Rational Control of the Selectivity of a Ruthenium Catalyst for Hydrogenation of 4-Nitrostyrene by Strain Regulation

Article abstract of DOI:10.1002/anie.201706645

Tuning the selectivity of metal catalysts is of paramount importance yet a great challenge. A new strategy to effectively control the selectivity of metal catalysts, by tuning the lattice strain, is reported. A certain amount of Co atoms is introduced into Ru catalysts to compress the Ru lattice, as confirmed by aberration-corrected high-resolution transmission electron microscopy (HRTEM) and X-ray absorption fine structure (XAFS) measurements. We discover that the lattice strain of Ru catalysts can greatly affect their selectivity, and Ru with 3 % lattice compression exhibits extremely high catalytic selectivity for hydrogenation of 4-nitrostyrene to 4-aminostyrene compared to pristine Ru (99 % vs. 66 %). Theoretical studies confirm that the optimized lateral compressive strain facilitates hydrogenation of the nitro group but impedes the hydrogenation of the vinyl group. This study provides a new guideline for designing metal catalysts with high selectivity.

Full text of DOI:10.1002/anie.201706645

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Accepted Article
Title: Rational Control on the Selectivity of Ru Catalyst for
Hydrogenation of 4-Nitrostyrene via Strain Regulation
Authors: Yadong Li, Junjie Mao, Wenxing Chen, Wenming Sun, Zheng
Chen, Jiajing Pei, Dongsheng He, Chunlin Lv, and Dingsheng
Wang
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COMMUNICATION
Rational Control on the Selectivity of Ru Catalyst for
Hydrogenation of 4-Nitrostyrene via Strain Regulation
+
+
+
Junjie Mao , Wenxing Chen , Wenming Sun , Zheng Chen, Jiajing Pei, Dongsheng He, Chunlin Lv,
Dingsheng Wang , Yadong Li

Abstract: Tuning the selectivity of metal catalysts is of paramount
importance, yet a great challenge. Here, a new strategy to effectively
control the selectivity of metal catalysts, by tuning the lattice strain, is
reported. In this approach, we introduce a certain amount of Co
atoms into Ru catalysts to compress the Ru lattice, as confirmed by
species and, thereby, changes the activation barriers for proton-
and electron-transfer processes.[4] In this regard, tuning the
lattice strain of metal catalysts might be a new effective strategy
to control their catalytic selectivity.
aberration
corrected
high-resolution transmission electron
microscopy (HRTEM) and X-ray absorption fine structure (XAFS)
measurements. We discover that, the lattice strain of Ru catalysts
can greatly affect their selectivity and Ru with 3% lattice
compression exhibits extremely high catalytic selectivity for
hydrogenation of 4-nitrostyrene to 4-aminostyrene compared to
pristine Ru (99% Vs. 66%). The theoretical studies prove that the
optimized lateral compressive strain facilitates hydrogenation of
nitro-group but impedes the hydrogenation of vinyl-group. This study
provides a new guideline for designing metal catalysts with high
selectivity.
Tuning the selectivity of metal catalysts is highly desirable due to
their significance for the development of energy-saving chemical
processes. Generally, a molecule with one functional group can
be converted into a desired product using a certain metal
catalyst. But it's very challenging to selectively handle just a
specific functional group when other competing functional
[
1]
groups exist in the same molecule. For instance, selective
reduction of nitro-group in the presence of vinyl-group is a
crucial step to obtain functionalized anilines.[2] However, the
conventional Pt, Pd and Ru catalysts can simultaneously reduce
the nitro- and vinyl- groups, leading to undesired byproducts.
Thus, there is a strong incentive to develop effective strategies
for improving the selectivity of metal catalysts.
Figure 1. Representative (a) TEM, (b) STEM image and (c) EDS elemental
mappings of Co-Ru NPs. (d) Atomic-resolution HAADF-STEM images of Co-
Ru NPs. (e) εxx strain component determined via geometric phase analysis.
In this study, we discover that the selectivity of Ru catalysts
can be rationally controlled by compressing Ru lattice strain. The
lattice compression of Ru is achieved via preparing a novel
dumbbell-shaped Co-Ru nanostructure composed of a Co
nanorod with two ends capped with Ru nanoplates. The crystal
lattice of Ru at both ends is compressed due to the connection
of Co at the center compared to pristine Ru, as confirmed by
aberration corrected HRTEM and XAFS studies. The
hydrogenation of 4-nitrostyrene demonstrates that, Ru with 3%
lattice compression can achieve nearly total conversion of 4-
nitrostyrene to 4-aminostyrene, which is superior to pristine Ru.
Density functional theory (DFT) calculations reveal that the
optimized lateral compressive strain facilitates hydrogenation of
The compressed or expanded arrangements of surface
atoms will alter the crystal lattice strain. Recent reports
demonstrated that the catalytic activity could be influenced by
tuning the lattice strain of metal catalysts because the lattice
strain can modify the electronic structure of catalysts and further
affect the adsorption of reactants.[3] Take oxygen reduction
reaction (ORR) as an example, lattice strain can tune the ORR
activity by modifying the bind energy of intermediate oxygenated
Dr. J. Mao[+], Dr. W. Chen[+], Dr. Z. Chen, J. Pei, Dr. D. He, Dr. C.
[*]
Lv, Prof. D. Wang, Prof. Y. Li
Department of Chemistry, Tsinghua University, Beijing 100084
China
PhNO
2 2 4
but impedes the hydrogenation of C H , which help to
understand the strain effects of metal catalysts.
E-mail: wangdingsheng@mail.tsinghua.edu.cn
ydli@mail.tsinghua.edu.cn
Dr. W. Sun[+]
As shown by transmission electron microscopy (TEM, Figure
a) and scanning electron microscopy (SEM, Figure S1 in the
1
Supporting Information), the as-obtained products have uniform
dumbbell-shaped nanostructures consisting of one nanorod and
two nanoplates grown on its ends respectively. The high-angle
annular dark-field scanning transmission electron microscopy
(HAADF-STEM) image (Figure 1b) and the corresponding
energy-dispersive x-ray (EDX) elemental mapping (Figure 1c)
State Key Laboratory of Green Building Materials, China Building
Materials Academy, 100041 Beijing, China
[
+] These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
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show that the prepared nanoparticles (NPs) are composed of
core rich in Co atoms and shell rich in Ru atoms. We utilized
aberration-corrected HAADF-STEM (Figure 1d and Figure S2) to
investigate the compressive lattice strain of Ru induced by effect
of Co. As shown in Figure 1d, the measured lattice fringe on
both ends (Ru) is 2.08 Å which is smaller than that of pristine Ru
insert in Figure 2c) shows that a shoulder peak exists at about
2.1 Å, and its intensity seen to be stronger and stronger with the
variation of Ru content. Here, we suppose that the shoulder
peak is due to Ru-Co scattering. Similar case can be seen in FT-
EXAFS curves of Co K-edge (Figure 2d). The main peak at
about 2.2 Å is due to Co-Co single scattering and the shoulder
peak at about 2.5 Å results from Co-Ru interaction. The above
results revealed that there is a strong interaction between Co
core and Ru shell, and Ru-Ru bond gradually shrinks with
increasing the Co component in Co-Ru NPs. Additional
information of Ru K-edge and Co K-edge is provided in the
Supplementary Information (Figure S13-S17, Table S1-S2).
(
0001) (2.14Å), representing ~3% compressive strain. In order to
study the effect of Co atoms on the compressive strain of Ru, we
conducted the geometric phase analysis (GPA) and the εxx
component of the strain tensor is shown in Figure 1e (the εyy
component and diffractogram are shown in Figure S3 and Figure
S4, respectively). It illustrates that the inner part of the
nanoparticle is more compressive than the outer part, which
demonstrates that the introduction of Co atoms into Ru
nanostructures resulted in smaller lattice distance of Ru, i.e. the
compressive stress. X-ray diffraction (XRD) analysis was
conducted to characterize the crystallinity of the Co-Ru NPs
(
Figure S5). The broadened (0001) and (10-11) peaks together
with (10-10) peak can be assigned to the hexagonal close-
packed (hcp) structure of Ru, and no obvious Co diffraction
peaks can be found. The composition of the prepared NPs was
analyzed using EDX and inductively coupled plasma-mass
spectrometry (ICP-MS). The Co/Ru atomic ratio determined by
EDX analysis was 0.23/0.77 (Figure S6), which was coincide
with ICP-MS results. Co-Ru NPs with different Co/Ru ratios
were easily achieved by varying the feeding ratio of
2 3
Co(acac) /Ru (CO)12 and analyzed by TEM (Figure S7) and
EDX (Figure S8-S10). As shown in Figure S11, there is a linear
correlation between the synthetic feeding ratio of Co/Ru and
analyzed molar ratio. We also monitored the reaction process of
the Co-Ru NPs (Figure S12). First, the samples were obtained
along the "axial growth" mode at the initial stage of NPs
formation. As the reaction continues, the growth mode of
samples changed from "axial growth" mode to "radial growth"
mode. When the reaction was extended to 2.0 h, the stable
phase Co-Ru NPs were formed, and the “radial growth” finished.
Figure 2. XANES spectra of Co-Ru NPs for (a) Ru K-edge and (b) Co K-edge.
EXAFS spectra for (c) Ru K-edge and (d) Co K-edge.
We used X-ray absorption near-edge structure (XANES) and
extended X-ray absorption fine structure (EXAFS) to further
investigate the local atomic and electronic structures of the Co-
Ru NPs. Figure 2a shows the XANES curves of Ru K-edge. It is
found that the Ru K-edge of the samples is close to that of Ru
foil reference, suggesting that the oxidation state of Ru in the
samples should be zero. The slightly lower intensity of Ru K-
edge XANES oscillation of the samples may be due to the size
effect and heteroatomic interaction in binary NPs.[5] From the
XANES spectra of Co K-edge in Figure 2b, we can find that the
intensity of the white line peaks (the peak A) of the samples is
stronger than that of Co foil and the absorption threshold (shown
in the dashed frame) shifts to higher energy, indicating the
variation of the Co 3d-band electron density.[6] Interestingly, the
position of the peak B is regularly changed with the Co content.
The above phenomena indicated that the Co core interacts with
the Ru shell. In order to further investigate the interaction
between Ru and Co, Fourier transform (FT) EXAFS (without
phase correction) analysis is performed at Ru K-edge (Figure
As is well-known, Ru-based NPs have been widely used in
many catalytic reactions.[7] As a proof-of-concept application, the
Co-Ru NPs with different compressive strain were used in
hydrogenation of 4-nitrostyrene to study the relationship
between lattice strain and catalytic selectivity. The introduction
of Co atoms into Ru NPs would slightly decrease the reaction
rate. All the catalysts could achieve complete conversion after
12 hours. Figure 3a shows three typical products for 4-
nitrostyrene (a) hydrogenation in a reaction scheme. The
hydrogenation reaction proceeds through two routes, i.e.,
selective reduction of nitro-group giving target product 4-
aminostyrene (b), or preferential attack of the C=C functionality
producing undesired by-product 4-nitroethylbenzene (c). Then,
fully hydrogenated byproduct 4-ethylbenzenamine (d) would be
produced through above two routes. The selectivity of b and c
when reached complete conversion were showed in Figure 3b
as contrast. We found that Ru and Co0.46-Ru0.54 NPs produced
comparable 4-nitroethylbenzene (c) to 4-aminostyrene (b);
Co0.12-Ru0.88 and Co0.38-Ru0.62 gave relative lower selectivity of c.
2c) and Co K-edge (Figure 2d). In FT-EXAFS spectra of Ru K-
edge, there is a strong peak located at 2.0 to 2.6 Å and it is
related to Ru-Ru single scattering. Locally amplified graph (the
Notably, almost no 4-nitroethylbenzene was found using Co0.23
-
Ru0.77 as
a
catalyst, indicating its specific hydrogenation
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selectivity on nitro-group. Interestingly, the selectivity of b is in a
volcano-type fashion with increasing the compressive lattice
strain of Ru. Pristine Ru gave only 66% selectivity of b, and the
selectivity was increased to 99% when compressing the Ru
lattice strain with 3%; however, decreased selectivity was found
when further increasing the compressive lattice strain gradually.
The above data collectively demonstrated that Ru with 3%
compressive strain could realize highly selective performance in
catalytic hydrogenation of 4-nitrostyrene to 4-aminostyrene.
Moreover, the Co0.23-Ru0.77 catalysts could be easily recycled for
at least 4 times without any obvious loss of activity and
selectivity, demonstrating the high stability of the catalysts.
hydrogenation are investigated according to the Horuit-Polanyi
mechanism[9] with two elementary steps C
H
4
2
2 5
* + H*→C H * and
C H * + H*→C H *. The reaction pathways are shown in Figure
2 5 2 6
4a. Ethylene adopts the π adsorption mode when hydrogen atom
covers on the surface, which is consistent with Christopher’s
study.[10] The first hydrogen addition step is endothermic, while
the second hydrogen addition step is exothermic by 10.41
kcal/mol. The activation barriers for the first and second steps
are 29.25 and 12.64 kcal/mol, indicating that the first
hydrogenation process is the rate-limiting step. When the lateral
strains were applied, the full reaction pathways changed
significantly. Under 3% lateral compressive strain, the first
activation barrier increases slightly, while the second barrier
increases significantly compared with the lateral strain free
system, making the second step as the rate-limiting step. By
increasing the lateral compressive strain to 6%, the first
activation barrier decreases to 17.25 kcal/mol, which facilitates
the hydrogenation from ethylene to ethyl.
2
For PhNO @Ru (0001), previous studies have indicated that
the parallel adsorption mode over the metal surface is preferable
over vertical adsorption mode. Meanwhile, the direct reaction
pathway is preferable over indirect reaction pathway.[11] Hence,
in this study, only the parallel adsorption mode together with
direct reaction pathway are considered. Because identifying all
transition-state structures along the potential energy surface is
computationally prohibitive for this system, we optimized the
geometries of key intermediates in the direct pathways to
compare the stability of the intermediates based on the scheme
provided by Mahata et al.[12] In parallel adsorption mode,
nitrobenzene was placed parallel to the Ru (0001) surface,
where the π-electron of the aromatic ring is in direct interaction
with metal surface. PhNO
2
is first reduced to nitrosobenzene
(
PhNO), which is accompanied by energy release (20.61
Kcal/mol, Fig 4b.) Hydrogen atom can attack PhNO intermediate
either on O-atom or N-atom which subsequently forms PhNOH
and PhNHO intermediates respectively. These two steps are
calculated to be endothermic by 10.75 and 5.27 Kcal/mol,
respectively. In the next step, one hydrogen atom interacts with
either PhNOH or PhNHO intermediate to form PhNHON
intermediate. These two steps are calculated to be endothermic
by 9.37 and 14.85 Kcal/mol, respectively. As PhNHOH is a very
stable intermediate,[13] the formation of PhNHOH should not
proceed through high endothermic pathway (via PhNHO
intermediate). The formed PhNHOH react with one hydrogen
atom to form the PhNH intermediate. The high exothermic value
(
-38.30 Kcal/mol) was due to the N-O bond breaking. Generally,
Figure 3. (a) Reaction network of the hydrogenation of 4-nitrostyrene, (b) The
selectivity of 4-aminostyrene and 4-nitroethylbenzene using Co-Ru catalysts
the reaction steps of nitrobenzene to aniline are exothermic.
When the lateral strains were applied, the energy profiles
changed significantly. When a 3% lateral compressive strain
was applied on the surface, all the relative energies of
intermediates changed slightly expect for PhNHOH. Exothermic
value for step PhNOH→PhNHOH changed from -9.37 to -5.92
Kcal/mol, which facilitates the reaction. However, under an even
larger lateral compressive strain, say 6%, the reduction reaction
may be blocked. Firstly, a huge endothermic value is needed in
the formation of PhNOOH. Secondly, the PhNOH is highly
unstable in this condition, which would make the PhNHO→
PhNHOH step as the preferable step. Overall, a 3% lateral
with different compressive lattice strain, and (c) Recycle test of the Co0.23
-
Ru0.77 catalysts in the hydrogenation of 4-nitrostyrene.
DFT calculations were carried out to verify whether the
selectivity of catalyst is determined by the lattice strain of Ru.
Two prototypes, C
chosen to investigate the catalysis selectivity. For C
0001), one carbon atom was located at the Ru top site, and the
2
H
4
@Ru(0001) and PhNO
2
@Ru(0001), were
2
H
4
@Ru
(
other one was located at the hollow site, which is consistent with
the early study.[8] The full reaction pathways for ethylene
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Angewandte Chemie International Edition
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COMMUNICATION
compressive strain can facilitate the reaction. When a larger
lateral compressive strain (6%) is applied, the entire reaction
may be blocked. Based on the above results of both
National Natural Science Foundation of China (21521091,
21390393, U1463202, 21471089, 21671117). We thank the
1W1B station for XAFS measurement in Beijing Synchrotron
Radiation Facility (BSRF) and the BL10B for XPS measurement
at National Synchrotron Radiation Laboratory (NSRL) in Hefei,
China.
C
2
H
4
@Ru(0001) and PhNO
small lateral compressive strain facilitates hydrogenation of
PhNO2 but impedes the hydrogenation of C . With increasing
lateral strain, the hydrogenation of PhNO is impedes but the
hydrogenation of C process is facilitated.
2
@Ru(0001), we determined that the
2
H
4
2
2
H
4
Keywords: Ru nanoparticle • metal catalysts • lattice strain •
hydrogenation reaction
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2
to
2
.
In summary, we have demonstrated that the selectivity of
metal catalysts could be effectively controlled by rationally tuning
metal lattice strain. The aberration corrected HRTEM and XAFS
studies proved that introducing Co atoms into Ru catalysts could
compress the Ru lattice strain. We observed obvious
improvement (from 66% to 99%) in Ru catalytic selectivity for
hydrogenation of 4-nitrostyrene to 4-aminostyrene under 3%
lattice compression, which is consistent with the theoretical
calcination results. We believe that such an approach could help
us to achieve the rational design of ideal metal catalysts, which
have wide applications beyond hydrogenation reaction.
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Acknowledgements
2
This work was supported by China Ministry of Science and
Technology under Contract of 2016YFA (0202801), and the
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COMMUNICATION
COMMUNICATION
Introducing Co atoms into Ru
catalyst could compress the
Ru lattice strain, thus further
affect catalytic selectivity for
hydrogenation of 4-
Junjie Mao, Wenxing Chen,
Wenming Sun, Zheng Chen,
Jiajing Pei, Dongsheng He,
Chunlin Lv, Dingsheng Wang*
and Yadong Li*
nitrostyrene to 4-
aminostyrene. The theoretical
studies reveal that the
Page No. – Page No
Rational Control on the
Selectivity of Ru Catalyst for
Hydrogenation of 4-
Nitrostyrene via Strain
Regulation
optimized lateral compressive
strain facilitates
hydrogenation of nitro-group
but impedes the
hydrogenation of vinyl-group.
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