Synthesis and characterization of a layered aluminosilicate NUD-11 and its transformation to a 3D stable zeolite

Article abstract of DOI:10.1039/d0dt02449j

Aluminosilicate zeolites are a well-known class of crystalline materials that have wide applications in various industrial fields due to their selective adsorption, acidic sites, and stable hydrothermal stability. Great efforts have been devoted to discovering new zeolite structures. As one of the effective methods, layered silicates have been used as precursors to produce stable zeolites through topotactic transformation. Herein, a new layered aluminosilicate, named NUD-11, was hydrothermally synthesized using N,N-dimethylbenzimidazolium as the structure directing agent (SDA). It was then converted into a stable crystalline zeolite by linking the interlayer Si-OH groups with a silylation agent, diethoxymethylsilane. Studies showed that the resulting NUD-11S consisted of alkylsilicate-O-Si(CH3)2-O-linkages between the adjacent layers to form interconnecting 10-and 12-membered ring channels. The calcined NUD-11S possessed micropores of 0.74 nm and 1.2 nm in diameter with a large specific surface area of 314 m2 g-1. The abundant microporosity would make NUD-11S useful as adsorbents or catalysts.

Full text of DOI:10.1039/d0dt02449j

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Synthesis and characterization of a layered
aluminosilicate NUD-11 and its transformation to a
D stable zeolite†
Cite this: Dalton Trans., 2020, 49,
11682
3
a
b
a
a
a
Wen-Wen Zi, Jun Zhang,
Xian-Shu Cai, Feng Jiao and Hong-Bin Du
*
Aluminosilicate zeolites are a well-known class of crystalline materials that have wide applications in
various industrial fields due to their selective adsorption, acidic sites, and stable hydrothermal stability.
Great efforts have been devoted to discovering new zeolite structures. As one of the effective methods,
layered silicates have been used as precursors to produce stable zeolites through topotactic transform-
ation. Herein, a new layered aluminosilicate, named NUD-11, was hydrothermally synthesized using N,N-
dimethylbenzimidazolium as the structure directing agent (SDA). It was then converted into a stable crys-
talline zeolite by linking the interlayer Si–OH groups with a silylation agent, diethoxymethylsilane. Studies
showed that the resulting NUD-11S consisted of alkylsilicate –O–Si(CH ) –O– linkages between the adja-
Received 11th July 2020,
Accepted 27th July 2020
3
2
cent layers to form interconnecting 10- and 12-membered ring channels. The calcined NUD-11S pos-
DOI: 10.1039/d0dt02449j
sessed micropores of 0.74 nm and 1.2 nm in diameter with a large specific surface area of 314 m g−1
2
.
rsc.li/dalton
The abundant microporosity would make NUD-11S useful as adsorbents or catalysts.
of Ge-containing zeolites. Three-dimensional (3D) crystalline
zeolites were then obtained by the condensation of the inter-
Introduction
Zeolites, consisting of SiO4 tetrahedral units, are extensively layer Si–OH units via calcination at high temperature, or the
used in various applications like ion exchange, separations, connection of interlayer Si–OH with inorganic or organic
1
,2
catalysis and so on. For instance, zeolites doped with alumi- building units such as silica and silyl species via
1
1,12
num are widely used in catalysis due to their acidic sites and intercalation.
Until now, a number of zeolites, like
3
,4
13
14
15
16
17
18
19
stability, promoting the development of industrial catalysis.
MWW, FER, CDO, RRO, NSI, SOD, RWR, and
2
0
To meet the requirement of various applications, the synthesis CAS, have been known to have corresponding lamellar pre-
of new zeolites with novel framework structures has been paid cursors. The FER layer, a typical lamellar precursor, has been
great attention. In recent years, a number of new zeolites have studied intensively, from which about 20 different materials
been prepared hydrothermally using appropriate organic struc- have been reported to date by controlling the number of
ture directing agents or the incorporation of heteroatoms like defects in the layer, the arrangement of neighbouring layers,
Ge, B, Be, etc. To date, however, the synthesis of new zeolites and the linkages between the layers.
remains a great challenge, mainly arising from the applied tra- method provides possibilities for preparing zeolites with a
ditional, unpredicted, trial-and-error hydrothermal methods. more opened channel structure and larger specific surface
Recently, a number of new zeolites have been prepared area, which could show great catalytic performance. In
5
–7
21
This preparative
2
2
8
–10
through a new method called topotactic transformation.
several cases, it produced new zeolites that could not be syn-
During the synthesis, 2-dimensional (2D) layered silicate pre- thesized directly using the traditional hydrothermal method.
cursors consisting of abundant Si–OH groups were obtained For instance, RUB-41 (RRO) was obtained from the layered sili-
from the direct synthesis or exfoliation through degermanation cate RUB-39, which has not been synthesized by a direct hydro-
2
3
thermal method.
Herein, we report the synthesis of a new layer-structured
aluminosilicate NUD-11. The layers of NUD-11 resemble those
of RUB-39, but with a different packing scheme. The connec-
tion of the interlayer Si–OH groups in NUD-11 with a silylation
agent diethoxymethylsilane (DEDMS) produces a new 3D
microporous zeolite NUD-11S. The layered precursor and the
resulted microporous zeolite were studied from the aspects
a
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical
Engineering, Nanjing University, Nanjing, 210023, China. E-mail: hbdu@nju.edu.cn
b
School of Materials and Chemistry Engineering, Anhui Jianzhu University, Hefei,
2
30601, China
†
Electronic supplementary information (ESI) available. CCDC 2011086. For ESI
and crystallographic data in CIF or other electronic format see DOI: 10.1039/
D0DT02449J
11682 | Dalton Trans., 2020, 49, 11682–11688
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including the crystal structure, elemental analysis, solid MAS Nitrogen sorption isotherms at 77 K were obtained on an ASAP
NMR analysis, thermogravimetric analysis, and N2 2020 Micrometrics instrument. Before tests, the sample was
1
3
physisorption.
activated at 573 K for 2 h. Liquid C NMR spectra were
recorded on a Bruker AVANCE III 400 MHz. Solid-state magic-
angle spinning (MAS) NMR spectra were recorded on a Bruker
1
3
Experimental
Synthesis of SDA N,N-dimethylbenzimidazolium iodide
Av-400 spectrometer at room temperature. The C MAS NMR
spectra were acquired at a 100.62 MHz resonance frequency
using a cross-polarization (CP) MAS sequence. Si MAS NMR
and Al MAS NMR spectra were collected at 79.5 MHz and
04.3 MHz, respectively. Fourier-transformed infrared (FTIR)
2
9
1
7.7075 g (0.15 mol) of benzimidazole and 7.2 g (0.18 mol) of
sodium hydroxide were dissolved in 300 mL of acetonitrile in a
00 mL round-bottom flask. The mixture was kept under stir-
ring at 80 °C for about one day and then cooled to room temp-
erature. Then, 28 mL (0.45 mol) of CH I was added. The solu-
27
1
5
spectra were recorded on a NICOLET iS10 spectrometer.
A Bruker AXS diffractometer equipped with a Ga liquid-
metal jet X-ray source (Excilum, Ga Kα 0.13414 nm) was used
to collect the single crystal diffraction data of NUD-11. The
SAINT and SADABS programs were used for data reduction
and absorption corrections, respectively. The structure model
was initially built using the direct method incorporated in the
SHELXTL-2014 program, and was then refined with full-matrix
3
tion was stirred for another day at 40 °C. The raw product was
obtained by filtration, and recrystallized in water to give a
white solid (19.2 g, yield 87%). H NMR (DMSO-d
1
6
): 4.10 (s,
6
H, CH ), 7.75 (dd, ArH4/7), 8.05 (ddd, 2H, ArH5/6), 9.68 (s, 1H,
3
NHC). The hydroxide form of SDA was converted from the
iodide salt by anion exchange and used in zeolite synthesis.
2
least squares on F . The detailed data collection and crystallo-
graphic data are listed in Table S1 in ESI.† The CCDC reference
number is 2011086.†
Synthesis of the lamellar precursor
NUD-11 was synthesized according to the previous pro-
2
4
cedure.
.15 mmol) was first added into the SDA(OH) solution
6.5 mL, 0.75 mmol) under stirring and kept for about half an
hour. To the above solution, tetraethyl orthosilicate (TEOS)
335 μL, 1.5 mmol) was added, followed by the addition of
Typically, aluminum isopropoxide (0.0306 g, Structure model building and Refinement
0
(
Based on the single crystal structure, a structure model for
NUD-11S was first built and optimized by the Forcite module
implemented in the Materials Studio software (Table S2†).
(
hydrofluoric acid (33 μL, 0.75 mmol) after stirring for 1 h.
Excess water and the hydrolyzed alcohols were then evaporated
Results and discussion
Synthesis and structure of NUD-11
at 80 °C to give the gel with a stoichiometry of 1 SiO
OH): 0.05 Al O : 0.5 HF: 10 H O. The gel was then added into
2
: 0.5 SDA
(
2
3
2
a Teflon-lined reactor and crystallized at 160 °C for 5 d. The
products were obtained by filtration and washing with water.
NUD-11 was hydrothermally synthesized at 160 °C for 5 days
using N,N-dimethylbenzimidazolium as a structure directing
agent in the presence of F. During the synthesis process,
aluminum was found to be necessary for the formation of
Interlayer-expansion of the NUD-11 precursor
The lamellar zeolite NUD-11 was silylated with Me Si(OEt)2 NUD-11. Otherwise, an amorphous material was obtained. A
2
(DEDMS) in acid media to form an interlayer-expanded struc- large-pore zeolite ITQ-27 was crystallized under similar con-
ture. Typically, NUD-11 powder (0.1 g) was added into a ditions with lower aluminum contents. From Fig. 1, it can be
mixture of DEDMS (40 μL) and 2 M HNO3 (6 mL) solution seen that the powder X-ray diffraction pattern of the pristine
under stirring for at least half an hour, then the resulting NUD-11 matched well with the pattern calculated from the
mixture was kept in a Teflon-lined autoclave at 443 K under single-crystal structure data. The scanning electron microscopy
static conditions for 24 h. The silylated product, named (SEM) image in Fig. 1 showed that NUD-11 consisted of irregu-
NUD-11S, was filtered, washed with deionized water and lar plate-like crystals.
ethanol and dried at 353 K overnight. It was then calcined at
The crystal structure of NUD-11 was determined by single
7
73 K for 2 h to generate the NUD-11S-cal sample.
crystal X-ray diffraction over a single crystal with a size of 45 ×
3
25 × 4 μm . The single crystal structure analysis revealed that
Characterization
NUD-11 crystallized in a monoclinic space group C2/c with
A Bruker D8 Advance diffractometer (Cu Ka λ = 1.5418 Å, 40 lattice parameters of a = 15.767(4) Å, b = 25.561(6) Å, c = 7.380
3
kV, 40 mA) was used for powder X-ray diffraction (PXRD) ana- (2) Å, β = 91.264(6)°, and V = 3090(1) Å . As depicted in Fig. 2,
2
4
lyses. The element analyses of C, H, and N were performed NUD-11 is built from a composite building unit (CBU) [4 5 ]
using an Elementar Vario MICRO Elemental Analyzer. cage, consisting of two 4-MRs and four 5-MRs. This CBU is
2
5
26
Scanning electron microscopy (SEM) images were taken on a called bre that has been found in zeolites BRE, CON,
2
7
28
16
Hitachi S-4800 microscope equipped with a field emission IWR, IWW, RRO, etc. In NUD-11, the bre CBUs connect
scanning electron microanalyzer (10 kV and mA). with each other by sharing common Si vertices on 5-MRs to
5
Thermogravimetric (TG) analyses were carried out on a form infinite 1D chains. The 1D chains lie parallel and further
PerkinElmer thermal analyzer at a ramping rate of 5 °C min−
1
.
connect with each other via sharing O atoms to form a 2D
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Fig. 1 PXRD pattern of synthesized NUD-11 together with the simu-
lated pattern based on the crystal structure. The inset shows the SEM
image of NUD-11.
Fig. 3 Polyhedral presentation of NUD-11, showing the occluded SDA
cations and F− (cross) located in two cavities. The H atoms are omitted
for clarity.
and F− anions played an important role in stabilizing the
layered material.
The 2D layer in NUD-11 is similar to that in RUB-39 (Fig. 2a
and Fig S1a†). However, the stacking sequence of the layers
and channel systems in these two materials are different.
RUB-39 crystallized in the monoclinic space group C2/c with a
=
1
7.33122(5) Å, b = 10.72380(13) Å, c = 17.51354(12) Å, and β =
15.69(6)°. The layers in RUB-39 are stacked in an AA
1
4
manner, resulting in one kind of cavity channel created by pro-
truding Si–OH in the layers (Fig. S1b†). In NUD-11, the 2D
layers are stacked in an ABAB manner, forming two kinds of
cavity channels as viewed along the c-axis direction (Fig. 2b). It
can be viewed that every other layer in RUB-39 shifted a half of
the unit cell along the crystallographic c axis to generate the
stacking layers in NUD-11. As a result, the two cavity channels
in the c-axis direction of NUD-11 intersect at an angle of 45°
with triangular cavity channels in the ac direction (Fig. 2d).
However, the cavity channels in the a-axis direction of RUB-39
run across small channels in the c-axis direction at an angle of
Fig. 2 Polyhedral views of (a) a 2D layer formed by bre CBUs, and the
stacked layers of NUD-11 along (b) the c-axis, (c) the a-axis and (d) the
(
101) direction. The SDAs are omitted for clarity.
sheet. Each 2D sheet is then stacked parallel to its two neigh-
boring mirror duplicates to generate a layered structure. The
Si–OH groups in each layer stick out into the interlayer space.
They do not directly point to each other, but instead shift half
of the unit cell (3.69 Å) along the crystallographic c axis. As a
result, there are two kinds of cavity channels in NUD-11
created by protruding Si–OH in the layers, in which the SDA
cations are located (Fig. 3). These SDAs formed π–π inter-
actions between the planar benzimidazolium rings, with an
interatomic distance of 3.2 Å or 3.6 Å between the ring planes.
The benzimidazolium planar rings of SDAs are not parallel to
the ab plane, but tilted ±66.0° or ±74.9° from the c-axis. It is
64.3° (Fig. S1c†). In addition, the interlayer Si–OH groups
between the adjacent layers in RUB-39 nearly directly point to
each other, with a closest distance of 2.39 Å between the O
atoms (Fig. S1b and c†). In contrast, the interlayer Si–OH
groups in NUD-11 are misaligned to each other along the crys-
tallographic c axis (Fig. 2b and d). The shortest O…O distance
between the interlayer Si–OH groups in NUD-11 is 5.60 Å.
Physicochemical properties of NUD-11
noted that the F− ions are located near the SDA cations as The C solid state MAS NMR spectra showed that the spectra
charge-balance ions (Fig. 3). Besides as charge-balance of NUD-11 matched well with those of the OSDA in solution
counter-parts, F− played a mineralizing role during the for- (Fig. S2†), indicating that the OSDAs were occluded intact in
mation and crystal growth of NUD-11. These guest SDA cations NUD-11. Element analyses showed that the ratio of C and N
13
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was 4.44 in NUD-11, in agreement with the theoretical ratio of signals, consistent with the terminal silanol groups observed
2
7
4
.5. Thermogravimetric analyses of NUD-11 (Fig. S3†) showed in the single crystal structure. In the Al MAS NMR spectra, a
a total weight loss of 36.8% between 30 and 800 °C. The first small peak appeared at 0 ppm, and it was attributed to the six-
step of weight loss ranging from 50 to 250 °C was attributed to coordinated Al species. A strong peak at ca. −55 ppm corre-
the removal of water. The second one between 250 and 800 °C sponded to the four-coordinated Al species. The results
was mainly due to the removal of the organic cation and water suggested that most of the Al species have been incorporated
arising from the condensation of hydroxyl groups attached to into the framework with a minor proportion likely located in
the interlayer surface. After the removal of SDAs and the con- extra-framework positions.
densation of the silanol groups, the calcined sample became
amorphous, as shown in the PXRD pattern (Fig. S4†).
The Si and Al solid state MAS NMR spectra were used to
investigate the coordination environment of NUD-11. As
Expansion of lamellar NUD-11
2
9
27
Generally, 2D layered silicates can be converted into 3D zeo-
1
7,29
lites directly by calcination,
or by intercalation with in-
2
9
shown in Fig. 4, three peaks were observed in the Si MAS
3
0,31
organic or organic building units.
Recent studies showed
NMR spectra of NUD-11. The peaks at about −107 ppm and
that structurally distinct lamellar zeolitic precursors but with a
similar crystal surface topography could be topotactically con-
verted into similar 3D zeolites through the organization-reas-
4
−113 ppm were attributed to the Si(OSi)
4
Q signals, while the
3
3
shoulder peak at −101 ppm belonged to the Si(OH)(OSi) Q
3
2
14
sembly process. Unlike RUB-39, the layered aluminosilcate
NUD-11 could not be directly transformed to a 3D zeolite by
calcination. Probably because of the occluded SDAs and the
malpositioned Si–OH groups, once calcined at high tempera-
ture, the structure collapsed into an amorphous material.
However, NUD-11 could be converted into a stable 3D zeolite
by silylation using the agent diethoxymethylsilane (DEDMS) in
nitric acid solution.
Fig. 5 shows the PXRD patterns of the silylated NUD-11
(
named NUD-11S) before and after calcination (named
NUD-11S-cal). The presence of obvious PXRD peaks in
NUD-11S indicated that NUD-11S retained its crystalline struc-
ture after being silylated with DEDMS in acid solution.
However, the crystallinity deteriorated, likely due to the frame-
work being partially damaged by acid. Meanwhile, the PXRD
patterns of NUD-11S changed significantly in comparison with
those of pristine NUD-11. The peak at 2θ = 6.7° due to the
plane (0 2 0) in NUD-11 shifted toward higher diffraction
angles in NUD-11S, indicating the shrinkage of the interlayer
2
9
Fig. 4
Si MAS NMR spectra of (a) NUD-11 and (b) NUD-11S silylated
Fig. 5 PXRD patterns of pristine NUD-11, NUD-11S and NUD-11S-cal
(550 °C).
27
with DEDMS in 2 M HNO
3
and (c) Al MAS NMR spectra of NUD-11.
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distances (i.e. along the crystallographic b-axis) upon silylation.
The peaks due to the planes (2 0 0) and (4 0 0) in NUD-11,
however, did not shift in NUD-11S, suggesting the integrity of
the layer structure and the layer arrangement along the crystal-
lographic a-axis. After calcination at 550 °C, PXRD studies
showed that the obtained NUD-11S-cal retained its framework
structure (Fig. 5). The SEM images (Fig. S5†) of NUD-11S
showed an irregular aggregated plate crystalline morphology
about 0.5 μm in thickness.
Fig. 6 shows the N
NUD-11S-cal, with the deduced BET surface area and volume
listed in Table 1. NUD-11 displayed poor N adsorption ability,
2
physisorption isotherms of NUD-11 and
2
and its adsorption isotherm was characteristic of nonporous
materials. However, the isotherm of NUD-11S-cal showed a
steep N
to micropore filling and suggested the presence of micropores.
The isotherm slowly increased along with an increase in P/P0 Fig. 7 IR spectra of (a) silylated NUD-11S and (b) pristine NUD-11.
and showed a sharp increase at higher P/P due to capillary
2 0
uptake below P/P = 0.1, which was usually attributed
0
condensation. Moreover, a type H4 hysteresis at a relatively
high relative pressure of 0.4–1.0 was observed, implying the
presence of mesopores formed by the random aggregation of pore size distribution calculations showed that NUD-11S-cal
thin plates. The calculations based on the adsorption iso- mainly consisted of narrowly distributed micropores at ca.
therms showed that NUD-11S-cal possessed a large BET 0.74 nm and 1.2 nm, respectively, with a minor contribution of
2
−1
3
−1
surface area of 314 m g and a pore volume of 0.39 cm g
,
mesopores at ca. 3.0 nm (Fig. S6†).
2
−1
with a mesopore surface area of 110 m
g
, suggesting the
To elucidate the structure of NUD-11S, Fourier-transformed
dominance of micropores in NUD-11S-cal. Consistently, the infrared spectroscopy (FTIR) was performed. As shown in
Fig. 7, the FTIR spectra showed that new bands at 2969 and
51 cm− appeared for NUD-11S after silylation in comparison
1
8
with NUD-11. These bands could be assigned to the asym-
metric vibration absorption of the CH groups attached to
confirming the incorporation of the (CH Si moiety
3
3
3,34
Si,
3 2
)
into the framework. In addition, TG analyses showed that the
SDA molecules in NUD-11S were mostly extracted during the
acid treatment of silylation (Fig. S3†). CHN elemental analyses
indicated that the silylated sample contained 7.26 wt% carbon
and 1.00 wt% nitrogen with a C/N atomic ratio of about 8.5.
The decreased N content and C/N atomic ratio in NUD-11S
confirmed the removal of the majority of the SDAs and the
incorporation of (CH
3
)
2
Si groups.
Si groups in NUD-11S has been
The incorporation of (CH )
3 2
1
3
29
further investigated by C MAS NMR and Si MAS NMR tech-
1
3
niques. From the C MAS NMR spectrum in Fig. S2,† it can be
seen that the silylated NUD-11S exhibited a new strong reso-
nance at −3.05 ppm, which could be attributed to the (CH ) Si
3
2
groups, confirming the successful interlayer silylation. A set of
physisorption isotherms of NUD-11, NUD-11S and NUD-11S- weak peaks belong to the DMBI cation in NUD-11S, indicating
the incomplete extraction of the SDAs during the silylation.
Fig. 6
cal.
N
2
2
9
Fig. 4(b) shows the Si MAS NMR spectra of NUD-11S.
3
Compared to NUD-11, the Q resonance at −108 ppm in
NUD-11S decreased greatly in intensity, while a new resonance
at −16 ppm appeared. This new signal was due to the silicon
Table 1 Physicochemical properties of lamellar precursor NUD-11 and
interlayer expanded zeolite NUD-11S
atoms from the Si(CH
3
)
2
(OSi)
2
groups as a result of
3
5,36
3
silylation.
The decrease in the intensity of the Q peak
Sample
NUD-11 NUD-11S NUD-11S-cal
suggested that not all Si–OH groups have been silylated by
DEDMS. The results clearly suggested that the silylation
occurred through the reaction of DEDMS with the silanols on
BET (m g−1)
2
67
59
40
0.17
314
110
0.39
t-plot external surface area (m g−1) 111
Pore volume (cm g
2
3
−1
)
0.14
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structure directing agent. It consisted of 2D layers built from a
2
4
composite building unit (CBU) [4 5 ] cage, similar to those of
RUB-39 but with different stacking sequences. Although unstable
after calcination, NUD-11 can be transformed into a stable 3D
porous structure, i.e. NUD-11S by silylation with DEDMS in acid
medium. The calcined NUD-11S retained its crystalline framework
and showed a large BET surface area and pore volume with nar-
rowly distributed micropore sizes. The studies showed that
DEDMS reacted with Si–OH on the surface of the 2D layers to
produce a stable crystalline 3D zeolitic framework, in which the Si–
O–Si(CH ) –O–Si linkages located between the adjacent layers to
3
2
form interconnecting 10- and 12-membered ring channels. The
resulted zeolitic material could be of use in adsorption and
catalysis.
Fig. 8 Polyhedral views of NUD-11S along (a) the c axis and (b) the
(
101) direction.
Conflicts of interest
There are no conflicts to declare.
the layer surface to form pillaring alkylsilicate species between
the layers. The presence of alkyl groups in NUD-11S might
affect its surface hydrophilicity and afford the zeolite unique
properties in adsorption and catalysis.
Acknowledgements
Based on the above results, we speculated a possible
mechanism for interlayer silylation. In the process of the silyla-
tion of NUD-11, the DEDMS molecules reacted with the silanol
groups on the layer surface, resulting in the incorporation of
monomeric alkylsilicate groups and formation of Si–O–Si
The authors are grateful for financial support from the
National Natural Science Foundation of China (grant number
21673115).
(
3 2
CH ) –O–Si linkages between the adjacent layers. Meanwhile,
Notes and references
the SDAs were extruded out, likely due to ion exchange in the
acid. The linkage led to the contraction of the interlayer dis-
tance from 13.3 Å in NUD-11 to 11.4 Å in NUD-11S to form a
1 H. B. Du, C. Fairbridge, H. Yang and Z. Ring, Appl. Catal.,
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3
D crystalline framework, as evidenced by PXRD studies. Upon
calcination at high temperature to remove the organic groups,
the O–Si(CH –O groups were likely converted into flexible O–
2 M. Moliner, C. Martinez and A. Corma, Angew. Chem., Int.
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3 N. Nakazawa, T. Ikeda, N. Hiyoshi, Y. Yoshida, Q. Han,
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7989–7997.
3
)
2
2
Si(OH) –O Q units. According to the above results, a theore-
tical structure model of NUD-11S was built. As shown in Fig. 8,
2
NUD-11S possesses two different pore channels consisting of
4 J. Dedecek, E. Tabor and S. Sklenak, ChemSusChem, 2018,
12, 556–576.
1
0- and 12-membered rings, respectively, running along the
crystallographic c-axis. The two channels are interconnected
with each other through eclipsed 10-membered rings running
in the (101) direction. The largest interatomic distances across
the three channels are 6.2 × 5.8 Å (12-MR), 6.6 × 4.2 Å (10-MR)
and 6.1 × 2.3 Å (10-MR), respectively (taking into account an
oxygen radius of 1.35 Å). The PXRD patterns simulated from
the structure model matched reasonably well with the experi-
mental one (Fig. S7†). In addition, the pore size distribution
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