One methyl group makes a major difference: Shape-selective catalysis by zeolite nanoreactors in liquid-phase condensation reactions

Article abstract of DOI:10.1039/c7ta04187j

The precise sizes of zeolites' micropores can induce sharp shape/size-selectivity with precision of less than 1 ? in gas-phase reactions, e.g. methanol to olefin reactions (MTO). However, it is still a major challenge and an unachieved task in liquid-phas

Full text of DOI:10.1039/c7ta04187j

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Kun Chang, Zhaorong Chang et al.
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Table of Contents
Shape-selectivity with one-methyl-group-precision can be realized in Knoevenagel
condensation reactions on zeolite crystals encapsulating basic active sites.

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One Methyl Group Makes Major Difference: Shape‐Selective
Catalysis by Zeolite Nanoreactor in Liquid‐Phase Condensation
Reactions
Received 00th January 20xx,
Accepted 00th January 20xx
Chang Liu, Changyan Cao*, Jian Liu, Xiaoshi Wang, Yanan Zhu and Weiguo Song*
DOI: 10.1039/x0xx00000x
www.rsc.org/
The precise sizes of zeolites’ micropores can induce sharp shape/size‐selectivity with precisions less than 1 Å in gas‐phase
reactions, e.g. methanol to olefin reactions (MTO). However, it is still a major challenge and un‐achieved task in the liquid‐
phase reactions. In this study, we demonstrate that shape‐selectivity with one‐methyl‐group‐precision can be realized in
Knoevenagel condensation reactions on basic active sites encapsulated zeolite crystals. Furthermore, Pd nanoparticles can
also be introduced to the interior of hollow zeolite crystals, resulting in a multifunctional and shape‐selective catalyst in
one‐pot Knoevenagel condensation–hydrogenation cascade reaction.
Introduction
Besides, other porous materials, like poly‐dendrimers, MOF,
Zeolite is widely used in industry and research for its superior
stability, various acid sites and well‐defined pores1‐6
.
COF, were studied in size‐selective catalysis with their dense
microporous structures12,21‐24
However, most of these
.
Particularly, its well‐defined micropores can differentiate
molecules with precisions less than 1 Å 7, allowing it to be used
in size‐selective catalysis in the gas phase reactions. Their
uniform pores with sizes in the range of 4‐13 Å8 are efficient in
probing selectivity with substrates of comparable sizes9.
Size‐selective heterogeneous catalysts have been a long
time goal in catalysis10‐15. In 1965, Weitz et al selectively
hydrogenated n‐butanol at the presence of iso‐butanol
(difference in kinetic diameter less than 1Å) using acid zeolite
catalyst16. Nowadays, a straight forward and effective strategy
is to encapsulate metal nanoparticles in zeolite shell to form a
multi‐functional nanostructure. Xiao et al reported the direct
synthesis of the Pd@S‐1 complex in the presence of PVP
stabilized Pd nanoparticles which showed impressive furan
selectivity in the hydrogenation of biomass‐derived furfural17.
Li et al synthesized a series of Pd, Pt, Au nanoparticles inside
the silicalite‐1 to apply the size‐selective catalysis in gas phase
reactions18,19. Yu et al developed a synthetic protocol for
encapsulating ultrasmall Pd clusters within nanosized silicalite‐
1 zeolite under direct hydrothermal conditions using soluble
metal precursors20.
methods are restricted to metal nanoparticles, and the
reaction was restricted to hydrogenation reaction25. Moreover,
in the limited reports about size‐selectivity in liquid‐phase
reactions, usually only two extreme scenarios were studied:
very small substrate molecules that were fully converted and
very large molecules that were unable to be converted10,14,18
.
No subtle selectivity change among slightly different molecules,
such as one methylene or methyl group difference, was
reported. Thus, it’s particularly interesting to improve the
multifunctional catalyst and expand their application in more
reaction systems for size selective catalysis.
Knoevenagel condensation is of great significance in organic
chemistry, producing key products essential for anionic
polymerization and therapeutic drugs26. It is the condensation
of aldehydes and malonic esters with active methylene group
to form a new C‐C bond on basic sites. Weak bases like primary,
secondary, tertiary amine and ammonium salts under
homogeneous conditions have been traditional catalysts for
this reaction27‐29. However, the recovery of conventional base
catalysts is difficult and their utilization is associated with
environmental pollution. Besides, homogeneous catalysts
usually don’t possess shape selectivity30. Thus, microporous
zeolites with shape selectivity31, 32 and encapsulated polymer
with abundant ammine groups are ideal shape‐selective
catalyst for Knoevenagel condensation.
a. C. Liu, Dr. C. Cao, J. Liu, X. Wang, Y. Zhu, Prof. W. Song
Beijing National Laboratory for Molecular Sciences
Laboratory of Molecular Nanostructures and Nanotechnology
CAS Research/Education Center for Excellence in Molecular Sciences
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
E‐mail: cycao@iccas.ac.cn, wsong@iccas.ac.cn
Inspired by the hollow silicalite‐1 structure reported by Guo
group33‐35, we fabricate a hierarchically porous (microporous
shell and mesoporous core) nanoreactor with encapsulated
b. C. Liu, Dr. C. Cao, J. Liu, X. Wang, Y. Zhu, Prof. W. Song
University of Chinese Academy of Sciences, Beijing 100049 (China)
† Footnotes relaꢀng to the ꢀtle and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [supporting figures]. See
DOI: 10.1039/x0xx00000x
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basic polymer through the “ship‐in‐a‐bottle” method36‐38
Journal Name
.
slurry was stirred for 16 h at room temperature. TVhieewnArtthicele Osonllinide
DOI: 10.1039/C7TA04187J
Combined with the alkaline polymer nanoparticles, the catalyst was recovered by centrifugation, washed and dried in the
exhibits superior size‐selectivity with one‐methyl‐group‐ vacuum. The resulting mixture was treated with 0.5 M TPAOH
precision toward Knoevenagel condensation reactions. In each water solution in an autoclave at 160 ºC for 24 h to obtain a
－
case, a pronounced and subtle size‐selectivity effect consistent mesoporous core of the silicalite‐1. Excess TPA+ and OH was
with the pore dimensions was observed. Three groups of washed away to ensure purity of the material. Then the
reactions were observed with about 100% conversion, 50% material was put into the tube furnace at high temperature to
conversion and 0% conversion, respectively. And these results remove the template and denoted as HS‐1.
were explained by reactant or product shape‐selectivity.
Moreover, Pd nanoparticles can be introduced into the Synthesis of The Polymers
resultant and can be used in the hydrogenation of unsaturated
nitrile, showing excellent activity and shape selectivity in one‐
pot Knoevenagel condensation–hydrogenation multistep
cascade reaction.
CTC and EDA were mixed and heated at 90ºC for 9 hours. After
cooled down, they were put in the vacuum oven to remove
the rest liquid.
Synthesis of Pd nanoparticles loaded on Polymers inside
silicalite‐1 zeolite shell (denoted as Pd/PHS‐1)
Experimental
0.5 g PHS‐1 was mixed with 2.575 mL Na2PdCl4 aqueous
Synthesis of S‐1 zeolite
solution (0.0564 M) and stirred for 24 hours at RT. Then 70 mL
Parent silicalite‐1 zeolite was synthesized from the clear
solution method with some modifications using a starting
composition of 1 SiO2:0.27 TPAOH:46 H2O. 15 g TPAOH
aqueous solution (25 wt%), 48 mL H2O and 15.4 mL
tetraethoxysilane (TEOS) was mixed and stirred at room
temperature for 3 h to ensure complete TEOS hydrolysis to
form a clear solution. The gel was then crystallized in a 100‐mL
Teflon‐lined steel autoclave at 90 °C for 24 h. The product was
recovered and calcined to remove the template in static air at
823 K for 8 h and denoted as S‐1.
of 0.15 M sodiumformate solution was added and the mixture
stirred for 5 h. The solid was recovered by centrifugation and
washed with distilled water for three times. After dried in an
oven, Pd nanoparticles loaded on Polymers inside silicalite‐1
zeolite shell was obtained.
Condensation reaction test
The size‐selective catalysis was carried out in a glass reactor.
Typically, 50 mg catalysts, 0.5 mmol benzaldehyde, 1mmol
ethyl cyanoacetate and 10 mL methanol were put into a glass
reactor (total volume: 25 ml). The reactor was heated at 50 ºC.
Each hour the reaction sample was taken and analysed by GC‐
2010 Plus.
Synthesis of Polymers encapsulated in silicalite‐1 zeolite shell
(denoted as PHS‐1)
0.5 g silicalite‐1 was added into 15 mL of dichloromethane,
then the mixture was added with 0.773 mL 3‐
aminopropyltrimethoxysilane (APTMS), and the slurry was
stirred for 16 h at room temperature. Then the solid was
recovered by centrifugation, washed and dried in the vacuum.
The resulting mixture was treated with 0.5 M TPAOH water
Condensation‐hydrogenation reaction test
The size‐selective catalysis was carried out in a Teflon‐lined
stainless steel reactor. Typically, 50 mg catalysts, 0.5 mmol
cyclohexanone, 1mmol malononitrile and 10 mL methanol
were put into the reactor (total volume: 25 ml). The reactor
was sealed and purged with high‐purity H2 for three times
under stirring to replace the air. Then the reactor was sealed
and H2 pressure was adjusted to 1 MPa. The autoclave was
heated to 50 ºC and lasted for 1.5 hour. The reaction mixtures
were filtered to remove catalyst particles, then the liquid was
analyzed by GC (Shimadzu GC‐2010) equipped with an
ionization detector (FID) and an Rtx‐5capillary column (0.25
mm in diameter, 30 m in length). The product was qualitatively
determined by GC‐MS (Shimadzu GCMS‐QP2010S) with a HP‐
5MS capillary column (0.25 mm in diameter, 30 m in length).
solution in an autoclave at 160
ºC for 24 h to obtain a
－
mesoporous core of the silicalite‐1. Excess TPA+ and OH was
washed away to ensure purity of the material. Then the
material was put into the tube furnace at 823 K for 8 h to
remove the template. The obtained powder was mixed with
3.46 g carbon tetrachloride (CTC) and 1.56 g ethylenediamine
(EDA). They were heated at 90ºC for 9 hours. After cooled
down, it was washed with distilled water and ethanol ten
times to make sure all the polymers attached to the outside of
the zeolite was removed. After drying in a vacuum oven,
polymers encapsulated in silicalite‐1 zeolite shell was obtained.
Characterization
Synthesis of Hierarchical mesoporous silicalite‐1 nanospheres
with different sized‐mesopores (denoted as HS‐1 (APTMS
Concentration))
Scanning electron microscopy (SEM) images were obtained on
a JEOL‐6701F scanning electron microscope at 10.0 kV.
Transmission electron microscopy (TEM) was carried out on a
JEOL 2100F electron microscope operated at 200 kV. The XRD
measurements were carried out in Shimadzu XRD‐7000
diffractometer equipped with Cu Kα radiation (wavelengths λ =
0.5 g silicalite‐1 was added into 15 mL of dichloromethane,
then the mixture was added with 0.515 mL, 0.644 mL, 0.773
mL 3‐aminopropyltrimethoxysilane (APTMS), for HS‐1 (0.164
M), HS‐1 (0.205 M), HS‐1 (0.246 M), respectively, and the
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0.154 nm). The hydrogenation products were measured using of reactant, intermediates and product shape selectivity, while
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DOI: 10.1039/C7TA04187J
Shimadzu GC‐2010 Plus (Rtx‐5). Nitrogen adsorption‐ the encapsulated polymer is the base catalyst.
desorption isotherms was obtained on Quantachrome
Transmission electron microscopic (TEM) images of PHS‐1
Autosorb AS‐1. Elemental analysis was obtained on Flash EA are presented in Fig. 1. These images revealed that mesopores
1112. X‐ray photoelectron spectroscopy was obtained on VG distributed inside the zeolites were uniform, indicating
ESCA Lab 220i‐XL equipped with Mg/Al ultra‐high vacuum X‐ successful construction of mesoporous structure in the interior
ray binode‐system. Thermogravimetric (TG) analysis was of S‐1 zeolite single crystal. This alkaline‐treated zeolite with
conducted on
a SHIMADZU DTG‐60 thermogravimetric abundant intra crystalline pores was an excellent platform for
analyzer. Temperature‐programmed desorption (TPD) encapsulation of polymer nanoparticles. The embedded
experiments were carried out on a Micromeritics Auto Chem II mesopores have a narrow size distribution in the range of
2920 type instrument. Fourier transform infrared spectrum 3.5−4.3 nm as esꢀmated from the TEM images (Fig. 1a and Fig.
was performed on a TENSOR‐27 type infrared spectrometer.
S1f). SEM images of PHS‐1 demonstrated that the zeolite shell
was intact (Fig. S2). Elemental mapping images (Fig. 1c‐1f)
showed that the polymer nanoparticles (mainly from element
N and Cl) were evenly dispersed within the hierarchical porous
nanospheres.
Results and discussion
Scheme 1 Synthesis route of polymer nanoparticles encapsulated in silicalite‐1 zeolite
shell (PHS−1).
The synthesis route of polymer nanoparticles encapsulated
in hierarchical silicalite‐1 zeolite shell (denoted as PHS−1)
mainly includes three steps (Scheme 1). First, silicalite‐1 was
modified
with
ammine
group
using
3‐
aminopropyltrimethoxysilane (APTMS). Then, with the
protection of amino propyl group, interior mesopores were
successfully generated by controlled silicon leaching under
tetrapropylammonium hydroxide (TPAOH) treatment at 160 °C.
Fig. S1 presented the TEM images of the hierarchical silicalite‐1
zeolites (denoted as HS−1). When the concentration of APTMS
used in the modifying procedure increased from 0.164 M to
0.246 M, the size of the mesopore decreased, along with the
more even distribution of the mesopores (Fig. S1a‐1c). A large
hollow void is created in the interior of the silicalite‐1 without
APTMS treatment (Fig. S1d). These results demonstrated the
role of amino propyl groups in the alkaline treatment
procedure. With amino propyl groups evenly distributed in the
zeolite, mesopores were formed inside the zeolite while the
shell was intact and retained the microstructure of silicalite‐1
after TPAOH etching. Finally, the composite was mixed with
carbon tetrachloride (CTC) and ethylenediamine (EDA), and
heated at 90 °C, encapsulating polymer nanoparticles into the
interior mesopores. Since CTC and EDA molecules were small
enough to diffuse in and out of the micropores, they formed
polymer nanoparticles in the zeolite core. Meanwhile, the
polymer nanoparticles were sufficiently large to stay inside the
zeolite. The retained micropores of the zeolite wall is the origin
Fig. 1 (a) Bright field TEM image of PHS‐1; (b) Dark field TEM image of PHS‐1; (c) Si Kα1,
(d) O Kα1, (e) N Kα1 and (f) Cl Kα1 EDS elemental mappings of PHS−1.
The crystallinity and phase composition of the materials
were characterized using wide‐angle X‐ray diffraction (WAXRD).
As shown in Fig. 2a, the XRD pattern of PHS‐1 matched well
with those of S‐1 and HS‐1, which illustrated PHS‐1 still
maintained its original crystal structure after alkali treatment
and polymer encapsulaꢀon. The porosity of the core−shell
catalyst
adsorpꢀon−desorpꢀon isotherms, as shown in Fig. 2b. The
sample displayed type IV isotherm, confirming the
was
further
confirmed
by
Nitrogen
a
mesoporous structure of PHS‐1. The Brunauer−Emmeꢁ−Teller
(BET) surface area and pore volume were calculated to be
267.4 m2∙g−1 and 0.30 cm3∙g−1, respectively, which was
apparently lower than that of S‐1 and HS‐1. The Nitrogen
adsorption‐desorption isotherms of S‐1 and HS‐1 was shown in
Fig. S3. The decrease of BET surface area and pore volume was
attributed to the presence of dense cross‐linked polymers that
occupied the inner mesopores. From the pore size analysis
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Table 1 Knoevenagel condensation reaction sequences towards different substrates
(inset of Fig. 3b), the PHS‐1 had a rather narrow pore size
distribution centred at 3.7 nm.
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DOI: 10.1039/C7TA04187J
The FTIR spectrum of PHS‐1 contained the characteristic
peaks of S‐1 (Fig. 2c). The band at 1085 cm−1 and 804 cm−1 can
be assigned to the Si–O–Si asymmetric and symmetric
stretching vibrations, respectively. Besides, the appearance of
absorption bands at 3400 cm−1 corroborated with Si‐OH
stretching and bending vibrations on the surface of the zeolite.
The internal and external asymmetric stretching modes of
vibrations were also observed at 1105 cm−1 and 1230 cm−1,
respectively. For the polymers, the band at around 3400 cm−1,
2920 cm−1, 1110 cm−1 was attributed to amine groups (–NH–)39,
alkyl groups (–CH2–)40 and C–N groups41, respectively. Above
results indicated that the polymer nanoparticles were
encapsulated in the interior of zeolites.
Fig. 2 (a) XRD patterns of S‐1, HS‐1 and PHS‐1; (b) Nitrogen adsorption‐desorption
isotherms of PHS‐1; (c) FTIR spectrums of PHS‐1 and the pure polymer; (d) Carbon
dioxide TPD spectra of PHS‐1.
Reaction conditions: Aldehyde (A) (0.5 mmol), Nitrile (B) (1 mmol), MeOH (10 mL),
catalyst (50 mg). 50 ºC. Conversion and yield were determined by GC analysis using
para‐xylene as internal standard. The conversion is all based on Aldehyde (A).
Temperature‐programmed desorption with CO2 (CO2‐TPD)
as probe molecule was conducted to test the basicity of the
catalyst. CO2 desorption bands were observed between 230 °C
and 300 °C for PHS‐1 (Fig. 2d). Typically, the desorption
temperature is an indication of the basic site strength, and
higher desorption temperature suggests stronger basicity.
Therefore, PHS‐1 exhibited very high basicity when comparing
with other amines functionalized catalysts, which was in
agreement with the total amounts of adsorbed CO2 (Fig. S4a).
Thermogravimetric analysis (Fig. S4b) showed that there was
about 14% weight loss from 100 °C to 700 °C for PHS‐1,
indicating its stability in liquid‐phase reactions.
In order to investigate the size‐selectivity of PHS‐1,
Knoevenagel condensation reaction was chosen due to the
basicity of the encapsulated polymer. Meanwhile, the pure
polymer was also used for comparison. Eight substrates were
tested (Table 1) and they were classified into three groups
according to their different conversions (Fig. S5a). In the first
group, complete conversions and nearly 100 % yields were
obtained in a few hours when Benzaldehyde (0.43×0.60 nm) or
p‐tolualdehyde (0.43×0.68 nm) reacted with ethyl
cyanoacetate (0.47×0.65 nm) (Table 1, entries 1‐3 and Fig. S5b).
In the second group, the conversion of phenylacetaldehyde
(0.43×0.72 nm) or isopropyl 2‐cyanoacetate (0.47×0.61 nm)
only reached up to 54 % conversion no matter how long the
reaction lasted (Table 1, entries 4‐5 and Fig. S5c). In the third
group, for 2‐fenyl‐1‐propanal (0.44×0.73 nm), ethyl
cyanoacetate (0.47×0.65 nm) and isopropyl 2‐cyanoacetate
(0.47×0.61 nm), which were all smaller than micropores, less
than 3% conversion was observed after 3 hours (Table 1,
entries 6‐7 and Fig. S5d). In addition and as expected,
diphenylacetaldehyde (0.96×0.73 nm) reacted very little
because its size is larger than the zeolite micropores (Table 1,
entry 8 and Fig. S5d). The little conversions in entries 6‐8 were
probably attributed to the residue basic sites on the outer
surface of S‐1. For comparison, all above reactions reached
100 % conversion within 1 h on pure polymer catalyst, proving
that the basicity of the polymer was high enough for the
condensation reactions listed above. The diffusion barrier
imposed by the zeolite micropore was accounted for the
observed reactivity difference.
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The size‐selectivity performance of PHS‐1 catalyst could be hydrogenation product detected. Such result was expected as
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DOI: 10.1039/C7TA04187J
directly attributed to the molecular sieving characteristics of no Knoevenagel condensation reaction occurred between
silicalite‐1. Because the size of silicalite‐1 micropores these two molecules.
(0.53×0.56 nm) is larger than that of benzaldehyde (0.43×0.60
nm), p‐tolualdehyde (0.43×0.68 nm), ethyl cyanoacetate
(0.47×0.65 nm) and isopropyl 2‐cyanoacetate (0.47×0.61 nm),
Conclusions
the mass transfer of them in liquid‐phase solution was facile,
and 100 % conversion was reached within hours. However,
subtle reaction rate difference was observed. In the first group,
the reaction rates reduced distinctly when the size of the
reactant molecules enlarged slightly by adding a methyl group
to benzene ring or to the ester (Fig. S5b). It illustrated that the
size‐selectivity of the catalyst was quite sensitive as to
recognize one carbon difference on the molecule chain.
In the second group (Fig. S5c), the reaction was slower and
the conversion reached a plateau at about 54% conversion. A
possible reason for the 54% conversion was that reactant,
intermediate or product molecules were adsorbed on the
surface of micropores, leading to the block of the pores. Thus,
no reactants could approach the polymer, no intermediates
could form and no products could transport from the zeolites.
It was very interesting that phenylacetaldehyde only had one
more methylene group than phenylacetaldehyde, which was in
the first group, and there was significant conversion difference
(Table 1, entry 1 & 4).
In the third group (Fig. S5d), though 2‐fenyl‐1‐propanal
could move in and out of the micropores with ease, there was
no product detected. The main reason was that the product
molecules were too large to diffuse out of the micropores,
showing an example of product shape selectivity. In addition,
the minimum size of diphenylacetaldehyde (0.96×0.73 nm)
was significantly larger than that of silicalite‐1 micropores, it
was unable to diffuse through the shell and enter the cavity to
reach active sites of polymer nanoparticles. Thus, no
conversion was observed.
These results also confirmed that nearly all polymer
nanoparticles were located inside the zeolite, and all
composite catalyst had integral structure (no broken zeolite).
The micropores not only differentiate the size of the reactant
molecules, but also the product molecules. The results
demonstrated that the shape‐selective catalysis for different
size of reactant molecules could be adjusted effectively by the
micropore in the shell of PHS‐1.
Moreover, Pd nanoparticles can be introduced into the PHS‐
1 (denoted as Pd/PHS‐1). The synthesis route is shown in
Scheme S1. Transmission electron microscopic (TEM) images
of Pd/PHS‐1 are presented in Fig. S6, which showed that the
ultra‐small Pd nanoparticles were evenly distributed inside the
zeolite, owing to the binding of the Pd nanoparticles to the
amine groups at the surface of the polymer. XRD pattern of
Pd/PHS‐1 matched well with those of S‐1 and PHS‐1 (Fig. S7b).
The obtained Pd/PHS‐1 can be used in one‐pot Knoevenagel
condensation–hydrogenation multistep cascade reaction.
Cyclohexanone and Malononitrile were converted to
Cyclohexanemalononitrile in 1.5 h, affording excellent activity.
However, for 2‐phenyl‐1‐propanal and ethyl cyanoacetate,
diphenylacetaldehyde and malononitrile, there was no
We produced a multifunctional catalyst by combining the
hierarchically porous (microporous shell and mesoporous core)
zeolite with basic polymer nanoparticles. The catalyst
exhibited superior size‐selectivity with one‐methyl‐group‐
precision towards Knoevenagel condensation reactions.
Because of the micropores on the zeolite shell, it not only
differentiates the size of the reactant molecules, but also the
product molecules, leading to a three distinct groups of
reactions. Furthermore, Pd nanoparticles can be introduced
into the resultant, generating it as a multifunctional and
shape‐selective
catalyst
for
one‐pot
Knoevenagel
condensation–hydrogenation cascade reaction. This structure
will be a useful platform for fabricating more stable,
multifunctional, and recyclable and green catalysts applied in
shape/size‐selective reactions and one‐pot cascade reactions.
Acknowledgements
We thank the financial supports from the National Natural
Science Foundation of China (NSFC 21333009, 21273244,
21573245), Chinese Academy of Sciences‐Peking University
Pioneer Cooperation Team and the Youth Innovation
Promotion Association of CAS (2017049).
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