Affecting the Formation of the Micro-structure and Meso/macro-structure of SAPO-34 zeolite by Amphipathic Molecules

Article abstract of DOI:10.1002/cctc.202000794

SAPO-34 is an important member in the family of zeolites, which shows excellent catalytic activity in MTO reaction, but suffers from the diffusion bottleneck. To overcome the diffusion problem, porogen was added to generate meso/macro pores in SAPO-34 zeolite. In this work, amphipathic molecules were designed as CSDA to synthesize a tri-level hierarchically porous SAPO-34, and the introduction of CSDA could promote the Si atoms incorporating into the AlPO₄ framework, change the morphology of particles and decrease the acidity of prepared SAPO-34 zeolite. The prepared SAPO-34 catalyst exhibits higher selectivity of C₂H₄ and C₃H₆ in the MTO reaction than the conventional SAPO-34 zeolite. The morphology and the microstructure of the prepared samples vary with the carbon chain of the amphipathic molecules due to the matching between amphipathic molecules and topological structure of CHA.

Full text of DOI:10.1002/cctc.202000794

The European Society Journal for Catalysis
Supported by
Accepted Article
Title: Affecting the Formation of the Micro-structure and Meso/macro-
structure of SAPO-34 zeolite by Amphipathic Molecules
Authors: Xuefeng Shen, Yujue Du, Jiajia Ding, Chuanming Wang,
Hongxing Liu, Weimin Yang, and Zaiku Xie
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To be cited as: ChemCatChem 10.1002/cctc.202000794
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10.1002/cctc.202000794
ChemCatChem
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Affecting the Formation of the Micro-structure and Meso/macro-
structure of SAPO-34 zeolite by Amphipathic Molecules
Xuefeng Shen,[b] Yujue Du,[b] Jiajia Ding,[b] Chuanming Wang,[b] Hongxing Liu,*[b] Weimin Yang,*[b] and
Zaiku Xie*[a]
[a]
Prof. Z. Xie
China Petrochemical Corporation (SINOPEC Group)
Beijing 100728, (P.R. China)
E-mail: xzk@sinopec.com
[b]
Dr. X. Shen, Y. Du, J. Ding, Prof. C. Wang, H. Liu, W. Yang
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis
SINOPEC Shanghai Research Institute of Petrochemical Technology,
Shanghai 201208, (P.R. China)
E-mail: liuhx.sshy@sinopec.com，yangwm.sshy@sinopec.com
Supporting information for this article is given via a link at the end of the document.
Abstract: SAPO-34 is an important member in the family of zeolites,
which shows excellent catalytic activity in MTO reaction, but suffers
from the diffusion bottleneck. To overcome the diffusion problem,
porogen was added to generate meso/macro pores in SAPO-34
zeolite. In this work, amphipathic molecules were designed as CSDA
to synthesize a tri-level hierarchically porous SAPO-34, and the
introduction of CSDA could promote the Si atoms incorporating into
the AlPO4 framework, change the morphology of particles and
decrease the acidity of prepared SAPO-34 zeolite. The prepared
SAPO-34 catalyst exhibits higher selectivity of C2H4 and C3H6 in the
MTO reaction than the conventional SAPO-34 zeolite. The
morphology and the microstructure of the prepared samples vary with
the carbon chain of the amphipathic molecules due to the matching
between amphipathic molecules and topological structure of CHA.
cationic surfactant are usually acted as mesoporous template,
which only affect the meso/macro-structure of SAPO-34. Yu and
coworkers prepared SAPO-34 with the tri-level hierarchically
intracrystalline micro-meso-macro-pore structure using PEG
2000 as soft template.[8b] Then, Yu selected [3-(trimethoxysilyl)
propyl] octade-cyldimethylammonium chloride (TPOAC) as the
meso-pore-generating
agent
to
prepare
cubic-shaped
micrometer-sized SAPO-34 resulting from the agglomeration of
cubic-like nanocrystals,[3b] in which TPOAC acted as not only the
soft template, but also a part of the silicon source. Liu and
coworkers synthesized hierarchical SAPO-34 with [2-
(diethoxyphosphono)
propyl]-hexadecyldimethylammonium
bromide (DPHAB) as soft template and a part of the phosphor
source.[8d]
Quaternary ammoniums are widely used as template to
synthesize zeolites. Because the special molecular dimension
and steric configuration of quaternary ammoniums make them
closely bound to inorganic species, then guided the synthesis of
kinds of zeolites.[9] Amphipathic molecules with quaternary
ammoniums at both ends are usually used as templates to
synthesize hierarchical MFI zeolites.[10] It is notable that only the
meso/macro-structure change by tuning the chain length of the
intermediate of amphipathic molecules in most cases. Okubo
synthesized the hierarchically and sequentially intergrown MFI
zeolites by dimers of the tetrapropylammonium cation,[10a] and
they found that the lengths of alkyl spacers between two
tetrapropylammonium cations affected the morphology of the
obtained MFI crystals.[10b] Che used dimers of the N-methyl
pyrrolidiniums as templates to synthesize MFI or MTW zeolites
via changing the carbon chain lengths,[10d] in which the species of
quaternary ammonium is a crucial factor. For different kinds of
zeolites, specific amines/ammoniums cooperating with different
chain lengths could affect the micro/meso/macro-structure of
obtained zeolites, due to dimers of amines/ammoniums with
different chain lengths may geometrically matching different
zeolite topologies.
Introduction
Zeolites are crystals with high surface area, adjustable pore size,
acidity, high stability and compositional diversity, which are widely
used in petrochemical and fine-chemical industries.[1] SAPO-34 is
an important member of zeolite, with the topological structure of
CHA. SAPO-34 has been considered as an excellent catalyst for
the methanol-to-olefin (MTO) conversion, which produces light
olefins from nonpetroleum sources, then solves the problem of oil
crisis to a great extent.[2] The CHA topological structure of SAPO-
34 defines the channel structure of it (cage: 9.4 Å in diameter and
8-ring pore: 3.8 Å × 3.8 Å).[3] The narrow pore opening (~0.38 nm)
impedes the diffusion of reactants and leads to rapid deactivation
of catalyst.[4] Inspired by the meso-porous materials, introducing
meso/macro-pores into SAPO-34 crystals is considered as an
efficient way to overcome the inherent diffusion limitations and
retard coke deposition to prolong the catalytic lifetime.
Until now, many strategies have been proposed to synthesize
hierarchical SAPO-34 zeolite, such as dry gel conversion
method,[5] post-treat method,[6] hard template[7] and soft
template[8]. Comparing with other strategies, the relatively simple
synthetic process, well controlled mesopores and no destruction
of Brønsted acid sites of SAPO-34 zeolite make soft template
method perferably selected. As for the template method, polymer,
Herein, amphipathic molecules were synthesized as the co-
structure-directing agent (CSDA), which are dimers of the
tetraethylammonium cation connected by carbon chain
([N+(CH2CH3)3-CnH2n-N+( CH2CH3)3 ] [Br-]2, n = 4, 6, 8, 10， 12,
denoted as Cn，Figure S1), because the tetraethylammonium
1
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10.1002/cctc.202000794
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cation is a very common and energetically favored structure-
directing agent (SDA) for CHA zeolite formation. In the synthesis
of SAPO-34，triethylamine (TEA) was not only as the SDA, but
also the alkali source, so TEA still was the SDA in the present
work. The prepared SAPO zeolites were well characterized,
which showed different morphologies and micro-structures
depending on the different carbon chain lengths of CSDA. The
status of the CSDA was investigated by various characterizations.
The MTO catalytic performance of synthesized SAPO-34 is also
evaluated.
of SAPO-5/SAPO-34 shows no relationship with the carbon chain
length of CSDA.
Results and Discussion
Figure 2. (a) N2 adsorption and desorption isotherm and pore size distribution
curve of CZ-6 (obtained from adsorption branch ， inset), (b) pore size
distribution curve of CZ-6 determined by mercury intrusion porosimetry. (c-d)
TEM images of CZ-6. The selected area diffraction pattern (inset) was taken
from the area of the red circle in (d), taken along to the [010] direction of CHA
structure.
The N2 adsorption and desorption isotherm (Figure 2a) of CZ-6
molecule shows the Brunauer-Emmett-Teller (BET) surface area,
micropore volume and mesopore volume of this sample are 564
m2/g, 0.25 cm3/g and 0.03 cm3/g, respectively. The pore size
distribution curve shows the existence of mesopores in the
hierarchically porous CZ-6. The N2 adsorption and desorption
isotherm of other samples are shown in Figure S4, and the textual
properties of all samples are shown in Table S1. There is no
peaks in the pore size distribution curves of CZ-4, CZ-8, CZ-10
and CZ-12, indicating no mesostructure existence in these
samples. Compared with the conventional SAPO-34, the uptakes
near saturation pressure in the isotherms of other samples (CZ-4,
CZ-6, CZ-8, CZ-10 and CZ-12) are observed, indicating the
existence of macropores in these samples. The macropore size
distribution determined by mercury intrusion porosimetry shows
three different sizes of macropores existing in CZ-6, that is,
micrometer-sized macropores (ca. 0.9 μm and 1.5 μm)
corresponding to the stacking of the nanosheets and nanometer-
sized macrochannels (ca. <100 nm) corresponding to the
intracrystalline macropores. The TEM images of CZ-6 show that
Figure 1. Powder XRD patterns (a) of CZ-4 ~ CZ-12 and SEM images (b-d) of
CZ-6.
Well-resolved peaks in the range of 5-50°are observed in the XRD
patterns for these SAPO zeolite samples, as shown in Figure 1;
The diffraction peaks at 2θ of 9.4, 12.9, 16.1, 20.5, 26.0 and 30.5°
are indexed to (101), (110), (021), (121), (220) and (401) planes
of SAPO-34, respectively;[11] whereas those at 7.5, 14.9, 19.7,
21.1, 22.4 and 26.0° are attributed to (100), (200), (210), (002)
and (220) planes of SAPO-5, respectively.[12] Obviously, CZ-6
displays the diffraction peaks of pure phase SAPO-34 with good
crystallinity, whereas the CZ-4, CZ-8, CZ-10 and CZ-12 are
mixture of SAPO-34 and SAPO-5 zeolites.
The SEM images reveal that CZ-6 exhibits flower-like morphology
composed of nanosheets (Figure 1b and 1c), which is very
different with the rhombohedral morphology of conventional
SAPO-34 (Figure S2). The nanosheet is hexagonal-like with the
thickness of ~300 nm and size of ~1 μm. The outside edge of the
nanosheet is smooth and the center part is composed of
triangular-pyramid-shaped subunits (Figure 1b and 1d). SEM
images of other four samples are shown in Supporting Information
Figure S3, which also give the evidence that these four samples
are mixture of SAPO-34 and SAPO-5 zeolites. The particle size
macropores are existing in the nanosheet, which has a
hexagonal-like morphology (Figure 2c-2d). So the CZ-6 is tri-level
hierarchical SAPO-34 zeolite with intracrystalline micro-meso-
macroporosity.
In order to better understand the effect of carbon chain length of
amphipathic molecules for the directing of zeolite framework
structures, ab initio molecular dynamics (AIMD) simulations and
static structure optimization were employed to evaluate the
interaction energies between selected CSDAs and AlPO-34 or
AlPO-5 frameworks. The interaction energies of the CSDAs with
AlPO-34 and AlPO-5 were depicted in Figure 3, and the optimized
2
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structures were shown in Figure 4 and Figure S5. It can be seen
that the interaction energy of CSDAs with AlPO-5 decreases
linearly with the carbon chain length, indicating that the steric
confinement effect is negligible and the van der Waals (vdW)
effect dominates the interaction in AlPO-5. In the case of CSDAs
in AlPO-34, the interaction between C6-CSDA and AlPO-34 is
stronger than that between C4-CSDA/C8-CSDA with AlPO-34 as
described by the average interaction energies, agreeing well with
the experimental findings. The breaking of linear scaling relations
with the carbon chain length indicates that the steric confinement
effect is very important for the structure directing effect in AlPO-
34. In addition, the interaction energies change obviously with the
different configuration of CSDAs in AlPO-34 as indicated by the
wide variation range of energy for each CSDA. This is especially
obvious for C12-CSDA in AlPO-34. As the interaction energy
gradually decreases in AlPO-5 while the steric confinement effect
increases with the chain length of CSDAs in AlPO-34, the AlPO-
5 structure could not be excluded in the preparation using CSDAs
with higher chains. As mentioned above, C6-CSDA could match
well with AlPO-34, while C4, C8, C10 and C12 molecules are
more favorable fitting in the channel of AlPO-5 as a result of vdW
stabilization interaction and steric repulsion interaction.
of CZ-6, as shown in Figure 4. The tetraethylammonium cation is
also widely used in synthesizing SAPO-34 zeolite. So C6
molecules could cooperate with TEA molecules to direct the
formation of the crystalline frameworks of CHA, resulting in pure
phase SAPO-34 with flower-like morphology. At the early stage
of synthesis, a particular crystal morphology composed of
pyramidal parts were generated, due to the growth of CHA
preferentially along certain directions.[13] For the conventional
SAPO-34 zeolite, pyramidal parts grow to form a regular-shaped
rhombohedral crystal with further ageing.[13a] In the synthesis
procedure of CZ-6, C6 molecules may act as the crystal growth
inhibitor in the next stage, preventing the growth of pyramidal
parts to rhombohedral crystal. Meanwhile, C6 molecules may also
act as the porogen to generate meso/macro-pores in the SAPO-
34 crystals, due to the strong interaction of tetraethylammonium
cations and aluminophosphate precursor species. Flower-like
SAPO-34 with tri-level hierarchical structure was generated with
the combination of TEA and C6. For C4, C8, C10 and C12
molecules, they could not load in the cages of CHA mainly due to
the steric repulsion interaction, and they tended to load in the
channel of SAPO-5, leading to the formation of SAPO-5 crystals.
With further ageing, they may also act as crystal growth inhibitor
to decrease the size of SAPO-5 crystals (C4, Figure S3a) or
porogen to generate macro-pores in SAPO-5 crystals (C8, C10
and C12, Figure S3b-S3d, Table S1).
The chemical environment of the framework atoms in CZ-6 and
conventional SAPO-34 was evaluated by 27Al, 31P, and 29Si MAS
NMR. The 27Al MAS NMR spectrum (Figure 5a) proved the
presence of tetrahedrally coordinated Al (signal at ca. 35 ppm)
and octahedrally coordinated framework Al (signal at ca. -10
ppm).[14] The signals at -3.2 ppm and 75 ppm might be attributed
to the formation of [Al(H2O)5(PO-)]2+ species and Al(OSi)x
species.[15] The dominating signals at -30 ppm in the 31P MAS
NMR spectra (Figure 5b) is assigned to tetrahedrally coordinated
phosphorus atoms in the coordination state of (P(OAl)4).[13a, 16]
The signals at -6 ppm and -55 ppm are from spinning
sidebands.[17] In the 29Si MAS NMR spectra (Figure 5c), the
signals with a chemical shift of about -91 ppm is assigned to the
coordination state of Si(0Si4Al), and the peaks around -94 ppm, -
100 ppm and -105 ppm are ascribed to the Si(1Si3Al), Si(2Si2Al)
and Si(3Si1Al), respectively.[13a,18] The signal at about -110 ppm
is ascribed to the Si(4Si0Al), demonstrating the existence of Si
islands, which is very weak compared with these dominate signals.
The CZ-6 crystal shows more tetrahedrally aluminum atoms as
well as less coordination state of (P(OAl)4) than conventional
SAPO-34 crystal, and the results of XRF (X-ray Fluorescence)
Figure 3. Interaction energies of CSDAs with different carbon chain lengths in
AlPO-34 and AlPO-5 frameworks. The energies of five different configurations
of each CSDA in AlPO-34 were depicted in grey line and the average value
were depicted in red.
According to the theoretical calculations, C6 molecules locate in
the adjacent cages of CHA structure during the synthesis process
Figure 4. Optimized representative structures of CSDAs with different carbon chain lengths in AlPO-34.
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Figure 5. 27Al (a), 31P (b) and 29Si (c) MAS NMR spectra of calcined CZ-6 and calcined conventional SAPO-34.
show the CZ-6 has higher silica content and lower phosphorus
content than the conventional SAPO-34 (Table 1), which indicates
that C6 molecules promotes the incorporating of Si atoms into the
AlPO4 framework mainly by SM2 mechanism and less partly by
SM3 mechanism. The CZ-6 crystal shows coordination state of
Si(1Si3Al), Si(2Si2Al) and Si(4Si0Al) increase, especially for
Si(1Si3Al), indicating the size of Si islands is small.[19] The
coordination state of Si(0Si4Al) decrease, which is the main
source of the bridge hydroxyl groups of Si(OH)Al.[17] Due to the
Brønsted acid originates from the bridging hydroxyl groups,[19] the
CZ-6 shows lower Brønsted acid concentration.
respectively. The conventional SAPO-34 shows two desorption
peaks centered at about 190℃ and 421℃, which correspond to
the weak and strong acid sites, respectively.[5] For CZ-6, the
desorption temperature of the weak acid site is nearly the same
with the conventional SAPO-34, while the desorption temperature
of the strong acid site is obviously lower than the conventional
SAPO-34. The weak acid site is attributed to T-OH (T = Si, P, Al)
hydroxyl groups or lattice imperfection;[8a, 16, 20] and the strong acid
site is mainly attributed to the adsorption of NH3 on the Brønsted
acid sites,[21] which have close relationship with the MTO catalytic
properties.[22] The strength of the Brønsted acid of CZ-6 is
obviously weaker than that of the conventional SAPO-34.
The solid 13C NMR spectra of as-made conventional SAPO-34,
as-made CZ-6 and C6 (Figure S6) are used to verify C6
molecules keeping intact during the entire synthetic process. The
thermogravimetric analyses (TGA) curve (Figure S7) of CZ-6
shows that the content of template molecules in the as-made CZ-
6 is approximately 19.6 wt %, larger than that of conventional
SAPO-34 (18.2 wt %), due to the additional C6 molecules in CZ-
6. Two obvious weight losses can be recognized from TGA curves:
a low-temperature weight loss before 150°C and a high-
temperature weight loss after 300°C, which are ascribed to
desorption of water and templates, respectively.[23] The template
molecule begins to decompose after 300°C, which is obviously
higher than the crystallization temperature, so the TGA curve also
give the evidence that C6 molecules keep intact during the entire
synthetic process.
Table 1. The XRF results of CZ-6 and conventional SAPO-34 (mol %).
Samples
CZ-6
Al2O3
46.58
SiO2
8.43
P2O5
44.99
Conventional
SAPO-34
46.89
6.69
46.41
Catalytic tests of methanol conversion were performed in a fixed
bed reactor at 733 K over the CZ-6 and conventional SAPO-34
catalysts. The selectivity of C2H4 and C3H6 versus TOS over CZ-
6 and conventional SAPO-34 catalysts are shown in Figure 7a,
and the detailed MTO results are summarized in Table S2.
Compared with the conventional SAPO-34, CZ-6 shows higher
selectivity of C2H4 and C3H6, and the difference in selectivity
increases with the TOS. The selectivity of C2H4 and C3H6 of CZ-6
(85.05%) has improved nearly 3% compared to that of the
conventional SAPO-34 (81.99%), which is mainly due to the lower
acidity concentration and relatively weaker acid strength of CZ-
6.[22] Hydrogen transfer is the major route in catalytic conversion
of MTO for the formation of nonolefinic byproducts,[24] which
mainly take place on Brønsted acid sites (Si-OH-Al).[25] The CZ-6
shows lower acidity than the conventional SAPO-34, which make
it less reactive for the hydrogen transfer compared with the
conventional SAPO-34, leading to a higher selectivity to light
olefins.[26] The hierarchical porosity is also beneficial to improve
Figure 6. The NH3-TPD curves of CZ-6 and the conventional SAPO-34.
Figure 6 shows the NH3-TPD profiles of the CZ-6 and the
conventional SAPO-34, which is used to evaluate the acidity of
samples. The strength and concentration of acid sites are
represented by desorption temperature and the peak area,
4
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SAPO-34 zeolite. The CZ-6 exhibits superior MTO performance
with the selectivity of C2H4 and C3H6 up to 85.01%, which has
improved more than 3% than the conventional SAPO-34. For C4,
C8, C10 or C12, the products are mixture of SAPO-34/5, as a
result of the mismatch between CSDA with the CHA structure of
SAPO-34. This work demonstrates that adding amphipathic
molecules is an effective way to control meso/macro structure and
affect the formation of micro-structure of SAPO-34 zeolite. We
hope our strategy will provide a new way for the design and
synthesis of hierarchical SAPO-34 for high catalytic activity.
Experimental Section
Materials
Orthophosphoric acid (H3PO4, 85 wt%), TEA (99 wt%), acetonitrile (99
wt%), diethyl ether (99 wt%), colloidal silica (SiO2, 40 wt%),
pseudoboehmite (Al2O3, 70 wt%), 1,4-dibromobutane (98 wt%), 1,6-
dibromohexane (98 wt%), 1,8-dibromooctanewere (98 wt%), 1,10-
dibromodecane (98 wt%) and 1,12-dibromododecane (98 wt%) were
purchased from Sinopharm Chemical ReagentCo., Ltd. All chemicals were
used as received without further purification.
Synthesis of Cn
10.8 g of 1,4-dibromobutane (0.05 mol) and 10.25 g (0.25 mol) of
triethylamine were mixed in 150 ml of acetonitrile and stirred at 84 ℃ for
12 h. Then removal of acetonitrile by rotary evaporator and the
[N+(CH2CH3)3-CnH2n-N+( CH2CH3)3 ] [Br-]2, (C4) was filtered and washed
with diethyl ether three times. Then C4 was dried in a vacuum. C6, C8,
C10 and C12 were also obtained by substituting 4-dibromobutane with 1,
6-dibromohexane, 1, 8-dibromooctane, 1,10-dibromodecane and 1,12-
dibromododecane. The molecule structure are shown in supporting
information (Figure S1).
Figure 7. Catalytic performance of CZ-6 and conventional SAPO-34 in the MTO
reaction: (a) the selectivity of C2H4 and C3H6 variation with time-on-stream
(TOS) and (b) methanol conversion variation with TOS. Experimental
conditions: WHSV = 2.4 h-1, T = 733 K, catalyst weight = 2 g, 40% methanol.
Synthesis of SAPO-34/ SAPO-5
A typical synthesis procedure was as follows. A certain amount of
pseudoboehmite was firstly added into deionized water. Then, desired
amount of phosphoric acid was added in sequence. After further stirring
for 3 h, a certain amount of triethylamine was added in the obtained gel
and stirred for 1h. Then colloidal silica and Cn were added in sequence
and stirred for 12h. Then the obtained gel was transferred into a stainless
steel autoclave and heated rotationally (15 rpm) at 200 ℃ for 24h and
120 ℃ for 10h under autogenous pressure. The products were recovered
by filtration, washed with deionized water and dried in air. The molar
composition of the gel is 0.5Cn : 1.0P2O5 : 1.0Al2O3 : 0.38SiO2 : 3.0TEA :
59H2O. The product donated as CZ-n (n = 4, 6, 8, 10, 12). For comparison,
conventional SAPO-34 was prepared by using the corresponding SDA but
without any CSDA.
the catalytic activity and selectivity.[3b, 27] Besides, the lifetime of
CZ-6 is longer than the conventional SAPO-34 (Figure 7b). The
tri-level structure of CZ-6 can greatly enhance the diffusion
efficiency of products from narrow pores to outside space, then
reduces the coke formation, which effectively prolong the lifetime
27]
and improve the product selectivity.[8b,
Meanwhile, the
decreased acidic strength and acidic concentration of CZ-6
catalysts can also retard the coke formation and thus prolong the
lifetime of CZ-6.[28]
Conclusion
Computational details
In summary, the amphipathic molecules, consisting of dimers of
the tetraethylammonium cation connected by carbon chain, affect
the formation of micro-structure and meso/macro-structure of
SAPO-34 zeolite. Only C6 molecules can cooperate with TEA to
directly synthesize the tri-level hierarchically porous SAPO-34
zeolite, which has flower like morphology. The C6 molecules not
only serve as the porogen to generate hierarchical structure, but
also inhibit the growth of pyramidal parts, formed in the early
stage, growing to rhombohedral crystal. It also can be found that
the introduction of C6 molecules promotes Si atoms into the
AlPO4 framework, and decrease the acidity of the prepared
The AlPO-34 framework was represented by a periodic 36T hexagonal cell,
and the AlPO-5 framework was represented by 96T super cell constructed
by repeating the unit cell forth in direction of the twelve-membered channel.
All density functional theory (DFT) calculations were performed using
VASP software with Grimme-D3 corrected Perdew-Burke-Ernzerhof XC
functional (PBE-D3). The projector augmented wave (PAW) was used to
describe electronic interaction with the plane wave basis set kinetic energy
cutoff equal to 400 eV. The sampling of Brillouin zone was only with Г point.
A force threshold of 0.02 eV/Å was employed for structure optimization.
The AIMD simulations were performed using NVT ensemble at 873 K for
10 ps with a time step of 1 fs to relax the structure of SDAs in AlPO-34.
Five structures were selected every 2 ps for structure optimization. The
5
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positive charge of CSDAs was balanced by the background charge of the
system, and the energetics were calibrated using charged ammonia for the
comparison of interaction energies of CSDAs in AlPO-34 and AlPO-5.
[5] H. Q. Yang, Z. C. Liu, H. X. Gao, Z. K. Xie, J. Mater. Chem. 2010, 20,
3227-3231.
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Characterization
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XRD patterns were obtained using Bruker D8 Advance diffractometer, with
an accelerated voltage of 40 kV and detector current of 200 mA. Cu-Kα
radiation (λ = 51.540589 Å) was used for a continuous scanning with the
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Keywords: Amphipathic molecules • Geometrical matching •
Hierarchical zeolite • SAPO-34 zeolite
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