High Ethylene Selectivity in Methanol-to-Olefin (MTO) Reaction over MOR-Zeolite Nanosheets

Article abstract of DOI:10.1002/anie.202000269

Precisely controlled crystal growth endows zeolites with special textural and catalytic properties. A nanosheet mordenite zeolite with a thickness of ca. 11 nm, named as MOR-NS, has been prepared using a well-designed gemini-type amphiphilic surfactant as

Full text of DOI:10.1002/anie.202000269

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Accepted Article
Title: High ethylene selectivity in methanol-to-olefin (MTO) reaction
over MOR nanosheets
Authors: Kun Lu, Ju Huang, Li Ren, Chao Li, Yejun Guan, Bingwen Hu,
Hao Xu, Jingang Jiang, Yanhang Ma, and Peng Wu
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202000269
Angew. Chem. 10.1002/ange.202000269
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10.1002/anie.202000269
Angewandte Chemie International Edition
COMMUNICATION
High ethylene selectivity in methanol-to-olefin (MTO) reaction
over MOR nanosheets
Kun Lu†,+, Ju Huang§,+, Li Ren†, Chao Li‡, Yejun Guan†, Bingwen Hu‡, Hao Xu†,*, Jingang Jiang†,
Yanhang Ma§,*, Peng Wu†,*
Abstract: Precisely controlled crystal growth endows zeolites with
special textural and catalytic properties. A nanosheet mordenite
zeolite with a thickness of ~11 nm, named as MOR-NS, has been
prepared using a well-designed gemini-type amphiphilic surfactant as
bifunctional structure-directing agent (SDA). Its benzyl diquarternary
ammonium cations structurally directed the formation of MOR
topology, whereas the long and hydrophobic hexadecyl tailing group
prevented the extensive crystal growth along b axis. This kind of
orientated crystallization took place through the inorganic-organic
interaction between silica species and SDA molecules existing in the
whole process. The thin MOR nanosheets, with highly exposed (010)
planes and 8-membered ring (MR) windows therein, exhibited an
extremely higher ethylene selectivity (42.1%) for methanol-to-olefin
rectangular-shape crystals[8] and nanocrystal aggregates.[9]
Reducing the particle size of MFI along desired axis could even
achieved by adding modifiers of spermine, tributylphosphine
oxide, etc.[10] A major breakthrough was made by Ryoo et al. who
succeeded in synthesizing unilamellar/multilamellar MFI
nanosheets,[11] using rationally designed Gemini-type amphiphilic
surfactants with dual structure-directing functionalities. The MFI
nanosheets exposed large amount of acid sites on the external
surface, improving the catalytic conversion of large organic
molecules. Using the similar strategy, the Beta,[12] MRE,[12]
MTW,[11,12] MOR,[13] FAU[13], CHA[13] and MWW[14,15] zeolites with
nanosheets,
nanosponges,
nanoparticles
or
nanorods
morphologies were synthesized with two or more quaternary
reactions when compared with conventional bulk MOR crystals (3.3%). ammonium head group-containing amphiphilic surfactants.
Moreover, MOR-NS also possessed hierarchical structure and larger
external surface area, making it a promising catalyst for processing
bulky reactions like the alkylation of anisole with benzyl alcohol.
Zeolites are typical microporous crystalline materials that are
widely used as catalysts in industrial processes, providing strong
solid acidity and prominent shape-selective catalysis behaviors.[1]
The 3-dimensional (3D) micropore structures usually impose
strong diffusion constrain in particular for bulky molecules, limiting
the applications of conventional zeolite catalysts.[2] To address
this problem, hierarchical zeolites with secondary mesopore
system or nanosized crystals have been synthesized, decreasing
the diffusion length and enhancing the accessibility to the active
sites.[3] Nanosized zeolites, with significantly reduced crystal size
along at least one dimension, always exhibit hierarchical porosity.
The crystal size could be reduced through altering silica
sources,[4] gel compositions,[5] or using hard templates,[6] special
organic templates[7] to control initial nucleation and crystal growth
thereafter. With strong structure-directing ability, organic
quaternary ammonium cations are more possible to control the
zeolite morphology or even to induce oriented crystallization and
crystal growth under appropriate conditions. Taking the most
studied MFI-type zeolite as an example, using different SDAs
resulted in various morphologies, such as coffin crystals,[8]
Scheme 1. Graphic description for the formation of MOR nanosheet structure.
Mordenite (MOR), as a widely used solid acid catalyst, is
characterized by a pore system composed of 12-MR main
channel (0.65*0.7 nm) and elliptic 8-MR channel (0.26*0.57 nm)
parallelly running along c axis, which are interconnected by 8-MR
windows (0.34*0.48 nm) along b axis.[16] Recently, it was reported
that the 8-MR pores in MOR exhibited special shape-selective
catalysis in the carbonylation of dimethyl ether to methyl
acetate[17,18] and in the syngas conversion to ethylene.[19] Thus,
exposing more 8-MR windows by reducing the thickness along b
axis of MOR topology would achieve specific catalytic selectivity.
The MOR nanocrystals with 20 - 50 nm dimensions have been
fabricated by using the amphiphilic templates with multi-
quaternary ammonium heads[13] or the combination of tetraethyl
ammonium hydroxide and commercial amphiphilic surfactants,[20]
but the crystal orientation and size were uncontrollable. Shen et
al. synthesized the MOR nanosheets with of 20 - 40 nm thickness
along c axis using a single quaternary ammonium surfactant.[18]
Bearing these previous studies in mind, it is highly desirable to
control the MOR crystals with further reduced size along b axis
under rational expectation. We communicate here a high-silica
aluminosilicate of MOR nanosheets, named as MOR-NS, using
an amphiphilic bifunctional surfactant of C16H33-N+(CH3)2-C4H8-
[†] Shanghai Key Laboratory of Green Chemistry and Chemical
Processes, School of Chemistry and Molecular Engineering, East
China Normal University, North Zhongshan Road 3663, Shanghai
200062, China
E-mail address: hxu@chem.ecnu.edu.cn (H. Xu);
pwu@chem.ecnu.edu.cn (P. Wu)
[§] School of Physical Science and Technology, ShanghaiTech University,
Shanghai 201210, China
E-mail address: mayh2@shanghaitech.edu.cn (Y. Ma)
[‡] Shanghai Key Laboratory of Magnetic Resonance, State Key
Laboratory of Precision Spectroscopy, School of Physics and Materials
Science, East China Normal University, Shanghai 200062, 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))
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10.1002/anie.202000269
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N+(CH3)2-benzylamine (designated as Bza-4-16 hereafter) as
SDA (Figure S1 and S2). Bza-4-16 with suitable spatial distance
between two quaternary ammonium cations was designed to
direct the formation of MOR structure while the hydrophobic tail of
surfactant molecules in supporting the inorganic MOR layers
(Figure S8b). The 29Si signals in the range of -118 to -105 ppm,
assigned to the zeolite Q4 species,[21] exhibited the strongest
correlations with that of the -N+(CH3)3 segment in Bza-4-16,
cetyl group to terminate the continuous crystal growth along b axis. implying the strong intermolecular interactions between the
This synthesis route gave rise to multilayer MOR nanosheeets
with highly exposed (010) crystal planes (Scheme 1).
quaternary ammonium head groups and the zeolite frameworks.
On the other hand, the 1H NMR resonance at ca. 3.9 ppm, mainly
due to the long chain of cetyl groups, had relatively weak
correlation with either Q3 or Q4 inorganic framework silicon atoms.
This indicated the tail groups of Bza-4-16 were spatially distant to
the zeolite framework. This would further verify that the
hydrophobic tails most possibly existed in the interlayer region but
they were not embedded within zeolite pores. It should be noted
that the benzyl head group of Bza-4-16 with a cross section of ~
0.6 nm matches in size with the diameter (0.65 * 0.7 nm) of the
MOR 12-MR pores. The most stable configuration of SDA in MOR
structure was described using the molecular mechanics
simulation (Figure S9). Considering the length of hydrophobic tail
of SDA, the interlayer space would reach ~ 2 nm if the surfactant
was packed in a vertical configuration. Hence, the alkyl chain
groups were probably packed in an oblique or bended style in the
interlayer space (Figure 1e). The two quaternary cations took the
positions on the outsides of two 8-MR windows along b axis, with
one in main 12-MR channel and the other one in broken 8-MR
channel. This kind of configuration made the organic -(CH2)4-
butylene group between two quaternary ammonium cations firmly
embedded within the inorganic framework. The location of Bza-4-
16 was also confirmed by the TG-DTG analysis (Figure S10 and
Table S2). The calculation based on the mass of organic SDA and
inorganic zeolite indicated that MOR-NS-P contained about one
SDA molecule per unit cell.
The PXRD pattern of MOR-NS was characteristic of the MOR
topology, confirmed by Pawley refinement (Figure S3). However,
the diffraction peaks especially those related to b axis were much
broader for as-made MOR-NS-P in comparison to traditional
MOR zeolite (Figure S4b and S4e), suggesting that MOR-NS
probably possessed a b-axis orientated structure. The framework
of MOR-NS was well-preserved after high-temperature
calcination and hash acid treatment (Figure S4c and S4d),
indicating it was thermally and hydrothermally stable.
e
Figure 1. SEM (a) and TEM images (b-d) of MOR-NS-P. The schematic
diagram of MOR-NS-P structure viewed along
c axis (e), in which the
diquarternary ammonium cations are locked firmly by two 8-MR windows, with
the benzyl headgroup pointing to 12-MR pore, whereas the long-chain cetyl
tailing group to the opposite direction.
To investigate the structure evolution of MOR-NS, the solid
products withdrawn from the synthetic mixture at different time
were characterized by PXRD, SEM and TEM techniques. The
PXRD pattern of initial synthetic gel of MOR-NS was
corresponding to an amorphous phase (Figure S11a). After 24
hours, the diffraction characteristic of mesophase appeared in the
low-angle region (Figure S11b), as a result of self-assembly
between the micelle of amphiphilic SDA molecules and the
silica/alumina sources. The mesophase disappeared after 96
hours (Figure S11d), while minor diffractions appeared in the
high-angle region of 2θ = 25 - 30° after 192 hours (Figure S11e),
implying that the meta-stable mesophase was dissolved or
reorganized to provide the nutrition for the later zeolite
crystallization. Highly crystalline MOR phase was obtained for
MOR-NS after 504 hours (Figure S11i). The crystallization
process was also traced by SEM and TEM images (Figure S12
and S13), revealing very similar results for the phase evolution.
The crystallization process of MOR-NS was graphically described
in Scheme 1.
The SEM images revealed that MOR-NS exhibited
a
morphology significantly different from that of traditional MOR.
The MOR-NS crystals were composed of flower-like thin
nanosheets with a thickness around 10 nm (Figure 1a), whereas
the traditional MOR zeolites showed nanoparticle or bulk
morphologies, with the sizes ranging from 50 to several hundred
nanometers depending on synthesis methods (Figure S5). The
TEM images of MOR-NS were further collected to investigate its
unique structure (Figure 1b and Figure S6), which were consistent
with the SEM images indicative of highly ordered zeolite layers in
MOR-NS. Under higher magnification along a axis, it was obvious
that the as-synthesized MOR-NS-P composite was composed of
alternating 2.0 nm-thick inorganic MOR layers and 1.1 nm-thick
organic surfactant layers, possessing an overall thickness of ~ 11
nm (Figure 1c). Figure 1d further suggests that the MOR layers
expanded within the (010) planes and stacked along b axis, in
good agreement with the above mentioned PXRD patterns.
A systematic study was conducted to determine the synthetic
window for the phase-discrimination of MOR-NS (Table S3 and
Figure S14). The crystalline phases of the products were largely
affected by the Si/Al ratio in the initial gel, and MOR-NS with pure
MOR phase was obtained in a relatively narrow Si/Al ratio range
of 25 - 35 (Table S3, No. 3 - 5). At lower Si/Al ratios of 10 - 20,
conventional MOR phase was obtained (Figure S15 and Figure
S16. At higher Si/Al molar ratios of 45, layered silicate was formed
as the major phase (Figure S15d and Figure S17). As reported in
previous studies,[22,23] traditional MOR zeolite was easily
crystallized in the synthetic gel with lower Si/Al ratios, in good
Considering the organic surfactant pillared the specific MOR
layers as revealed by the TEM images, the organic-inorganic
interaction was supposed to be crucial for the crystallization of
multilamellar MOR zeolite. The elemental analysis and 13C NMR
spectroscopy firstly proved that the chemical structure of SDA
molecules was well-preserved in the crystallization process
(Table S1 and Figure S7). The 2D 1H-29Si HETCOR NMR
spectrum of MOR-NS-P revealed the essential role of the organic
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10.1002/anie.202000269
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agreement with the phenomena observed in the present study.
The effect of SDA, H2O and Na+ amount were also investigated in
the supporting information.
(Figure S22). A major resonance at 58 ppm, assigned to
tetrahedrally coordinated Al species,[24] was observed for the two
kinds of MOR materials and their acid-treated derivatives,
indicating almost all of the Al species were tetrahedrally
coordinated in MOR framework. The IR spectra were further
recorded in the hydroxyl stretching region to confirm the Al
coordination (Figure S23). The IR band at 3610 cm-1 was
associated with the bridging hydroxyls of framework aluminum
(Si-OH-Al), which proved that the Al species mainly existed in
framework. H-MOR-NS showed a more intense 3740 cm−1 band,
attributing to isolated terminal silanol groups,[25] which should be
contributed by its highly exposed external surface on ac planes.
The catalytic properties of aluminosilicates greatly depend on
their Brønsted and Lewis acidity. Thus, pyridine adsorbed IR
spectra were measured (Figure S24) and revealed that the
amount and strength of Brønsted and Lewis acid sites were very
similar for the two kinds of MOR materials with comparable Si/Al
ratios of 31 and 28. The NH3-TPD investigation also gave similar
results (Figure S25).
The physicochemical properties of calcined MOR-NS
nanosheets were compared with conventional MOR bulk crystals.
The pristine conventional MOR was acid treated to achieve
comparable Si/Al ratio as MOR-NS, and they exhibited well-
preserved crystallinity and morphology (Figure S5, e-g and Figure
S18, e-g). The MOR-NS zeolite and its acid-treated derivative
possessed both micropores and mesopores, while the traditional
MOR zeolites exhibited only microporosity (Figure S19 and Table
S4). The infrared spectra indicated that the dealumination
procedure for MOR nanosheets was nonselective toward Al sites
in 12-MR or 8-MR (Figure S20, a and b). With respect to the
microporosity, MOR-NS and bulk MOR both showed the main
peak around 6 Å in pore size distribution curves (Figure S21), due
to the same main 12-MR channels of MOR topology. Meanwhile,
the formation of mesopores in MOR-NS was highly related to the
intergrown crystals, as the SDA species served as pillars to
support each other and to prevent full condensation of the
neighboring zeolite layers. On the other hand, the slight
dislocation of the up-and-down layers would also cause the
incomplete condensation.
The MOR-NS, with comparable acidity but greatly different
crystal morphology and porosity in comparison to traditional MOR,
is expected to exhibit distinct catalytic properties, which were
probed in methanol-to-olefins (MTO) and Friedel-Crafts alkylation
reactions. Figure 2 shows the time courses of methanol
conversion and product selectivity of MTO over the MOR zeolites.
The methanol conversions over MOR-NS-AT and MOR-C were
kept over 97% for 360 min, indicating a slow deactivation rate.
However, the corresponding samples with lower Si/Al ratios
deactivated rapidly after 90 min (Figure 2A), due to the severe
carbon deposition aroused by high acid density.[26] The main
A
100
a
b
90
c
=
=
80
d
products of MTO reaction were lower olefins (C2 - C4 ), with
MOR-NS-AT showing a higher total olefins selectivity close to ca.
80% (Figure 2B). More interestingly, the lower olefin distribution
varied with the morphology of MOR zeolites. The MOR-NS-AT
had unexpectedly high selectivity for ethylene (42.1%), while the
main product of MOR-C was propylene (45.3%) and butene
(24.3%) (Table S5). For the currently used zeolites (such as
SAPO-34, MOR and MFI) as MTO catalysts, propylene was the
primary product. These results demonstrated that the structural
features of MOR-NS had obvious effects on the hydrocarbon
product selectivity. The previous researches showed that the acid
site distribution within MOR pores has a significant impact on
ethylene production. Bao et al.[19] provided experimental evidence
that the high selectivity of ethylene in the syngas conversion was
achieved more likely over the 8-MR sites in MOR framework.
Similarly, the C-C coupling to produce light olefins in MTO
reaction was controlled by the confined environment of zeolite
pores and acid sites.[27] The MOR-NS nanosheets, possessing
highly exposed (010) planes as a result of crystal thinning along
the b-axis, not only enhanced the accessibility of methanol to 8-
MR windows, but also increased the diffusion rate of smaller olefin
molecules along the b-axis, giving rise to a higher ethylene
selectivity than conventional MOR zeolite at comparable Si/Al
ratio. To confirm this, four MOR zeolites with different crystal
morphologies were investigated in the MTO reaction at
comparable Si/Al ratios of 85 - 91. As shown in Figure 3, all the
MOR catalysts achieved 100% methanol conversion, and MOR-
NS-AT showed higher light olefins selectivity than the other three
conventional MOR zeolites. Especially, the ethylene selectivity in
lower olefins decreased monotonically with increasing thickness
70
60
0
50 100 150 200 250 300 350
Time-on-stream (min)
100
80
60
40
20
0
C3=
C4=
C2=
B
MOR-NS-AT
MOR-C
5
5
60
60
120
240
360
180
300
240 360
180
300
120
Time-on-stream (min)
Figure 2. (A) Conversion of methanol over the catalysts of MOR-C (a), MOR-
NS-AT (b), MOR-D (c) and H-MOR-NS (d) in MTO reaction. (B) The comparison
of low olefins (C2-4=) selectivity between MOR-C and MOR-NS-AT. MTO
reaction conditions: cat., 0.1 g; N2 flow rate, 30 mL min-1; temp., 673 K; WHSV,
1.0 h-1.
The coordination environment of Al ions in MOR-NS and
traditional MOR zeolites was revealed by 27Al MAS NMR spectra
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10.1002/anie.202000269
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In conclusion, the bifunctional amphiphilic surfactant allowed
us to synthesize multilamellar MOR-type zeolite. The Si/Al ratio
was critical for the formation of monolayers stacking along b axis.
The multilamellar structure was converted to 3D MOR
nanosheets with highly exposed (010) crystal planes, which
favored the ethylene production in the MTO reactions. Moreover,
the hierarchical pore system of MOR-NS was beneficial to
depress the coke formation in the MTO reaction and also to
enhance the catalytic activity in the alkylation of anisole with
benzyl alcohol.
=
0
C2-4
C1-4
C5+
aromatics
MOR-B
MOR-A
MOR-C
MOR-NS-AT
70
60
50
40
30
20
10
0
100
80
60
40
20
0
Experimental Section
100
300
10
50
Experimental details are provided in the Supporting Information.
Crystal thickness along b axis (nm)
Figure 3. The dependence of product distribution (Stacked-Column) and C2=
selectivity in low olefins (curve) on the crystal thickness along the b axis of MOR
zeolites with different crystal morphologies. The comparison was made at
comparable Si/Al ratios of around 90 and 100% MeOH conversion. MTO
reaction conditions: cat., 0.1 g; N2 flow rate, 30 mL min-1; temp., 673 K; WHSV,
1.0 h-1; time-on-stream, 60 min. The TEM images show the image of
representative primary crystal of each MOR sample.
Acknowledgements
The authors gratefully acknowledge the financial support from
NSFC of China (21533002, 21872052 and 21972044), China
Ministry of Science and Technology (2016YFA0202804).
along the b-axis. By contrast, it had no relevance to the thickness
along the c-axis (Figure S26). More detailed investigations were
performed to disclose the relationship between the special acid
site located in 8-MR pockets and high ethylene selectivity. When
the H+ species in the 8-MR pockets of MOR-NS-AT were partially
exchanged by Na+, the ethylene selectivity was declined from
42.1 % to 24.5 % (Figure S27, a and b). However, selectively
shielding the acidic sites located within the 12-MR channel only
slightly decreased the ethylene selectivity by introducing pyridine
in the reaction feedstock (Figure S27, a and c). Figure S28
displays the GC-MS chromatograms of organic species retained
in spent catalysts. More lower methylbenzenes retained in spent
MOR-NS-AT, which promoted ethylene formation as
intermediates. Besides, the ethylene in the reaction system could
not be converted to propylene by methylation (Figure S29). The
above results demonstrated that the formation of ethylene was
mainly driven by aromatic-based pathway over the exposing
specific 8-MR acid sites in MOR framework. The TG-DTG curves
proved that the used MOR-NS-AT catalyst possessed smaller
amount of carbon deposition (7.25 wt.%) than that of MOR-C
(8.35 wt.%) (Figure S30), mostly because the former had a
hierarchical porosity composed of micropores and mesopores
that were useful for releasing diffusion constrains in MTO reaction.
Conflict of interest
The authors declare no conflict of interest.
Keywords: MOR zeolite, nanosheet, orientated crystal growth,
hierarchical structure, MTO reaction
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10.1002/anie.202000269
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Kun Lu, Ju Huang, Li Ren, Chao Li,
Yejun Guan, Bingwen Hu, Hao Xu*,
Jingang Jiang, Yanhang Ma*, Peng
Wu*
Page No. – Page No.
High selectivity for ethylene in
methanol-to-olefin (MTO) reactions
over the MOR nanosheets
Multilamellar MOR-type zeolite with highly exposed (010) crystal planes was
prepared using a specially designed bifunctional amphiphilic surfactant, which
favored the more selective production of ethylene in MTO reaction.
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