In Situ Construction of Pt–Ni NF?Ni-MOF-74 for Selective Hydrogenation of p-Nitrostyrene by Ammonia Borane

Article abstract of DOI:10.1002/chem.202002305

Pt–Ni nanoframes (Pt–Ni NFs) exhibit outstanding catalytic properties for several reactions owing to the large numbers of exposed surface active sites, but its stability and selectivity need to be improved. Herein, an in situ method for construction of a core–shell structured Pt-Ni NF?Ni-MOF-74 is reported using Pt–Ni rhombic dodecahedral as self-sacrificial template. The obtained sample exhibits not only 100 % conversion for the selective hydrogenation of p-nitrostyrene to p-aminostyrene conducted at room temperature, but also good selectivity (92 %) and high stability (no activity loss after fifteen runs) during the reaction. This is attributed to the Ni-MOF-74 shell in situ formed in the preparation process, which can stabilize the evolved Pt–Ni NF and donate electrons to the Pt metals that facilitate the preferential adsorption of electrophilic NO₂ group. This study opens up new vistas for the design of highly active, selective, and stable noble-metal-containing materials for selective hydrogenation reactions.

Full text of DOI:10.1002/chem.202002305

Accepted Article
Accepted Article
Title: In-situ construction of Pt-Ni NF@Ni-MOF-74 for selective
hydrogenation of p-nitrostyrene by ammonia borane
Authors: Shuyan Song, Jinhui Xu, Junjiang Zhu, Yu Liu, Yan Long,
Jing Feng, Xiangguang Yang, Yibo Zhang, and Hongjjie
Zhang
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.202002305
Link to VoR: https://doi.org/10.1002/chem.202002305
0
1/2020

Chemistry - A European Journal
10.1002/chem.202002305
COMMUNICATION
In-situ Construction of Pt-Ni NF@Ni-MOF-74 for Selective
Hydrogenation of p-nitrostyrene by Ammonia Borane
[
a,b]
[c]
[a]
[a]
[a,b]
[a,b]
[a,b]
Jinhui Xu,
Junjiang Zhu, Yu Liu, Yan Long, Jing Feng,
Xiangguang Yang,
Yibo Zhang,*
[
a,b]
[a,b,d]
Shuyan Song,*
and Hongjie Zhang
Abstract: Pt-Ni nanoframes (Pt-Ni NFs) exhibit outstanding catalytic
for varied reactions owing to the large numbers of exposed surface
active sites, but its stability and selectivity need to be improved.
they can be pre-designed and post-modified at wish, thus the
pore size and surface functional groups can be facially
[
6]
controlled. Indeed, MOFs have been wildly used in catalytic
reactions owing to the large specific surface area, structural and
functional diversity, and specific pore structure. Therefore,
MOFs are considered to be a suitable shell for the construction
Herein, we reported an in-situ method for construction of
a
core@shell structured Pt-Ni NF@Ni-MOF-74 using Pt-Ni rhombic
dodecahedral as self-sacrificial template, finding that the sample
exhibits not only 100% conversion for the selective hydrogenation of
p-nitrostyrene to p-aminostyrene conducted at room temperature,
but also good selectivity (92%) and high stability (no activity loss
after fifteen runs) during the reaction. This is attributed to the Ni-
MOF-74 shell in situ formed in the preparation process, which can
stabilize the evolved Pt-Ni NF and donate electrons to the Pt metals
[
7]
of core@shell materials, and there are many works reporting
the package of metal nanoparticles into the MOFs tunnel, e.g.,
[
5b,8]
Pt, Pd, Au, Ag (NPs@MOFs).
Fabrication of NPs@MOFs core-shell can be achieved by
[
9]
three strategies: 1) loading NPs to pre-synthesized MOFs, 2)
the simultaneous growth of NPs and MOFs by one-step
[
10]
that facilitate the preferential adsorption of electrophilic–NO
2
group.
synthesis,
NPs,
and 3) the growth of MOFs on pre-synthesized
but they are not feasible to fabricate alloy@MOFs
[
7b,11]
This study provides a new vista to design highly active, selective and
stable noble metal containing materials for selective hydrogenation
reactions.
core-shell. In-situ self-sacrificing template method is an
attractive method to use metal atoms from alloy to coordinate
with ligands and form MOFs around the nanoparticles. Li et al.
prepared a Pt-Ni hollow frame and wrapped it in the bulk of
Recently, bimetallic alloyed Pt-M nanoframes (Pt-M NFs),
such as Pt-Ag, Pt-Cu, and Pt-Ni, have been widely used in
[12]
MOF. Later, Kuang et al. used the same method to synthesize
Rh-Ni NF@Ni-MOF-74 and the thickness of MOF was adjusted
[
1]
electrocatalysis. The Alloying of transition metal can adjust the
geometry and electronic structure of Pt and thus affect the
overall catalytic performance, increasing the Pt utilization and
[13]
by controlling the Ni content.
However, the dispersion of
current alloy@MOFs is a problem, and it is essential to improve
the synthesis strategy and explore the impact of MOF thickness
on the catalytic performances.
In this work, we used an in-situ encapsulation method to coat
Pt-Ni nanoparticles with Ni-MOF-74, and tested its activity for
the hydrogenation of p-nitrostyrene to p-aminostyrene using
ammonia borane as hydrogen donator. We first synthesized Pt-
[
2]
reducing the catalyst’s cost. Catalytic materials with nanoframe
structures exhibit large surface area and expose rich surface
[
3]
defects, which are beneficial to surface catalytic reactions.
However, the stability of Pt-M NF materials is a challenge, in that
the shape of Pt-M NFs is slender and easy to be collapsed, and
the transition metals would be dissolved under severe catalytic
conditions. Also, the atoms at the apex and edge of the frame
are easy to be corroded in the reaction due to its high surface
Ni rhombic dodecahedral (Pt-Ni RD) according to a previous
[14]
work,
and then transferred it to a solution containing N,N-
(DMF), hexadecyltrimethylammonium
dimethylformamide
[
4]
energy. However, although the exposure of more active sites is
beneficial to increase the catalytic activity, it may decrease the
selectivity and stability of catalytic materials. A lot of work is
working on this topic, but remains a challenging task.
bromide (CTAB) and acetic acid (HAc). The mixture was finally
hydrothermallized to form Pt-Ni NF@Ni-MOF-74 (see the
Supporting Information for details). In this process, the Pt-Ni RD
2+
will be gradually etched by the HAc to release Ni ions, which
Encapsulation of active materials with porous shell, to
fabricate core@shell structure, is an effective way to enhance
will be captured by 2, 5-dihydroxyterephthalic acid (DOT) to form
Ni-MOF-74 shell. In particular, the thickness of Ni-MOF-74 can
be adjusted by changing the Pt/Ni molar ratio of Pt-Ni RD, and
subsequently affects the catalytic activity and selectivity of p-
nitrostyrene hydrogenation. Results indicated that the sample
with Pt/Ni molar ratio of 1:1.6, i.e., Pt-Ni1.6 NF@Ni-MOF-74, is
the best catalyst for p-nitrostyrene hydrogenation reaction,
showing 92% p-aminostyreneselectivity at p-nitrostyrene
conversion of 100%, and can be reused for at least fifteen runs
with no appreciable loss of conversion and selectivity.
[
5]
the stability and improve the catalytic selectivity. In this respect,
metal-organic frameworks (MOFs) are of special interest, as
[
a]
J. Xu, Y. Liu, Dr. Y. Long, Prof. J. Feng, Prof. X. Yang, Dr. Y. Zhang,
Prof. S. Song, Prof. H. Zhang
State Key Laboratory of Rare Earth Resource Utilization
Changchun Institute of Applied Chemistry, Chinese Academy of
Sciences,Changchun 130022, P. R. China
Email: songsy@ciac.ac.cn; yibozhang@ciac.ac.cn
J. Xu, Prof. J. Feng, Prof. X. Yang, Dr. Y. Zhang, Prof. S. Song,
Prof. H. Zhang
School of Applied Chemistry and Engineering, University of Science
and Technology of China, Hefei 230026, P. R. China
Prof. J. Zhu
[
[
b]
c]
The Pt-Ni NF@Ni-MOF-74 was in situ synthesized using Pt-Ni
RD as self-sacrificial template. The synthesis procedure is
described in Scheme 1.First, Pt-Ni RD with expected structure
[
14]
and morphology was synthesized according to previous work.
Hubei Key Laboratory of Biomass Fibers and Eco-dyeing &
Finishing, College of Chemistry and Chemical Engineering, Wuhan
Textile University, Wuhan 430200, P.R. China
Prof. H. Zhang
Department of Chemistry Tsinghua University, Beijing 100084, P. R.
China
Then, CTAB was introduced to replace the oleylamine on the
surface of Pt-Ni RD, in order to disperse the Pt-Ni RD in DMF
solution for MOF encapsulation. Thereafter, DOT and HAc were
added to the above solution and the mixture was hydrothermally
[
d]
o
treated at 110 C，to enable the etching of Pt-Ni RD and the
Supporting information for this article is given via a link at the end of
the documemt.
formation of Ni-MOF-74 (see the Supporting Information).
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.202002305
COMMUNICATION
Scheme 1. Schematic illustration for the synthesis of Pt-Ni NF
@Ni-MOF-74.
X-ray diffraction (XRD) patterns indicate that the Pt-Ni alloy
and Ni-MOF-74 are successfully formed in the samples, Figure
1a. For Pt-Ni-RD, three diffraction peaks locating at 2θ= 42.2°,
48.6°, and 70.5° appear, which are in between these of Pt and
Ni metals, thus suggesting that the Pt-Ni alloy is formed. The
diffraction peaks were slightly shift to 2θ= 41.6°, 48.3°, 70.4° for
Pt-Ni NF@Ni-MOF-74 due to the transformation from Ni-rich Pt-
Ni RD to Pt-rich Pt-Ni NF, as supported by the ICP-OES results,
Table S1, which shows that the Pt/Ni molar ratio changed from
1
:2.3 for Pt-Ni RD to 1:0.67 for Pt-Ni NF@Ni-MOF-74. Besides
the diffraction peaks of Pt-Ni alloy, two weak peaks at 2θ=
.8°and 11.9°are also observed for Pt-Ni NF@Ni-MOF-74, which
6
can be assigned to the Ni-MOF-74 shell, as referenced to the
standard PDF card of Ni-MOF-74. The weak peak intensity the
Ni-MOF-74 shell is thin and has poor crystallinity. To verify the
formation of Ni-MOF-74, Fourier transform infrared (FT-IR)
spectra of the Pt-Ni NF@Ni-MOF-74 was performed and the
profile was presented in Figure S1. The absorption bands of Pt-
Ni NF@Ni-MOF-74 match well with that of the pure Ni-MOF-74
while no appreciable band is observed for Pt-Ni NF. Similarly,
the absorption bands of Pt-Ni NF@Ni-MOF-74 are obviously
weaker than that of the pure Ni-MOF-74, due to the ultra-thin
shell covered on the Pt-Ni NF.
Figure 1. (a) XRD patterns of Pt-Ni RD, Ni-MOF-74 and Pt-Ni
NF@Ni-MOF-74; (b) TEM images, (c) STEM-EDX mappings
and (d) high-resolution TEM image of Pt-Ni NF@Ni-MOF-74; (e)
Pt 4f XPS spectra of Pt-Ni NF and Pt-Ni NF@Ni-MOF-74.
shows that the sample has lattice spacing (d) of 0.206 and 0.185
nm, corresponding to the (111) and (200) planes of face-
centered cubic Pt-Ni alloy. X-ray photoelectron spectroscopy
(XPS) confirms also the core@shell nanostructures of Pt-Ni
NF@Ni-MOF-74, Figure 1e and Figure S5, which show that the
peak intensity of Pt and Ni of Pt-Ni NF@Ni-MOF-74 are lower
than that of Pt-Ni NF, due to the covering of Ni-MOF-74 shells.
The binding energy of Pt 4f decreases while that of Ni 2p
increases when compared with Pt-Ni NF to Pt-Ni NF@Ni-MOF-
74. This implies the formation of Pt-Ni alloy and the transfer of
electrons from Ni to Pt.
The thin shell of Pt-Ni NF@Ni-MOF-74 is also supported by
TEM images. Figure S3 shows that the Pt-Ni RD has uniform
rhombic dodecahedral morphology with average diameter of 45
±
3 nm, and Figure S4 demonstrates that the Ni atoms are
homogeneously distributed inside the particles while the Pt
atoms are on the edges, and the density of Ni atoms is higher
[
3,15]
than that of Pt atoms in accordance to previous work.
After
o
hydrothermal treatment in autoclave at 110 C by DOT and HAc,
the Pt-Ni RD was etched and transformed to Pt-Ni NF core,
together with the formation of Ni-MOF-74 shells, as proved by
TEM images in Figure 1b and Figure S2. Meanwhile, the Pt
atoms were concentrated in the cores with higher density than
that of dispersed Ni atoms, Figure 1c.The transformation of Ni-
rich Pt-Ni RD to Pt-rich Pt-Ni NF can be the reason that there
are trace amounts of oxygen in the solution during the
nanoparticles synthesis, which promotes the etching of low-
In order to understand the evolution process of Pt-Ni NF@Ni-
MOF-74, the time course study on the morphology by TEM
images was performed, and the results were presented in
Figure 2.When the Pt-Ni RD was etched by HAc, Ni was
2+
[14,16]
converted to Ni and captured by DOT to form Ni-MOF-74.
With increasing the etching time, Pt-Ni RD was gradually
transformed to Pt-Ni NF together with the formation of Ni-MOF-
74 shell. In details, at etching time of 3 h, the Pt-Ni RD was
etched and the structure changed notably, with a very thin Ni-
MOF-74 shell being formed. When the etching time increased to
6 h, more pores were generated in the structure of Pt-Ni RD and
the thickness of Ni-MOF-74 shell increased but not uniform. At
etching time of 9 h, Pt-Ni alloy with rib shape were visible and
was wrapped with a thin, relatively uniform shell. As the etching
[
14]
coordinated Ni along the edges. So the edges of Pt-Ni NF are
mainly composed of Pt atoms when the Ni atoms were etched
away to form Ni-MOF-74 shells. HR-TEM image in Figure 1d
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.202002305
COMMUNICATION
Figure 2. TEM images of the samples obtained at different reaction times.
time prolonged to 12 h, the edges of the Pt-Ni alloy were clearly
visible and surrounded with an evenly thin layer.
CTAB-modified Pt-Ni does not contribute to catalytic activity and
selectivity. So the catalytic selectivity of Pt-Ni NF@Ni-MOF-74 is
indeed the role of MOF.
Pt-Ni NF@Ni-MOF-74 shows considerable PN conversion and
especially excellent PA selectivity (92%) as compared to the
individuals. The slight decrease in PN conversion, relative to that
of Pt-Ni NF, can be that the presence of Ni-MOF-74 shell
restrains the diffusion rate of PN to Pt-Ni surface. The high PA
selectivity can be attributed to the electron transfer from Ni-
MOF-74 to Pt (see XPS results, Figure 1e), which makes the Pt
In particular, the thickness of the shell can be tuned by simply
changing the Pt/Ni molar ratio of Pt-Ni RD, as supported by the
thicknesses of Ni-MOF-74 shells formed using Pt-Ni1.7 RD, Pt-
Ni1.8RD and Pt-Ni2.0RD as self-sacrificial template, Figure S6–
S8. The higher the Ni content in Pt-Ni RD, the thicker the Ni-
[
13]
MOF-74 shell will be in accordance to previous work.
The
change of Pt/Ni molar ratio in them is confirmed by XRD
patterns, ICP-OES analysis, and XPS measurements. Namely,
with the change from Pt-Ni1.7 RD to Pt-Ni1.8 RD and to Pt-Ni2.0RD, surface electron-rich and favors the adsorption of electrophilic –
[
16c]
the relative peak intensities of Pt metal detected by XRD and
XPS decrease (Figure S9-S10), and the molar ratio of Pt/Ni
analyzed by ICP-OES changes from 1/0.78 to 1/1.57 and to
NO
NO
2
group in accordance to previous work.
Therefore, the –
2
group will be preferentially hydrogenated and high PA
selectivity is obtained.
1
/3.90 (Table S1).
Functionalized aromatic amines are important intermediates to
Effect of the thickness of Ni-MOF-74 on the catalytic
performance was also studied, and it is found that both the PN
conversion and the PA selectivity decrease with increasing the
produce pharmaceuticals, pesticides, fine chemicals, dyes and
[
17]
polymers. They are usually obtained by chemoselective
hydrogenation of nitro compound suing as hydrogen
but the selectivity to aromatic amines is low.
Hydrogen-rich ammonia borane (AB) is a promising hydrogen
thickness, Figure 4, Table S2. The shell thickness of Pt-Ni
x
H
2
NF@Ni-MOF-74 (x = 1.6, 1.7, 1.8, 2.0) increases with the x
value and can be found in Figure S6-S8. The decrease in PN
conversion can be due to the restraint of Ni-MOF-74 shell for PN
[
18]
donors,
[
17,19]
source for selective hydrogenation reactions,
but its stable
structure makes the release of hydrogen at mild conditions a
[
20]
challenge. In this work, we show that the in-situ synthesized
Pt-Ni NF@Ni-MOF-74 is active for hydrogen release from AB
and exhibits excellent selectivity for selective hydrogenation of
4-nitrostyrenearomatic amines, even being conducted at room
temperature (RT), potentiating its great applications for selective
hydrogenation reactions.
Figure 3a shows the catalytic conversion of Pt-Ni NF@Ni-
MOF-74, Pt-Ni NF, and Ni-MOF-74 for selective hydrogenation
of p-nitrostyrene (PN) to p-aminostyrene (PA), using AB as
hydrogen donors, and the products selectivity obtained from
each sample was presented in Figure 3b-3d，Table S2. The
Pt-Ni NF exhibits the highest PN conversion especially at the
initial 3 minutes, which could be that it is the active site and is
mostly exposed to the reaction. However, this leads to low
selectivity to PN, as the Pt-Ni NF can catalyze the hydrogenation
of both –NO
2
and C=C groups, yielding PA and PAE
simultaneously. Ni-MOF-74 exhibits low activity for the reaction,
and it seems preferable to catalyze the hydrogenation of C=C
[
21]
group owing to the presence of apical Ni active sites. It has
been reported that the apical metal in the MOF networks can be
active sites for various organic reactions, supporting our
results. Figure S11 shows the conversion of PN , selectivity to
PA, PAE, PNE from CTAB modified Pt-Ni RD and without any
catalytic materials. The PN conversion decreased and the
selectivity of PA hardly changed with CTAB modified Pt-Ni RD
and PN had no conversion without any catalytic materials.The
Figure 3. Catalytic activity of the catalytic materials for selective
hydrogenation of p-nitrostyrene (PN) to p-aminostyrene (PA):
selectivity of PA obtained from the three catalytic materials (a);
selectivity to p-aminostyrene (PA), p-aminoethylbenzene (PAE)
and p-nitroethylbenzene (PNE) obtained from Pt-Ni NF (b), Ni-
MOF-74 (c) and Pt-Ni1.6NF@Ni-MOF-74 (d).
[
22]
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.202002305
COMMUNICATION
diffusion, as said above. The thicker the Ni-MOF-74 shell, the
more the restraint for PN diffusion, and the lower the reaction
rate. As for the PA selectivity, remember that the Ni-MOF-74
shell is active for the hydrogenation of C=C group (Figure 3c),
the presence of more (or thicker) Ni-MOF-74 shell thus will
promote the rate of C=C hydrogenation, and hence decrease the
selectivity to PA. We also tested the catalytic materials
conversion of Pt-Ni NF@Ni-MOF-74, Pt-Ni NF, and Ni-MOF-74
for selective hydrogenation of p-nitrostyrene (PN) to p-
process. The thickness of the Ni-MOF-74 shell can be adjusted
by turning the Ni content of the Pt-Ni RD self-sacrificial template.
The obtained Pt-Ni1.6 NF@Ni-MOF-74 shows high activity for
selective hydrogenation of p-nitrostyrene to p-aminostyrene
using ammonia borane as hydrogen donor, with conversion of
~100% and selectivity of 92%. The presence of Ni-MOF-74 shell
can avoid the over-hydrogenation caused by the highly active
Pt-Ni NF, but will yield less amounts of PNE, as the shell itself
has a certain activity to hydrogenate the C=C groups. Thus the
thickness of the shell should be controlled at a certain value to
achieve the optimum activity. Reusability tests showed that the
Pt-Ni1.6 NF@Ni-MOF-74material is highly stable in the reaction,
with no appreciable loss of activity after fifteen runs. In addition,
the synthesis route reported here may provide new opportunities
for preparing core@shell-structured alloy@MOF nanomaterials
with various compositions.
aminostyrene (PA), using H
2
as hydrogen donors at room
temperature and pressurein Figure S12. The Pt-Ni NF@Ni-
MOF-74 exhibits the PN conversion (100%) at the 120 minutes
and PA selectivity (50%), using H
obvious that AB as hydrogen donors has a higher rate and
better selectivity for PA than H as hydrogen donors.
2
as hydrogen donors. It is
2
Acknowledgements
This work was supported by the financial aid from the National
Natural Science Foundation of China (Grant No. 21771173 and
21590794), K. C. Wong Education Foundation (GJTD-2018-09),
and the project development plan of science and technology of
Jilin Province (20180101179JC).
Figure 4.Catalytic activities of Pt-Ni
r
NF@Ni-MOF-74 (r = 1.6 ~
2.0) for the hydrogenation reaction as a function of reaction time:
(a) conversion of PN; (b) selectivity to PA.
Keywords: Ni-MOF-74 • Pt-Ni nanoframes • core@shell
Stability is one important factor to evaluate the catalytic
structure • ammonia borane • hydrogenation of p-nitrostyrene
performance of catalytic material. In this respect, we tested the
reusability of Pt-Ni1.6 NF@Ni-MOF-74 for the reaction, which
[1]
a) M. Tsuji, M. Hamasaki, A. Yajima, M. Hattori, T. Tsuji, H. Kawazumi,
Mater. Lett. 2014, 121, 113-117; b) Y. Wang, Y. Chen, C. Nan, L. Li, D.
Wang, Q. Peng, Y. Li, Nano Res. 2015,8, 140-155; c) J. Park, M. K.
Kabiraz, H. Kwon, S. Park, H. Baik, S.-I Choi, K. Lee, ACS Nano 2017,
was done by filtering the catalytic material after reaction, dried at
o
8
0 C and then used for the next run. Figure 5 shows that the
material is stable in the reaction for fifteen runs, with no
appreciable loss in either PN conversion (>99%) or PA
selectivity (92%). Characterizations from XRD patterns and TEM
image show that no change in the crystalline structure (Figure
S13a) and the morphology (Figure S13b) happens for the fresh
and used materials. This suggests that the present Pt-Ni1.6
NF@Ni-MOF-74 can be a stable catalytic materials for selective
hydrogenation reactions.
1
1, 10844-10851; d) A. Oh, Y. J. Sa, H. Hwang, H. Baik, J. Kim, B. Kim,
S. H. Joo, K. Lee, Nanoscale 2016, 8, 16379-16386; e) G. Gruzel, P.
Piekarz, M. Pawlyta, M. Donten, M. Parlinska-Wojtan, ACS Appl. Mater.
Interfaces 2019, 11, 22352-22363.
[2]
C. Fan, G. Wang, L. Zou, J. Fang, Z. Zou, H. Yang, J. Power Sources
2019,429, 1-8.
[
[
3]
4]
Y. Long, J. Li, L. Wu, Q. Wang, Y. Liu, X. Wang, S. Song, H. Zhang,
Nano Res. 2019, 12, 869-875.
a) R. Lin, X. Cai, H. Zeng, Z. Yu, Adv. Mater. 2018, 30, 1705332; b) S.
Luo, P. K. Shen, ACS Nano 2017, 11, 11946-11953; c) H. Kwon, M. K.
Kabiraz, J. Park, A. Oh, H. Baik, S.-I.Choi, K. Lee, Nano Lett. 2018,18,
2930-2936; d) T. Kwon, M. Jun, H. Y. Kim, A. Oh, J. Park, H. Baik, S. H.
Joo, K. Lee, Adv. Funct. Mater. 2018, 28, 1706440.
[
5]
a) L. Chen, R. Luque, Y. Li, Chem. Soc. Rev. 2017, 46, 4614-4630; b)
M. Zhao, K. Yuan, Y. Wang, G. Li, J. Guo, L. Gu, W. Hu, H. Zhao, Z.
Tang, Nature 2016, 539, 76-80.
[
[
6]
7]
a) Z.-X. Cai, Z.-L. Wang, J. Kim, Y. Yamauchi, Adv. Mater. 2019, 31,
1804903; b) Q. Wang, D. Astruc, Chem.Rev. 2020, 120, 1438-1511.
a) Y. Long, S. Song, J. Li, L. Wu, Q. Wang, Y. Liu, R. Jin, H. Zhang,
ACS Catal. 2018, 8, 8506-8512; b) W. Zhang, G. Lu, C. Cui, Y. Liu, S.
Li, W. Yan, C. Xing, Y. R.Chi, Y. Yang, F. Huo, Adv. Mater. 2014, 26,
4056-4060.
Figure 5. Reusability of the Pt-Ni1.6 NF@Ni-MOF-74 for
[
8]
a) B. Yuan, Y. Pan, Y. Li, B.Yin, H. Jiang, Angew. Chem. Int. Ed. 2010,
49, 4054-4058; b) H.-L. Jiang, B. Liu, T. Akita, M. Haruta, H. Sakurai, Q.
Xu, J. Am. Chem. Soc. 2009,131, 11302-11303; c) L. Chen,T. Wang, Y.
Xue, X. Zhou, J. Zhou, X. Cheng, Z. Xie, Q. Kuang, L. Zheng, Adv.
Mater. Interfaces 2018, 5, 1801168.
selective hydrogenation of p-nitrostyrene to p-aminostyrene.
In summary, core@shell structured Pt-Ni NF@Ni-MOF-74
has been fabricated using DOT as organic ligands to in situ
2+
combine with Ni released from Pt-Ni RD during the etching
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.202002305
COMMUNICATION
[
[
[
9]
a) A. Aijaz, A. Karkamkar, Y. J. Choi, N.Tsumori, E. Roennebro, T.
W. Huang, X. Hong, Y. Wu, Y. Li, Chem. Eur. J. 2015, 21, 13181-
13185; c) N. Zhang, Q. Shao, P. Wang, X. Zhu, X. Huang, Small 2018,
14, 1704318.
Autrey, H. Shioyama, Q. Xu, J. Am. Chem. Soc. 2012, 134, 13926-
13929; b) H.-X. Zhang, M. Liu, X. Bu, J. Zhang,Sci. Rep. 2014, 4, 3923.
10] a) L. He, Y. Liu, J. Liu, Y. Xiong, J. Zheng, Y. Liu, Z. Tang, Angew.
Chem. Int. Ed. 2013, 52, 3741-3745; b) H. Liu, L. Chang, C. Bai, L.
Chen, R. Luque, Y. Li, Angew. Chem. Int. Ed. 2016, 55, 5019-5023.
11] a) K. Sugikawa, Y. Furukawa, K. Sada,Chem. Mater. 2011,23, 3132-
[17] O. Metin, H. Can, K. Sendil, M. S. Gultekin, J. Colloid Interface Sci.
2017, 498, 378-386.
[18] a) P. Serna, A. Corma, ACS Catal. 2015, 5, 7114-7121; b) Y. Tan, X. Y.
Liu, L. Zhang, A. Wang, L. Li, X. Pan, S. Miao, M. Haruta, H. Wei, H.
Wang, F. Wang, X. Wang, T. Zhang, Angew. Chem. Int. Ed. 2017, 56,
2709-2713.
3134; b) X. Liu, L. He, J. Zheng, J. Guo, F. Bi, X. Ma, K. Zhao, Y. Liu, R.
Song, Z. Tang, Adv. Mater. 2015, 27, 3273-3277.
[
[
12] Z. Li, R. Yu, J. Huang, Y. Shi, D. Zhang, X. Zhong, D. Wang, Y. Wu, Y.
Li, Nat. Commun. 2015, 6, 8248.
[19] H. Salahshournia, M. Ghiaci, Appl. Org. Chem. 2019, 33, e4832.
[20] a) C. W. Hamilton, R. T. Baker, A. Staubitz, I. Manners, Chem. Soc.
Rev. 2009, 38, 279-293; b) T. B. Marder, Angew. Chem. Int. Ed. 2007,
46, 8116-8118; c) L. Yang, N. Cao, C. Du, H. Dai, K. Hu, W. Luo, G.
Cheng, Mater. Lett. 2014, 115, 113-116; d) W. Grochala, P. P. Edwards,
Chem. Rev. 2004, 104, 1283-1315; e) D. H. A. Boom, A. R. Jupp, J. C.
Slootweg, Chem. Eur. J. 2019, 25, 9133-9152.
13] a) L. Chen, H. Li, W. Zhan, Z. Cao, J. Chen, Q. Jiang, Y. Jiang, Z. Xie,
Q. Kuang, L. Zheng, ACS Appl. Mater. Interfaces 2016, 8, 31059-31066;
b) L. Chen, X. Zhang, J. Zhou, Z. Xie, Q. Kuang, L. Zheng, Nanoscale
2019, 11, 3292-3299; c) L.-N.Chen, H.-Q.Li, M.-W. Yan, C.-F. Yuan,
W.-W. Zhan, Y.-Q. Jiang, Z.-X. Xie, Q. Kuang, L.-S. Zheng, Small 2017,
1
3, 1700683; d) N. Zhang, Q. Shao, P. Wang, X. Zhu, X. Huang, Small
[21] a) K. Nakatsuka, T. Yoshii, Y. Kuwahara, K. Mori, H. Yamashita, Chem.
Eur. J. 2018, 24, 898-905; b) P. D. C. Dietzel, B. Panella, M. Hirscher,
R. Blom, H. Fjellvag, Chem. Commun. 2006, 9, 959-961.
[22] a) Z. Li, F. Meng, J. Zhang, J. Xie, B. Dai, Org. Biomol. Chem. 2016,14,
10861-10865; b) N. V. Maksimchuk, K. A. Kovalenko, V. P. Fedin, O. A.
Kholdeeva,Chem. Commun. 2012, 48, 6812-6814; c) Y. Kuwahara, H.
Kango, H. Yamashita, ACS Sustainable Chem. Eng. 2017, 5, 1141-
1152.
2018, 14, 1704318.
[
14] C. Chen, Y. Kang, Z. Huo, Z. Zhu, W. Huang, H. L. Xin, J. D. Snyder, D.
Li, J. A. Herron, M. Mavrikakis, M. Chi, K. L. More, Y. Li, N. M. Markovic,
G. A. Somorjai, P. Yang, V. R. Stamenkovic, Science 2014, 343, 1339-
1343.
[
[
15] N. Becknell, Y. Son, D. Kim, D. Li, Y. Yu, Z. Niu, T. Lei, B. T. Sneed, K.
L. More, N. M. Markovic, V. R. Stamenkovic, P. Yang, J. Am. Chem.
Soc. 2017, 139, 11678-11681.
16] a) Y. Wu, D. Wang, Z. Niu, P. Chen, G. Zhou, Y. Li, Angew. Chem. Int.
Ed. 2012, 51, 12524-12528; b) F. Ren, Z. Wang, L. Luo, H. Lu, G. Zhou,
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.202002305
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
The Pt-Ni NF@Ni-MOF-74
was in situ synthesized using
Pt-Ni RD as self-sacrificial
template and exhibited
enhanced catalytic
Jinhui Xu, Junjiang Zhu, Yu Liu,
Yan Long, Jing Feng,
Xiangguang Yang, Yibo Zhang,*
Shuyan Song,* and Hongjie
Zhang
performance for the
hydrogenation of p-
Page No. – Page No.
nitrostyrene to p-aminostyrene
using ammonia borane as
hydrogen donator.
In-situ Construction of Pt-Ni
NF@Ni-MOF-74 for Selective
Hydrogenation of p-
nitrostyrene by Ammonia
Borane
This article is protected by copyright. All rights reserved.