Effective and Selective Catalysts for Cinnamaldehyde Hydrogenation: Hydrophobic Hybrids of Metal–Organic Frameworks, Metal Nanoparticles, and Micro- and Mesoporous Polymers

Article abstract of DOI:10.1002/anie.201801289

Metal–organic frameworks (MOFs) as selectivity regulators for catalytic reactions have attracted much attention, especially MOFs and metal nanoparticle (NP) shelled structures, e.g., MOFs@NPs@MOFs. Nevertheless, making hydrophilic MOF shells for gathering hydrophobic reactants is challenging. Described here is a new and viable approach employing conjugated micro- and mesoporous polymers with iron(III) porphyrin (FeP-CMPs) as a new shell to fabricate MIL-101@Pt@FeP-CMP. It is not only hydrophobic and porous for enriching reactants, but also possesses iron sites to activate C=O bonds, thereby regulating the selectivity for cinnamyl alcohol in the hydrogenation of cinnamaldehyde. Interestingly, MIL-101@Pt@FeP-CMP^sponge can achieve a high turnover frequency (1516.1 h^?1), with 97.3 % selectivity for cinnamyl alcohol at 97.6 % conversion.

Full text of DOI:10.1002/anie.201801289

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
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Accepted Article
Title: Highly Effective and Selective Catalysts for Cinnamaldehyde
Hydrogenation by Hydrophobic Hybrids of Metal-organic
Frameworks, Metal Nanoparticles and Micro- & Mesoporous
Polymers
Authors: Wenping Hu, Kuo Yuan, Tianqun Song, Dawei Wang, Xiaotao
Zhang, Xiong Gao, Ye Zou, Huanli Dong, and ZHiyong Tang
This manuscript has been accepted after peer review and appears as an
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201801289
Angew. Chem. 10.1002/ange.201801289
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10.1002/anie.201801289
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Highly Effective and Selective Catalysts for Cinnamaldehyde
Hydrogenation by Hydrophobic Hybrids of Metal-organic Frameworks,
Metal Nanoparticles and Micro- & Mesoporous Polymers
Kuo Yuan[a], Tianqun Song[a], Dawei Wang[b], Xiaotao Zhang*[a], Xiong Gao[a], Ye Zou[c], Huanli Dong[c],
Zhiyong Tang*[b], and Wenping Hu*[a]
Abstract: As for heterogeneous catalysis, the activity and selectivity
are two key factors for evaluating catalysts. Metal-organic
frameworks (MOFs) as selectivity regulators for catalytic reaction
have attracted much attention, especially MOFs and metal
nanoparticles (NPs) shelled structures, e.g., MOFs@NPs@MOFs.
Nevertheless, the hydrophilic MOFs shell is challenging to gather
one side directly contacts with the support and most of the
surface do not, which is usually incompetent to significantly
improve the selectivity for the production of thermodynamically
unfavoured products.[3] The surfactants wrap NPs tightly but
bring steric hindrance decreasing the catalytic activity.[3]
Recently, emerging as intriguing porous crystalline materials,
metal-organic frameworks (MOFs) have drawn much attention
by virtue of ordered and tunable pores, large surface area,
diversified structure and particularly unsaturated metal sites,
which offer great potential to versatile applications.[4] Up to now,
MOFs containing metal NPs have been intensively investigated,
on account of unique and synergistic functionalities. In particular,
MOFs@NPs@MOFs structure can change the chemical
environment surrounding NPs thoroughly and simultaneously
keep reactants access to active sites.[4]
As we all know, many substrates of hydrogenation, such as
cinnamaldehyde, are hydrophobic, so the environmental
wettability of catalytic site plays a crucial role in modifying the
catalytic performance.[5] However, the surface and channels of
many kinds of MOFs are hydrophilic, resulting in inconvenience
of gathering hydrophobic molecules.[6] Hence, the new shell
should better be composed of porous and hydrophobic materials
and possess iron sites to activate the C=O bond.[3] Considering
these factors, FeP-CMPs are chosen to construct the shell.[7]
Since the integration of the hydrophobic CMPs and wettable
NPs is highly challenging,[8] here we innovate a new and viable
approach, using well-designed hybrids consisting of MOFs, NPs
and FeP-CMPs, to solve this problem. To the best of our
knowledge, it has never been reported.
hydrophobic reactants. Here, we innovate
a new and viable
approach to solve this problem. By employing conjugated micro- and
mesoporous polymers with iron(Ⅲ) porphyrin (FeP-CMPs) as the
new shell, MIL-101@Pt@FeP-CMP was fabricated firstly, which not
only is hydrophobic and porous to enrich reactants, but also
possesses iron sites to activate C=O bond and thereby regulate the
selectivity for cinnamyl alcohol in hydrogenation of cinnamaldehyde.
Interestingly, MIL-101@Pt@FeP-CMPsponge can reach ultrahigh
turnover frequency (TOF) as high as 1516.1 h-1 with 97.3 %
selectivity towards cinnamyl alcohol and 97.6 % conversion. The
results open up a new avenue for decorating and protecting MOFs,
which will play an important role in both academia and industry.
On account of limited natural source and enormous demand,
selective hydrogenation of cinnamaldehyde (A) to cinnamyl
alcohol (B) is very important in flavouring, perfume and
pharmaceutical industries.[1] So far, much work mainly focuses
on improving the selectivity of B, but little attention was paid on
catalytic efficiency which was simply improved by rigorous
conditions (high temperature or H2 pressure).[2] Take catalytic
efficiency of the industrial process into consideration, milder
working conditions and shorter working period will bring more
economical benefit. Therefore, many research groups focus on
NPs catalysts, such as Pd, Au, Pt, Ru, Ir NPs, etc.[3] Due to high
specific surface, metal NPs not only exhibit excellent activity, but
also can be regulated easily by supports or special surfactants.[3]
As for the traditional strategy of metal oxides loading NPs, only
MIL-101 (Cr3F(H2O)2O[(O2C)-C6H4-(CO2)]3·H 2O), one of the
most popular MOFs in recent researches about composite
catalysts, was employed to load Pt NPs on the surface, due to
very large pore sizes (~30 to 34 Å), surface area (SLangmuir
=
3100 m2/g) and excellent stability.[9] The fantastic crystal
structure and ultrastable framework endowed MIL-101 with
possibility of postsynthetic modification (PSM), such as
decorating skeleton, exchanging metals, loading NPs and
coating the surface with polymers, etc.[10] By a simple method,
as-synthesized Pt NPs were adsorbed on the surface of MIL-
101.[11] However, on the basis of literatures and experimental
results (Figure S1), MIL-101 was not stable in alkaline aqueous
solution at high temperature, so the synthetic conditions of shell
were slightly modified (Supplementary information for details).[12]
Finally, by liquid epitaxial growth, we succeeded in coating MIL-
101@Pt with FeP-CMPs (Figure 1a). In order to study the
function of iron sites, a series of MIL-101@Pt@CMP without iron
was prepared.
[a]
[b]
[c]
Dr. K. Yuan, Dr. T. Song, Dr. X. Zhang, Mr. X. Gao, Prof. Dr. W. Hu
Tianjin Key Laboratory of Molecular Optoelectronic Sciences
Department of Chemistry, School of Sciences, Tianjin University
& Collaborative Innovation Center of Chemical Science and
Engineering (Tianjin)
Tianjin 300072, China
E-mail: zhangxt@tju.edu.cn; huwp@tju.edu.cn
Dr. D. Wang, Prof. Dr. Z Tang
Chinese Academy of Sciences (CAS)
Key Laboratory of Nanosystem and Hierarchy Fabrication
CAS Center for Excellence in Nanoscience, National Center for
Nanoscience and Technology
Beijing 100190, China
E-mail: zytang@nanoctr.cn
Dr. Y. Zou, Prof. H. Dong, Prof. Dr. W. Hu
National Laboratory for Molecular Sciences
Key Laboratory of Organic Solids
Institute of Chemistry, Chinese Academy of Sciences
Beijing 100190, China
By scanning electron microscopy (SEM) and transmission
electron microscopy (TEM), we approximatively determined the
distribution of MIL-101, Pt NPs and FeP- CMP in the composite.
As the growth of organic shell, the surface of sandwich hybrids
became gradually rougher (Figure S2). Figure 1c exhibited that
Supporting information for this article is given via a link at the end of
the document.
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Pt NPs were distributed uniformly on the surface of the MIL-101.
Due to the heavier contrast of Pt, sandwiching Pt NPs between
the two kinds of porous materials were easily distinguished
(Figure 1d-h). The resulting shell of MIL-101@Pt@FeP-
CMPsponge became thick but non-flat morphology looking like
sponge and the other one was only about 5.5 nm thickness by
decreasing amount of precursors (Figure S3). Similarly, the
thickness of shell in MIL-101@Pt@CMP system could be
adjusted from 9.3 nm to 7.9 nm to 3.1 nm (Figure S4). In order
to get more direct evidence, we applied energy dispersive
spectra (EDS) to map the distribution of different metals (Cr and
Fe) using TEM. Fe was dispersed more widespread and outer
than Cr in images of MIL-101@Pt@FeP-CMP system, proving
that FeP-CMP wrapped MIL-101@Pt (Figure 1i and j).
Aforementioned results of TEM and SEM all exactly matched
our design.
Figure 1. a, Design strategy to synthesize MIL-101@Pt@FeP-CMP. TEM images of MIL-101 (b), MIL-101@Pt (c), MIL-101@Pt@FeP-CMPsponge (d), MIL-
101@Pt@FeP-CMP5.5 (e), MIL-101@Pt@CMP9.3 (f), MIL-101@Pt@CMP7.9 (g) and MIL-101@Pt@CMP3.1 (h). High-angle annular dark-field scanning
transmission electron microscopy (HAADF-STEM) images and corresponding EDS elemental (Cr and Fe) mapping of MIL-101@Pt@FeP-CMPsponge (i) and MIL-
101@Pt@FeP-CMP5.5 (j).
The Fourier Transform Infrared Spectrometer (FT-IR)
analysis was carried out to verify the existence of FeP-CMP. As
shown in Figure 2a, by contrasting spectra of the sandwich
heteroarchitectures and MIL-101@Pt, the new characteristic
peaks at 653cm-1, 697 cm-1, 801 cm-1, 1001 cm-1 (Fe-N), 1072
cm-1, 1203 cm-1, 1336 cm-1, 1485 cm-1, originating from the new
shell, confirmed the formation of FeP-CMP, and some others
were covered. Note that the presence of peak at 1001 cm-1
caused by N-Fe bond vibrating and the absence at 960 cm-1
resulting from N-H bond stretching both proved iron containing in
porphyrin. Moreover, the UV-vis absorption spectra of MIL-
101@Pt@FeP-CMP displayed new bands at 432 nm attributing
to the Soret band and 580, 624 and 672 nm representing the Q
bands of iron(Ⅲ) porphyrin units, which were all indexed to FeP-
CMP and the relative intensity increased with the thickness of
FeP-CMP growing (Figure 2b and S5). Analogously, the forming
of CMP shell was also certified by FT-IR and VU-vis absorption
spectra (Figure S6 and S7).
In order to certify the intact crystallinity of MIL-101 and Pt
NPs, the powder X-ray diffraction (PXRD) studies were
conducted. As shown in Figure 3a, the PXRD profile confirmed
the amorphous character of FeP-CMP and suggested that the
crystalline characters of the parental MIL-101 in the hybrids
were maintained. However, MIL-101@Pt@CMP3.1 became
amorphous, which might attribute to the thin shell (Figure S8).
So the thick shell could protect the core from alkali solution. The
PXRD pattern of MIL-101@Pt had a very weak peak at 40o,
corresponding to (111) plane of fcc Pt, ascribing to the low
content and uniformly dispersion (Figure S9). Due to the limit of
PXRD, the high resolution transmission electron microscopy
(HRTEM) was applied to reveal the high crystallinity of
embedded Pt NPs. HRTEM image further indicated that each Pt
NP (3.3 nm average diameter) was highly crystalline with the
interplanar spacing of 0.23 nm, corresponding to the (111) plane
of face centered cubic (fcc) Pt (Figure S10). After coating the
new shell, Figure S11 exhibited the same interplanar spacing of
sandwiched Pt NPs, proving intact crystallinity.
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The N2 adsorption-desorption isotherms were analyzed by
Brunauer-Emmet-Teller method and the surface areas of FeP-
CMP in the pores of MIL-101 and the low surface area of FeP-
CMP.[8] Based on density functional theory (DFT) study, pore
sizes of FeP-CMP (~0.7 and ~1.3 nm) allowed reactant
molecules to diffuse through the shell and access to the
encapsulated Pt NPs (Figure S12). However, the surface area of
CMP (59 m2/g) was much smaller than FeP-CMP, resulting in
difficulty of penetration of substrates through shell (Figure S13).
CMP,
MIL-101,
MIL-101@Pt@FeP-CMP5.5
and
MIL-
101@Pt@FeP-CMPsponge were measured as 255, 2949, 1480
and 1176 m2/g, respectively (Figure 3b). As the FeP-CMP
thickness increased, the surface area of composite decreased.
Compared with MIL-101, the reduced surface areas of MIL-
101@Pt@FeP-CMP could be attributed to the inclusion of FeP-
Figure 2. a, FT-IR spectra of MIL-101@Pt (black line), MIL-101@Pt@FeP-CMP5.5 (red line), MIL-101@Pt@FeP-CMPsponge (blue line) and FeP-CMP (green line).
b, UV-vis absorption spectra of MIL-101@Pt (black line), MIL-101@Pt@FeP-CMP5.5 (red line), MIL-101@Pt@FeP-CMPsponge (blue line).
Figure 3. a, XRD patterns and (b) N2 adsorption-desorption isotherms of MIL-101 (black line), MIL-101@Pt@FeP-CMP5.5 (blue line), MIL-101@Pt@FeP-
CMPsponge (red line) and FeP-CMP (pink line).
In general, due to the hydrophily of surface and channels,
MOFs are very good at absorbing water.[8] Therefore, in spite of
lower densities than water, MIL-101 powder was thrown into
water and directly dropped to the bottom. Nevertheless, with the
help of hydrophobic shell, MIL-101@Pt@FeP-CMP and MIL-
101@Pt@CMP could float on the water (Figure S14). After
drastic shaking, only MIL-101@Pt@FeP-CMP5.5 drowned,
ascribing to thin shell (Figure S15). In order to precisely study
chemical changes of the surface properties, water contact angle
was measured on the pellet of each material. MIL-101 showed
complete water wetting, which adsorbed a drop of water
immediately (Figure 4a). As shown in Figure 4b and c, the water
contact angles gradually increase from 88.6o (MIL-
101@Pt@FeP-CMP5.5) to 122.9o (MIL-101@Pt@FeP-CMPsponge),
which were positively related to the FeP-CMP thickness. In the
MIL-101@Pt@ CMP system, the contact angles changed from
115.4o to 138.7o to 142.7o, with the CMP shell growing (Figure
16d-f).
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Figure 4. Water contact angle measurements of MIL-101 (a), MIL-101@Pt@FeP-CMPsponge (b), MIL-101@Pt@FeP-CMP5.5 (c). Cinnamaldehyde adsorption
(Details in SI) with 4 mg materials (d).
It was expected that the hydrophobic shell would improve
catalytic efficiency significantly and iron sites could help to
FeP-CMP, based on 25 mg FeP), in the catalytic system (2 ml
solution of catalysts), MIL-101@Pt@FeP-CMPsponge and MIL-
101@Pt@FeP-CMP5.5 could be regarded as MIL-101@Pt@1.6
mg FeP-CMP and MIL-101@Pt@0.5 mg FeP-CMP. As
expected, MIL-101@Pt/1 mg FeP-CMP only exhibited 26.3%
conversion, 39.6% selectivity of B and TOF as 356.6 h-1 (Table 1,
entry 10), which was a bit better than MIL-101@Pt but much
worse than sandwich composites. With increasing amount of
physically mixing FeP-CMP (2 mg, Table 1, entry 11), the
selectivity towards B (43.3%) and activity (TOF, 347.1 h-1)
improved slightly. These results indicated that the FeP-CMP
shell of well designed structure could enrich reactants around
the interface of MIL-101 and FeP-CMP, where the Pt NPs were
embedded, to accelerate catalytic efficiency.
XPS measurements of MIL-101@Pt and MIL-101@Pt@FeP-
CMP5.5 revealed that almost no electron of Pt NPs transferred to
FeP-CMP (Figure S19).[3] On the one hand, it was because of
low content of Fe within FeP-CMP (3.27 wt%).[7] On the other
hand, the interaction of Pt NPs with FeP-CMP was much weaker
than MIL-101, which could be confirmed by the low Pt loading
amount of FeP-CMP@Pt (Figure S20). Previous works had
demonstrated that the reduced electron density of Pt NPs was a
possible reason for the decreased hydrogenation activity.[13] In
this work, the FeP-CMP shell succeeded in maintaining the
activity of Pt NPs.
As for the selectivity towards B, FT-IR survey of A molecule
adsorbed on MIL-101@Pt@FeP-CMPsponge showed an obvious
red shift of the νC=O bond from 1678 cm-1 to 1670 cm-1, indicating
the specific interaction between coordinatively unsaturated iron
site and C=O bonds (Figure S21).[3] As expected, MIL-
101@Pt@FeP-CMPsponge could also perform excellent catalytic
properties in other α, β-unsaturated aldehydes (Table S3).
In previous work, MIL-101@Pt@MIL-101(Fe)2.9 could
exhibited 95.6% selectivity at almost full conversion (99.8%),
which only showed a TOF of 16.9 h-1.[3c] Inspiringly, within MIL-
101@Pt@FeP-CMP system, the similar conversion and
regulate selectivity. Hydrogenation of A,
a classical and
important reaction performed on Pt NPs, was chosen to evaluate
catalytic performance and conducted under the similar reaction
condition with previous work.[2b] We compared the performances
of catalysts, especially efficiency, at the same reaction time (15
min). The pure MIL-101, FeP-CMP and MIL-101@FeP-
CMPsponge did not possess catalytic ability of hydrogenation
(Table 1, entries 1-3), demonstrating that Pt NPs are the only
catalytic sites. MIL-101@Pt achieved 15.0% conversion of A
and 23.3% selectivity to B and the TOF was only 203.4 h-1
(Table 1, entry 4). Nevertheless, on account of coating FeP-
CMP, the MIL-101@Pt@FeP-CMPsponge and MIL-101@Pt@FeP-
CMP5.5 realized 97.6% and 97.9% conversion after 15 min,
respectively. Owing to the thicker shell, MIL-101@Pt@FeP-
CMPsponge exhibited better selectivity to B (97.3%) than MIL-
101@Pt@FeP-CMP5.5 (82.6%) but still kept the ultrahigh TOF
(1516.1 h-1) (Table 1, entries 5 and 6). TEM images exhibited
that the used MIL-101@Pt@FeP-CMPsponge still kept sandwich
structure, suggesting that FeP-CMP shell was not peeled off
during reaction (Figure S17).
As for the ultrahigh catalytic activity, FeP-CMP shell played
an important role in the catalytic reaction. Firstly, owing to the
hydrophobic and porous shell, MIL-101@Pt@FeP-CMP system
showed much better adsorption of A, proving enrichment of
reactant around Pt NPs (Figure 4d). MIL-101@Pt@CMP
showed the similar properties (Figure S18). However, CMP shell
hindered A to access to active sites due to the small surface
areas (Figure 3b and S13). By contrast to MIL-101@Pt, MIL-
101@Pt@CMP3.1 (25.4% conversion, 31.7% selectivity and
398.4 h-1), MIL-101@Pt@CMP7.9 (27.4% conversion, 18.0%
selectivity and 417.5 h-1) and MIL-101@Pt@CMP9.2 (31.6%
conversion, 29.4% selectivity and 468.1 h-1) showed very slight
improvement in catalytic activity (Table 1, entries 7-9). In spite of
excellent collection of A, MIL-101@Pt@CMP system couldn’t
improved catalytic efficiency a lot.
selectivity were maintained but
a
remarkable 89-fold
Furthermore, in order to verify the superiority of sandwich
structure, simply physical mixtures of MIL-101@Pt and FeP-
CMP (MIL-101@Pt/ x mg FeP-CMP) were tested in catalytic
reaction. According to yield of as-synthesized FeP-CMP (20 mg
enhancement of TOF (1516.1 h-1) was realized by simply
altering shell from MOF to FeP-CMP (Table 1 entry 5). Our MIL-
101@Pt@FeP-CMPsponge outperformed state-of-the-art catalysts,
especially in terms of catalytic efficiency (Table S4).
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COMMUNICATION
Table 1 Selective hydrogenation of cinnamaldehyde by different catalysts.[a]
Reaction
Selectivity [%][b]
Entry
Catalysts
Conversion [%][b]
TOF [h-1][c]
B
C
-
D
-
1
MIL-101
0
-
-
2
FeP-CMP
0
-
-
-
-
3
MIL-101@FeP-CMPsponge
0
-
-
-
-
4
MIL-101@Pt
15.0
97.6
97.9
31.6
27.4
25.4
26.3
25.6
23.3
97.3
82.6
29.4
18.0
31.7
39.6
43.3
76.7
2.6
13.9
70.6
82.0
68.3
60.4
56.7
0
0
3.5
0
0
0
0
0
203.4
1516.1
1463.9
468.1
417.5
398.4
356.6
347.1
5
MIL-101@Pt@FeP-CMPsponge
MIL-101@Pt@FeP-CMP5.5
MIL-101@Pt@CMP9.2
MIL-101@Pt@CMP7.9
MIL-101@Pt@CMP3.1
MIL-101@Pt/1 mg FeP-CMP
MIL-101@Pt/2 mg FeP-CMP
6
7
8
9
10
11
A, cinnamaldehyde; B, cinnamyl alcohol; C, benzenepropanal; D, phenylpropanol. [a] Reaction condition: 2 ml solution of catalysts; the reaction requires 125 ul
triethylamine, 2.5 ul mesitylene and 0.4 mmol A, room temperature, 3 MPa H2 for 15 min. [b] Determined by GC. [c] TOF was calculated by the mole number of
converted A (mole number of total Pt)-1 h-1. The amount of Pt NPs of each catalyst was determined by ICP (Table S2).
2014, 4, 1340-1348; c) I. Cano, A. M. Chapman, A. Urakawa, P. W. N.
In summary, our work is the first report on integration of
MOFs, NPs and CMPs, which opens up a new avenue for the
construction of sandwich hybrids. By replacing MOFs shell with
Leeuwen, J. Am. Chem. Soc. 2014, 136, 2520-2528.
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FeP-CMP, we succeeded in modifying environmental of Pt NPs,
Am. Chem. Soc. 2014, 136, 520-526; c) M. Zhao, K. Yuan, Y. Wang, G. Li,
which not only changed the wettability to enrich A, but activated
J. Guo, L. Gu, W. Hu, H. Zhao, Z. Tang, Nature 2016, 539, 76-80.
C=O bond to improve selectivity to B. TOF of hydrogenation
[4] a) H. Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi, Science 2013,
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MOFs@NPs@FeP-CMPs
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heteroarchitectures may prove to be effective when targeting
important but challenging reactions. We anticipate that this
simple but ingenious design will provide versatile material
platforms for other kinds of catalysts, aiming at resolving the
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some other practical applications, such as energy, environment
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Experimental Section
The experimental details included in Supporting Information.
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Acknowledgements
The authors are grateful for the financial support from Ministry of
Science and Technology of China (Grants 2016YFB0401100,
2017YFA0204503), National Natural Science Foundation of
China (51633006, 51725304, 91433115, 51733004), and the
Strategic Priority Research Program of Chinese Academy of
Sciences (XDB12030300, XDB12010400, XDB12020200).
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10.1002/anie.201801289
Angewandte Chemie International Edition
COMMUNICATION
We synthesized a series of MIL-
101@Pt@FeP-CMP coating with
hydrophobic and porous shell. In
Kuo Yuan, Tianqun Song, Dawei
Wang, Xiaotao Zhang*, Xiong Gao,
Ye Zou, Huanli Dong, Zhiyong
Tang*, Wenping Hu *
the
hydrogenation
of
cinnamaldehyde, FeP-CMP shell
not only maintains selectivity with
the help of iron(Ⅲ) porphyrin but
also promotes catalytic efficiency
Page No. – Page No.
Highly Effective and Selective
Catalysts for Cinnamaldehyde
Hydrogenation by Hydrophobic
Hybrids of Metal-organic
Frameworks, Metal Nanoparticles
and Conjugated Micro- &
due
to
the
environmental
hydrophobicity. Especially, MIL-
101@Pt@FeP-CMPsponge catalyst
reached the highest TOF (1516.1
h-1) and outperformed state-of-
the-art catalysts.
Mesoporous Polymers
This article is protected by copyright. All rights reserved.