. Furthermore, Si/Al
ratio of Al-ITH zeolite is determined to be 70 by inductively
coupled plasma (ICP) technique. Figure 2D shows 29Si MAS
NMR spectrum of as-made Al-ITH zeolite, giving four peaks with
the chemical shift centered at -116.8, -114.2, -111.3, and -105.4
ppm. The first three peaks are assigned to Si(4Si) species, and
the fourth one is attributed to the Si(3Si, OH) and/or Si(3Si, 1Al).
Figure 2E exhibits 19F MAS NMR spectrum of as-made Al-ITH
zeolite, displaying two peaks at -35.5 and -63.8 ppm, which are
assigned to fluoride species in the double four member rings
and the [415262] cage, respectively.[33] Figure 2F gives 27Al MAS
NMR spectrum of as-made Al-ITH zeolite, showing a peak at
53.3 ppm associated with four-coordinated aluminum species in
the ITH zeolite framework. We cannot observe the peak at round
0 ppm, implying the absence of six-coordinated aluminum
species in the Al-ITH zeolite product. Figure 2G shows
temperature programmed desorption of ammonia (NH3-TPD)
curve of the H-Al-ITH zeolite, showing two desorption peaks
centered at about 185 °C and 390 °C, which are very similar to
those of Al-Ge-ITH zeolite synthesized by direct method
reported in the literature.[28] Thermal analysis (TG-DTA, Figure
2H) of as-made Al-ITH zeolite shows a weight loss of 15.69 % in
the region of 200-600 °C, which is attributed to the
decomposition of OSDA1. 13C nuclear magnetic resonance
(NMR) spectrum of the liquid phase obtained by dissolving as-
made Al-ITH zeolite with a dilute HF solution is close to that of
the OSDA1 solution (Figure 2I). In addition, many weak peaks
300
B
A
C
F
I
250
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150
100
50
0
5
10
15
20
25
30
35
40
0
0.2
0.4
0.6
0.8
1
Relative Pressure (P/Po)
2 Theta (degree)
D
E
-90 -95 -100 -105 -110 -115 -120 -125 -130
Chemical shift (ppm)
0
-20
-40
-60
-80
-100
100
80
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40
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0
-20
Chemical shift (ppm)
Chemical shift (ppm)
0
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-0.02
-0.04
-0.06
-0.08
-0.1
G
H
2.18%
4
21
3
6
5
b
90
15.69%
-0.12
-0.14
-0.16
-0.18
-0.2
85
a
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100
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0
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800
100
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60
40
20
0
Temperature (°C)
Temprature (℃)
Chemical shift (ppm)
Figure 2 (A) XRD pattern (wavelength: 1.5406 Å), (B) SEM image, (C) N2 sorption isotherm, (D) 29Si MAS NMR, (E) 19F MAS NMR, (F) 27Al MAS NMR, (G) NH3-
TPD curve, (H) TG-DTA curve of Al-ITH zeolite product; and (I) 13C NMR of a) template solution and b) template dissolved from Al-ITH sample.
3
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10.1002/anie.202003282
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RESEARCH ARTICLE
have been observed in the dissolved solution treated from Al-
ITH zeolite, which could be related to the Hoffmann elimination
of a small amount of OSDA1 at relatively high temperature
(Figure S4). Combining with the results of NMR and TG-DTA
characterizations, it is concluded that the OSDA1 mainly exists
in the micropores of the Al-ITH zeolite.
(HAADF) image, qDPC-STEM shows advantages on visualizing
both heavy and light elements at the same time.[41–46] As a result,
it is possible to obtain information on organic templates in the Al-
ITH zeolite micropores using qDPC-STEM images. From the
structure model of ITH zeolite (Figure S5), straight channels of
10 MR and 9 MR ring would be clearly seen along [010] and
[100] zone axes, respectively. Therefore, qDPC-STEM images
should be taken along these two directions to observe organic
templates. However, Al-ITH zeolite is a nanosheet-like material
and [001] zone axis is vertical to the plate, which means that the
Al-ITH crystals along [010] or [100] zone axis would be difficult
to find otherwise it is too thick to take qDPC-STEM images
clearly. Fortunately, we were able to find a crystal with the thin
section along [010] zone axis and thus obtain the HAADF-STEM
and qDPC-STEM images of Al-ITH zeolite, as shown in Figure 4.
Compared with HAADF image (Figure 4a) without the
observation of any organic template due to the limitation of
HAADF technique, it would be clearly seen that there are some
white contrasts in qDPC-STEM image (Figure 4b), which might
be related to organic template molecules occluded in the zeolite
micropore channels. Combining with the result of theoretical
simulation, NMR and TG-DTA characterizations, and qDPC-
STEM images, it would further be concluded that the OSDA1
molecule, which is fully positioned in the micropore of
aluminosilicate Al-ITH zeolite, is indeed an organic template for
directing the formation of aluminosilicate Al-ITH zeolite structure.
Figure 3 shows selected-area electron diffraction (SAED)
patterns and transmission electron microscopy (TEM) images of
as-synthesized Al-ITH zeolite. Figure 3a-3c are collected from a
nanosheet-like crystal lying flat on the grid. The indexing of
SAED pattern with sharp diffraction spots and comparison of
experimental and simulated high-resolution TEM images
indicate that the crystal has a preferred orientation along the c
axis. Another crystal standing vertically on the grid was aligned
to the [100] zone axis with assistance of Zones program (Figure
3d-f).[38] The TEM image viewed along the a axis shows that the
thickness of the crystal is around 30 nm, in good agreement with
that of SEM images. Both projections along these two zone axes
match well with the simulated images using the ITH zeolite
framework (Figures S5-S7). These results confirm the
successful synthesis of Al-ITH zeolite with ITH structure in the
presence of the novel cationic oligomer.
Quantitative differential phase contrast (qDPC) has emerged
as an effective approach to study e-beam sensitive porous
materials using scanning transmission electron microscopy
(STEM) mode.[39,40] Compared with high-angle annular dark field
Figure 3 SAED patterns and TEM images of Al-ITH zeolite viewed along the [001] (a, b and c) and [100] (d, e and f) zone axes. The insets in (c) and (f) are
symmetry-averaged (left) and simulated images (right), respectively. The settings of defocus values and thickness for (c) and (f) are 500 nm & 5.2 nm and -140
nm & 13 nm, respectively.
4
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10.1002/anie.202003282
Angewandte Chemie International Edition
RESEARCH ARTICLE
Figure 4 HAADF-STEM (a) and qDPC-STEM (b) images of as-synthesized Al-ITH zeolite viewed along [010] zone axis. Circles on Figure 4b with the white
contrast spots might represent organic templates molecules inside the zeolite channel.
To understand the Al-ITH crystallization, XRD, SEM, and
MAS NMR characterization techniques were used. Before the
crystallization, only an amorphous phase is observed (Figure
S8a and Figure S9a). After 4 days of crystallization, the XRD
pattern of the sample shows very weak peaks associated with
the Al-ITH zeolite (Figure S8b). At the same time, the Al-ITH
zeolite crystals with nanosheet-like morphology can clearly be
seen from the SEM image (Figure S9b). Increasing the
crystallization time from 5 to 8 days, the XRD peak intensity of
Al-ITH zeolite has extraordinarily hydrothermal stability, which
would be favorable for its industrial application.
Figure 5 and Figure S14 show the catalytic performances in
the MTP reaction over Al-ITH-70, Al-ITH-94, SiGeAl-ITH,
SiAl(B)-ITH, and ZSM-5 zeolites. Table S7 presents the catalytic
data after 2 h time on stream. Obviously, the Al-ITH zeolites
combine the advantages of high selectivity for propylene and
long catalytic lifetime among the tested zeolite samples. In
addition, it is worth noting that the absence of Ge species would
stabilize the structure of Al-ITH zeolite against the irreversible
hydrothermal effect of the water produced in the MTO reaction.
Therefore, the above results are potentially important for
selective production of propylene in the industrial applications.
the
samples
gradually
increases
(Figures
S8c-8f).
Correspondingly, more Al-ITH zeolite crystals are observed in
the SEM images (Figures S9c-9f). After 10 days, Al-ITH zeolite
is obtained with high crystallinity (Figure S8g and Figure S9g).
The dependence of the Al-ITH zeolite crystallinity on the
crystallization time is shown in Figure S10. Figures S11 and S12
show 27Al and 29Si MAS NMR spectra of Al-ITH zeolite products
obtained after the different crystallization times. As shown in
Figure S11, the products after 4 to 10 days of crystallization
have a peak near 60 ppm associated with 4-coordinated
aluminum species, while the aluminum species are 6-
coordinated at the beginning in the crystallization. These results
show that 6-coordinated aluminum species have been
completely transferred into 4-coordinated species in the initial
stage of the crystallization. As shown in Figure S12 and Tables
S3-S4, the maximum percentage of Si(3Si) species (-101.9
ppm) appears at 5 days. Correspondingly, the XRD data show
the crystallization happening fast at this stage. Possibly, the
rearrangement of silicon species with the intermediate of Si(3Si)
under assistance of organic templates plays a critical role in the
crystallization.
100
80
60
40
20
0
0
20
40
60
80
100 120 140
Time on stream (h)
It is well known that high hydrothermal stability is a key
factor for many industrial applications of zeolites.[47,48] Therefore,
it is very crucial to investigate the hydrothermal stability of Al-ITH
zeolite in this work. After steaming treatment at 800 °C for 5 h
with 10% water, the crystallinity, surface area, and pore volume
of aged H-Al-ITH zeolite are very close to those of the fresh one
(Figure S13, Tables S5-S6). These results demonstrate that the
Figure 5 Dependences of methanol conversion and product selectivity on
=
reaction time in MTP reaction over the Al-ITH-70 zeolite at 480 °C. ●: C2
selectivity, ▲: C3= selectivity, ◆: C4= selectivity, ★: Conversion of methanol.
In addition, it has been reported that the structural and acidic
properties of Al-ITH make it a good alternative to ZSM-5 as
shape selective FCC additive for producing propylene.[27,49] Thus,
5
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10.1002/anie.202003282
Angewandte Chemie International Edition
RESEARCH ARTICLE
form using an anion exchange resin (IRN-78) in water, and the obtained
solution was titrated using 0.1 M HCl.
the catalytic behaviour of the Al-ITH sample and two ZSM-5
samples have been compared for catalytic cracking of a vacuum
gasoil (VGO, see Table S8 for VGO properties) in a microactivity
test unit.[28] The results are shown in Figures S15-S17. The
presence of the additives results in all cases in a decrease of the
gasoline fraction and an increase of the gases produced due to
cracking of the olefins and paraffins present in the gasoline. The
drop in gasoline yield is higher for the ZSM-5 additive with the
highest Al content and lowest for the H-Al-ITH. Diesel and coke
selectivity are not affected. The highlight is the Al-ITH additive
increases propylene yield to levels close to those obtained with
ZSM-5 (113) but without increasing the yield of propane.
Moreover, it also increases the yield to the linear butenes to
values comparable to those given by the ZSM-5 zeolites with no
increase of the saturated butanes. This results in higher olefin to
paraffin ratios in the C3 and C4 fractions. When comparing the
catalytic behaviour of Al-ITH with that of a AlGe-ITH (Si/Ge=10,
(Si+Ge)/Al=50) described previously,[27] it can be seen that the
latter, with a higher Al content, produces more gases by
gasoline and even diesel cracking (see Figure S18a). However,
Al-ITH, although yielding less propene, presents comparable
propene/propane ratio (see Figure S18b) and the additional
advantage of its higher thermal and hydrothermal stability due to
the absence of Ge. Therefore, the above results show that Al-
ITH zeolite is indeed a good candidate as an FCC additive.
After the successful synthesis of Al-ITH zeolite with a Si/Al
ratio of 70 in the final product (Table S9, Run 1), Al-ITH zeolites
with various Si/Al ratios (57, 94, and 120) are also synthesized
(Table S9, Run 2-4). All products have a good crystallinity, four-
coordinated aluminum species, and crystals with nanosheet-like
morphology (Figures S19-S21). The details for all the synthesis
process are presented in Table S9.
As a typical run for synthesis of Al-ITH zeolite, boehmite (0-24 mg, 0-0.16
mmol Al2O3) and 10.67 g of organic template solution (OSDA1, 0.36
mol/L OH-) were mixed. Then, 0.935 g of fumed silica (15.58 mmol) was
added under stirring. After stirring the mixture for another 6 h, 0.05 g of
siliceous ITH zeolite seeds and 0.190 mL of HF (40%, 3.3 mmol) were
added. After partial water evaporation from starting gel (H2O/SiO2 > 30),
the final molar composition of the mixture was 1.0 SiO2 : 0-0.01 Al2O3
:
0.005 OSDA1 : 0.2 HF : 1-3 H2O. Finally, the mixture was transferred into
a Teflon-lined autoclave and heated at 160 °C for 10 days under rotation
condition (50 rpm). The solid zeolite product, which was denoted as Al-
ITH-x, where x was the Si/Al ratios in the starting gel, was then filtered,
washed with deionized water, dried at 100 °C and calcined at 550 °C for
5 h and named as H-Al-ITH-x. After hydrothermal treatment of H-Al-ITH
zeolite samples at 800 °C with 10% H2O for 5 h, the aged zeolite product
was obtained.
To evaluate the complexation ability of organic templates with aluminum
species, 0.05 g AlF3 and 10.67 g of template solution (0.36 mol/L OH- in
OSDA1 and OSDA2 aqueous solution) were mixed at room temperature.
After stirring for 30 min, the Al concentration of the supernatant was
analysed using inductively coupled plasma (ICP). Considering the AlF3 is
not soluble in water and does not react with base, if the supernatant has
higher Al species concentration, it means the better complexation with Al
species.
Acknowledgements
This work is supported by National Key Research and
Development Program of China (2017YFB0702803), National
Natural Science Foundation of China (21703203, 21673205,
21835002 and 21875140), Shanghai Pujiang Program
(17PJ1406400) and the Young Elite Scientist Sponsorship
Program by CAST (2017QNRC001). This work is partially
supported by CħEM, SPST, ShanghaiTech (Grant 02161943),
the Spanish Government-MICINN through “Severo Ochoa” (SEV
2012-0267) and RTI2018-101033-B-I00, and the European
Union through ERC-AdG-2014-671093 (SynCatMatch). This
work was also supported by BASF INCOE program.
Conclusion
In summary, the direct synthesis of Al-ITH zeolite with different
Si/Al ratios is successful in the presence of a cationic oligomer
as an organic template. The key to the successful synthesis is
the synergistic feature of the cationic oligomer with both the
structural directing ability for crystallization of ITH zeolite and the
strong complexation ability of aluminum species. The obtained
Al-ITH zeolite has superior hydrothermal stability. Catalytic tests
in MTP reaction show that the Al-ITH zeolite is active and
selective for the production of propylene together with a long
catalytic lifetime. In addition, Al-ITH zeolite is a good candidate
as a shape selective FCC additive. The use of the cationic
oligomers might open an alternative way in the future to
synthesize other zeolites directly that up to now could not yet be
crystallized as aluminosilicates.
Keywords: zeolite • aluminosilicate ITH • cationic oligomer •
direct synthesis • MTP reaction
[1]
[2]
[3]
[4]
[5]
J. Shin, D. Jo, S. B. Hong, Acc. Chem. Res. 2019, 52, 1419–1427.
P. Tian, Y. Wei, M. Ye, Z. Liu, ACS Catal. 2015, 5, 1922–1938.
F. Liu, Y. Yu, H. He, Chem. Commun. 2014, 50, 8445–8463.
M. Dusselier, M. E. Davis, Chem. Rev. 2018, 118, 5265–5329.
V. Vattipalli, A. M. Paracha, W. Hu, H. Chen, W. Fan, Angew. Chem. Int.
Ed. 2018, 57, 3607–3611.
[6]
Z. Liu, T. Wakihara, K. Oshima, D. Nishioka, Y. Hotta, S. P. Elangovan,
Y. Yanaba, T. Yoshikawa, W. Chaikittisilp, T. Matsuo, T. Takewaki, T.
Okubo, Angew. Chem. Int. Ed. 2015, 54, 5683–5687.
Q. Sun, N. Wang, R. Bai, X. Chen, J. Yu, J. Mater. Chem. A 2016, 4,
14978–14982.
[7]
[8]
Experimental Section
X. Zhu, J. P. Hofmann, B. Mezari, N. Kosinov, L. Wu, Q. Qian, B. M.
Weckhuysen, S. Asahina, J. Ruiz-Martínez, E. J. M. Hensen, ACS
Catal. 2016, 6, 2163–2177.
As a typical example for the organic template synthesis, 17.231 g of
N,N,N’,N’-tetramethylhexane-1,6-diamine (0.1 mol) was mixed with
21.591 g of 1,4-dibromobutane (0.1 mol) and 50 mL of ethanol. The
mixture was put under reflux for 12 h. Then, the solvent was evaporated,
and the white sediment was washed with ether and dried under vacuum.
Gel permeation chromatography (GPC) analysis showed that the
bromide salt form of the template had a molecular weight between 4291
and 8669 (n=11-22). The bromide form was converted to the hydroxide
[9]
R. Li, N. Linares, J. G. Sutjianto, A. Chawla, J. Garcia‐Martinez, J. D.
Rimer, Angew. Chem. Int. Ed. 2018, 57, 11283–11288.
[10] X. Liu, H. Xu, L. Zhang, L. Han, J. Jiang, P. Oleynikov, L. Chen, P. Wu,
ACS Catal. 2016, 6, 8420–8431.
6
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[11] D. Xie, L. B. McCusker, C. Baerlocher, S. I. Zones, W. Wan, X. Zou, J.
Am. Chem. Soc. 2013, 135, 10519–10524.
[46] A. Ishizuka, M. Oka, K. Ishizuka, T. Seki, N. Shibata, Microsc.
Microanal. 2017, 23, 34–35.
[12] D. W. Fickel, E. D’Addio, J. A. Lauterbach, R. F. Lobo, Appl. Catal. B
Environ. 2011, 102, 441–448.
[47] T. Ryu, N. H. Ahn, S. Seo, J. Cho, H. Kim, D. Jo, G. T. Park, P. S. Kim,
C. H. Kim, E. L. Bruce, P. A. Wright, I.-S. Nam, S. B. Hong, Angew.
Chem. Int. Ed. 2017, 56, 3256–3260.
[13] M. T. Conato, M. D. Oleksiak, B. P. McGrail, R. K. Motkuri, J. D. Rimer,
Chem. Commun. 2015, 51, 269–272.
[48] L. Zhu, L. Ren, S. Zeng, C. Yang, H. Zhang, X. Meng, M. Rigutto, A.
van der Made, F.-S. Xiao, Chem. Commun. 2013, 49, 10495–10497.
[49] A. I. Hussain, A. Palani, A. M. Aitani, J. Čejka, M. Shamzhy, M. Kubŭ, S.
S. Al-Khattaf, Fuel Process. Technol. 2017, 161, 23–32.
[14] D. Jo, J. Bin Lim, T. Ryu, I.-S. Nam, M. A. Camblor, S. Bong Hong, J.
Mater. Chem. A 2015, 3, 19322–19329.
[15] M. Choi, K. Na, J. Kim, Y. Sakamoto, O. Terasaki, R. Ryoo, Nature
2009, 461, 246–249.
[16] Q. Wu, X. Meng, X. Gao, F.-S. Xiao, Acc. Chem. Res. 2018, 51, 1396–
1403.
[17] A. Rojas, E. Martínez-Morales, C. M. Zicovich-Wilson, M. A. Camblor, J.
Am. Chem. Soc. 2012, 134, 2255–2263.
[18] C. Li, M. Moliner, A. Corma, Angew. Chem. Int. Ed. 2018, 57, 15330–
15353.
[19] B. W. Boal, J. E. Schmidt, M. A. Deimund, M. W. Deem, L. M. Henling,
S. K. Brand, S. I. Zones, M. E. Davis, Chem. Mater. 2015, 27, 7774–
7779.
[20] E.-P. Ng, D. Chateigner, T. Bein, V. Valtchev, S. Mintova, Science 2012,
335, 70–73.
[21] V. Valtchev, L. Tosheva, Chem. Rev. 2013, 113, 6734–6760.
[22] N. Funase, T. Tanigawa, Y. Yamasaki, N. Tsunoji, M. Sadakane, T.
Sano, J. Mater. Chem. A 2017, 5, 19245–19254.
[23] A. Corma, M. J. Díaz-Cabañas, J. Martínez-Triguero, F. Rey, J. Rius,
Nature 2002, 418, 514–517.
[24] G. Zhang, P. Feng, W. Zhang, H. Liu, C. Wang, H. Ma, D. Wang, Z.
Tian, Microporous Mesoporous Mater. 2017, 247, 158–165.
[25] X. Liu, W. Mao, J. Jiang, X. Lu, M. Peng, H. Xu, L. Han, S. Che, P. Wu,
Chem. Eur. J. 2019, 25, 4520–4529.
[26] P. Zeng, X. Guo, X. Zhu, Q. Guo, Y. Wang, S. Ren, B. Shen,
Microporous Mesoporous Mater. 2017, 246, 186–192.
[27] R. Castaneda, A. Corma, V. Fornes, J. Martineztriguero, S. Valencia, J.
Catal. 2006, 238, 79–87.
[28] L. Li, Y. Chen, S. Xu, J. Li, M. Dong, Z. Liu, H. Jiao, J. Wang, W. Fan, J.
Catal. 2016, 344, 242–251.
[29] H. Ma, Y. Chen, S. Wang, Z. Wei, Z. Qin, M. Dong, J. Li, W. Fan, J.
Wang, Catal. Sci. Technol. 2018, 8, 521–533.
[30] A. Corma, M. Puche, F. Rey, G. Sankar, S. J. Teat, Angew. Chem. Int.
Ed. 2003, 42, 1156–1159.
[31] G. Xu, X. Zhu, X. Li, S. Xie, S. Liu, L. Xu, Microporous Mesoporous
Mater. 2010, 129, 278–284.
[32] X. Liu, U. Ravon, A. Tuel, Microporous Mesoporous Mater. 2012, 156,
257–261.
[33] Q. Wu, X. Liu, L. Zhu, X. Meng, F. Deng, F. Fan, Z. Feng, C. Li, S.
Maurer, M. Feyen, U. Müller, F.-S. Xiao, Chin. J. Chem. 2017, 35, 572–
576.
[34] A. Corma, M. E. Davis, ChemPhysChem 2004, 5, 304–313.
[35] S. Liu, P. Zhang, X. Meng, D. Liang, N. Xiao, F.-S. Xiao, Microporous
Mesoporous Mater. 2010, 132, 352–356.
[36] R. H. Daniels, G. T. Kerr, L. D. Rollmann, J. Am. Chem. Soc. 1978, 100,
3097–3100.
[37] J. Zhu, Y. Zhu, L. Zhu, M. Rigutto, A. van der Made, C. Yang, S. Pan, L.
Wang, L. Zhu, Y. Jin, Q. Sun, Q. Wu, X. Meng, D. Zhang, Y. Han, J. Li,
Y. Chu, A. Zheng, S. Qiu, X. Zheng, F.-S. Xiao, J. Am. Chem. Soc.
2014, 136, 2503–2510.
[38] Y. Zhang, R. Yan, T. Sun, Y. Ma, Ultramicroscopy 2020, 211, 112941.
[39] B. Shen, X. Chen, D. Cai, H. Xiong, X. Liu, C. Meng, Y. Han, F. Wei,
Adv. Mater. 2020, 32, 1906103.
[40] L. Liu, N. Wang, C. Zhu, X. Liu, Y. Zhu, P. Guo, L. Alfilfil, X. Dong, D.
Zhang, Y. Han, Angew. Chem. Int. Ed. 2020, 132, 829–835.
[41] N. Shibata, Y. Kohno, S. D. Findlay, H. Sawada, Y. Kondo, Y. Ikuhara,
J. Electron Microsc. (Tokyo) 2010, 59, 473–479.
[42] N. Shibata, S. D. Findlay, Y. Kohno, H. Sawada, Y. Kondo, Y. Ikuhara,
Nat. Phys. 2012, 8, 611–615.
[43] E. Yücelen, I. Lazić, E. G. T. Bosch, Sci. Rep. 2018, 8, 1–10.
[44] I. Lazić, E. G. T. Bosch, S. Lazar, Ultramicroscopy 2016, 160, 265–280.
[45] A. Ishizuka, M. Oka, T. Seki, N. Shibata, K. Ishizuka, Microscopy 2017,
66, 397–405.
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This work shows a way to directly synthesize aluminosilicate ITH (Al-ITH) zeolite using a cationic oligomer as an organic template,
where the strong complexation ability with aluminum species is a key factor for the successful preparation.
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