Rational Manipulation of Stacking Arrangements in Three-Dimensional Zeolites Built from Two-Dimensional Zeolitic Nanosheets

Article abstract of DOI:10.1002/anie.202009336

Unit-cell-thin zeolitic nanosheets have emerged as fascinating materials for catalysis and separation. The controllability of nanosheet stacking is extremely challenging in the chemistry of two-dimensional zeolitic materials. To date, the organization of zeolitic nanosheets in hydrothermal synthesis has been limited by the lack of tunable control over the guest–host interactions between organic structure-directing agents (OSDAs) and zeolitic nanosheets. A direct synthetic methodology is reported that enables systematic manipulation of the aluminosilicate MWW-type nanosheet stacking. Variable control of guest–host interactions is rationally achieved by synergistically altering the charge density of OSDAs and synthetic silica-to-alumina composition. These finely controlled interactions allow successful preparation of a series of three-dimensional (3D) zeolites, with MWW-layer stacking in wide ranges from variably disorder to fully ordered, leading to tunable catalytic activity in the cracking reaction. These results highlight unprecedented opportunities to modulate zeolitic nanosheets arrangement in 3D zeolites whose structure can be tailored for catalysis and separation.

Full text of DOI:10.1002/anie.202009336

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
International Edition Chemie
www.angewandte.org
Accepted Article
Title: Rational Manipulation of Stacking Arrangements in Three-
Dimensional Zeolites Built from Two-Dimensional Zeolitic
Nanosheets
Authors: Le Xu, Tianqiong Ma, Yihan Shen, Yong Wang, Lu Han,
Watcharop Chaittisilp, Toshiyuki Yokoi, Junliang Sun, Toru
Wakihara, and Tatsuya Okubo
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202009336
Link to VoR: https://doi.org/10.1002/anie.202009336

Angewandte Chemie International Edition
10.1002/anie.202009336
COMMUNICATION
Rational Manipulation of Stacking Arrangements in Three-Dimensional
Zeolites Built from Two-Dimensional Zeolitic Nanosheets
*
Le Xu, Tianqiong Ma, Yihan Shen, Yong Wang, Lu Han , Watcharop Chaittisilp, Toshiyuki Yokoi, Junliang
Sun , Toru Wakihara, and Tatsuya Okubo*
*
Abstract: Unit-cell-thin zeolitic nanosheets have emerged as
fascinating materials for catalysis and separation. The controllability
of nanosheets stacking is extremely challenging in the chemistry of
two-dimensional zeolitic materials. So far, the organization of zeolitic
nanosheets in hydrothermal synthesis has been limited by the lack
of tunable control over the guest-host interactions between organic
structure-directing agents (OSDAs) and zeolitic nanosheets. Here,
we report a direct synthetic methodology that enables systematic
manipulation of the aluminosilicate MWW-type nanosheets stacking.
Variable control of guest-host interactions is rationally achieved by
synergistically altering the charge density of OSDAs and synthetic
silica-to-alumina composition. These finely-controlled interactions
allow the successful preparation of series of three-dimensional (3D)
zeolites with MWW-layer stacking in wide ranges from variations of
disorder to fully-order, leading to tunable catalytic activity in cracking
reaction. These results highlight unprecedented opportunities to
modulate zeolitic nanosheets arrangement in 3D zeolites whose
structure can be tailored for catalysis and separation.
treatment processes. In hydrothermal synthesis, the formation and
organization of zeolitic nanosheets is controlled by the guest-host
interactions between OSDA and zeolitic nanosheets. A suitable
OSDA with strong interaction with a specific Miller plane of zeolite
structure would inhibit crystal growth along one crystallographic
dimension, leading to the formation of 2D zeolitic nanosheets
[6]
stacking in energetic favorable modes. However, owing to the lack
of understanding of zeolite crystallization and poor control of guest-
host interactions, rational design of a synthetic method for finely
controlling nanosheets stacking remains a fundamental challenge.
Herein, we reported the systematic and tunable manipulation of
the typical MWW-layer stacking through controllable guest-host
interactions between OSDAs and 2D zeolitic nanosheets.
Conceptually, this variable control was rationally realized by altering
the charge density of OSDA and synthetic silica-to-alumina
composition. First, our synthesis utilized three related OSDAs
containing the same imidazolium moiety but with different alkylated
groups, which are isobutyl, cyclohexyl and cycloheptyl, resulting in
three OSDAs, namely 1,3-bis(isobutyl) imidazolium (C
bis(cyclohexyl) imidazolium (C -IM) and 1,3-bis(cycloheptyl)
imidazolium (C -IM), respectively (Figs. 1a, 1c and 1e). The key
4
-IM), 1,3-
Z
eolites, a class of crystalline microporous materials, have been
6
widely utilized as solid acid catalysts in the conversion of petroleum-
7
[1]
derived hydrocarbons to valuable chemical products. As a sub-
family of zeolitic materials, two-dimensional (2D) lamellar zeolites
have gained much attention as promising materials in catalysis and
separation fields due to the unit-cell-thin nanosheet thickness and
benefit of using these OSDAs is that the difference of substituents
on the aromatic ring would influence the charge density in the
resulting OSDAs, which can be demonstrated by density functional
theory (DFT) calculations. The calculated electrostatic potential
(ESP) mapping showed a significant difference in the ESP surface
(i.e., charge density) among three OSDAs, as the ESP of OSDA
gradually decreased with the increasing size of substituents (ESP:
[
2]
flexible stacking feature. In fundamental zeolite chemistry, zeolitic
nanosheets provide a unique platform to construct zeolites by linking
[3]
2
D building blocks in different patterns. Various stacking modes
and linkages between zeolitic nanosheets have expanded the types
C
4
-IM > C
had the same total positive charge of +1, C
positive charge density, which gradually decreased in C
6
-IM > C
7
-IM, Figs. 1b, 1d and 1f). Although three OSDAs
-IM exhibited the highest
-IM and
[4]
of zeolite structures with different pore entrances, which intimately
determine its size/shape selectivity in applications. In this respect,
the control of nanosheets stacking is of paramount significance for
constructing targeted zeolites with tailored porosity and function.
Although postsynthetic approaches have been developed to regulate
4
6
[5]
nanosheets stacking, they often lack of precise control over the
[
*
]
Dr. L. Xu, Prof. T. Wakihara, Prof. T. Okubo
Department of Chemical System Engineering, The University of Tokyo
Tokyo 113-8656, Japan
E-mail: okubo@chemsys.t.u-tokyo.ac.jp
Dr. T. Ma, Y. Shen, Prof. J. Sun
College of Chemistry and Molecular Engineering, Peking University
Beijing 100871, China
E-mail: junliang.sun@pku.edu.cn
Prof. L. Han
School of Chemical Science and Engineering, Tongji University
Shanghai 200092, China
E-mail: luhan@tongji.edu.cn
Dr. Y. Wang, Prof. T. Yokoi,
Chemical Resources Laboratory, Tokyo Institute of Technology
Yokohama 226-8503, Japan
Figure 1. Three related OSDAs that used for zeolite synthesis in this work.
(a) 1,3-bis(isobutyl) imidazolium (C -IM), (c) 1,3-bis(cyclohexyl) imidazolium
-IM) and (e) 1,3-bis(cycloheptyl) imidazolium (C -IM). The electrostatic
potentials (ESP) mapped onto their electron density surface were given to (b)
-IM, (d) C -IM and (f) C -IM, respectively. The positive charge density of
three OSDAs gradually decreased with the increasing size of alkylated
groups on the imidazolium ring, as demonstrated by the decreasing ESP
4 6 7
energy in the order of C -IM, C -IM and C -IM.
Prof. W. Chaikittisilp
4
(
C
6
7
Research and Services Division of Materials Data and Integrated System
National Institute for Materials Sciences (NIMS)
Ibaraki 305-0044, Japan
C
4
6
7
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.202009336
COMMUNICATION
2
A−2C). Therefore, our findings indicated these
OSDAs not only played the role of structure-
direction for the MWW-type layered structure, but
also acted as a modulator to regulate zeolitic
nanosheets stacking in different SAR ranges. As
is well-known that OSDAs have been extensively
employed in zeolite synthesis with the aims to
[
10]
search for new structure,
regulate crystallite
alternate framework
composition and control of aluminum location
[11]
morphology and size,
[12]
[13]
and proximity, however, this modulation effect
of OSDA on zeolitic layer stacking has never
been discovered to the best of our knowledge.
More interestingly, different synthetic SAR
ranges for stacking transition were observed for
different OSDAs. The transition from disordered
to ordered nanosheet stacking occurred in the
highest synthetic SAR range of 200−90 for C
4
-IM
(Figs. 2Ac−2Ag), while the lowest synthetic SAR
7
range of 80−50 was observed for C -IM (Figs.
2
6
Ch−2Ck). With C -IM as OSDA, the medium
synthetic SAR range (90−60) worked for stacking
transition (Figs. 2Bg−2Bj). Elemental analysis
confirmed the above tendency that OSDA with a
smaller substituent produced zeolites with
a
4 6 7
Figure 2. XRD patterns of zeolites that synthesized using (A) C -IM, (B) C -IM, and (C) C -IM as
higher SAR range for stacking transition (Tables
2 2 3
OSDA and with different synthetic SiO /Al O ratios (SAR) in gels: (a) 800, (b) 400, (c) 200, (d) 150,
+
(
e) 120, (f) 100, (g) 90, (h) 80, (i) 70, (j) 60, (k) 50 and (l) 40. The structure models of (D) shifted
S1−S3). Besides, trace amounts of Na were
ABAB, (E) shifted ABCABC and (F) ordered AA MWW-layer stacking. (G) The simulated XRD
patterns of (a) ABAB stacking, (b) ABCABC stacking, (c) 50% ABAB and 50% ABCABC stacking
and (d) AA stacking. The experimental XRD patterns plotted in black in (A–C) indicated the faulted
structure containing two shifted stacking modes. The XRD patterns in blue indicated the structure
transformation due to the MWW-layer stacking change from disorder to order. The XRD patterns in
red represented the ordered MWW-layer stacking in the AA mode. The main differences of XRD
patterns among different materials were highlighted in yellow regions. The two shifted structures (D
and E) were found to intergrow to form a disordered stacking with nearly 50% ABAB and 50%
found in the as-synthesized zeolites within the
structure transition range, while the OSDA
contents were much higher by comparison (Fig.
S4). This indicated OSDA played a much more
important role in governing MWW-layers stacking
+
compared with trace amount of Na .
o
ABCABC mode, leading to a broad XRD peak at 2θ of 9 (Gc). The typical MWW topology contained
the ordered AA MWW-layer stacking, resulting in two well-resolved 101 and 102 XRD peaks (Gd).
27
Al MAS NMR spectra of as-synthesized
products with -IM as OSDA indicated Al
C
6
7
C -IM, respectively. Therefore, it was clear that the charge density of
species were incorporated into the tetrahedral sites in MWW-layer
OSDA could be adjusted according to the size of alkylated groups on
the imidazolium ring.
−
(
Fig. S5). Since the substitution of anionic AlO4/2 for framework
SiO4/2 tetrahedral units would introduce the anionic lattice charges,
cationic OSDA was generally needed in the high-silica zeolite
synthesis to provide the electrostatic compensation for anionic lattice
With three related OSDAs, the systematic variations of a single
variable (OSDA-type) in zeolite synthesis could be achieved at a
specific silica-to-alumina ratio (SiO
2
/Al
2
O
3
, SAR) in synthetic gel.
[14]
charges. For layered zeolite synthesis, the influence of guest-host
Moreover, for each OSDA, the synthetic SAR composition was
varied in a wide range of 800−40 to investigate the structure-
directing behavior of OSDAs under different synthetic SAR
conditions. First, 2D MWW layered precursors were obtained for
each OSDA in all synthetic SAR ranges, as evidenced by the typical
change in their X-ray diffraction (XRD) patterns of as-synthesized
interactions on nanosheet stacking would become much more
significant when related OSDAs had similar structure-directing ability
but possessed different charge densities. The mismatch between the
charge density of OSDA and synthetic SAR seems to provide the
driving force to move MWW nanosheets. With the highest positive
charge density, C
anionic zeolite lattice (i.e. high framework SARs) at their interface
much stronger than C -IM and C -IM, probably providing more
4
-IM would interact with less negatively-charged
[3a,7]
samples during calcination (Figs. S1−S3).
For the synthesis with
a high synthetic SAR of 800, the zeolites with similar highly-
disordered structure were produced with each OSDA (Figs. 2Aa,
6
7
stabilization energy to overcome the energetic barrier for nanosheet
stacking mode transition. Thus, the stacking transition was observed
2
Ba and 2Ca), which was consistent with previous reports that these
OSDAs directed the SSZ-70 zeolite (*-SVY topology) containing
among zeolites with high SARs ranging from 182 to 80 for C
4
-IM
[8]
disordered MWW-layer stacking (Figs. 2D, 2E and 2Gc). However,
an unexpected transition of MWW-layer stacking from disorder to
order was observed when the synthetic SAR decreased, regardless
of OSDA-types (Figs. 2A−2C and Figs. S1−S3). The intensity of the
(
Figs. 2Ac−2Ag, and Table S1). In contrast, C -IM with the lowest
7
positive charge density would interact with zeolite lattice strong
enough to induce nanosheet stacking transition, only when zeolite
lattice had low SARs of 62−36 and thus became much more
negatively-charged (Figs. 2Ch−2Ck and Table S3).
o
broad XRD reflection centered at 2θ of 9 in the XRD pattern,
[9]
representing the disordered MWW-layer stacking,
gradually
Although the mechanism of zeolite crystallization has not been
well-clarified, it was reasonable to speculate the guest-host
interactions between OSDAs and anionic zeolitic lattice during
crystallization could be adjusted according to the charge density of
OSDAs and synthetic SAR composition. For each OSDA, the
decreased with the decreasing synthetic SAR, and eventually
disappeared at a low synthetic SAR. Meanwhile, the new 101 and
1
2
02 reflections, typical for the ordered MWW-layer stacking (Fig.
[3a,7b]
Gd),
started to appear with the decreasing synthetic SAR (Figs.
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.202009336
COMMUNICATION
possessed different contents of stacking modes (Fig. S7). Based on
these three zeolites, it would be interesting to explore the influence
of stacking structures on the property and function of zeolite.
Scanning electron microscopy (SEM) images of three zeolites
showed the typical flask-like crystal morphology and similar crystal
13
dimension (Fig. S8). C MAS NMR spectra demonstrated three
OSDAs kept intact in the as-synthesized layered precursors (Fig.
27
S9). Although Al MAS NMR spectra of as-synthesized materials
indicated Al species were incorporated into MWW-layers (Fig. S10),
it was interesting to observe less dealumination in the calcined-form
6 7
MWW-C -SAR60 and MWW-C -SAR62 zeolites (Figs. 4Bb and 4Bc).
We postulated that the different dealumination degrees might be, at
least partially, related to the MWW-layer stacking. Previous NMR
4
investigation has shown that C -IM directed 94% of framework Al
[16]
atoms sited near the MWW-layer surface. According to the MWW-
layer structure, T1 site was one possible position to hold the surface
Al atoms (Fig. S11). Since there was no T1–O–T1 linkage in the as-
synthesized precursors, Al atoms were allowed to simultaneously
distribute at T1 sites on both sides of adjacent MWW-layers.
However, the interlayer condensation would lead to the formation of
bridged T1–O–T1 bonds between layers. Owing to the Löwenstein’s
Figure 3. (A) TEM image and corresponding SAED pattern of the zeolite
MWW-C -SAR60, which was synthesized with C -IM as OSDA and had a
6 6
SAR of 60 (determined by ICP-AES analysis). (B−D) The Fourier filtered TEM
images with AA, ABAB and ABCABC stacking sequences, respectively
tunable control of the guest-host interactions was realized by altering
the synthetic SAR compositions. For the synthesis with a specific
synthetic SAR, the variable control was achieved by using different
OSDAs. Thus, a great advantage of our synthetic approach is that
the cooperation of three relevant OSDAs and various synthetic SAR
compositions allowed the preparation of three zeolite families with
well-controlled MWW-layer stacking modes in wide ranges from
variations of highly-disorder to fully-order, which has not been
achieved in previous studies.
[17]
rule,
framework during calcination, when both paired T1 sites on
neighboring layers were occupied by Al atoms. For MWW-C -SAR64,
some Al species would force to remove out of zeolite
4
calcination led to the condensation between each pair of T1–OH (Fig.
S11a), rising more chances to generate the energetically
unfavorable Al–O–Al linkages. With less contents of ordered
6 7
stacking in MWW-C -SAR60 and MWW-C -SAR62 (Fig. S7), less
To investigate the stacking structure of MWW-layer in the
T1–O–T1 bridges would be generated during calcination (Fig. S11b),
probably leading to less chance to produce extra-framework Al (EF-
Al) species. Thus, the adjustable manipulation of MWW-layer
6 6
resulting material, zeolite MWW-C -SAR60 that synthesized with C -
IM as OSDA and had a SAR of 60 was used for transmission
electron microscopy (TEM) investigations. The selected-area
electron diffraction (SAED) pattern showed sharp diffraction spots for
reflections with indices h = 3n while streaks for reflections with h =
6 7
stacking might endow MWW-C -SAR60 and MWW-C -SAR62
resistance to dealumination during calcination.
In addition to dealumination, the stacking control of zeolitic
nanosheets also affected the intracrystalline defects and acid
strengths of the resulting materials. IR spectra of the acid form of
three zeolites exhibited the vibrations corresponding to bridged
3
n ± 1, indicating the shift of layers along ±1/3a* (a* denotes the
reciprocal space vector). The organization of MWW layers with
various stacking sequences could be identified from the high
resolution TEM (HRTEM) image, which clearly showed the material
contained the stacking of MWW-layers in not only the ordered AA
sequence but also the shifted ABAB and ABCABC stacking modes
-
1
-1
hydroxyl groups at 3620 cm and external silanol at 3744 cm (Fig.
-
1
S12). A shoulder at 3728 cm assigned to the intracrystalline
silanols was also observed, and its intensity increased with the
increasing content of disordered stacking structure. A previous study
demonstrated the disordered MWW zeolite material contained two
kinds of silanols on the layer surface, namely the single terminal Si–
(
Fig. 3). It is worthy to note that this is the first time to directly
observe a zeolite material that constructed with three different
stacking modes of MWW-layer. Moreover, focusing on zeolites
[
9a,18]
prepared with C
Figs. 2Ba−2Bl), XRD simulation by the Discry program indicated
that the content of AA stacking was negligible in the high SAR range
640−88), but gradually enhanced during structure transition (SAR of
6
-IM as OSDA in the wide SAR range of 640−28
OH and a cluster of 3 Si–OH (Fig. S13).
more intracrystalline defects in MWW-C
Thus, the presence of
-SAR60 and MWW-C
[15]
(
6
7
-
SAR62 was consistent with the higsh contents of disordered
stacking structure in these two materials (Fig. S7). The highly-
(
7
4
6−52), and finally became the main phase in the low SAR range of
0−28 (Fig. S6). Meanwhile, the contents of shifted structures
ordered MWW-C
4
-SAR64 had less intracrystalline defects, which
[
19]
have also been observed in MCM-22.
Moreover, pyridine was
(
ABAB and ABCABC) gradually decreased with the increasing
readily adsorbed at room temperature on dehydrated samples (Figs.
4Da, 4Ea and 4Fa). However, a large amount of protonated pyridine
content of AA stacking mode.
With the advantage of well-controlled zeolitic MWW-layer
stacking, our synthetic method offered an unprecedented opportunity
to prepare zeolites with comparable SAR compositions but in
different stacking modes. The most interesting examples were three
different zeolites with a closed measured SAR around 60 could be
was still retained on MWW-C
4Dd and Table S4), indicating the higher amount of strong acid sites,
as compared with MWW-C -SAR60 and MWW-C -SAR62 that
4
-SAR64 after desorption at 450 °C (Fig.
6
7
showed gradually decreased amount of strong acid sites, especially
the Brønsted acid sites (Figs. 4E, 4F and Table S4). This
synthesized with three different OSDAs. In particular, C
MWW-C -SAR64 zeolite with the highly-ordered MWW-layer
stacking (Figs. 2Ai and 4Aa), while the partially-disordered MWW-
-SAR60 zeolite (Figs. 2Bi and 4Ab) and the highly-disordered
MWW-C -SAR62 zeolite (Figs. 2Ch and 4Ac) were prepared with C
IM and C -IM, respectively. XRD simulation revealed that they
4
-IM directed
observation was further confirmed by NH
controlled materials (Fig. 4C).
3
-TPD results of three
4
With the highly-ordered stacking, MWW-C
higher specific surface area and larger micropore volume,
compared with other two materials (Fig. S14 and Table S5).
However, the partially-disordered MWW-C -SAR60 zeolite and
4
-SAR64 exhibited a
C
6
a
7
6
-
7
6
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.202009336
COMMUNICATION
In summary, we report a new synthetic system that for the first
time realizes the systematic manipulation of zeolitic nanosheet
stacking. Owing to the tunable charge density of OSDAs and
synthetic SAR compositions, the adjustable guest-host interactions
become possible, leading to three new zeolite families containing
well-controlled MWW-layer stacking modes in a wide range of
variations from disorder to fully-order manners. Our study reveals
that a new role of OSDA during zeolite crystallization, in which the
OSDA can not only play the role of structure-direction, but also act
as a modulator to regulate the nanosheet stacking. Furthermore, the
concept of this new approach opens us to the possibility that this
modulation effect would not be restricted to the MWW-type
aluminosilicate, but should be applicable to other layered zeolites in
general. More than 15 known zeolite topologies can be prepared
through 2D layered precursor containing various trivalent/divalent
heteroatoms. Therefore, the significance of this new synthetic
approach is offering the possibility to design well-controlled zeolitic
nanosheet arrangements in 3D zeolites whose structural features
can be tailored for applications in catalysis and separation.
Figure 4. (A) XRD patterns, (B) solid-state 27Al MAS NMR spectra and (C)
NH
b) MWW-C
spectra of proton-type calcined zeolite products: (D) MWW-C
MWW-C -SAR60 and (F) MWW-C -SAR62 after desorption at (a) 150 °C, (b)
50 °C, (c) 350 °C and (d) 450 °C, respectively. In (D−F), the 1543 cm and
454 cm-1 peak represented the pyridine-bonded Brønsted and Lewis acidic
3
-TPD of the proton-type calcined zeolite products: (a) MWW-C
-SAR60 and (c) MWW-C -SAR62. Pyridine-adsorption FTIR
-SAR64, (E)
4
-SAR64,
(
6
7
4
6
7
-1
Acknowledgement
2
1
L.X. acknowledge Japan Society for the Promotion of Science (JSPS)
for providing the research fellowship. L.H. and J.S. thanks the financial
support from National Natural Science Foundation of China (L.H.: Grant
nos. 21922304 and 21873072; J.S.: Grant no. 21871009) and Natural
Science Foundation of Shanghai (L.H.: Grant no. 18ZR1442400).
sites, respectively.
7
highly-disordered MWW-C -SAR62 zeolite showed lower but similar
specific surface area and micropore volume, which could be caused
by the combined effects of structure and dealumination. Although a
Keywords: crystal growth
• layered compounds • structure
higher content of the ordered AA stacking in MWW-C
compared with MWW-C -SAR62, Fig. S7) would lead to a relative
higher adsorption capacity (Fig. S15), more serious
dealumination led to partial micropore-blockage in MWW-C -SAR60
Fig. 4Bb). In contrast, the dealumination-related micropore blockage
6
-SAR60
transformation • zeolites • catalysis
(
7
N
2
[1] M. E. Davis, Nature 2002, 417, 813.
[
2] a) A. Corma, V. Fornes, S. B. Pergher, T. L. M. Maesen, J. G. Buglass,
Nature 1998, 396, 353; b) K. Varoon, X. Zhang, B. Elyassi, D. D. Brewer,
M. Gettel, S. Kumar, J. A. Lee, S. Maheshwari, A. Mittal, C. Sung, M.
Cococcioni, L. F. Francis, A. V. McCormick, K. A. Mkhoyan, M. Tsapatsis,
Science 2011, 334, 72; c) H. Luo, V. Michaelis, S. Hodges, R. Griffin, Y.
Roman-Leshkov, Chem. Sci. 2015, 6, 6320; d) V. Margarit, M. Martinez-
Armero, T. Navarro, C. Martinez, A. Corma, Angew. Chem. Int. Ed. 2015,
54, 13724; (e) L. Xu, X. Ji, S. Li, Z. Zhou, X. Du, J. Sun, F. Deng, S. Che,
P. Wu, Chem. Mater. 2016, 28, 4512; f) Y. Zhou, Y. Mu, H. Hsieh, B.
Kabius, C. Pacheco, C. Bator, R. M. Rioux, J. D. Rimer, J. Am. Chem.
Soc. 2020, 142, 8211.
6
(
7
was less significant for MWW-C -SAR62 because of less EF-Al
species (Fig. 4Bc). This combined effects resulted in the comparable
specific surface area and micropore volume between MWW-C
SAR60 and MWW-C -SAR62.
6
-
7
Therefore, three OSDAs regulated the stacking of MWW-layer
in three resulting materials, which exhibited well-tuned properties in
many aspects, such as dealumination, intracrystalline defect, acid
strength and microporosity, among which the highly-ordered MWW-
[3] a) M. E. Leonowicz, J. A. Lawton, S. L. Lawton, M. K. Rubin, Science 1994,
C
4
-SAR64 zeolite exhibited higher specific surface area, larger
micropore volume and higher amount of strong acid sites. Besides,
although the partially-disordered MWW-C -SAR60 and highly-
disordered MWW-C -SAR62 zeolites had the lower but comparable
microporosity, they exhibited different acid strengths. MWW-C
SAR60 zeolite had the medium acidity, while MWW-C -SAR62 only
264, 1910; b) W. J. Roth, P. Nachtigall, R. E. Morris, J. Čejka, Chem. Rev.
2014, 114, 4807; c) P. Eliasova, M. Opanasenko, P. S. Wheatley, M.
6
Shamzhy, M. Mazur, P. Nachtigall, W. J. Roth, R. E. Morris, J. Čejka,
Chem. Soc. Rev. 2015, 44, 7177; d) P. S. Wheatley, P. Chlubna-Eliášová,
H. Greer, W. Zhou, V. R. Seymour, D. M. Dawson, S. E. Ashbrook, A. B.
Pinar, L. B. McCusker, M. Opanasenko, J. Čejka, R. E. Morris, Angew.
Chem. Int. Ed. 2014, 53, 13210.
7
6
-
7
possessed a weak acidity. The catalytic cracking of n-hexane was
[
4] B. Marler, Y. Wang, J. Song, H. Gies, Dalton Trans. 2014, 43, 10396.
5] a) T. Moteki, W. Chaikittsilp, A. Shimojima, T. Okubo, J. Am. Chem. Soc.
used as a model reaction to investigate their catalytic behaviors.
[
4
Compared with other two materials, MWW-C -SAR64 led to a higher
2008, 130, 15780; b) L. Xu, J. Sun, Adv. Energy Mater. 2016, 6, 1600441;
conversion of n-hexane and higher selectivity for the ethylene and
c) L. Xu, P. Wu, New J. Chem. 2016, 40, 3958.
6] M. Witman, S. Ling, P. Boyd, S. Barthel, M. Haranczyk, B. Slater, B. Smit,
ACS Cent. Sci. 2018, 4, 235.
propylene (Figs. S16 and S17), probably due to the benefit of larger
[
specific surface area and strong acid strength.
comparable hexane conversion was observed for MWW-C
and MWW-C -SAR62 zeolites, indicating the comparable amount of
A
lower but
6
-SAR60
[7] a) M. K. Rubin, P. Chu, US Patent 1990, 4954325; b) M. A. Camblor, A.
Corma, M. Diaz-Cabanas, C. Baerlocher, J. Phys. Chem. B 1998, 102, 44.
7
[
8] a) R. H. Archer, J. R. Carpenter, S. Hwang, A. W. Burton, C. Chen, S. I.
Zones, M. E. Davis, Chem. Mater. 2010, 22, 2563; b) R. H. Archer, S. I.
Zones, M. E. Davis, Microporous Mesoporous Mater. 2010, 130, 255.
9] a) S. Smeets, Z. J. Berkson, D. Xie, S. I. Zones, W. Wan, X. Zou, M. Hsieh,
B. F. Chmelka, L. B. McCusker, C. Baerlocher, J. Am. Chem. Soc. 2017,
reactant hexane could diffuse into the two independent channel
systems and interact with acidic active sites in these two materials.
For partially disordered and highly disordered zeolites, owing to the
[
medium strong acidity of MWW-C
6
-SAR60 zeolite, relatively more
-SAR62 zeolite with
propylene was produced. However, MWW-C
7
139, 16803; b) L. Xu, X. Ji, J. Jiang, L. Han, S. Che, P. Wu, Chem. Mater.
the weak acid strength produced less propylene but more butane
and butene isomers. Overall, the porosity and acidity parameters
can be finely tuned, as a result of different stacking modes in three
catalysts, leading to the controlled catalytic performances.
2
015, 27, 7852.
[10] M. Moliner, F. Rey, A. Corma, Angew. Chem. Int. Ed. 2013, 52, 13880.
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.202009336
COMMUNICATION
[
11] a) G. Bonilla, I. Diaz, M. Tsapatsis, H. Jeong, Y. Lee, D. G. Vlachos,
Chem. Mater. 2004, 16, 5697; b) S. Mintova, J. P. Gilson, V. Valtchev,
Nanoscale 2013, 5, 6693.
[15] X. Wang, Y. Shen, R. Liu, X. Liu, C. Lin, D. Shi, Y. Chen, F. Liao, J. Lin, J.
Sun, Acta Cryst. 2019, B75, 333.
[16] Z. J. Berkson, M. Hsieh, S. Smeets, D. Gajan, A. Lund, A. Lesage. D. Xie,
S. I. Zones, L. B. McCusker, C. Baerlocher, B. F. Chmelka, Angew. Chem.
Int. Ed. 2019, 58, 6255.
[12] R. M. Barrer, P. J. Denny, J. Chem. Soc. 1961, 971.
[
13] a) J. R. Di Iorio, C. T. Nimlos, R. Gounder, ACS Catal. 2017, 7, 6663; b) K.
Muraoka, W. Chaikittsilp, Y. Yanaba, T. Yoshikawa, T. Okubo, Angew.
Chem. Int. Ed. 2018, 57, 3742.
[17] W. Löwenstein, Am. Mineral. 1954, 39, 92.
[18] C. Schroeder, C. Muck-Lichtenfeld, L. Xu, N. A. Grosso-Giordano, A.
Okrut, C. Chen, S. I. Zones, A. Katz, M. R. Hansen, H. Koller, Angew.
Chem. Int. Ed. 2020, 59, 10939.
[
14] a) M. E. Davis, R. F. Lobo, Chem. Mater. 1992, 4, 756; b) Y. Li, H. Cao, J.
Yu, ACS Nano 2018, 12, 4096; c) J. H. Lee, M. B. Park, J. K. Lee, H. Min,
M. K. Song, S. B. Hong, J. Am. Chem. Soc. 2010, 132, 12971.
[19] A. Corma, C. Corell, V. Fornes, W. Kolodzjski, J. Perez-Pariente, Zeolites,
1995, 15, 576.
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.202009336
COMMUNICATION
COMMUNICATION
L. Xu, T. Ma, Y. Shen, Y. Wang, L. Han*,
W. Chaikittisilp, T. Yokoi, J. Sun*, T.
Wakihara, and T. Okubo*
Page No. – Page No.
Rational Manipulation of Stacking
Arrangements in Three-Dimensional
Zeolites Built from Two-Dimensional
Zeolitic Nanosheets
Stacking Modulation. A new synthetic method for the first time realizes the systematic manipulation of two-dimensional
zeolitic nanosheets stacking in 3D zeolite, opening the possibilities of designing zeolitic nanosheet arrangements whose
structure can be tailored for applications in catalysis and separation.
This article is protected by copyright. All rights reserved.