Synthesis of Extra-Large-Pore Zeolite ECNU-9 with Intersecting 14*12-Ring Channels

Article abstract of DOI:10.1002/anie.201805535

Highly crystalline and (hydro)thermally stable zeolites with extra-large pores [≥14-ring (14-R)] are desirable as catalysts. A novel zeolite, ECNU-9, with an intersecting 14*12-R channel system was rationally designed and synthesized by a building block strategy, in which the interlayer expansion of a two-dimensional silicate structure was realized by combining organic amine assisted layer-stacking reorganization and subsequent silylation with a square-shaped single 4-ring (S4R) silane, 1,3,5,7-tetramethylcyclotetrasiloxane (TMCS). The PLS-3 precursor was disassembled into building blocks and then intercalated with flexible and removable organic amine pillars to offer enough interlayer spacing for accommodating TMCS molecules. The additionally introduced building blocks interconnected the neighboring layers to construct new 14-R and 12-R pores. ECNU-9 possesses a well-ordered structure with a novel topology. The corresponding Ti-ECNU-9, with tetrahedral Ti ions in the framework, showed superior catalytic performance in the selective epoxidation of bulky alkenes.

Full text of DOI:10.1002/anie.201805535

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Accepted Article
Title: Lego Chemistry-Inspired Synthesis of Extra-large Pore Zeolite
ECNU-9 with Intersecting 14*12-Ring Channels
Authors: Boting Yang, Jingang Jiang, Hao Xu, Haihong Wu, Minyuan
He, and Peng Wu
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201805535
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Angewandte Chemie International Edition
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COMMUNICATION
Lego Chemistry-Inspired Synthesis of Extra-large Pore Zeolite
ECNU-9 with Intersecting 14*12-Ring Channels
Boting Yang+§‡, Jin-Gang Jiang+§, Hao Xu* , Haihong Wu , Mingyuan He , and Peng Wu*
§
§
§
§
Abstract: Highly crystalline and (hydro)thermally stable zeolites with
extra-large pores (≥14-ring) are highly desirable in term of catalytic
viewpoint of processing bulky molecules. A novel zeolite ECNU-9
with an intersecting 14*12-ring (R) channel system was rationally
designed and post-synthesized from a layered precursor of PLS-3
silicate through a LEGO chemistry strategy, in which the interlayer
expansion of two-dimensional silicate structure was realized by
structure properties.6 Several structural modification routes,
including swelling,7 delamination,8 pillaring,9 and silylation,
have been reported to enlarge the external surface area or pore
sizes, which releases effectively the diffusion constrains of large-
size substrates. Among these, silylation induces an accurate
interlayer structural expansion, normally achieved via reacting
with monomer silane agents in acidic aqueous, although metal-
linker has also been reported.10 Larger silane agents, like
dimeric silane and 1,4-bis(triethoxysilyl)benzene, have also been
applied to expand interlayer pores with the ring number
10
combining
together
organic
amine-assisted
layer-stacking
square-shaped
reorganization and subsequent silylation with
a
single 4-ring (S4R) silane, 1,3,5,7-tetramethylcyclotetrasiloxane
TMCS). The PLS-3 precursor, consisting of the ferrierite (FER)-type
11
(
increased by 4 or even to build interlayer mesopores. The
interlayer insertion of large silane molecules required the pre-
swelling process in alkaline media, which may cause an
extensive desilication to the silicate framework.7 The
enlargement of interlayer space can also be achieved by
intercalation with larger-size guest molecules.12 Since the
nanosheets are loosely packed in layered zeolite, it would be
marvelous to disassemble them into LEGO-bricks and then
insert new structural component to construct novel frameworks
through a so called “bottom-up” strategy. In present study, a
LEGO-inspired method was employed to synthesize novel
ECNU-9 zeolite with intersection 14*12-R pore channels by
interlayer expansion of layered FER silicate PLS-3 with a S4R-
shaped silane. As shown in Scheme 1, the layered PLS-3
precursor was firstly disassembled into LEGO bricks, that is, a
sub-zeolite ECNU-8 composed of FER-type nanosheets,13 in
HCl/Ethanol solution by extracting some of the OSDA
nanosheets, was disassembled to LEGO bricks by partially breaking
interlayer hydrogen bondings, and then intercalated with flexible and
removable organic amine pillars to offer enough interlayer spacing
for accommodating guest TMCS silane molecules, which condensed
with the silanol groups on up-down layer sheets. The additionally
introduced structural building blocks interconnected the neighbouring
layers to construct new 14-R and 12-R pores along [001] and [010]
directions, respectively. The resulting ECNU-9 zeolite possessed a
well-ordered structure with a novel topology never obtained by direct
synthesis or other approaches. The corresponding titanosilicate Ti-
ECNU-9 with tetrahedral Ti ions in framework showed superior
catalytic performances in the liquid-phase selective epoxidation of
bulky alkenes with hydrogen peroxide.
Microporous zeolites are widely used in catalysis, ion-
exchange, adsorption and separation.1 However, the narrow
pores of conventional zeolites have restricted their applications
to processing the substrates with relatively small sizes. Design
synthesis of novel porous materials in particular with extra-large
pores of 14-R or more is highly demanded, which would
definitely expand the practical applications of zeolites.2
+
tetraethylammonium (TEA ) cations after partially breaking the
interlayer hydrogen bonding linkage. These LEGO bricks
subsequently were reassembled or reorganized with the help of
4
-amion-2,2,6,6-tetramentylniperidine (TEMP) intercalation, a
14
classical OSDA for the synthesis of PREFER silicate. With
enough expanded interlayer space between these LEGO bricks,
the TMCS silane molecules are possibly introduced as linkers to
interconnect the up-down layers, creating new 14-R and 12-R
pores.
Employing large-size organic structural-directing agents
4
(
OSDA)3 and/or Ge atoms in the hydrothermal synthetic gels
are useful strategies for developing novel zeolites with open
pore systems. Nevertheless, the complexity involved in synthetic
process as well as the high cost of the OSDAs and Ge sources
cannot be ignored. The structural instability of extra-large pore
germanosilicates is also a concerned issue in real applications,
although various post-treatments have been reported to
5
enhance their (hydro)thermal stability. As a special family of
zeolitic materials, layered silicates, with relatively weak interlayer
hydrogen bondings, are endowed with modifiable and flexible
[
§]
Dr. B.T. Yang, Dr. J. Jiang, Dr. H. Xu, Prof. Dr. H. Wu, Prof. M. He,
Prof. Dr. P. Wu, Shanghai Key Laboratory of Green Chemistry and
Chemical Processes, School of Chemistry and Molecular
Engineering, East China Normal University, 3663 North Zhongshan
Road, Shanghai, 200062 (P.R. China)
E-mail: pwu@chem.ecnu.edu.cn; hxu@chem.ecnu.edu.cn
Dr. B.T. Yang, Department of Chemistry and Biology, Beihua
University, Jilin, 132013 (P. R. China)
[
[
‡]
+]
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))
Scheme 1. LEGO-inspired synthesis of extra-large pore ECNU-9 via structural
expansion of PLS-3 silicate with 4R building units.
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Angewandte Chemie International Edition
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COMMUNICATION
[
200]
O
Si
O
framework and nanocrystals was not observed from the SEM
images (Figure S2). This could be attributed to the recognition or
matching between FER nanosheet structure and TEMP
molecule configuration, very similar to the observed interlayer
A
f
B
d
CH
3
O
e
d
c
b
c
16
reinsertion when treating 3D MWW zeolite with piperidine. By
CH3
CH2
N
immersing the ECNU-9(P) precursor in HCl/Ethanol solution with
the S4R-shaped TMCS silane, the [200] diffraction moved to
even lower 2θ angle of 6.3º as a result of further interlayer
expansion (Figure 1Ae). This interlayer expanded structure kept
intact upon calcination up to 773 K, while it suffered minor
degradation at higher temperature of 823 K (Figure S3). As a
control experiment, an identical silylation process with TMCS
silane was carried out directly on the PLS-3 precursor (Figure
S4). However, the resultant structure is identical to that
expanded by monomeric silane,17 because of the limited
interlayer spacing of PLS-3. To realize an interlayer silylation
with S4R silane with a relatively large molecular dimension, it is
critical to make the entrance match the size of guest molecules,
which could be realized by present strategy of interlayer
dissembling and reorganization.
b
C3
CH3
NH2
C2
C
1
C
2
C1
C3
N
H
a
a
5
10
15
20
25
30
35
80
60
40
20
0
-20
2Theta (deg.)
Chemical shift (ppm)
C
D
-1
4
96 cm
6
.3 Å
3
.2 Å
b
a
b
a
4
00
600
800 1000 1200 1400
3
4
5
6
7
8
9
10
-1
The organic-inorganic interaction played an important role in
the expansion of PLS-3 lamellar silicate with S4R silane.
According to TG analysis, PLS-3 precursor contained ca. 20.1
Wavenumber (cm )
Pore width (Å)
Figure 1. (A) XRD patterns of PLS-3 (a), ECNU-8 (b), ECNU-9(P) (c), ECNU-
+
13
wt% of TEA species, while the HCl/Ethanol treatment removed
9
(P)-cal823 (d), ECNU-9 (e), and ECNU-9-cal823 (f). (B) C MAS NMR
spectra of conventional PREFER (a), PLS-3 (b), ECNU-9(P) (c) and ECNU-9
d). (C) UV-Raman spectra and (D) pore size distribution of PLS-3 (a) and
them by 80% (Table S1, No. 2), disturbing extensively the
original ordered layer stacking (Figure 1Ab). The TEMP
treatment on ECNU-8 increased the content of organic species
from 4 to 21.8 wt% at 20 h (Table S1, No. 6), indicative of the
intercalation of TEMP molecules and responsible for the [200]
reflection shifting to lower angle (Figure 1Ac). Consistent with
(
ECNU-9 (b) both after calcination at 823 K.
The PLS-3 precursor exhibited a characteristic diffraction at
θ = 7.6º (Figure 1Aa), assigned to the [200] plane of the
layered structure that was composed of the FER nanosheets
and the TEA cations alternatively interlaced along a axis.15 Any
diffraction broadness should be mainly due to the fact that PLS-
was of nanosized crystals (Figure S2a). The HCl/Ethanol
treatment for 40 min disassembled the PLS-3 precursor to a
sub-zeolite ECNU-8 lacking long-range ordered structure (Figure
Ab). The layer-related [200] diffraction was broadened and
shifted to higher angle, meanwhile the (hkl) diffractions with h ≠
, such as [200], [220], [400], [202] and [600] planes, were
severely weakened in intensity corresponding to its partially
collapsed structure along a axis.13 Then the LEGO bricks of
FER-type nanosheets were rapidly reorganized in TEMP
solution within 15 min (Figure S1). The resultants showed
shaper and more intensive reflections and the layer-related [200]
one moved to a lower angle (2θ = 6.6º) than that of PLS-3 (2θ =
2
this, the resonance bands attributed to TEMP appeared in the
1
3C NMR spectrum of ECNU-9(P) after the intercalation (Figure
+
1Bc), which is very similar to that of PREFER directly
synthesized with TEMP as OSDA (Figure 1Ba). Meanwhile, the
3
+
relatively weak resonances attributed to TEA around 7.8 and
5
2.4 ppm were still observed after intercalation due to the
incomplete extraction in the former HCl/Ethanol treatment. Upon
silylation with TMCS silane, these resonances attributed to TEA+
and TEMP disappeared and a new one around -5.2 ppm was
1
0
developed (Figure 1Bd), which is attributed to the CH
3
Si(OSi)
3
groups,1 suggesting the insertion of organic silane into the
inorganic framework. During the hydrothermal process in acid
solution, the four hydrogen atoms in TMCS silane were oxidized
and hydrolyzed into four hydroxyl groups. They then interacted
and condensed with the silanol groups on up-down layers to
make the silane ring fixed between the nanosheets, while
keeping the four inert methyl groups intact.
0c
7
.5º), indicative of re-ordering of the layer stacking and
simultaneous expansion of the interlayer spacing. The intensity
levelled-off when the treatment time reached 16 h (Figure S1f),
implying completion of reassembling process. With the TEMP
molecules, the classical OSDA for PREFER synthesis, were
intercalated into ECNU-8 sub-zeolite,
ECNU-9(P) with structural analogy to PREFER was obtained
Figure 1Ac). Its [200]-related diffraction moved to higher angle
2θ = 9.4º) upon calcination and a conventional 3D FER
structure was constructed (Figure 1Ad), indicating the removable
organic pillars only changed the interlayer spacing. Although the
TEMP aqueous solution is alkaline, the dissolving of zeolite
The pure TMCS silane exhibited three IR vibration bands at
-
1
1
260, 836 and 770 cm , attributed to the C-H deformation, C-H
rocking and Si-C stretching mode of -CH groups, respectively
Figure S5a). Neither PLS-3 nor ECNU-9(P) showed such
vibration bands (Figure S5b and c). Upon TMCS silylation, the
3
(
a layered precursor
-
1
vibration bands at 1278 and 775 cm together with the relatively
weak and board one around 841 cm-1 emerged in the IR
spectrum of ECNU-9 (Figure S5d), indicating the existence of Si-
(
(
CH
temperature increasing and totally disappeared at 823 K (Figure
S5, e-g), indicating the complete removal of –CH groups via
3
moiety.18 These bands became weaker with the calcination
3
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COMMUNICATION
calcination. Figure 1C shows the UV-Raman spectra of PLS-3
and ECNU-9 both in their calcined form. In comparison to
calcined PLS-3, ECNU-9-cal823 showed an extra band around
unit cell composition of Si44
O
84
C
8
H
24. ECNU-9 possessed the
lattice parameters of a = 27.5048 Å, b = 13.7513 Å and c =
7.2637 Å (Table S4). Its b and c parameters were very
comparable to those of PLS-3 (a = 18.721 Å, b = 13.987 Å, c =
7.415 Å), but its parameter a was enlarged by 8.8 Å, simply
because the structural expansion occurred dominantly along
[100] direction. The orientation of the methyl groups attached to
the Si atoms in inserted S4R units was considered. Among all
the possible structural models, the one with the four methyl
groups sit on the same side of S4R units exhibited highest
symmetry and minimum energy (Figure S9). ECNU-9-cal823
was also refined, exhibiting well-matched simulated and
experimental data (Figure S10).
-
1
19
496 cm , corresponding to the S4R structure units, also
indicated the insertion of S4R silane. The silylation process also
changed the coordination state of silicon as evidenced by 29Si
MAS NMR spectra (Figure S6). ECNU-9(P) possessed 23%
3
4
(
3 4
OH)Si(SiO) (Q ) species and 77% Si(OSi) groups (Q ) (Figure
S6a and Table S2). After the silylation with TMCS, the
3
resonance attributed to Q groups decreased by 80% (Figure
S6b and Table S2) and a new one was developed at -65.9 ppm,
attributed to the (CH )Si(OSi)
3 3
groups (T3).10a This qualitatively
verified that the incorporation of silane molecules into the
structure was realized by reacting with the silanol groups on the
PLS-3 layer surface. After calcination at 773 K for 6 h, the T3
resonance band became extremely weaker while the Q3 one
was intensified (Figure S6c), because the -CH groups attached
3
to silicon were replaced by -OH groups. The T3 band
disappeared by increasing the temperature to 823 K (Figure
Experimental
Simulated
Difference
Observed reflection
S6d), as a result of completed decomposition of -CH
3
groups.
species
Nevertheless, the resonance attributed to (OH)
2
Si(SiO)
2
2
(Q ) around -91 ppm also appeared upon calcination, probably
due to a partial ring-opening of the inserted S4R units at higher
calcination temperatures.
2
N and Ar adsorptions were performed to characterize the
porosity of PLS-3-derived zeolites. The surface area and the
total pore volume are given in Table S3. With partial collapsed
structure, ECNU-8 exhibited the lowest surface area and pore
volume (Figure S7 and Table S3, No. 2). Despite exhibiting
identical framework type of FER, the calcined ECNU-9(P)
showed slightly lower surface area and pore volume than PLS-3
5
10
15
20
2
25
30
35
40
45
Theta (deg.)
Figure 2. Rietveld refinement of X-ray powder pattern of as-made ECNU-9.
Experimental (black) and calculated (red) XRD patterns as well as the
difference profile are shown (blue). The short tick marks (green) below the
patterns give the position of the Bragg reflections (A). Structure of ECNU-9
along [001] and [010] directions (inset). Projection of the experimental electron
density map along [001] was shown on top of the structure model.
(Figure S7 and Table S3, No. 1 and 3), because the larger
interlayer distance in ECNU-9(P) caused a partial irregular
condensation upon calcination.20 With an interlayer expanded
structure, the ECNU-9 samples calcined at different
temperatures showed higher surface area (Figure S7 and Table
S3, Nos. 4-6). The total pore volume increased with the
Ti ions were isomorphously incorporated into ECNU-9
framework via the treatment in H TiF6 aqueous solution. The
2
XRD pattern of Ti-ECNU-9 was similar to that of ECNU-9,
calcination temperature by removing the pore blocking –CH
3
indicating the structure was well-preserved after the H TiF6
2
groups. However, ECNU-9-cal823 possessed a comparable
pore volume to calcined PLS-3, because higher temperature
caused partial structural degradation, as evidence by XRD
patterns (Figure S3). The pore size distribution was centred at
treatment (Figure S11). Ti-ECNU-9 showed a sharp band
around 215 nm in the UV-vis spectrum (Figure S12), disclosing
that the Ti ions were tetrahedrally coordinated in the framework
and excluded the existence of extraframework Ti species as well
3
.2 Å and 6.3 Å for PLS-3 and ECNU-9, respectively (Figure 1D). as anatase.21 Table S6 compared the catalytic performance of
The enlarged 3.1 Å is almost twice the length of Si-O bond (1.6
Å), in good agreement with insertion of two Si-O bonds along
Ti-ECNU-9 with other traditional titanosilicates in the epoxidation
of 1-hexene. Ti-MWW exhibited the highest conversion while Ti-
ECNU-9 gave the highest turnover number (TON) value per Ti
site. Within the family of three FER-related titanosilicates, the
specific catalytic activity took an order of ECNU-9 (14*12-R) >>
[100] direction. More direct and strong proofs were given by
TEM images (Figure S8). Under the same magnification, the
interlayer distance of the calcined ECNU-9 sample was
obviously larger than PLS-3 by 2.9 Å along [100] direction,
meaning the successful insertion of S4R units.
Ti-IEZ-PLS-3 (12*10-R)
>
Ti-PLS-3 (FER-type 10*8-R),
corresponding to their pore sizes. For larger substrate of
cyclohexene, Ti-ECNU-9 showed a much higher activity than the
representative titanosilicates like Ti-MWW, TS-1, Ti-Beta and Ti-
MOR and other FER-type zeolites, providing an extremely high
TON value of ~300 at 2 h (Figure 3 and Table S7). The extra-
large 14*12-R pore system of Ti-ECNU-9 would release
efficiently the diffusion constrains of bulky molecules and then
contribute to the superior catalytic performance for processing
bulky molecules.
Considering the above characterization, a structure model
was built for ECNU-9 with the collection of FER sheets
expanded by S4R cyclosiloxane units (Figure 2, inset), which
possessed intersecting 14*12-R channels. The S4R linker
across the interlayer space was obviously observed in the
electron density map. Then, the structural refinement was
performed (Figure 2), giving the space group of IMM2 and the
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Angewandte Chemie International Edition
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COMMUNICATION
4
3
3
2
2
1
1
00
50
00
50
00
50
00
[
4] a) J. H. Kang, D. Xie, S. I. Zone, S. Smeets, L. B. McCusker, M. E. Davis,
Chem. Mater. 2016, 28, 6250-6259; b) J. L. Paillaud, B. Harbuzaru, J.
Patarin, N. Bats, Science 2004, 304, 990-992.
[
5]
a) H. Xu, J.-G. Jiang, B. T. Yang, L. Zhang, M. Y. He, P. Wu, Angew.
Chem. Int. Ed. 2014, 53, 1355-1359; b) L. Burel, N. Kasian, A. Tuel,
Angew. Chem. Int. Ed. 2014, 53, 1360-1363; c) F. F. Gao, M. Jaber, K.
Bozhilov, A. Vicente, C. Fernandez, V. Valtchev, J. Am. Chem. Soc.
2009, 131, 16580-16586; d) M. El-Roz, L. Lakiss, A. Vicente, K. N.
Bozhilov, F. Thibault-Starzyk, V. Valtchev, Chem. Sci. 2014, 5, 68-80;
e) M. V. Shamzhy, P. Eliasova, D. Vitvarova, M. V. Opanasenko, D. S.
Firth, R. E. Morris, Chem. Eur. J. 2016, 22, 17377-17386.
5
0
0
a
[6]
[7]
a) L. Xu, P. Wu, New J. Chem. 2016, 40, 3968-3981; b) W. J. Roth, P.
Nachtigall, R. E. Morris, J. Cejka, Chem. Rev. 2014, 114, 4807-4837.
S. Maheshwari, E. Jordan, S. Kumar, F. S. Bates, R. L. Penn, D. F.
Shantz, M. Tsapatsis, J. Am. Chem. Soc. 2008, 130, 1507-1516.
a) A. Corma, V. Fornes, S. B. Pergher, Th. L. M. Maesen, J. G. Buglass,
Nature 1998, 396, 353-356; b) P. Wu, D. Nuntasri, J. Ruan, Y. Liu, M.
He, W. Fan, O. Terasaki, T. Tatsumi, J. Phys. Chem. B 2004, 108,
-1
S-3
U-9
TS
Ti-FER
Ti-Bet
Ti-MOR
Ti-MWW
Ti-ECN
Ti-IEZ-PL
-
1
Figure 3. The turnover number (TON in mol (mol-Ti) ) for the epoxidation of
cyclohexene with hydrogen peroxide over various titanosilicates. Reaction
conditions: see Table S6.
[
8]
19126-19131; c) I. Ogino, M. M. Nigra, S.-J. Hwang, J.-M. Ha, T. Rea,
S. I. Zones, A. Katz, J. Am. Chem. Soc. 2011, 133, 3288-3291.
In conclusion, a novel extra-large pore zeolite ECNU-9 was
synthesized by LEGO-inspired interlayer expansion of layered
PLS-3 silicate with S4R-shaped silane molecules which linked
the neighboring layers, forming new structural units and
constructing intersecting 14*12-R pores. With open pore system
and less diffusion constrains, Ti-incorporated ECNU-9 showed
superior catalytic performance for bulky substrates. This LEGO-
inspired method is potentially expanded to other layered
precursors for developing novel zeolitic catalysts.
[
[
9]
a) K. Na, M. Choi, W. Park, Y. Sakamoto, O. Terasaki, R. Ryoo, J. Am.
Chem. Soc. 2010, 132, 4169-4177; b) Y. J. He, G. S. Nivarthy, F. Eder,
K. Seshan, J. A. Lercher, Micropor. Mesopor. Mater. 1998, 25, 207-224.
10] a) P. Wu, J. Ruan, L. Wang, L. Wu, Y. Wang, Y. Liu, W. Fan, M. He, O.
Terasaki, T. Tatsumi, J. Am. Chem. Soc. 2008, 130, 8178-8187; b) L.
Wang, Y. Wang, Y. Liu, H. Wu, M. He, P. Wu, J. Mater. Chem. 2009,
19, 8594-8602; c) H. Xu, B.T. Yang, J.-G. Jiang, L. Jia, M. He, P. Wu,
Micropor. Mesopor. Mater. 2013, 169, 88-96; d) J.-G. Jiang, L. Jia, B.T.
Yang, H. Xu, P. Wu, Chem. Mater. 2013, 25, 4710-4718; e) H. Gies, U.
Muller, B. Yilmaz, M. Feyen, T. Tatsumi, H. Imai, H. Zhang, B. Xie, F.-
S. Xiao, X. Bao, W. Zhang, T. De Baerdemaeker, D. De Vos, Chem.
Mater. 2012, 24, 1536-1545; f) H. Gies, U. Muller, B. Yilmaz, T. Tatsumi,
B. Xie, F.-S. Xiao, X. Bao, W. Zhang, D. De Vos, Chem. Mater. 2011,
Experimental Section
23, 2545-2554; g) H. Gies, M. Feyen, T. De Baerdemaeker, D. De Vos,
B. Yilmaz, U. Müller, X. J. Meng, F-S. Xiao, W. P. Zhang, T. Yokoi, T.
Tatsumi, X. H. Bao, Micropor. Mesopor. Mater. 2016, 222, 235-240.
a) A. Corma, U. Diaz, T. Garcia, G. Sastre, A. Velty, J. Am. Chem. Soc.
The layered silicate PLS-3 was synthesized through
conversion of protonated kanemite using TEAOH as the structure-
directing agent (SDA).16 Then, ECNU-8 sub-zeolite was obtained by
a solid-state
[11]
2
010, 132, 15011-15021; b) H. Xu, L. Fu, J.-G. Jiang, M. He, P. Wu,
Micropor. Mesopor. Mater. 2014, 189, 41-48.
12] Y. Komori, Y. Sugahara, K. Kuroda, Chem. Mater. 1999, 11, 3–6.
treating PLS-3 zeolite in HCl/Ethanol solution at 443 K for 40 min. By
immersing ECNU-8 zeolite in TEMP solution for 20 h, an analogy of
PREFER was prepared and named as ECNU-9(P). Finally, ECNU-9
zeolite was synthesized by the structural expansion of ECNU-9(P) with
TMCS silane in HCl/Ethanol. For experimental details, please see
supporting information.
[
[
13] a) B. T. Yang, P. Wu, Chin. Chem. Lett. 2014, 25, 1511-1514; b) B.T.
Yang, J.-G. Jiang, H. Xu, P. Ji, P. Wu, Micropor. Mesopor. Mater. 2015,
203, 54-62.
[
[
[
14] L. Schreyeck, P. Caullet, J. C. Mougenel, J. L. Guth, B. Marler, Micropor.
Mater. 1996, 6, 259-271.
15]
T. Ikeda, S. Kayamori, F. Mizukami, J. Mater. Chem. 2009, 19, 5518-
Acknowledgements
5525.
16]
a) P. Wu, T. Tatsumi, Chem. Commun. 2002, 10, 1026-1027; b) L. Xu,
X. Ji, J.-G. Jiang, H. Lu, S. Che, P. Wu, Chem. Mater. 2015, 27, 7852-
The authors gratefully acknowledge the financial supports from
the NSFC of China (21533002, 21603075) and China Ministry of
Science and Technology (2016YFA0202804).
7
860; c) L. Xu, X. Ji, S. Li, Z. Zhou, X. Du, J. Sun, F. Deng, S. Che, P.
Wu, Chem. Mater. 2016, 28, 4512-4521.
17] a) T. Ikeda, S. Kayamori, Y. Oumi, F. Mizukami, J. Phys. Chem. C 2010,
14, 3466-3476; b) B.T. Yang, H. Wu, P. Wu, J. Phys. Chem. C 2014,
[
1
Keywords: layered zeolite • LEGO-inspired • extra-large pore •
118, 24662-24669; c) B.T. Yang, J.-G. Jiang, K. Zhang, P. Wu, Chem.
Mater. 2016, 28, 5295-5303.
interlayer expansion • titanosilicate
[
[
18] J. Joo, T. Hyeon, J. Hyeon-Lee, Chem. Commun. 2000, 16, 1487-1488.
19] Q. M. Wu, X. Wang, G. D. Qi, Q. Guo, S. X. Pan, X. J. Meng, J. Xu, F.
Deng, F. T. Fan, Z. C. Feng, C. Li, S. Maurer, U. Muller, F. S. Xiao, J.
Am. Chem. Soc. 2014, 136, 4019-4025.
[
[
1]
2]
M. E. Davis, Nature 2002, 417, 813-821.
a) J. H. Yu, R. Xu, Acc. Chem. Res. 2010, 43, 1195-1204; b) J. Y. Li, A.
Corma, J. H. Yu, Chem. Soc. Rev. 2015, 44, 7112-7127. c) J. X. Jiang,
J. H. Yu, A. Corma, Angew. Chem. Int. Ed. 2010, 49, 3120-3145.
a) J. L. Sun, C. Bonneau, Á. Cantín, A. Corma, M. J. Díaz-Cabañas, M.
Moliner, D. L. Zhang, M. R. Li, X. D. Zou, Nature 2009, 458, 1154-1157;
b) J. X. Jiang, J. L. Jorda, J. H. Yu, L. A. Baumes, E. Mugnaioli, M. J.
Díaz-Cabañas, U. Kolb, A. Corma, Science 2011, 333, 1131-1134.
[
[
20] a) M. Choi, K. Na, J. Kim, Y. Sakamoto, O. Terasaki, R. Ryoo, Nature
2009, 461, 246-249; b) J. Wang, L. Xu, K. Zhang, H. Peng, H. Wu, J.-G.
[
3]
Jiang, Y. Liu, P. Wu, J. Catal. 2012, 288, 16-23.
21] P. Wu, T. Tatsumi, T. Komatsu, T. Yashima, J. Catal. 2001, 202, 245-
255.
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Angewandte Chemie International Edition
10.1002/anie.201805535
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
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§‡
+§
Boting Yang , Jin-Gang Jiang , Hao
§
§
§
Xu* , Haihong Wu , Mingyuan He , and
Peng Wu*§
Page No. – Page No.
Lego Chemistry-Inspired Synthesis of
Extra-large Pore Zeolite ECNU-9 with
Intersecting 14*12-Ring Channels
A novel extra-large pore zeolite of ECNU-9 was synthesized via a LEGO-inspired
structural expansion of layered PLS-3 silicate with S4R-shaped silane.
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