Fe-Co Alloyed Nanoparticles Catalyzing Efficient Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol in Water

Article abstract of DOI:10.1002/anie.202009913

Selective hydrogenation of C=O against the conjugated C=C in cinnamaldehyde (CAL) is indispensable to produce cinnamyl alcohol (COL). Nonetheless, it is challenged by the low selectivity and the need to use organic solvents. Herein, for the first time, we report the use of Fe-Co alloy nanoparticles (NPs) on N-doped carbon support as a selective hydrogenation catalyst to efficiently convert CAL to COL. The resultant catalyst with the optimized Fe/Co ratio of 0.5 can achieve an exceptional COL selectivity of 91.7 % at a CAL conversion of 95.1 % in pure water medium under mild reaction conditions, ranking it the best performed catalyst reported to date. The experimental results confirm that the COL selectivity and CAL conversion efficiency are, respectively promoted by the presence of Fe and Co, while the synergism of the alloyed Fe-Co is the key to concurrently achieve high COL selectivity and CAL conversion efficiency.

Full text of DOI:10.1002/anie.202009913

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
www.angewandte.org
Accepted Article
Title: Fe-Co Alloyed Nanoparticles Catalysed Efficient Hydrogenation
of Cinnamaldehyde to Cinnamyl Alcohol in Water
Authors: Yang Lv, Miaomiao Han, Wanbing Gong, Dongdong Wang,
Chun Chen, Guozhong Wang, Haimin Zhang, and Huijun
Zhao
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: Angew. Chem. Int. Ed. 10.1002/anie.202009913
Link to VoR: https://doi.org/10.1002/anie.202009913

10.1002/anie.202009913
Angewandte Chemie International Edition
COMMUNICATION
Fe-Co Alloyed Nanoparticles Catalysed Efficient Hydrogenation
of Cinnamaldehyde to Cinnamyl Alcohol in Water
Yang Lv,+[a,b] Miaomiao Han,+[a] Wanbing Gong,*[a] Dongdong Wang,[a,b] Chun Chen,[a] Guozhong Wang,
[a] Haimin Zhang[a] and Huijun Zhao*[a,c]
have constantly demanded to replace organic solvents with
water, however, the development of new catalysts capable of
SH of CAL in pure aqueous medium is required.
Abstract: Selective hydrogenation of C=O against the conjugated
C=C in cinnamaldehyde (CAL) is indispensable to produce cinnamyl
alcohol (COL), nonetheless, challenged by the low selectivity and
the need to use organic solvents. Herein, for the first time, we report
the use of Fe-Co alloy nanoparticles (NPs) on N-doped carbon
support as a selective hydrogenation catalyst to efficiently convert
CAL to COL. The resultant catalyst with the optimized Fe/Co ratio of
0.5 can achieve an exceptional COL selectivity of 91.7% at a CAL
conversion of 95.1% in pure water medium under mild reaction
conditions, ranking it the best performed catalyst reported to date.
The experimental results confirm that the COL selectivity and CAL
conversion efficiency are respectively promoted by the presence of
Fe and Co, while the synergism of the alloyed Fe-Co is the key to
concurrently achieve high COL selectivity and CAL conversion
efficiency.
To improve the selectivity towards COL, various strategies
have been reported. One widely investigated strategy is to
create a steric hindrance barrier on the catalyst surface via
chelating organic ligands[9,11,12] or encapsulating the catalytic
active sites by metal−organic frameworks (MOFs)[1,5,13] that
regulates the spatial orientation of CAL to facilitate CAL
approaching the catalytic active sites with its C=O group.
Nonetheless, the enhanced COL selectivity is accompanied by
the reduced CAL conversion efficiency due to the suppressed
mass transport by the selectivity barriers.[1,9] Another strategy
employs transition-metal/noble-metal (Pt is the most used)
bimetallic catalysts to create synergetic electronic effects that
thermodynamically favoured the hydrogenation of C=O in
CAL.[6,14-16] In theory, this strategy can enhance COL selectivity
without compromising the CAL conversion efficiency, however,
the use of scarce and expensive noble-metals is undesirable.
Cinnamyl alcohol (COL) is an essential substance/precursor
highly demanded by flavouring, perfume and pharmaceutical
industries.[1-4] To date, the industrial production of COL has been
carried out exclusively via the selective hydrogenation (SH) of
cinnamaldehyde (CAL) in organic solvents.[5-7] The efficiently
utilizing CAL is the most critical issue for COL production
because large quantities of CAL can only be obtained in an
economically viable manner via extraction processes from the
bark of cinnamon and other CAL containing trees with limited
nature reserves. Presently, SH of CAL to COL is challenged by
the unfavoured thermodynamics that leads to low selectivity
toward COL.[1,8-10] Also, the use of organic solvent in COL
production pollutes the environment and requires post-
production separation. For these reasons, the relevant industries
Up till now, only few literatures reported the use of water as
the solvent and nonprecious metals as the catalyst for SH of
CAL.[11,17] For example, Ni2P innovatively chelated with p-
fluorothiophenol was reported by Zou’s group to create steric
and electronic effects for SH of CAL in both aqueous and
organic solvents.[11] They successfully demonstrated a high COL
selectivity of 91.2%, but with a reduced CAL conversion to
40.2%, due to the chelating layer induced mass transport
resistance. Another example employed
a copper cluster
encapsulated by dendrimer selectivity barrier for
a
hydrogenation of a series of substrates including CAL. The
catalyst is capable of SH of CAL to produce COL in water with
excellent selectivity and conversion efficiency, nonetheless,
requiring to use a large amount of NaBH4 after each catalytic run
to regenerate the oxidized catalyst.[17] Recently, Yang’s group
reported the first systematic mechanistic investigation of SH of
CAL to COL at carbon nanotube (CNT) supported bimetallic
PtFe catalysts in pure water.[6] Their theoretic studies and the
[a]
Y. Lv+, Dr. M. Han+, Dr. W. Gong, D. Wang, Dr. C. Chen, Prof. G.
Wang, H. Zhang, H. Zhao
Key Laboratory of Materials Physics
Centre for Environmental and Energy Nanomaterials
Anhui Key Laboratory of Nanomaterials and Nanotechnology
CAS Centre for Excellence in Nanoscience, Institute of Solid State
Physics, Chinese Academy of Sciences
Hefei 230031, (P. R. China)
experimental results revealed
a direct water participation
hydrogen-exchange pathway that can dramatically reduce the
energy barrier of hydrogenation of C=O in CAL. The best
performed catalyst (Pt3Fe/CNT) can achieve a high COL
selectivity of 97.2% with a CAL conversion of 62.1%. Despite the
enormous efforts and noticeable progress, the highly efficient
nonprecious catalyst for SH of CAL to COL in pure water has yet
been developed.
Tel: (+86) 551 65591263
E-mail: h.zhao@griffith.edu.au, wbgong@issp.ac.cn
Y. Lv+, D. Wang,
University of Science and Technology of China
Hefei 230026, P. R. China
Prof. H. Zhao
Centre for Clean Environment and Energy
Gold Coast Campus
Griffith University
[b]
[c]
Queensland 4222, Australia
These authors contributed equally to this work
Herein, we report a bimetallic transition-metals alloying
strategy to realise highly efficient conversion of CAL to COL in
pure water medium. A solution-based metal ion impregnation
approach is innovatively combined with pyrolysis to achieve the
controllable synthesis of highly dispersed Fe-Co alloy
[+]
Supporting Information for this article is available on the WWW
under
This article is protected by copyright. All rights reserved.

10.1002/anie.202009913
Angewandte Chemie International Edition
COMMUNICATION
nanoparticles (NPs) on N-doped graphitic carbon support. The
Fe-Co alloy catalyst with an optimal Fe/Co molar ratio of 0.5 can
concurrently achieve an exceptional COL selectivity of 91.7% at
a CAL conversion of 95.1%, ranking it the best performed
catalyst reported to date.
analysis indicates a 46.8 wt.% cobalt content in the obtained
Co@NC (Table S1). The resultant Co@NC was dispersed in n-
hexane, and the aqueous solution containing Fe3+ was added
drop-wisely
under
ultrasonication
to
achieve
Fe3+
impregnation.[21,22] The resultant Co@NC with impregnated Fe3+
(denoted as Co@NC/Fe3+) was then thermally treated under a
reductive H2/Ar atmosphere to obtain Fe0.5Co@NC. The ICP
analysis confirm the presence of 17.9 wt.% and 37.1 wt.% of Fe
and Co, respectively, equivalent to a Fe/Co molar ratio of 0.51
(Table S1). Typical scanning electron microscopy (SEM) images
(Figure 1b) reveal that the size and shape of the obtained
Fe0.5Co@NC are similar to that of Co@NC. Transmission
electron microscopic (TEM) images (Figure 1c) confirm that the
metallic NPs with an average size of 15.7 nm are
homogeneously embedded on the carbon support. The high-
resolution TEM (HRTEM) images of a typical NP (Figure 1d)
display a d-spacing of 0.202 nm, corresponding to the {110}
faceted metallic Fe-Co alloy. The X-ray diffraction (XRD) pattern
(Figure 1e) shows two peaks centred at 44.9° and 65.3°, which
are the signature diffraction peaks of the (110)/(200) faceted Fe-
Co alloy phase (JCPDS No. 49-1568). The high-angle annular
dark-field scanning transmission electron microscopy (HAADF–
STEM) and the corresponding elemental mapping images
(Figure 1f) confirm that Fe and Co are homogeneously
distributed in the Fe-Co alloy NPs. The line profiles of
representative NPs (Figure 1g) further confirm the
homogeneously distributed Fe and Co in the alloyed NPs. The
survey X-ray photoelectron spectroscopy (XPS) spectrum of
Fe0.5Co@NC indicates the presence of Fe, Co, C and N (Figure
S4). The high resolution Fe 2p spectrum (Figure 1h) indicates
the presence of metallic (707.4 and 720.1 eV) and ionic (711.3
and 724.7 eV) forms of Fe, while the peaks centred at 714.4 and
733.5 eV can be attributed to the shakeup satellite peaks.[23-25]
The high resolution Co 2p spectrum (Figure 1i) indicates the
presence of Co0 (779.0 and 794.1 eV),[23,26] while the peaks
centred at 781.1 and 796.8 eV with shakeup satellites (786.4
and 803.2 eV) correspond to Co-Nx species.[19,26,27] The high
resolution N 1s (Figure 1j) and C 1s (Figure 1k) spectra reveal
the existence of pyridinic N (398.9 eV) and graphitic N (400.9
eV),[28,29] and sp2-hybridized carbon (284.8 eV), C-O bonds
(286.5 eV) and O-C=O group (288.8 eV).[26,30]
As shown in Figure 2, the SH of CAL could occur at C=O or
C=C or both, leading to the formation of COL or
hydrocinnamaldehyde (HCAL) or hydrocinnamyl alcohol (HCOL),
respectively. The catalytic performance of Fe0.5Co@NC was
evaluated. The effect of reaction temperature was firstly
investigated under 2 MPa H2 pressure for 2 h (Figure 2a). The
CAL conversion is found to increase from 34.2 to 99.1% as the
Figure 1. (a) Schematic illustration of synthetic procedure of FeXCo@NC; (b-
c) SEM (inset: high-magnification SEM image) and TEM (insets: high-
magnification TEM image and Fe-Co NPs size distribution) images; (d)
HRTEM image (inset: high-magnification HRTEM image) of a Fe-Co NP; (e)
XRD pattern; (f-g) HAADF-STEM, corresponding elemental mapping images
and line profile of Fe-Co NPs; (h-k) High resolution XPS spectra of Fe 2p, Co
2p, N 1s and C 1s of Fe0.5Co@NC.
o
temperature increasing from 50 to 100 C. Within 50-80 °C, the
COL selectivity decreased slightly from 93.1 to 91.7%, which
suggest that Fe0.5Co@NC catalysed hydrogenation on C=O is
more favourable than that of C=C under relatively low
temperatures. Interestingly, beyond 80 °C, the COL selectivity
decreased rapidly to 24.6%, accompanying by the rapidly
increased HCOL selectivity from 5.5 to 73.0%. These indicate
that the rapidly decreased COL selectivity at higher
temperatures is due to the occurrence of hydrogenation on both
C=O and C=C.[31] The effect of reaction time was then evaluated
under 2 MPa H2 pressure and 80°C. As revealed in Figure 2b,
an increase in the reaction time from 0.5 to 2 h leads to a rapid
Figure 1a schematically illustrates the synthetic procedure
of Fe-Co alloy NPs on N-doped graphitic carbon support
(denoted as FeXCo@NC, where, X represents the Fe/Co molar
ratio). In brief, the synthesised rhombic dodecahedron-shaped
ZIF-67 crystals[18-20] with sized between 1-2 µm (Figure S1) were
used as the precursor and firstly subjected to carbonization
treatment under H2/Ar atmosphere. The carbonized product
(denoted as Co@NC) retains the rhombic dodecahedron-shape
with densely populated Co NPs having an average size of 12.1
nm (Figures S2-3).[18,19] The inductively coupled plasma (ICP)
This article is protected by copyright. All rights reserved.

10.1002/anie.202009913
Angewandte Chemie International Edition
COMMUNICATION
Figure 2. Effect of (a) reaction temperature (2 h, 2 MPa H2, H2O); (b) reaction time (80 °C, 2 MPa H2, H2O); (c) H2 pressure (80 °C, 2 h, H2O) and (d) solvent
(80 °C, 2 MPa H2, 2 h) on CAL conversion efficiency and COL selectivity of Fe0.5Co@NC catalysed SH of CAL to COL. (e) Reusability of Fe0.5Co@NC (80 °C, 2
MPa H2, 2 h, H2O). (f) Catalytic performance of Fe@NC, Co@NC and FeXCo@NC (80 °C, 2 MPa H2, 2 h, H2O). Catalyst: 20 mg; CAL: 1 mmol; Solvent: 10 mL.
increase in CAL conversion from 44.5 to 95.1% and further
increase in the reaction time results in a neglectable increase in
CAL conversion. In contrast, the COL selectivity remained at
91.7% before decreased to 81.9% at 6 h due to the increased
HCAL selectivity beyond 5 h. The dependent on H2 pressure
was investigated at 80 °C with 2 h reaction time (Figure 2c). An
increase in H2 pressure to 2 MPa leads to a linearly increased
CAL conversion to 95.1% and levelled off with further increased
H2 pressures. As expected, within a 2 MPa H2 pressure range,
the COL selectivity increased slightly from 89.1 to 91.7%, then
linearly decreased to 68.0% with further increased H2 pressure
to 4 MPa due to the increased hydrogenation on both C=O and
C=C to form HCOL. In addition, the catalyst performance in
different solvents was studied (Figure 2d). The CAL conversion
efficiencies follow a trend of H2O (95.1%) > methanol (61.6%) >
ethanol (12.4%) > isopropanol (1.7%). This indicates that the
higher the solvent polarity, the higher the CAL conversion
efficiency. Such correlations between the solvent polarity and
CAL conversion efficiency was also observed by other
studies.[32,33] Another reason could be that N species enhance
the hydrophilicity of carbon-based catalysts, which is beneficial
for CAL approaching the surface of catalyst.[34,35] Although the
selectivity toward COL follows the same solvent polarity trend,
the generation of the by-products cannot be directly correlated to
the polarity of solvents. Nevertheless, the promotional effect of
H2O solvent to remarkably enhance the hydrogenation on C=O
and concurrently suppress the hydrogenation on C=C is
categorically confirmed. This is likely due to the strong
interactions/possible hydrogen-bond formations of H2O with
C=O and catalyst surface site that makes the selective
adsorption of CAL on catalyst surface site via C=O a preference
hydrogenation reaction step, leading to an accelerated reaction
kinetics and improved COL selectivity.[6] The achieved
performance of Fe0.5Co@NC under these conditions is the best
among the reported high performance catalysts for SH of CAL in
water (Tables S2 and 3). Impressively, when a high CAL
concentration of 5 mmol in water was used, a high CAL
conversion of 97.9% with a high COL selectivity of 90.5% can
still be attained (Table S4). The reusability is an important
catalyst performance indicator and was therefore investigated
(Figure 2e). The well-maintained catalytic performance after
four-consecutive runs demonstrate
a
high stability and
reusability of Fe0.5Co@NC. This can be attributed to the superior
structural stability of Fe0.5Co@NC as evidenced by the almost
unchanged structure, morphology, crystal phase and chemical
forms of the reused Fe0.5Co@NC (Figures S5-7).
The performance of a alloyed catalyst can be strongly
influenced by its alloy composition.[36] For comparative purpose,
the pure Co and Fe NPs (denoted as Co@NC and Fe@NC),
and FeXCo@NC with different Fe/Co molar ratios (x = 0.3, 0.7
and 1.0, Table S1) were synthesised. As shown in Figures S2
and 8, these catalysts possess similar shape and morphology as
that of Fe0.5Co@NC. However, the average alloyed NPs sizes
are found to increase with the increased Fe content. Their
corresponding HRTEM images (Figures S3 and 9) and XRD
This article is protected by copyright. All rights reserved.

10.1002/anie.202009913
Angewandte Chemie International Edition
COMMUNICATION
patterns (Figures S10) confirm the formation of Fe-Co alloys,
which are coincided with the phase diagram of Fe-Co (Figure
S11). The XPS survey spectra (Figure S4) and the high
resolution Fe 2p and Co 2p spectra (Figure S12) further confirm
the formation of Fe-Co alloys. The obviously shifted Fe and Co
binding energies in Figure S12 indicate the altered electronic
structures for both Fe and Co in the alloys.[23,37] The Raman
spectra display a pair of peaks at 1340 and 1600 cm−1 (Figure
S13), corresponding to the disordered carbon (D-band) and
graphitic carbon (G-band).[38] Noticeably, the BET surface areas
are found to decrease with increased Fe contents (Table S1 and
Figure S14).
electron cloud density of Co tends to attack the electrophilic
C=O rather than the nucleophilic C=C.[14,39-41]
The preferred adsorption and activation of CAL at the
alloyed metallic sites could be responsible for the high
performance achieved by the alloyed catalysts.[14,39] To verify
this hypothesis, H2 temperature-programmed desorption (H2-
TPD) on Co@NC and Fe0.5Co@NC was conducted. As shown in
Figure S15a, the desorption peak of Fe0.5Co@NC is 65 °C
higher than that of Co@NC, confirming a change of active sites
from Co to Fe-Co sites.[40,42] The preferred adsorption of CAL on
the Fe-Co alloyed surface can be directly evidenced by the
Fourier transform infrared (FT-IR) spectra shown in Figure S15b,
where, the adsorbed CAL on Fe0.5Co@NC is clearly visible.
The density function theory (DFT) calculations were
performed to unveil the critical role of Fe-Co alloy for the
improved COL selectivity. Based on the experimentally
measured structural characteristics of FeXCo@NC, the (111)
plane of Co and the (110) plane of Fe-Co alloy were chosen for
the DFT calculations. Figure 3 shows the most stable CAL
adsorption configurations with vertical and parallel adsorptions
on the (111) plane of Co and (110) plane of Fe-Co alloy. For Co
(111) and Fe-Co (110), the calculated adsorption energy (Ead)
with vertical configurations are -0.54 and -7.82 eV, respectively
(Figure 3a-b). However, with parallel configurations, Ead values
are -1.42 and -7.18 eV, respectively (Figure 3c-d), which mean
that CAL prefers to absorb on the (110) plane of the Fe-Co alloy
and (111) plane of the metallic Co with vertical and parallel
configurations, respectively. These DFT results are well
consistent with the obtained experimental results. The
preference of vertical configuration with Fe-Co alloy catalyst
imply that the high COL selectivity achieved by Fe0.5Co@NC is
likely due to the adsorption of CAL selectively through C=O.
Figure S16 shows the deformation charge density of CAL
adsorption on Fe-Co alloyed surface with the vertical
configuration. The transferred charge from the Fe-Co alloy
surface to the O atom in C=O of CAL is 0.26 e- more than that
from the pure Co surface, for which, the most of the transferred
electrons are contributed by the alloyed Fe atoms. This suggests
that the C=O in CAL is activated through losing electrons from
its O atom to the alloyed Fe atoms. Besides, the C=O in CAL is
activated through losing electrons, which can be reflected by
the increased C=O bond lengths from 1.230 to 1.264 and 1.268
Å for Co and Fe-Co activated CAL, respectively.
Figure 3. DFT Optimized geometries for CAL absorbed on the catalyst
surfaces with vertical and parallel configurations. (a) Co (111) and (b) Fe-Co
(110) with vertical configurations; (c) Co (111) and (d) Fe-Co (110) with
parallel configurations. Orange, blue, brown, red, and white spheres represent
iron, cobalt, carbon, oxygen and hydrogen atoms, respectively.
To identify the role of Fe and Co, the performance of
Fe@NC, Co@NC and FeXCo@NC were performed (Figure 2f
and Table S5). Fe@NC exhibits poor catalytic activity with 8.9%
CAL conversion efficiency, but a relatively high COL selectivity
(58.7%), indicating that the Fe catalysed hydrogenation on C=O
is more favoured. In strong contract, Co@NC possess high
catalytic activity to achieve almost 100% conversion, probably
due to the presence of Co-Nx active sites, which has been
demonstrated by our previous study,[28] however, very poor COL
selectivity (< 1%), indicating an indiscriminate hydrogenation of
C=C and the C=O by Co. As expected, for the alloyed catalysts,
an increase in the Fe content leads to a decreased CAL
conversion efficiency. Interestingly, the COL selectivity of
FexCo@NC is increased when Fe/Co molar ratios are increased
to 0.5, then decreased with further increased Fe/Co molar ratios,
indicating an alloying induced synergetic effect due to the
electronic structural changes of alloyed Fe and Co as evidenced
by the shifted Fe 2p and Co 2p peaks shown in Figure S12. To
be specific, the Co0 peak shifted from 779.3 eV in Co@NC to
779.0 eV in Fe0.5Co@NC, while the Fe0 peak shifted from 707.1
eV in Fe@NC to 707.4 eV in Fe0.5Co@NC, which are resulted
from an increased electron cloud density of Co by alloying with
Fe species. These suggest that CAL preferred to adsorb on Fe-
Co alloy via C=O bond rather than C=C because the higher
In summary, an alloying strategy is proposed and
experimentally validated to dramatically enhance the
performance of Fe-Co bimetallic catalysts toward the SH of CAL
to COL in pure water medium. The alloyed catalyst with the
optimal Fe/Co ratio of 0.5 can achieve an extraordinary COL
selectivity of 91.7% at a 95.1% CAL conversion efficiency. The
obtained results unveil that the CAL conversion efficiency and
COL selectivity can be readily tuned by altering the Fe and Co
molar ratio, while the synergism of the alloyed Fe-Co is key to
concurrently achieve high COL selectivity and CAL conversion
efficiency. The demonstrated transition-metals alloying strategy
in this work could be adaptable to concurrently improve the
conversion efficiency and selectivity of other hydrogenation
reactions.
This article is protected by copyright. All rights reserved.

10.1002/anie.202009913
Angewandte Chemie International Edition
COMMUNICATION
[33] W. Gong, C. Chen, Y. Zhang, H. Zhou, H. Wang, H. Zhang, Y. Zhang, G.
Wang, H. Zhao, ACS Sustainable Chem. Eng. 2017, 5, 2172 -2180.
[34] W. Yang, X. Liu, X. Yue, J. Jia, S. Guo, J. Am. Chem. Soc. 2015, 137,
1436-1440.
[35] L. He, F. Weniger, H. Neumann, M. Beller, Angew. Chem. Int. Ed. 2016,
55, 12582-12596.
[36] H. Guo, H. Li, K. Jarvis, H. Wan, P. Kunal, S. G. Dunning, Y. Liu, G.
Henkelman, S. M. Humphrey, ACS Catal. 2018, 8, 11386-11397.
[37] X. Zhu, T. Jin, C. Tian, C. Lu, X. Liu, M. Zeng, X. Zhuang, S. Yang, L. He,
H. Liu, S. Dai, Adv. Mater. 2017, 29 1704091.
[38] Y. Li, B. Jia, Y. Fan, K. Zhu, G. Li, C.-Y. Su, Adv. Energy Mater. 2018, 8,
1702048.
Acknowledgements
This work was financially supported by the Natural Science
Foundation of China (Grant No. 51871209 and 51902311), the
Postdoctoral Science Foundation of China (Grant No.
2019M652223).
Keywords: Fe-Co nanoalloys • Metal-organic frameworks •
Selective hydrogenation • Cinnamaldehyde • H2O solvent
[39] C. Yang, S. Bai, Y. Feng, X. Huang, ChemCatChem 2019, 11, 2265-2269.
[40] Y. S. Yang, D. M. Rao, Y. D. Chen, S. Y. Dong, B. Wang, X. Zhang, M.
Wei, ACS. Catal. 2018, 8, 11749-11760.
[41] Hui, T.; Miao, C.; Feng, J.; Liu, Y.; Wang, Q.; Wang, Y.; Li, D., J. Catal.
2020, 389, 229-240.
[1] M. Zhao, K. Yuan, Y. Wang, G. Li, J. Guo, L. Gu, W. Hu, H. Zhao, Z. Tang,
Nature 2016, 539, 76-80.
[2] C. H. Hao, X. N. Guo, Y. T. Pan, S. Chen, Z. F. Jiao, H. Yang, X. Y. Guo,
J. Am. Chem. Soc. 2016, 138, 9361-9364.
[3] R. G. Rao, R. Blume, T. W. Hansen, E. Fuentes, K. Dreyer, S. Moldovan,
O. Ersen, D. D. Hibbitts, Y. J. Chabal, R. Schlogl, J. P. Tessonnier, Nat
Commun. 2017, 8, 340-350.
[42] T. Ishihara, N. Horiuchi, T. Inoue, K. Eguchi, Y. Takika, H. Araii, J. Catal.
1992, 136, 232-241.
[4] C. M. Cova, A. Zuliani, M. J. Munoz-Batista, R. Luque, Green Chem. 2019,
21, 4712-4722.
[5] K. Yuan, T. Song, D. Wang, X. Zhang, X. Gao, Y. Zou, H. Dong, Z. Tang,
W. Hu, Angew. Chem. Int. Ed. 2018, 57, 5708-5713.
[6] Y. Dai, X. Gao, X. Chu, C. Jiang, Y. Yao, Z. Guo, C. Zhou, C. Wang, H.
Wang, Y. Yang, J. Catal. 2018, 364, 192-203.
[7] M. Butt, X. Feng, Y. Yamamoto, A. I. Almansour, N. Arumugam, R. S.
Kumar, M. Bao, Asian J. Org. Chem. 2017, 6, 867-872.
[8] S. Fujiwara, N. Takanashi, R. Nishiyabu, Y. Kubo, Green Chem. 2014, 16 ,
3230-3236.
[9] B. Wu, H. Huang, J. Yang, N. Zheng, G. Fu, Angew. Chem. Int. Ed. 2012,
51, 3440-3443.
[10] Y. Bonita, V. Jain, F. Geng, T. P. O’connell, N. X. Ramos, N. Rai, J. C.
Hicks, Appl. Catal. B. 2020, 277, 119272-119283.
[11] R. Gao, L. Pan, H. Wang, Y. Yao, X. Zhang, L. Wang, J. J. Zou, Adv. Sci.
2019, 6, 1900054.
[12] Y. Zhu, H. Qian, B. A. Drake, R. Jin, Angew. Chem. Int. Ed. 2010, 49,
1295-1298.
[13] H. Liu, L. Chang, L. Chen, Y. Li, ChemCatChem 2016, 8, 946-951.
[14] H. Wang, S. Bai, Y. Pi, Q. Shao, Y. Tan, X. Huang, ACS Catal. 2018, 9,
154-159.
[15] N. Mahata, F. Gonçalves, M. F. R. Pereira, J. L. Figueiredo, Appl. Catal. A.
2008, 339, 159-168.
[16] G. Wang, H. Xin, Q. Wang, P. Wu, X. Li, J. Catal. 2020, 382, 1-12.
[17] P. Maity, S. Yamazoe, T. Tsukuda, ACS Catal. 2013, 3, 182-185.
[18] B. Y. Xia, Y. Yan, N. Li, H. B. Wu, X. W. Lou, X. Wang, Nat. Energy 2016,
1, 15006-15014.
[19] S. Liu, Z. Wang, S. Zhou, F. Yu, M. Yu, C. Y. Chiang, W. Zhou, J. Zhao, J.
Qiu, Adv. Mater. 2017, 29, 1700874.
[20] J. Meng, C. Niu, L. Xu, J. Li, X. Liu, X. Wang, Y. Wu, X. Xu, W. Chen, Q.
Li, Z. Zhu, D. Zhao, L. Mai, J. Am. Chem. Soc. 2017, 139, 8212-8221.
[21] C. Zhao, X. Dai, T. Yao, W. Chen, X. Wang, J. Wang, J. Yang, S. Wei, Y.
Wu, Y. Li, J. Am. Chem. Soc. 2017, 139, 8078-8081.
[22] Y. Xiong, Y. Yang, F. J. Disalvo, H. D. Abruna, J. Am. Chem. Soc. 2019,
141, 10744-10750.
[23] C.-Y. Su, H. Cheng, W. Li, Z.-Q. Liu, N. Li, Z. Hou, F.-Q. Bai, H.-X. Zhang,
T.-Y. Ma, Adv. Energy Mater. 2017, 7, 1602420.
[24] H. Xin, Y. Xue, W. Zhang, P. Wu, X. Li, J. Catal. 2019, 380, 254-265.
[25] Jiang, M.; Fu, C.; Cheng, R.; Zhang, W.; Liu, T.; Wang, R.; Zhang, J.; Sun,
B., Adv. Sci. 2020, DOI: 10.1002/advs.202000747.
[26] S. Sultan, J. N. Tiwari, J.-H. Jang, A. M. Harzandi, F. Salehnia, S. J. Yoo,
K. S. Kim, Adv. Energy Mater. 2018, 8, 1801002.
[27] W. Zhang, X. Jiang, X. Wang, Y. V. Kaneti, Y. Chen, J. Liu, J. S. Jiang, Y.
Yamauchi, M. Hu, Angew. Chem. Int. Ed. 2017, 56, 8435-8440.
[28] Y. He, S. Hwang, D. A. Cullen, M. A. Uddin, L. Langhorst, B. Li, S.
Karakalos, A. J. Kropf, E. C. Wegener, J. Sokolowski, M. Chen, D. Myers,
D. Su, K. L. More, G. Wang, S. Litster, G. Wu, Energy Environ. Sci. 2019,
12, 250-260.
[29] W. Gong, Y. Lin, C. Chen, M. Al-Mamun, H. S. Lu, G. Wang, H. Zhang, H.
Zhao, Adv. Mater. 2019, 31, 1808341.
[30] Z. Wang, Y. Dong, H. Li, Z. Zhao, H. B. Wu, C. Hao, S. Liu, J. Qiu, X. W.
Lou, Nat. Commun. 2014, 5, 5002-5010.
[31] W. Gong, M. Han, C. Chen, Y. Lin, G. Wang, H. Zhang, H. Zhao,
ChemCatChem 2020, 12, 1019-1024.
[32] Y. Deng, R. Gao, L. Lin, T. Liu, X. D. Wen, S. Wang, D. Ma, J. Am. Chem.
Soc. 2018, 140, 14481-14489.
This article is protected by copyright. All rights reserved.

10.1002/anie.202009913
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
A bimetallic Fe-Co alloying strategy is
innovatively utilized to concurrently
enhance the selectivity and conversion
efficiency for selective hydrogenation
of cinnamaldehyde to cinnamyl alcohol
in water. A Fe-Co alloy catalyst with a
Fe/Co molar ratio of 0.5 achieves an
exceptional selectivity of 91.7% at
95.1% conversion.
Y. Lv+, M. Han+, W. Gong*, D. Wang, C.
Chen, G. Wang, H. Zhang, H. Zhao*
Page No. – Page No.
Fe-Co
Alloyed
Nanoparticles
Catalysed Efficient Hydrogenation of
Cinnamaldehyde to Cinnamyl Alcohol
in Water
This article is protected by copyright. All rights reserved.