Micron-Sized Zeolite Beta Single Crystals Featuring Intracrystal Interconnected Ordered Macro-Meso-Microporosity Displaying Superior Catalytic Performance

Article abstract of DOI:10.1002/anie.202007069

Zeolite Beta single crystals with intracrystalline hierarchical porosity at macro-, meso-, and micro-length scales can effectively overcome the diffusion limitations in the conversion of bulky molecules. However, the construction of large zeolite Beta single crystals with such porosity is a challenge. We report herein the synthesis of hierarchically ordered macro-mesoporous single-crystalline zeolite Beta (OMMS-Beta) with a rare micron-scale crystal size by an in situ bottom-up confined zeolite crystallization strategy. The fully interconnected intracrystalline macro-meso-microporous hierarchy and the micron-sized single-crystalline nature of OMMS-Beta lead to improved accessibility to active sites and outstanding (hydro)thermal stability. Higher catalytic performances in gas-phase and liquid-phase acid-catalyzed reactions involving bulky molecules are obtained compared to commercial Beta and nanosized Beta zeolites. The strategy has been extended to the synthesis of other zeolitic materials, including ZSM-5, TS-1, and SAPO-34.

Full text of DOI:10.1002/anie.202007069

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
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Accepted Article
Title: Micron-sized zeolite Beta single crystals featuring intracrystal
interconnected ordered macro-meso-microporosity displaying
superior catalytic performance
Authors: Bao-Lian Su, Ming-Hui Sun, Li-Hua Chen, Shen Yu, Xian-
Gang Zhou, Yu Li, Zhi-Yi Hu, Yu-Han Sun, and Yan Xu
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202007069
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10.1002/anie.202007069
Angewandte Chemie International Edition
RESEARCH ARTICLE
Micron-sized zeolite Beta single crystals featuring intracrystal
interconnected ordered macro-meso-microporosity displaying
superior catalytic performance
Ming-Hui Sun,[a,b] Li-Hua Chen,*[a] Shen Yu,[a] Yu Li,[a] Xian-Gang Zhou,[a,c] Zhi-Yi Hu,[a,c] Yu-Han
Sun,*[d,e] Yan Xu,[f] and Bao-Lian Su*[a,b]
[a]
M. H. Sun, L. H. Chen, S. Yu, Y. Li, X. G. Zhou, Z. Y. Hu, B. L. Su
Laboratory of Living Materials at the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing
Wuhan University of Technology
122 Luoshi Road, Wuhan 430070, P.R. China
E-mail: chenlihua@whut.edu.cn; baoliansu@whut.edu.cn
[b]
M. H. Sun, B. L. Su
CMI (Laboratory of Inorganic Materials Chemistry)
University of Namur
61 rue de Bruxelles, Namur B-5000, Belgium
E-mail: bao-lian.su@unamur.be
[c]
[d]
X. G. Zhou, Z. Y. Hu
NRC (Nanostructure Research Centre)
Wuhan University of Technology
122 Luoshi Road, Wuhan 430070, P.R. China
Y. H. Sun
CAS Key Laboratory of Low-Carbon Conversion Science and Engineering at Shanghai Advanced Research Institute
Chinese Academy of Science
99 Haike Road, Shanghai 201210, P.R. China
E-mail: sunyh@sari.ac.cn
[e]
[f]
Y. H. Sun
School of Physical Science and Technology
Shanghai-Tech University
319 Yueyang Road, Shanghai 200031, P. R. China
Y. Xu,
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry
College of Chemistry
Jilin University
2699 Qianjin Street, Changchun 130012, P. R. China
Supporting information for this article is given via a link at the end of the document.
Abstract: Serious diffusional limitations are frequently
commercial Beta and nanosized Beta zeolites. All these
observed for the conversion of bulky molecules over conventional
zeolite Beta crystals, which invoke for hierarchical structure to
improve the mass transportation property and the accessibility to
reactive sites. Zeolite single crystals with intracrystalline
hierarchical porosity at macro-, meso- and micro-length scales is
of great significance and provides the best solution. However, the
construction of large zeolite Beta single crystals with such
intracrystalline hierarchical porosity remains a critical challenge.
We report here the successful synthesis of hierarchically ordered
macro-mesoporous single-crystalline zeolite Beta (OMMS-Beta)
with a rare micron-scale crystal size by an in-situ bottom-up
confined zeolite crystallization strategy. The fully interconnected
intracrystalline macro-meso-microporous hierarchy and the
unique micron-sized single crystalline nature of OMMS-Beta lead
to highly improved accessibility to active sites and outstanding
(hydro)thermal stability, contributing to unprecedentedly high
catalytic performances in both gas-phase and liquid-phase acid-
catalyzed reactions involving bulky molecules compared to
unprecedented properties of our hierarchically porous micron-
scale zeolite Beta single crystals with excellent stability can be
fully exploited in various catalytic reactions with high catalytic
activity, selectivity and reusability. Most importantly, our in-situ
bottom-up confined crystallization strategy to hierarchically
porous zeolite single crystal is highly universal and has been
extended to the successful synthesis of other zeolitic materials,
including ZSM-5, TS-1 and SAPO-34. Such novel zeolite single
crystals with excellent properties can be applied to many other
industrial catalytic reactions.
Introduction
Zeolites Beta are widely used as heterogeneous acid catalysts for
many applications, especially in petroleum and petrochemical
processes related to cracking,1 alkylation,2 isomerization,3
acylation4 and as acid adsorbents in the separation of aromatics.5
1
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The remarkable catalytic performances of zeolites Beta are
closely related to their well-defined three-dimensional intersecting
12 oxygen-membered ring channels system and strong acidity.6
However, these narrow micropores frequently cause diffusional
limitations over bulky reactants,7 thus reducing the accessibility of
embedded internal catalytic active sites, increasing the coke
formation in catalytic reactions8 and affecting seriously not only
the zeolite activity but also the product selectivity and the catalyst
lifetime.9 Fabrication of hierarchically porous zeolites with intra- or
intercrystalline mesopores/macropores10 is a proven strategy to
shorten the diffusion path length and to reduce the diffusion
constraints.11 Considerable efforts are devoted to construct
zeolites with porous hierarchy using different techniques, such as
hard/soft-template method and desilication.11d Hierarchically
porous zeolites are reported to outperform other microporous
zeolites, with higher catalytic activities, longer catalytic lifetimes,
lower coke formation, slower deactivation rates and enhanced
desirable product selectivity in many acid-catalyzed reactions.12
Jacobsen et al. performed the pioneering work using commercial
carbon nanoparticles13 or carbon fibers14 for preparing
mesoporous MFI-type zeolite single crystals (ZSM-513a, 13b, 14 and
TS-113c), which were significantly more active in the catalytic
cracking and isomerization of n-hexadecane13a and the
epoxidation of cyclohexene13c than their microporous
counterparts. Tsapatsis and coworkers demonstrated the
ingenious synthesis of size-tunable zeolite nanocrystals (MFI,10c
process and poor (hydro)thermal stability in both synthetic and
22
catalytic processes restrict their further application.19b,
In
addition, most of the conventional synthetic strategies lead to the
formation of crystalline size of zeolites Beta in the range of 100-
23
600 nm with relatively poor stability.12g,
It is particularly
challenging to construct hierarchically porous structure within
such one small zeolite Beta crystal. Furthermore, most
hierarchically porous zeolite single crystals were designed and
synthesized with either mesopores or macropores while the
interconnection between different porosity is not guaranteed.12a
Simultaneously generated intracrystalline macropores and
mesopores within one zeolite single crystal allow for catalytic
performance enhancement by providing an unimpeded transport
path and enhancing accessibility to more active sites.24 It is thus
highly desirable to develop a new strategy to simultaneously
construct intracrystalline interconnected macro-mesopores within
one zeolite Beta crystal with a particle size at micrometer scale,
giving improved diffusion performance and high stability.
Here, we demonstrate the synthesis of micron-sized zeolite
Beta single crystals with a highly ordered and fully interconnected
intracrystalline macro-mesoporous hierarchy by an in-situ bottom-
up confined zeolite crystallization process. The single crystalline
nature together with the micron-sized crystals endow our
hierarchically porous single crystalline zeolite Beta with
outstanding (hydro)thermal stability. The highly ordered and fully
interconnected intracrystalline porous hierarchy of the resultant
micron-sized Beta single crystals contributes to the excellent
catalytic performance involving very high catalytic conversion and
product selectivity, excellent long-term catalytic stability, low coke
formation and significant reusability in both the gas-phase
cracking reaction of bulky 1,3,5-triisopropylbenzene (TIPB) and
the liquid-phase Friedel-Crafts alkylation of benzene with benzyl
alcohol in comparison with benchmark conventional zeolite Beta
and nanosized zeolite Beta. In addition, the acid sites poisoning
experiments prove that the external active sites are decisive for
the catalytic performance for these two reactions with bulky
molecules. The introduction of porous hierarchy within Beta single
crystal regulates the distribution of acid sites and gives a
substantial increase in the number of external active sites, leading
to the extraordinary high catalytic activity, long-term stability and
low coke formation. More importantly, our in-situ bottom-up
confined zeolite crystallization strategy presents as an effective
synthetic strategy to fabricate hierarchically porous single-
crystalline catalysts with any kind of zeolite structures and
zeotype materials.
Beta,15 LTA,15 FAU15 and LTL15) with
a wide range of
intercrystalline mesoporosities using mesoporous carbon
templates through either steam-assisted crystallization10c or
hydrothermal synthesis15 for improved applications in ethanol
dehydration.16 Schwieger and coworkers nicely synthesized a
family of MFI-type zeolites (Silicalite-1,11c ZSM-5,17 TS-118) with
large
intracrystalline
macropores
by
steam-assisted
crystallization of mesoporous silica particles. The additional
intracrystalline macropores, which were connected to the
micropores and the crystal external surface, can drastically
enhance the catalyst lifetime of ZSM-5 catalysts in the methanol
to olefins (MTO) reaction17 and increase both the alkene
conversion and epoxide selectivity of TS-1 catalysts in the liquid
phase epoxidation of 2-octene with hydrogen peroxide.18 Xiao’s
group used either a designed cationic amphiphilic copolymer12f or
a commercial cationic polymer12g to synthesize zeolite ZSM-5
single crystals with b-axis-aligned mesoporous channels12f or
zeolite Beta single crystal with interconnected mesopores.12g The
b-axis-aligned mesoporous ZSM-5 showed highly improved
catalytic conversions in the condensation reactions of
benzaldehyde with hydroxyacetophenone or 1-pentanol
compared to ZSM-5 with randomly oriented mesopores and
conventional ZSM-5.12f The single-crystalline nature gives
mesoporous zeolite Beta crystals better hydrothermal stability
and higher catalytic activity than that of conventional zeolite Beta
in the condensation of benzaldehyde with glycerol or
hydroxyacetophenone and the alkylation of benzene with benzyl
alcohol.12g Perez-Ramirez and coworkers made great
contributions on the controlled generation of mesoporosity within
zeolites by desilication19 and on the structural analysis to assess
the pore connectivity.20
Results and Discussion
Hierarchically macro-mesoporous micron-sized Beta single
crystals with Si/Al ratio of 28 were synthesized within the
confined-space in hierarchically ordered macro-mesoporous
carbon (OMMC) template via a steam-assisted crystallization
(SAC) process. In a typical synthesis (Figure 1a), the OMMC
template prepared using polystyrene spheres of 220 nm (Figure
S1 and Experiments), possessing interconnected mesopores and
macropores, was impregnated within a zeolite Beta precursor
slurry (Experiments). After slow evaporation of water at room
temperature, the obtained dry gel completely filled up the
mesopores and macropores in the OMMC template and then
crystallized through the SAC process (Figure 1a). It is worth
Pioneering work in the development of hierarchically porous
zeolite Beta focused most on the nanoparticle assembly21 but few
on the single crystals.12g Zeolite nanocrystals may to some extent
improve the accessibility of catalysts, but their difficult separation
2
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RESEARCH ARTICLE
Figure 1. Steam-assisted crystallization of OMMS-Beta and its structure configuration. (a) Schematic diagram of the synthesis route of OMMS-Beta. (b-h)
SEM images of OMMS-Beta(3) as a reference sample (b) and an individual crystal taken from three different directions (c-e) and corresponding schematic
illustrations (f-h), Scale bars: b, 2 μm; c-e, 500 nm. (i and j). (i) SEM image of the enlarged area of OMMS-Beta(3), Scale bar: 100 nm. (j) Illustration of hierarchically
ordered macro-meso-microporous structure in one single crystal of sample OMMS-Beta. The macropores are stemmed from the octahedral voids (Oh, red) and the
mesopores from the tetrahedral voids (Td, blue).
noting that the mass transport in the dry gel and thus the zeolite
crystallization rate within the confined spaces of the OMMC
template during the SAC process are much slower than that in the
traditional hydrothermal synthesis (HTS). This is a key point for
the formation of the rare micron-sized zeolite Beta single crystals
with hierarchically porous system. The calcined samples obtained
by different crystallization periods (initial, 1 day, 2 days and 3
days) are designed as OMMS-Beta(0), OMMS-Beta(1), OMMS-
Beta(2) and OMMS-Beta(3).
Using OMMS-Beta(3) as the representative sample (Figures
1b-1i), it can be seen that after the crystallization reaction of three
days, crystals of 1.5-2 μm are obtained (Figures 1b-1i). Each
zeolite crystal consists of a number of uniform zeolite spheres with
a size of 200 nm, being very similar to the size of polystyrene
spheres used for preparing OMMC template (Figure S1), in a
highly ordered and closely packed arrangement, as evidenced
from the SEM images (Figures 1c-1i). The neighboring spheres,
originally formed in each of adjacent macropores in the OMMC
template, are intergrown and tightly interconnected (the green
rectangle of Figure 1i) through the windows connecting each cage
of the OMMC template (Figure S1). Such highly ordered opaline
structure (Figures 1b-1i), in which each spherical element is
connected with 12 other adjacent elements, is an exact copy of
the highly ordered, interconnected and continuous air voids in the
OMMC template (Figure S1). These ordered spherical elements
in one individual OMMS-Beta single crystal contribute to the
formation of interstitial tetrahedral (Td) and octahedral (Oh) voids
by 4 and 6 spheres from two adjacent layers (Figure 1j),
respectively. Such periodically arranged Td and Oh voids within
one zeolite single crystal, which are highly connected each other
and are communicated with the micropores present in each
spherical element, lead to the creation of two different and
interconnected large porosities in addition to the intrinsic
microporosity of zeolite Beta, and provide ordered, fully
3
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Figure 2. Characterization of OMMS-Beta(3). (a) TEM image and ED pattern (inset) of an individual zeolite, Scale bar: 500 nm; the inset: 5 nm-1. (b) TEM image
of enlarged area outlined in (a), Scale bar: 200 nm. (c) HRTEM image of enlarged area outlined in (b), Scale bar: 20 nm. (d) XRD pattern, (e) Nitrogen adsorption-
desorption isotherms and micropore-size, mesopore-size distribution (inset) and (f) Mercury intrusion and macropore-szie distribution (inset) of OMMS-Beta(3).
interconnected meso- and macroporous structure, precisely
replicating the OMMC template (Figure 1j).
X-ray diffraction (PXRD) pattern (Figure 2d), corresponding to
(101) and (302) reflections of Beta-topology, respectively. No
other diffraction peaks but the Beta reflection peaks are observed,
confirming that the pure zeolite Beta without any impurity is
prepared. The nitrogen adsorption-desorption isotherm has two
Transmission Electron Microscopy (TEM) images (Figures
2a-2c) show the strongly faceted and ordered opal structure
constructed by intergrown and highly interconnected zeolite
spheres in one individual zeolite crystal of OMMS-Beta(3) as a
representative sample (indicated by the circles in Figure 2b),
which is in an excellent agreement with the SEM images (Figures
1b-1e and the green rectangle of Figure 1i). The corresponding
selected area electron diffraction (SAED) pattern (the inset of
Figure 2a) contains discrete diffraction spots, clearly indicating
the single crystalline nature of the OMMS-Beta(3) sample. The
high-resolution transmission electron microscopy (HRTEM,
Figure 2c) image reveals the high degree of crystallization and the
same oriented lattice fringes over the entire image region. No
grain boundary or interface between two small zeolite spheres are
observed, confirming these zeolite spheres are not independent
but tightly interconnected into a whole zeolite crystal, being in
good accordance with the electron diffraction pattern (inset of
Figure 2a) of the whole assembly and SEM images (Figures 1b-
1e and the green rectangle of Figure 1i). No amorphous
components, planar defects like stacking faults, twins formation
or dislocations are found between zeolite spheres, verifying the
pristine structure throughout the zeolite crystal and that all the
zeolite spheres are crystallized following the structure of the
OMMC template in the same orientation and intergrown to give
the entire zeolite single crystal.
steep steps in the p/p0
< 0.01 and p/p0 < 0.9 regions,
corresponding to the filling of the micropores and the capillary
condensation in the mesopores and macropores, respectively
(Figure 2e)12g
. The micropore diameter of OMMS-Beta(3)
determined using non-local density functional theory (NLDFT) is
around 0.6 nm (the inset of Figure 2e), which is the same as
observed in conventional zeolite Beta.23, 25 The micropore surface
area and volume of OMMS-Beta(3) are 179 m2·g−1 and 0.10
cm3·g−1, respectively (Table S1), indicating that the fabrication of
a hierarchically macro-mesoporous system within the zeolite Beta
does not influence its inherent microporous structure. The
mesopore size distribution determined using Barret-Joyner-
Halenda (BJH) model is centered at 40 nm (the inset of Figure 2e)
and the mesoporous surface area and total volume are 120 m2·g−1
and 0.28 m2·g−1 (Table S1), respectively. The presence of
additional meso- and macropores in OMMS-Beta(3) is further
confirmed by the mercury intrusion porosimetry measurement.26
The result shows a narrow mesopores distribution centered at
~32 nm, slightly lower than the value (~40 nm) obtained by the
nitrogen adsorption, and a broader macroporous distribution
centered at ~95 nm (Figure 2f). These interconnected and
periodically ordered mesopores and macropores stem from the
tetrahedral (Td) and octahedral (Oh) voids within the OMMS-
Beta(3) sample, respectively (Figure 1j).
Sample crystallized after three days evidently show two
feature peaks at Bragg angles 2θ of 7.6° and 22.6° in the powder
4
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Figure 3. Crystallization process of OMMS-Beta. SEM images and corresponding of schematic illustrations inset of (a) OMMS-Beta(0), (b) OMMS-Beta(1), (c)
OMMS-Beta(2) and (d) OMMS-Beta(3), Scale bars: a, b 100nm; c, d, 500nm.(e) XRD patterns, (f) 29Si NMR spectra, (g) 27Al NMR spectra and (h) nitrogen
adsorption isotherms of (I) OMMS-Beta(0), (II) OMMS-Beta(1), (III) OMMS-Beta(2) and (IV) OMMS-Beta(3).
Samples at different crystallization times were collected and
characterized by SEM, XRD, 27Al MAS NMR, 29Si MAS NMR and
nitrogen adsorption-desorption analysis to gain deeper insights
into the transformation process (Figure 3). Initially, all the air voids
in the OMMC template were filled with the precursor gel. After
drying the gel and removing the OMMC template, it is very
interesting to see that all the amorphous spheres of about 200 nm
are tightly packed and continuously connected together into a
highly ordered arrangement, which precisely replicated the
inverse opalline structure of the OMMC template (Figure 3a). It is
worth stressing that after filling up the air voids within the OMMC
template by the dried precursor gel, all the amorphous spheres
formed due to the confined space of the OMMC template are
already interconnected to form
a continuous gel structure
throughout the entire OMMC template. These confined
amorphous spheres then gradually crystallize within the OMMC
template under the SAC condition. With a crystallization time of
one day, OMMS-Beta(1) mainly consists of spheres (~200 nm)
5
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with rough surface and already visible crystallinity but without the
tight interconnection between the spheres as observed in OMMS-
Beta(0) (Figure 3b). It is intriguing that these spheres, originally
formed within the macropores of the OMMC template, all have a
small fraction of spheres attached on the surface (indicated by
arrows in Figure 3b and also observed on the out layer spheres
in Figure 3a). This means that the spheres in opalline structure
formed by amorphous dried gel are partially dissociated due to
the partial crystallization. This dissociation leads to the presence
of the small fraction of spheres attached to each sphere. The first
OMMS-Beta single crystals with a typical Beta-type zeolite cube-
like shape and a crystal size close to 1 μm are obtained after a
crystallization time of two days (Figure 3c). Each crystal is
constructed by several zeolite spheres (~200 nm) and all these
zeolite spheres are tightly bonded with each other. The
crystallinity is gradually increased as the crystallization time
proceeds. After a crystallization of 3 days, OMMS-Beta(3) sample
shows well shaped crystals (Figure 3d). Each crystal is
assembled by more spheres and the crystal size increases to 1.5
μm-2 μm (Figure 3d) as previously analyzed in Figure 1 and 2. It
is clearly observed that the crystalline degree of the resultant
OMMS-Beta samples increases with the prolonged crystallization
(Figure 3e). The crystallinity is largely improved, suggesting the
very well crystallization after three days. The coordination and
environment of the Si species in all the samples are further
studied by 29Si MAS NMR technique (Figure 3f). The OMMS-
Beta(0) features a small shoulder at δ=-96 ppm [Q2 groups
Si(OSi)2(OH)2], a broad signals at δ=-103 ppm [Q3 groups,
Si(OSi)3(OH)] and two other broad signals at δ=-109 nm and δ=-
116 ppm [Q4 groups, Si(OSi)4].27 As the crystallinity of the
samples increases, the shoulders at both δ=-96 nm [Q2 groups]
and δ=-103 nm [Q3 groups] disappear. A small shift of the Q4
groups towards higher magnetic field is observed while these Q4
signals become much narrower, suggesting that the coordination
states of the Si species transformed from an amorphous to a
crystalline framework. Moreover, three overlapping signals exist
in OMMS-Beta(1)-(3) samples at δ= -110, -112, -115 ppm, all
assigned to Q4 groups at different crystallographic non-equivalent
tetrahedral sites in the Beta structure.27 The fact that the
resonance peaks in OMMS-Beta become narrower is due to the
0.01 reveals the presence of micropores in all OMMS-Beta(1-3)
samples. The micropore size calculated by the NLDFT method is
around 0.6 nm, which is in good agreement with the pore size of
zeolite Beta.23 The surface area and pore volume of micropores
increase gradually with the increased crystallization time (Table
S1), which means that the amorphous domain has been gradually
transformed into microporous zeolitic phases. OMMS-Beta(1-3)
samples all exhibit type I isotherms with a steep increase and a
large hysteresis at p/p0 > 0.9, suggesting the presence of large
mesoporosity and macroporosity (Figure 3h). It is worth noting
that the mesopore size distribution centered at 40 nm can be
observed for all OMMS-Beta samples (Figure S2), indicating that
the in-situ bottom-up confined zeolite crystallization process can
be carried on within the OMMC template and precisely replicated
the inverse opal structure. It can thus be concluded that our in-
situ bottom-up confined zeolite crystallization process is a
successful strategy to create highly ordered and fully
interconnected intracrystalline porous hierarchy within one zeolite
Beta single crystal with a rare micron-sized crystal size and high
crystallinity.
The excellent thermal and hydrothermal stability of our OMMS-
Beta(3) single crystals have been evidenced through a series of
high-temperature treatment (1000°C for 1h) and high-temperature
treatment in vapor stream (780°C for 2h). The detailed N2
isotherms, XRD and SEM characterizations clearly show that
these thermally and hydrothermally treated samples maintain
intact the well-defined ordered hierarchically macro-meso-
microporous framework with a high crystallinity (Figures S3-S6).
The crystallinity before and after (hydro)thermal treatment is
verified using Eq (1) (Experiments). Therefore, the hydrothermally
and thermally treated OMMS-Beta(3) samples practically
maintain the same crystallinity as the as-synthesized OMMS-
Beta(3) sample. The surface area and pore volume equally
remain practically the same (Table S2). Such excellent thermal
and hydrothermal stability should be attributed to the single
crystalline nature of the rare micron-scale sized zeolite. The
outstanding (hydro)thermal stability under very severe conditions
is of great importance for their catalytic stability. All the above
observations clearly demonstrate that micron-sized zeolite Beta
single crystals with a high crystallinity, highly ordered and fully
homogeneity of the Si environment as the crystallization proceeds, interconnected
macro-mesoporous
structure,
excellent
indicating that the crystallinity of resultant Beta zeolitic framework
increases gradually with increasing reaction time.28 It is clearly
observed from the 27Al MAS NMR spectra (Figure 3g) that the
sharp and symmetrical signal at δ=55 ppm, assigned to the
tetrahedrally coordinated framework aluminum, is gradually
enhanced with increased crystallization time while the resonance
at δ=0 ppm, corresponding to the octahedrally coordinated extra-
framework aluminum, is absent for all the samples except for
OMMS-Beta(0).12g These results indicate that the amorphous
aluminum atoms have been successfully incorporated into the
zeolite Beta single crystalline framework in tetrahedral position
during the in-situ bottom-up confined zeolite crystallization
process. The N2 adsorption-desorption isotherms of the calcined
samples over various crystallization periods change from a type II
to a type I with two uptakes at p/p0 < 0.01 and p/p0 > 0.9,
respectively with increasing crystallization time (Figure 3h), also
indicating the gradual generation of microporosity, mesoporosity
thermal/hydrothermal stability are obtained.
To illustrate the extraordinary accessibility to active sites of
OMMS-Beta single crystals, the acidic properties and the
distribution of active sites are determined by the ammonia
temperature programmed desorption (NH3-TPD) analysis29 and
the organic base (triphenylphosphine, TPP) adsorption method 30
(Experiments), respectively. The ammonia molecule with a kinetic
diameter of 0.44 nm can penetrate into micropores and will give
the total acidity of zeolites while the basic TPP molecule is
sterically bulky with a kinetic diameter of 0.94 nm and can access
only the acid sites on the external surface out of micropores.31 For
comparison, the benchmark conventional zeolite Beta
(designated as C-Beta) and nanosized zeolite Beta (designated
as Nano-Beta) are used as reference catalysts. Both C-Beta and
Nano-Beta contain multimodal porosities confirmed from the
detailed adsorption-desorption characterizations (Figures S7-S9).
The C-Beta with a crystal size of 300-600 nm has mesopores at
3.2 nm and the Nano-Beta has interparticular mesopores at
and macroporosity in the products. The sharp uptake at p/p0
<
6
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clarity, the acid sites embedded within the micropores are labelled
as internal acid sites and all the acid sites out of micropores are
named as external acid sites. These three samples with the
similar Si/Al ratios exhibit almost the same total acidity shown by
the NH3-TPD analysis (Figure S10 and Table S3). It is worth
noting that a greater accessibility of the bulky TPP molecules
related to the external sites is achieved upon the fabrication of
intracrystalline interconnected meso-/macropores within the
zeolites. Due to its higher external surface area compared to that
of C-Beta, Nano-Beta has a higher adsorption capacity for TPP
(21 μmol·TPP·g-1 cat) than that of C-Beta (13 μmol·TPP·g-1 cat)
while OMMS-Beta(3) sample contains much higher external
surface acidity (28 μmol·TPP·g-1 cat), which is 2 times higher than
that of C-Beta and 33% higher than Nano-Beta, respectively.
These increased external catalytic sites within the OMMS-Beta(3)
catalysts are widely-open, indicating that more active sites are
exposed and accessible, being of great importance for the
catalytic performance.
The combination of the fully interconnected porous hierarchy,
the high (hydro)thermal stability, single crystalline nature and the
abundant external acid sites makes OMMS-Beta(3) an
extraordinary solid acid catalyst, especially for converting bulky
reactants. The catalytic activities of OMMS-Beta were firstly
evaluated in the gas-phase cracking reaction of bulky 1,3,5-TIPB
(Scheme S1). It is clearly observed that our OMMS-Beta(3)
catalyst exhibits a very high catalytic conversion of 49.0% even at
a low reaction temperature at 250°C, which is 5 and 2.2 times
higher than that of the C-Beta (9.8%) and the Nano-Beta (21.4%),
respectively (Figure 4a). The 1,3,5-TIPB conversion increases
slowly for both C-Beta and Nano-Beta as the reaction temperature
increases from 250°C to 500°C. In contrast, the 1,3,5-TIPB
conversion increases rapidly for OMMS-Beta(3) sample as the
temperature increases and can achieve an unprecedentedly high
value of 86.4% at 500°C, which is 4.0 and 2.0 times higher than
that of C-Beta (22.6%) and Nano-Beta (43.4%), respectively.
Such excellent catalytic activity of OMMS-Beta(3) is directly
related to its open, interconnected and ordered intracrystalline
hierarchically micro-meso-macroporous architecture and high
external surface acidity, which enhances the accessibility of bulky
1,3,5-TIPB molecules (with a kinetic molecular dimension of 0.95
nm) to the larger amount of external active sites. The high stability
of intracrystalline hierarchically porous structure and abundant
external acid sites are also of great importance for their long-term
catalytic stability and cycle stability in reactions involving bulky
reactants. C-Beta and Nano-Beta samples suffer from serious
deactivations in which about 70% of their catalytic activities are
lost after 30 pulse injections at 500 ℃. In contract, OMMS-Beta(3)
shows unchanged activity and the catalytic conversion stabilizes
at 86.0 % in the given 30 injections (Figure 4b). Generally, the
deep cracking of 1,3,5-TIPB usually takes three successive steps,
which are the first dealkylation of 1,3,5-TIPB to form
diisopropylbenzene (DIPB) and propylene, the second
dealkylation of DIPB to give isopropylbenzene (IPB) and
propylene and the third dealkylation of IPB to give benzene and
propylene (Figure S11). The propylene from deep cracking of
1,3,5-TIPB is a chemical urgently needed by the industry.
Consequently, it is highly desirable to realize the deep cracking
by developing novel catalysts. The main products catalyzed by C-
Beta are DIPB and propylene accompanied by few IPB and
benzene, indicating the low cracking degree of 1,3,5-TIPB. As the
Figure 4. Catalytic performance of various zeolite Beta catalysts in the
gas-phase cracking reaction of 1,3,5-TIPB the liquid-phase benzylation of
benzene with benzyl alcohol. (a) catalytic activities (1,3,5-TIPB conversions)
at different temperatures and (b) deactivation behavior at 500 ℃ in the 1,3,5-
TIPB cracking reaction. (c) Benzyl alcohol (BA) conversions and (d)
diphenylmethane (DPM) selectivities over OMMS-Beta, Nano-Beta and C-Beta.
(e) Benzyl alcohol (BA) conversions and (f) diphenylmethane (DPM)
selectivities over OMMS-Beta, Nano-Beta and C-Beta, micropore-poisoned
OMMS-Beta and TPP-poisoned OMMS-Beta.
10.6 nm and large macropores. Consequently, these two samples
with multi modal porous structure are thus excellent references
for comparison. The distribution of active sites is one of the most
important factors to determine the catalytic performance. The
introduction of intracrystalline interconnected porous hierarchy
within the zeolites not only improves their diffusion performance,
but also changes the distribution of active sites. For the sake of
7
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10.1002/anie.202007069
Angewandte Chemie International Edition
RESEARCH ARTICLE
injections increased, the increased DIPB content and the
decreased propylene content (Figure S12a) suggest the
decreased catalytic capacity and the deactivation of C-Beta. The
larger interparticlar mesoporous structure present in Nano-Beta
offers better accessible external active sites and facilitates the
diffusion of the bulky 1,3,5-TIPB as compared with C-Beta as
indicated by TPP adsorption experiment (Table S3). However, the
same deactivation trend is observed for Nano-Beta catalyst
although less DIPB but more Benzene and propylene in content
are obtained (Figure S12b), indicating that the same reduced
capacity of Nano-Beta and the catalyst is deactivated with
increasing the number of injections. Significantly, the average
selectivity of propylene from deep cracking of TIPB over OMMS-
Beta(3) catalyst can reach at a very high value of 58% (Figure
S12c), which is 2.0 and 1.5 times higher than that of C-Beta (29%)
and Nano-Beta (38%), respectively. The main products are
benzene and propylene with small content of IPB but without
DIPB, indicating the much deeper cracking degree of 1,3,5-TIPB
over OMMS-Beta(3) catalyst. Furthermore, the products
selectivity over OMMS-Beta(3) catalyst remains practically
constant up to 30 injections, indicating the high catalytic stability
of OMMS-Beta(3) catalyst. The much deeper cracking process
and excellent catalytic stability achieved on OMMS-Beta(3)
catalyst compared to C-Beta and Nano-Beta should be attributed
to their significant intracrystalline diffusion performance of guest
molecules and the low amount of coke deposition. The coke
deposition on the reacted samples was analysed by the
thermogravimetric analysis (TGA). OMMS-Beta(3) used in
cracking of 1,3,5-TIPB for 30 injections showed two times less
coke deposition (3.0 %) than C-Beta (7.3 %) and Nano-Beta
(6.0 %). It can be concluded that the presence of excellent
hierarchically porous diffusion system, strong accessible external
surface acidity together with high (hydro)thermal stability provides
a highly efficient catalyst, exhibiting enhanced catalytic activity,
significant selectivity of light olefins, excellent catalytic stability as
well as higher resistance to coke formation during the 1,3,5-TIPB
catalytic cracking.
outstanding mass transport properties of OMMS-Beta(3), which
can be further evidenced by the detailed catalytic evaluations of
the thermally/hydrothermally treated samples and the recycling
test of the regenerated catalysts (Tables S2 and S4). There is only
a very slight decrease in benzyl alcohol conversion and DPM
selectivity over both the thermally and the hydrothermally treated
OMMS-Beta(3) catalysts after 120 h reaction at 80°C (Table S2).
Significantly, the catalytic performance in terms of the benzyl
alcohol conversion and DPM selectivity of the regenerated
OMMS-Beta(3) catalysts after first, second and third cycles of 120
h reaction in benzene alkylation by benzyl alcohol remains
practically unchanged (Table S4). The OMMS-Beta(3) catalysts
discharged after first, second and third reaction cycles of 120
hours are further characterized by the detailed N2 adsorption-
desorption isotherms, XRD and SEM techniques, confirming that
the OMMS-Beta(3) catalyst has excellent reusability without any
pore structure modification after three reaction cycles and high
temperature multiple oxidative regeneration processes (Figures
S13-S14).
In order to further illustrate the catalyst performance
superiority of the interconnected and ordered micro-meso-
macroporous hierarchy of our micron-sized Beta single crystals,
the selective poisoning of the internal and the external acid sites
on all the C-Beta, Nano-Beta and OMMS-Beta(3) has been
realized, whose catalytic behaviors are again evaluated in the
liquid-phase alkylation of benzene with benzyl alcohol. The
internal acid sites within the micropores can be selectively
poisoned by completely blocking the micropores with carbon
species formed during the benzene isopropylation process
(designated as Micropore-poisoned sample, Experiments)32 and
the external acid sites located within the meso/macropores can
be poisoned by the chemisorption of triphenylphosphine (TPP) as
TPP molecules cannot penetrate into the micropores (designated
as TPP-poisoned sample, Experiments).2, 31 Figure 4e shows that
the benzyl alcohol conversion over the TPP-poisoned OMMS-
Beta(3) is very low with a value of 25% after reaction for 120 h. In
contrast, the Micropore-poisoned OMMS-Beta(3) still exhibits
very high conversion (71%, Figure 4e). More importantly, the
Micropore-poisoned OMMS-Beta(3) shows the same high DMP
selectivity as the pristine OMMS-Beta(3). The high DPM
selectivity of both the micropore-poisoned and the TPP-poisoned
OMMS-Beta(3) remain almost constant during the long-term
reaction for 120 h (Figure 4f). It can be inferred that the external
active sites of catalysts are decisive for both the catalytic
conversion and product selectivity in the alkylation of benzene
with benzyl alcohol, which is also evidenced by the catalytic
results obtained on both selective-poisoned C-Beta and Nano-
Beta (Figure S15). Both the micropore-poisoned Nano-Beta and
the TPP-poisoned Nano-Beta (Figures S15a-S15b) exhibit lower
catalytic conversion of benzyl alcohol than pristine Nano-Beta.
However, the catalytic activity loss and DPM selectivity loss on
the TPP-poisoning Nano-Beta are much higher than those on
Micropore-poisoned one, indicating clearly that external
accessible acid sites out of micropores contribute much more in
the benzene alkylation by benzyl alcohol than acid sites located
in their intrinsic micropores. In regards to C-Beta, in addition to
the intrinsic micropores, there is an additional small mesopores of
3.2 nm with low quantity, meaning that there exist less external
acid sites in the catalyst. The micropore-poisoned C-Beta thus
shows a much higher catalytic conversion loss and DPM
selectivity loss than that of TPP-poisoned C-Beta (Figures S15c-
The highly improved catalytic performance is further
evidenced in the liquid-phase Friedel-Crafts (F-C) alkylation of
benzene with benzyl alcohol (Scheme S2). The F-C benzylation
of benzene can produce value-added diphenylmethane (DPM),
which is important intermediate product widely used in
pharmaceuticals, petrochemicals, fine chemicals, dyes and many
other chemicals. Hierarchically porous zeolites are the ideal liquid
phase reaction catalysts due to their structural superiorities.2 It
can be clearly seen that the catalytic conversion of benzyl alcohol
over C-Beta and Nano-Beta at a reaction temperature of 80 ℃
can only reach
a maximum value of 19.8% and 50.4%,
respectively (Figure 4c and Table S2), while OMMS-Beta(3) gives
much higher conversion of 85.2%, which is 4.0 and 1.7 times
higher than that of C-Beta and Nano-Beta, respectively. The initial
DPM selectivities over C-Beta and Nano-Beta are 72.4 % and
80.0 % and decrease to 61.2% and 72.4% after 120 h reaction,
respectively (Figure 4d). The highest selectivity value towards
DPM of 88.1% is observed for OMMS-Beta(3) (Figure 4d). More
importantly, such high DPM selectivity remains unchanged over
OMMS-Beta(3) during the long-term reaction for 120 h. The liquid-
phase catalytic reactions of bulky molecules mainly take place on
the external surface of microporous zeolites. Such remarkable
catalytic activity and long-term catalytic stability are mainly
ascribed to the abundant external surface acid sites and
8
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10.1002/anie.202007069
Angewandte Chemie International Edition
RESEARCH ARTICLE
S15d). All the above results suggest that the alkylation reactions
continue on the abundant external active sites even after the
internal sites are deactivated. The OMMS-Beta(3) has much
higher external surface acidity contributed from the intracrystalline
interconnected hierarchically porosity (Table S3). As a result,
OMMS-Beta(3) exhibits much higher catalytic conversion and
product selectivity in comparison with C-Beta and Nano-Beta. A
large amount of accessible external active sites and superior
diffusion performance give our hierarchically meso-macroporous
Beta single crystalline catalyst an extraordinary performance in
comparison with benchmark conventional microporous Beta and
zeolite Beta nanocrystals. All these results clearly demonstrate
that the micron-sized zeolite Beta single crystals with fully
interconnected intracrystalline porous hierarchy exhibit
extraordinary catalytic performance involving high catalytic
conversion, high product selectivity, long-term catalytic stability
and superior reusability in both gas-phase and liquid-phase
catalytic reactions involving bulky molecules, which will be
expected to be extended to other catalytic reactions.
extended to the successful synthesis of other zeolitic materials,
including ZSM-5, TS-1 and SAPO-34. Such novel zeolite single
crystals with excellent properties can be applied to many other
industrial catalytic reactions.
Acknowledgements
This work is supported by Program for Changjiang Scholars and
Innovative Research Team in University (IRT_15R52) of the
Chinese Ministry of Education. B. L. Su acknowledges the
Chinese Ministry of Education for
a “Changjiang Chaire
Professor” position. L. H. Chen acknowledges Hubei Provincial
Department of Education for the “Chutian Scholar” program. This
work is also financially supported by NSFC-21671155, NSFC-
U1663225, Major programs of technical innovation in Hubei
(2018AAA012) and Hubei Provincial Natural Science Foundation
(2018CFA054). We thank the 111 Projects (Grant No. B17020
and B20002) for supporting this work.
Keywords: Hierarchical zeolites • zeolite Beta single crystals•
intracrystalline porous hierarchy • cracking • alkylation
Conclusion
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In summary, the rare micron-sized Beta zeolite single crystals
with a highly ordered and fully interconnected intracrystalline
macro-meso-microporous hierarchy have been successfully
synthesized by an in-situ bottom-up confined crystallization
process. The highly ordered and fully interconnected
hierarchically porous structure provides more efficient mass-
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triisopropylbenzene (TIPB) and the liquid-phase Friedel-Crafts
alkylation of benzene with benzyl alcohol, respectively.
Unprecedentedly high deep cracking degree, high selectivity of
propylene and much lower coke formation in the cracking of bulky
1,3,5-TIPB can be achieved over OMMS-Beta(3). More
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endows OMMS-Beta(3) with outstanding (hydro)thermal stability,
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long-term stability and excellent reusability in bulky molecules
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activity after three reaction cycles in the liquid-phase Friedel-
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scale zeolite Beta single crystals with excellent stability can be
fully exploited in various catalytic reactions with high catalytic
activity, selectivity and reusability. Most importantly, our in-situ
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10.1002/anie.202007069
Angewandte Chemie International Edition
RESEARCH ARTICLE
An in-situ bottom-up confined zeolite crystallization strategy is developed to construct micron-sized hierarchically ordered macro-
mesoporous single-crystalline zeolite Beta with improved accessibility to active sites and outstanding (hydro)thermal stability for both
gas-phase and liquid-phase acid-catalyzed reactions of bulky molecules.
11
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