Pd Nanoparticles Encapsulated in FER Zeolite through a Layer Reassembling Strategy as Shape-selective Hydrogenation Catalyst

Article abstract of DOI:10.1002/cctc.201800040

Noble metal nanoparticles (NPs) encapsulated in zeolites bearing distinct shape-selective properties at molecular level expand their new applications in catalysis. Here we report a synthesis strategy for the encapsulation of Pd NPs inside FER zeolite via a layer reassembling process. Pd precursors were introduced by swelling FER layers in RUB-36 through the surfactant cetyltrimethylammonium cations (CTA⁺) and then an ion-exchange process at ambient temperature. Pd@FER was formed with a uniform diameter distribution of Pd NPs at about 1.4 nm during the topotactic transformation from layered zeolite precursors to 3-dimensional zeolites followed by calcination. The as-prepared Pd@FER catalyst exhibits distinct shape-selective properties in hydrogenation reactions. It has relatively lower activity for 1-hexene and almost no activity for 1-phenyl-1-cyclohexene compared with Pd/RUB-37 catalyst prepared via wet impregnation due to the restrictions of channels in the FER zeolite. On the contrary, Pd@FER shows very high hydrogenation activity for benzaldehyde and very low activity for diphenylmethanone hydrogenation, while Pd/RUB-37 exhibits high hydrogenation activity for both benzaldehyde and diphenylmethanone. This synthesis strategy may be extended to other noble metals or two-dimensional layered zeolite systems for size-selective hydrogenation reactions.

Full text of DOI:10.1002/cctc.201800040

Accepted Article
Title: Pd Nanoparticles Encapsulated in FER Zeolite through Layer
Reassembling Strategy as the Shape-selective Hydrogenation
Catalyst
Authors: Zhenchao Zhao, Yanlu Li, Mathias Feyen, Robert McGuire,
Ulrich Müller, and Weiping Zhang
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To be cited as: ChemCatChem 10.1002/cctc.201800040
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10.1002/cctc.201800040
ChemCatChem
Pd Nanoparticles Encapsulated in FER Zeolite through Layer
Reassembling Strategy as the Shape-selective Hydrogenation Catalyst
Zhenchao Zhao,[a] Yanlu Li,[a] Mathias Feyen,[b] Robert McGuire,[b] Ulrich Müller,*[b] and
Weiping Zhang*[a]
[a]
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of
Technology, Dalian 116024, China
[b]
BASF SE, Process Research and Chemical Engineering, 67056 Ludwigshafen, Germany
*Corresponding authors. E-mail:ulrich.mueller@basf.com (U. Müller), wpzhang@dlut.edu.cn (W. Zhang)
Abstract: Noble metal nanoparticles (NPs) encapsulated in zeolites bearing distinct
shape-selective properties at molecular level expand their new applications in catalysis. Here
we report a synthesis strategy for the encapsulation of Pd NPs inside FER zeolite via alayer
reassembling process. Pd precursors were introduced by swelling FER layers in RUB-36
through the surfactant cetyltrimethylammonium cations (CTA+) and then the ion-exchange
process at ambient temperature. Pd@FER was formed with a uniform diameter distribution
of Pd NPs at about 1.4 nm during the topotactic transformation from layered zeolite
precursors to 3-dimensional zeolites followed by calcination. The as-prepared Pd@FER
catalyst exhibits distinct shape-selective properties in hydrogenation reactions. It has
relatively lower activity for 1-hexene and almost no activity for 1-phenyl-1-cyclohexene
compared with Pd/RUB-37 catalyst prepared via wet impregnation due to the restrictions of
channels in FER zeolite. On the contrary, Pd@FER shows very high hydrogenation activity
for benzaldehyde and very low activity for diphenylmethanone hydrogenation, while
Pd/RUB-37 exhibits high hydrogenation activity for both benzaldehyde and
diphenylmethanone. This synthesis strategy may be extended in other noble metals or
two-dimensional layered zeolite systems for size-selective hydrogenation reactions.
Keywords: Pd nanoparticles; FER zeolite; Layered zeolite; Layer reassembly;
Shape-selective hydrogenation catalyst
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1. Introduction
Metal nanoparticles (NPs) in zeolites are very intriguing catalysts as their distinct
selectivity and activity for various types of catalytic reactions.[1] Therefore, a variety of
approaches have been developed to prepare the metal NPs in zeolites. For large-pore zeolites
with 12-membered ring (MR) structures such as FAU, MOR, LTL, BEA, AFI, etc.,
encapsulation of metal NPs in the cages or channels has been generally achieved by
introducing metal precursors after zeolite crystallization using ion-exchange, impregnation,
or chemical vapor deposition.[1a, 2] For smaller-pore zeolites with 10 or 8-MR structures,
above mentioned methods are not so efficient as the smaller apertures. This problem has
been well addressed by introducing metal precursors or NPs during zeolite crystallization
process, and the metal precursors or NPs were embedded in the zeolite crystals during their
crystallization.[1b, 3] Metal NPs such as Ni, Au, Ag, Pt, Pd, Ru, and Rh were introduced in
MFI, SOD, BEA, FAU zeolites using metal complex or synthesized NPs during
crystallization of zeolite.[1b, 3a-e, 4] Although so many elegant methods have been developed,
the efficient introduction of metal NPs is still challenging. Charge densities, pore sizes of
zeolites and stability/size of the metal precursor have great impacts on the efficiency of
encapsulation. For ion-exchange method, the amount of metal introduced in zeolite matrix is
strongly dependent on the Si/Al ratios, which determines the available ion-exchange sites.
Whereas, introduction of metal precursors during the hydrothermal synthesis of zeolite
requires the metal precursors has high hydrothermal stability under alkaline condition.
Moreover, most of above investigations are focused on the 3-dimensional framework
zeolites. Some zeolites such as MCM-22, Ferrierite, Sodalite, RUB-24, CDS-1(RUB-37),
RUB-41, etc. can be obtained from their layered precursors (LPS) MCM-22P, PREFER,
RUB-15, RUB-18, PLS-1(RUB-36), RUB-39, respectively.[5] These LPS with flexible layer
distance, which may be very good candidates for the introduction of the guest metal
precursors/NPs.[6] The expansion of layer distance makes the layers accessible for most
metal precursors and even metal NPs. Very recently, subnanometric Pt clusters with 0.11 wt%
loading were prepared using dimethyl formamide (DMF) as a weak reduction and capping
agent during transformation of a 2D zeolite into 3D high silica MCM-22 zeolite.[7] Previous
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10.1002/cctc.201800040
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investigations of ours[8] and other groups[9] demonstrate that the layered structure in LPS can
be well preserved during the layer swelling and deswelling processes at room temperature,
and after calcination the 3-dimensional zeolite structure maintains. In swollen LPS, a large
amount of positively charged swelling agents balanced by negatively charged SiO- groups
provides very rich ion-exchange sites.[8, 10] Herein, we report a new synthesis strategy for
FER zeolite encapsulating Pd NPs via a layer reassembling process with Pd precursors
introduced at ambient temperature, which are proved to be very effective catalysts for the
size-selective hydrogenation reactions.
2. Results and Discussion
2.1 Our synthesis strategy
-
+
-
+
-
+
-
+
-
+
-
+
-
+
Sw ellin g
CTAOH
+
+
+
-
-
-
+
+
+
+
-
-
-
-
RUB-36
Io n Exchang e
Pd(en)2+
+
CTA
2
++
++
C alcin atio n
Reduction
-
-
-
-
-
DEDM A
Pd@ FER
+
CTA
++
Pd(en)2
+
2
Scheme 1. Illustration showing encapsulation of Pd NPs in FER zeolite through layer reassembling
strategy.
Scheme 1 illustrates the encapsulation process of Pd NPs in FER zeolite through layer
reassembling strategy. Firstly, RUB-36 was swollen into RUB-36SW composed by
negatively charged FER layers (SiO-) and positively charged cetyltrimethylammonium
cations(CTA+), and the original organic template diethyldimethyl ammonium (DEDMA) was
excluded. Then palladium precursor (Diethylenediamine palladium(II) acetate, Pd(en)2(Ac)2)
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10.1002/cctc.201800040
ChemCatChem
2+
was introduced via ion-exchange of CTA+ with Pd(en)2 in an ethanol solution at ambient
temperature. Simultaneously, the distances between FER layers recover due to removal of
2+
most long chain CTA+ with smaller Pd(en)2 . After washing in deionized water, most
Pd(en)22+ outside of FER layer aggregate were removed due to regeneration of silanol groups
under the neutral pH conditions. Finally, the formation of metal NPs and condensation of
silanol groups between the adjacent FER layers was accomplished via 500 °C calcination
and 350 °C reduction processes.
2.2 XRD and 13C NMR characterizations
(d)
(c)
(b)
(a)
10
20
30
40
50
2
4
2(degrees)
Figure 1. XRD patterns of (a) RUB-36; (b) swollen RUB-36; (c) deswelling material obtained by ion
exchange with Pd(en)22+ and En-HAc; (d) Pd@FER obtained after calcination and H2 reduction.
The encapsulating process of Pd NPs in FER zeolite was followed by the XRD patterns
as shown in Figure 1.Firstly, the distances between FER layers in RUB-36 were expanded
from 11.2 Å (2= 7.9º) to 29.4 Å (2= 3.0º) after swelling (Figure 1a-b). This distance
2+
2+
offering enough space allows Pd(en)2 to access to the FER layers. When Pd(en)2 was
introduced (Figure 1c) in the presence of ethylenediamine-acetic acid (En-HAc), the
low-angle diffractions of 2= 3.0º(100) and 2= 5.9º(200) diminish, and a new broad peak
near 2 = 9.0˚ appears, corresponding to FER layer distance of 9.7 Å. This is similar to our
previously reported deswelling process using dilute acidic solution to exclude CTA+.[8] Over
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10.1002/cctc.201800040
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calcination in air and reduction with hydrogen, the obtained Pd@FER (Figure 1d) has the
same diffraction pattern as FER zeolite with very good crystallinity.[11] Moreover, the
absence of the diffractions of Pd metal crystals near 40° and 46° means that PdNPs are
ultrafine without significant aggregated bulk ones. ICP-AES analysis shows that the Pd
loading is 1.4 wt%.
2
1
C3-17
N
1
3-17
1
C1
2+
Pd(en)2
Cb
Cc
C2
(d)
(c)
(b)
(a)
2+
Pd(en)2
90
80
70
60
50
40
ppm
30
20
10
0
-10
Figure 2. Solution 13C NMR spectra of (a) ethylenediamine-acetic acid (En-HAc) solution in ethanol; (b)
Pd(en)2(Ac)2 and En solution in ethanol. 13C CP/MAS NMR spectra of RUB-36SW (c) and deswelling
material obtained by ion exchange with Pd(en)22+ (d) .
As very rich amount of terminalsilanol groups on the surface of each FER layer, the
amount of Pd loadings could reach very high up to 13 wt%. It should be pointed out that a
certain amount of En-HAc solution should be co-added with Pd(en)22+ to obtain FER zeolite
2+
with high crystallinity. Even though Pd(en)2 can deswell RUB-36SW without En-HAc
(Supporting Information, Figure S1a), too much amount of Pd may hinder the ordered
condensation of silanol groups between the FER layers (Supporting Information, Figure
S1b). 13C CP/MAS NMR spectrum (Figure2c) of RUB-36SW indicates the signals are
attributed to CTA+. After deswelling, the remaining signals are still from the residual CTA+
(Figure 2d), which may also act as the structure-directing agent for the ordered stacking of
FER layers. Meanwhile, two new signals near 40 and 46 ppm are observed. According to the
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solution 13C NMR specra in Figures 2a-b, these signals can be assigned to pronated
[12]
ethylenediamine and Pd2+(en)2. It means that Pd precursors were successfully introduced
between the FER layers. The minor remaining signals of DEDMA may result from very
small amount of incompletely swollen RUB-36, which could be observed in XRD patterns
(Figures 1b-c).
2.3 Nanostructure and Morphology Analysis
a)
b)
Figure 3. SEM images of Pd@FER (a) and Pd/RUB-37 (b).
SEM images in Figure3 demonstrate that Pd@FER has the typical flake morphologies
similar to Pd/RUB-37 which was prepared by the incipient wetness impregnation using
calcined RUB-36 i.e. RUB-37 as the support with 0.9 wt% Pd loading. It’s worth noting that
some debris on the FER zeolite (Figure 3a) may result from disaggregation of amorphous
silica aggregate from RUB-36 during the alkaline swelling process.TEM and STEM images
(Figure 4a-c) indicate ultrafine and well dispersed Pd NPs with an average particle size of
1.4 nm intensively distributed in the zeolite support, and only very minor bulk ones near the
edge of zeolite sheet for Pd@FER (Figure 4a, red marks), which is reasonable due to the
migration of Pd atoms between FER layers and further sintering near the edges during high
temperature calcination. In comparison, Pd/RUB-37 (Figure 4e-g) shows Pd NPs with
relatively broad size distributions dispersed on the supports with an average particle size of
4.2 nm. It’s worth noting that the 1.4 nm size of Pd NPs embedded in FER zeolite is actually
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much larger than the pore diameters of 5.4 × 4.2 Å and the side-cages ( about 7 Å).[13] It can
be explained by the fact that both the formation of 3D zeolite and Pd NPs occurrs during the
calcination process, and once Pd NPs are formed larger than the pore size before the ordered
condensation of silanol groups, the defects may be created. This is further confirmed by 29Si
MAS NMR spectrum of Pd@FER which shows significant amount of SiOH groups
2+
remaining on the support (Figure S2). It’s also the case when too much Pd(en)2 was
introduced between the FER layers, the ordered FER structure could not be obtained
(Supporting Information, Figure S1). In comparison with Pd/RUB-37, even though the same
metal precursor Pd(en)2(Ac)2 was used, the homogeneous distribution of Pd NPs with
extremely high density within FER zeolite without significant sintering may result from its
distinctive two-dimensional structure. Pd precursors or NPs are separated by the FER layers
with no micropores, which hinders the particle sintering among different layers, and
therefore enhance the thermal stability of Pd NPs.[14] N2 adsorption/desorption isotherm of
Pd@FER shows a typical Langmuir-type adsorption (Figure S3), indicating the presence of
uniform micropores with a Brunauer-Emmett-Teller (BET) surface area of 325 m2/g, which
is close to that of 340 m2/g for FER zeolite obtained by the similar topotactic conversion
process.[8]
a)
c)
d)
d)
30
b)
dTEM=1.4 nm
20
10
0
0.5
1.0
1.5
2.0
2.5
3.0
Particle size (nm)
e)
f)
c
g)
h)
20
15
10
5
dTEM=4.2 nm
0
2
4
6
8
10
12
14
Particle size (nm)
Figure 4. TEM (a,b,e,f), STEM (c,g) images and corresponding particle size distributions of Pd@FER
(a,b,c,d) and Pd/RUB-37 (e,f,g,h) obtained after calcination and H2 reduction.
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X-ray photoelectron spectroscopy (XPS) was also used to study the chemical state of Pd
NPs with the spetra shown in Figure 5. Both samples show metallic Pd with 3d binding
[15]
energies (BE) near 340.3 and 335.0 eV, respectively.
The signal intensity of Pd/RUB-37
is significantly stronger than that of Pd@FER, which is in accordance with the fact that most
of Pd NPs are embeded between FER layers in FER zeolite while most of Pd NPs are located
on the surface of RUB-37 zeolite.
Pd 3d5/2
Pd 3d3/2
(b)
(a)
346
344
342
340
338
336
334
332
330
Binding Energy (eV)
Figure 5. XPS spectra of Pd@FER (a) and Pd/RUB-37 (b).
2.4 Catalytic Hydrogenation Performances
(a)
(b)
100
n-hexane (Pd/RUB-37)
2-hexene (Pd/RUB-37)
80
1-hexene:
Pd@FER
Pd/RUB-37
80
60
40
20
0
60
40
20
0
1-phenyl-1-cyclohexene:
Pd@FER
Pd/RUB-37
n-hexane (Pd@FER)
2-hexene (Pd@FER)
0
20
40
60
80
100
120
8
0
20
40
60
80
100
120
Time / min
Time/min
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Figure 6. Hydrogenation activities of 1-hexene and 1-phenyl-1-cyclohexene (a), and time on stream
product distributions for 1-hexene hydrogenation (b) over Pd@ZSM-35 and Pd/RUB-37 catalysts.
To further verify the successful encapsulation of Pd NPs in FER zeolite, model
hydrogenation reaction of 1-hexene (4.3 Å), and 1-phenyl-1-cyclohexene with different
steric hindrance were conducted. The reaction kinetic profiles of the olefin substrates and the
product distributions are shown in Figure 6. As FER zeolite has apore size of 5.4 × 4.2 Å,
1-hexene has amolecular size close to the pore apertures shows relatively lower reaction rate
for Pd@FER catalyst, and the 100% conversion of 1-hexene takes about 80 min(Figure 6a).
Whereas, 100% conversion reaches for Pd/RUB-37 within 30 min. When
1-phenyl-1-cycohexene with much larger steric hindrance is used as substrate, there is
almost no conversion for Pd@FER catalyst, while 30% 1-phenyl-1-cycohexene conversion
is obtained for Pd/RUB-37 catalyst. It is worth noting that for 1-hexene hydrogentaion
reaction, there is appreciable amount of isomerization product,2-hexene, for both catalysts
(Figure 6b), and further transformation of 2-hexene is again significant slower for Pd@FER
due to the steric hindrance.
Moreover, the selective C=O hydrogenation for benzaldehyde and diphenylmethanone
were also tested and the reaction kinetic curves and the product distributions are shown in
Figure 7. Pd@FER shows high hydrogenation activity for benzaldehyde, and the conversion
of benzaldehyde reaches 100% within 100 min. While Pd/RUB-37 shows lower
benzaldehyde conversion, it reaches about90% within 120 min (Figure 7a). Moreover, after
reaction for 120 min Pd/RUB-37 catalyst has significant amount of intermediate
hydrogenation product, benzylalcohol, and only 66% toluene yield is achieved (Figure 7b).
Whilefor Pd@FER catalyst 100% toluene yield is obtained.On the contrary, for the much
larger diphenylmethanone, Pd/RUB-37 show very high activity, and after 60 min
diphenylmethanone is 100% transformed into diphenylmethane. No more than 10% of
diphenylmethanoneis transformed after 120 min for Pd@FER due to the steric hindrance.
Thislowdiphenylmethanone conversion may result from theminor bulk Pd NPs near the edge
of the zeolite sheet (Figure 4a). All these results unambiguously demonstrate the
shape-dependentselectivity of Pd@FER for hydrogenation reactions, and confirm the
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successful encapsulation of most Pd NPs inside FER zeolite.
b)
a)
Benzadehyde hydrogenation
Pd@FER
100
100
80
60
40
20
0
Toluene (Pd/RUB-37)
Benzyl alcohol (Pd/RUB-37)
Pd/RUB-37
80
60
40
20
0
Toluene (Pd@FER)
Benzyl alcohol (Pd@FER)
Benzophenone hydrogenation
Pd@FER
Pd/RUB-37
0
20
40
60
80
100
120
0
20
40
60
Time/min
80
100
120
Time/min
Figure 7. Hydrogenation activities of benzaldehyde and diphenylmethanone (a), and time on stream
product distributions for benzaldehyde hydrogenation (b) over Pd@ZSM-35 and Pd/RUB-37 catalysts.
3. Conclusions
Pd@FER catalyst is successfully constructed via a new layer reassembling strategy. FER
layers in RUB-36 were expaned via cetyltrimethylammonium cations (CTA+) swelling.
2+
Subsequently, CTA+ was exchanged by Pd(en)2 , and Pd(en)22+ was enclosed between FER
layers. Pd NPs were embeded in FER zeolite during calcination when ordered condensation
of silanol groups occurred between adjacent FER layers. Pd@FER was formed during the
topotactic transformation from layered zeolite precursors to 3-dimensional zeolites during
calcination. The as-synthesized Pd@FER shows excellent shape-selectivity in the
hydrogenation of olefins, benzaldehyde and diphenylmethanone with different molecular
sizes or steric hindrance due to its unique nanostructure and microporosity. Our synthetic
strategy expands the scope of on-demand controlling the selectivity of metal nanoparticles
by using two dimensional layered zeolite precursors with open structure.
Experimental Section
Sample preparation
The layered silicate RUB-36 was prepared similarly to our previous procedures using
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10.1002/cctc.201800040
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diethyldimethylammonium hydroxide as the structure-directing agent (DEDMAOH, 20 wt%
solution in water, Sachem Inc.).[8, 16] In general, it was crystallized from the gel with a
composition of SiO2 : 0.5 SDA : 10 H2O. Aerosil 200 was utilized as the silica source.
Crystallization was carried out in an autoclave without stirring for 14 days. The resultant
product was filtered, washed with deionized water and dried at 100 C.
Preparation of diethylenediamine palladium (II) acetate solution (Pd(en)2(Ac)2) and
ethylenediamineacetic acid solution (en-HAc): 0.3 g palladium acetate (Aladdin Reagent)
was dispersed into 9 ml ethanol containing 0.5 g ethylenediamine (Tianjin Bodi Chemical
Co., Ltd.). After sonification for 10 min, a clear ethanol solution of Pd(en)2(Ac)2 was
obtained. 1.0 g acetic acid (Tianjin Fuyu Fine Chemical Co., Ltd.) was dissolved into 9.0 ml
ethanol containing 1.0 g ethylenediamine and 0.6 g deionized H2O to get a clear solution of
en-HAc.
RUB-36 was swollen by CTAOH (10 wt % solution in water, TCI) at room temperature
(RT). Typically, 0.5 g RUB-36 was dispersed in the 35.0 g CTAOH solution (4 wt % solution
in water). The mixture was stirred for 48 h, then filtered and washed with deionized water,
and finally dried at RT. Pd(en)2Ac2deswelling process was conducted by mixing 0.5 g
swollen sample with a mixture of 10 ml ethanol, 0.31 ml above prepared Pd(en)2Ac2 solution
and 1.25 ml en-HAc solution, then stirred for 4 h at RT. The product was recovered by
filtration, repeated washing with deionized water, ethanol and dried at RT. Calcination of
obtained samples were conducted at 500 C in static air for 4 h.
Pd/RUB-37 was prepared by incipient wetness impregnation method. Typically, 2.6 ml
deionized H2O was mixed with 0.2 ml en and 0.04 g Pd(Ac)2 to get a clear aqueous solution
of Pd(en)2Ac2. Then, above solution was dropwised into 2.0 g dried RUB-37. The sample
was dried at RT and calcined at 500 C in static air for 4 h. All the calcined samples were
reduced at 350 C under 30 ml/min 30% H2/N2 for 1 h.
Characterizations
XRD patterns were collected on the PANalytical X'Pert3 Powder X-ray diffractometer
with Cu Kα radiation in the 2θ range of 0.5-10° and 5-50° and scan step size of 0.026°.
Nitrogen adsorption/desorption measurements were carried out on a Micromeritics 2020
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10.1002/cctc.201800040
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analyzer at 77 K after the samples were degassed at 350 °C under vacuum. X-ray
photoelectron spectroscopy (XPS) measurements were performed on a Thermo Scientific
ESCALAB 250Xi spectrometer using an Al Karadiation (15 kV, 10.8 mA, hʋ = 1486.6 eV),
calibrated internally by the carbon deposit C(1s) (Eb = 284.6 eV). Solution 13C NMR,
solid-state 13C CP/MAS NMR and 29Si MAS NMR were performed on an Agilent DD2-500
13
MHz spectrometer at 125.7 and 99.3 MHz, respectively. C CP/MAS NMR spectra were
collected using a 4 mm MAS NMR probe with a spinning rate of 8 kHz, a contact time of 2
29
ms and a recycle delay of 4 s. Si MAS NMR spectrum was acquired using a 6 mm MAS
NMR probe with as spinning rate of 4 kHz and a recycle delay of 30 s. Pd contents of the
resulted catalysts were determined by Inductively Coupled Plasma Atomic Emission
Spectroscopy (ICP-AES, Optima 2000 DV, USA). SEM and STEM images were obtained
using a Hitachi S-5500 SEM equipped with a scanning transmission electron microscope
(STEM), operating at an accelerating voltage of 30 kV. Transmission electron microscopy
(TEM) images were recorded on Hitachi HT 7700 microscope operated at an acceleration
voltage of 100 kV.
Catalytic hydrogenation tests
The catalytic activities of Pd@FER and Pd/RUB-37 were evaluated by hydrogenation
reactions of 1-hexene (Aladdin Reagent), 1-phenyl-1-cyclohexene (Aladdin Reagent),
benzaldehyde (Aladdin Reagent) and diphenylmethanone (Aladdin Reagent) with hydrogen.
Typically, about 21 mg catalysts were loaded in a 50 ml stainless-steel autoclave equipped
with a magnetic stirrer in a thermostat. After air in the reactor was purged with nitrogen, and
the reactor was pressurized with hydrogen at 0.4 MPa and the catalysts were activated at 150
C for 1 h. After cooling down to RT, 20 ml n-heptane (Beijing Chemical Reagent) were
added, and the temperature was elevated to the desired one (40 C for 1-hexene and 90 C
for 1-phenyl-1cyclohexene). Then 2 ml 1-hexene or 0.5 ml 1-phenyl-1-cyclohexene were
added into the reactor. Immediately, 0.4 MPa H2 were flushed in the reactor. Benzaldehyde
and diphenylmethanone hydrogenation reactions were carried out at 80 C similarly to above
procedure. Specifically, 40 mg catalysts, 10 mmol benzaldehyde or 1 mmol
diphenylmethanone were added in 30 ml n-heptane or ethanol, respectively. 0.1 ml samples
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10.1002/cctc.201800040
ChemCatChem
were taken out from the reactor at regular intervals, and the products were analyzed by a gas
chromatography (Shimadzu GC-2014) equipped with a 30m HP-5 capillary column and
flame ionization detector.
Acknowledgements
This work was financially supported by the National Natural Science Foundation of
China (Nos. 21603022, 21673027), the Fundamental Research Funds for the Central
Universities in China (Nos. DUT16RC(3)002, DUT17TD04), Open Project Funds of the
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics (No.N-16-08) and
the INCOE (International Network of Centers of Excellence) project coordinated by BASF
SE, Germany.
Supporting Information
XRD patterns of only Pd(en)2Ac2deswollen RUB-36SW and calcined sample. 29Si
MAS NMR spectrum of Pd@FER. N2 adsorption/desorption isotherms of Pd@FER and
Pd/RUB-37.
References
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Table of Contents
Zhenchao Zhao, Yanlu Li, Mathias Feyen,
-
+
-
+
-
+
-
+
-
+
-
+
-
+
Sw ellin g
CTAOH
+
Robert McGuire, Ulrich Müller,* Weiping
+
+
-
-
-
+
+
+
+
-
-
-
-
RUB-36
1)Calcination
2)Im pregnation
Zhang*
1) Io n Exchan g e
Pd(en)2+
CTA+
2
Pdnanoparticlesencapsulated in FER
Pd(en)2+
2
3)Calcination
2)Calcination
zeolite through layer reassembling
strategy as the shape-selective
hydrogenation catalyst
Pd@ FER
Pd/RUB-37
FER zeolite encapsulating Pd nanoparticles with excellent shape-selective catalytic
properties were constructed and synthesized through swelling RUB-36, ion exchange, and
topotactic conversion processes.
15
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