Room-Temperature Chemoselective Reduction of 3-Nitrostyrene to 3-Vinylaniline by Ammonia Borane over Cu Nanoparticles

Article abstract of DOI:10.1021/jacs.8b11303

We report a new strategy of controlling catalytic activity and selectivity of Cu nanoparticles (NPs) for the ammonia borane initiated hydrogenation reaction. Cu NPs are active and selective for chemoselective reduction of nitrostyrene to vinylaniline under ambient conditions. Their activity, selectivity, and more importantly, stability are greatly enhanced by their anchoring on WO_2.72 nanorods, providing a room-temperature full conversion of nitrostyrene selectively to vinylaniline (>99% yield). Compared with all other catalysts developed thus far, our new Cu/WO_2.72 catalyst shows much enhanced hydrogenation selectivity and stability without the use of pressured hydrogen. The synthetic approach demonstrated here can be extended to prepare various M/WO_2.72 catalysts (M = Fe, Co, Ni), with M being stabilized for many chemical reactions.

Full text of DOI:10.1021/jacs.8b11303

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Communication
Room-temperature Chemoselective Reduction of 3-nitrostyrene
to 3-vinylaniline by Ammonia Borane over Cu Nanoparticles
Mengqi Shen, Hu Liu, Chao Yu, Zhouyang Yin, Michelle
Muzzio, Junrui Li, Zheng Xi, Yongsheng Yu, and Shouheng Sun
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b11303 • Publication Date (Web): 20 Nov 2018
Downloaded from http://pubs.acs.org on November 20, 2018
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Room-Temperature Chemoselective Reduction of 3-Nitrostyrene
to 3-Vinylaniline by Ammonia Borane over Cu Nanoparticles
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†
Mengqi Shen, Hu Liu, Chao Yu, Zhouyang Yin, Michelle Muzzio, Junrui Li, Zheng Xi,
Yongsheng Yu,2* and Shouheng Sun1*
9
1Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States
2MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and
Chemical Engineering, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China
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Herein, we report copper (Cu) nanoparticles (NPs) as a new non-
noble catalyst to catalyze AB for selective reduction of 3-
nitrostyrene to 3-vinylaniline in ethanol at room temperature under
atmospheric pressure. When Cu NPs are coupled to WO2.72
nanorods (NRs), they show much improved activity and stability
for both AB ethanolysis and nitrostyrene hydrogenation to
vinylaniline with > 99 % chemoselectivity from 100 % conversion
within 1.5 h at 298 K. Alloying Cu with Ni or Pd increased its
catalytic power, but lost its selectivity as 3-nitrostyrene was fully
converted to 3-ethylaniline.
ABSTRACT: We report a new strategy of controlling catalytic
activity and selectivity of Cu nanoparticles (NPs) for ammonia
borane-initiated hydrogenation reaction. Cu NPs are active and
selective for chemoselective reduction of nitrostyrene to
vinylaniline under ambient conditions. Their activity, selectivity,
and more importantly, stability is greatly enhanced by their
anchoring on WO2.72 nanorods, providing a room temperature full
conversion of nitrostyrene selectively to vinylaniline (>99% yield).
Compared with all other catalysts developed thus far, our new
Cu/WO2.72 catalyst shows much-enhanced hydrogenation
selectivity and stability without using the pressured hydrogen. The
synthetic approach demonstrated here can be extended to prepare
various M/WO2.72 catalysts (M = Fe, Co, Ni) with M being
stabilized for many chemical reactions.
Cu NPs were synthesized by reductive decomposition of copper
(I) acetate (CuOAc).28-30 Figure 1A is the transmission electron
microscopy (TEM) image of Cu NPs with an average size of 7.0±
0.4 nm. They are uniform in size and shape, and tend to self-
assemble into a 2D superlattice array (Figures 1A & S1). The high-
resolution TEM (HRTEM) image (inset of Figure 1A) shows clear
lattice fringes of Cu NPs with a spacing distance of 0.21 nm, which
corresponds to the interplanar spacing of (111) planes of face-
centered cubic (fcc) Cu. The Cu NPs were deposited on the carbon
or silica support to give Cu/C or Cu/SiO2 catalysts (Figure S2). The
WO2.72 NRs with an average length of 80 nm and width of 6 nm
(Figure 1B) were prepared by reacting WCl4 with oleic acid (OAc)
and oleylamine (OAm) in 1-octadecene (ODE) at 553 K for 10 h.31
The average inter-fringe spacing of WO2.72 NRs is 0.38 nm (Inset
of Figure 1B), matching the 0.378 nm of (010) interplanar distance
of monoclinic WO2.72. To deposit Cu NPs on WO2.72 NRs, we
mixed Cu NPs and WO2.72 NRs in OAm and OAc under an Ar
atmosphere and heated the mixture solution at 553 K for 0.5 h to
give Cu/WO2.72, as shown in the representative TEM image
(Figures 1C & S3). After coupling Cu NPs with WO2.72 NRs, the
inter-fringe distance of Cu NPs slightly expands from initial 0.21
nm to 0.23 nm (inset of Figure 1C). The X-ray diffraction (XRD)
patterns of both Cu NPs and Cu/WO2.72 NRs (Figures 1D & S4)
show (111) diffraction peaks of Cu, as well as Cu2O due to the
surface oxidation of Cu NPs. The (111) peak in Cu/WO2.72 slightly
shifts to the low diffraction angle. Both TEM and XRD show that
Cu NPs “swell” a little once coupled to WO2.72, indicating that there
exists a strong coupling between Cu NPs and WO2.72 NRs in the
Cu/WO2.72 structure.
Selective reduction of functional aryl nitro (Ar-NO2) to amine
(Ar-NH2) group is an important step towards preparation of a wide
variety of organic compounds for pharmaceutical, polymer,
herbicidal, and fine chemical applications.1-3 Nanosized transition
metals/metal oxides have shown great potential as heterogeneous
catalysts for the –NO2 reduction because of their high activity, ease
of separation, and recyclability.4 However, what is difficult to
achieve is selective reduction of Ar-NO2 without affecting other
reducible groups under the catalytic condition. In particular, the
selective reduction of Ar–NO2 over a vinyl group (Ar-C=C) in an
aromatic compound remains to be challenging due to the
uncontrolled hydrogenation of both Ar-NO2 and Ar-C=C.5-10 Since
Corma and Serna first reported that Au-based catalysts can show
good selectivity in the reduction of 3-nitrostyrene in 2006,5 much
progress has been made in using Au,6, 11-12 Pt,13-16 Ag,17 Pd,9 and
Ru10 catalysts for the selective reduction process. Recently, using
non-noble metals to catalyze the same reaction also attracted much
attention: Ni/TiO2 showed 90 % selectivity of 3-vinylaniline at 93 %
conversion under 723 K and 15 bar of H2;16 Fe2O3-based catalyst
gave 93 % selectivity on 100 % conversion under 393 K and 50 bar
of H2 after 16 h;18 and Co3O4-based catalyst was even more
efficient at 383 K, 50 bar H2, 6 h with 91 % selectivity and > 99 %
conversion.19 Despite the progress made in non-noble metal
catalysts for the selective hydrogenation process,20-21 the catalytic
reaction generally requires > 373 K temperature, high pressure of
H2 and hours of reaction time to complete.
Ammonia borane (AB) is regarded as a safe material for
hydrogen storage (19.6 wt % hydrogen) and transport (solid at
room temperature). In the presence of a transition metal catalyst,
H2 can be released from AB under ambient conditions,22-23 and AB
has been used widely for hydrogenation reaction in milder reaction
conditions to reduce nitrobenzenes to their amine derivatives.24-27
However, this hydrogenation process can become complicated
when there exists a second reducible functional group in the
aromatic structure as the competition between two reduction
reactions often causes poor selectivity.
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(Figure S7), which is supported by the previous report that WO2.72
NRs can stabilize Cu component in the CuPd alloy structure after
its strong coupling to WO2.72
32 SiO2 support can also improve the
activity of Cu NPs to a certain degree as compared with the carbon
support due to the stronger AB adsorption power of the hydrophilic
SiO2 surface.34
1
2
3
4
.
5
Next, we investigated the Cu NP catalysis for chemoselective
hydrogenation of Ar–NO2 into Ar–NH2 in the presence of Ar-C=C,
which is one of the most competitive and demanding selective
reduction reactions leading to the formation of functional amines.
We tested Cu/C, Cu/SiO2, or Cu/WO2.72 for AB-initiated
hydrogenation of a mixture of nitrobenzene and styrene at 298 K
(Table S1). They are all active and selective to the reduction of -
NO2 while –C=C in the styrene structure is intact, inferring that the
Cu NPs activate only Ar-NO2, not Ar–C=C. Cu/WO2.72 shows the
best hydrogenation activity among the three Cu NP catalysts
studied due to its more evident synergistic effect between Cu and
WO2.72. Then, we chose 3-nitrostyrene as a model molecule to
further study the chemoselectivity of Cu NPs. From our tests (Table
1), we can see that the Cu NPs show high selectivity to the
reduction of –NO2 to –NH2 in AB-initiated hydrogenation of 3-
nitrostyrene. Particularly, Cu/WO2.72 demonstrates an outstanding
chemoselectivity (> 99 %) to 3-vinylaniline at full conversion of 3-
nitrostyrene within 1.5 h at 298 K. No other byproducts were
detected. SiO2- and C-supported Cu NPs exhibit excellent
selectivity as well (98 % for SiO2-Cu, 95 % for C-Cu) after longer
time of reaction. Our Cu NPs are much superior to other non-noble
metal catalysts reported previously (Table S2). We tested the
Cu/WO2.72 catalyst for its hydrogenation of other nitroarenes that
contain vinyl or other reducible groups (Table S3). All these
nitroarenes are selectively hydrogenated. We further compared Cu
NP catalysis with CuNi26 and CuPd35 alloy NPs (Figure S8) that are
more active for AB hydrogen evolution than pure Cu NPs to
evaluate the hydrogenation of 3-nitrostyrene under the same
condition (Table 1). Both CuNi and CuPd NPs show poor
selectivity, catalyzing the hydrogenation of 3-nitrostyrene directly
to 3-ethylaniline (> 99 % yield within 1.5 h) (Table 1, Entries 4 &
5). However, when Ar-C=O co-exists with Ar-NO2, our Cu/WO2.72
catalyst did not show the desired chemoselective reduction of Ar-
NO2 due most likely to the high reducing power AB to Ar-C=O.36
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Figure 1. TEM (inset HRTEM) images of (A) Cu NPs; (B) WO2.72
NRs; (C) Cu/WO2.72 composites, and (D) XRD patterns of Cu NPs,
WO2.72 NRs and Cu/WO2.72 composites.
The electronic structure of Cu NPs and Cu/WO2.72 was
characterized by X-ray photoelectron spectroscopy (XPS). Once
Cu NPs are coupled with WO2.72 NRs, the binding energy of
Cu+/Cu0 (2p3/2 and 2p1/2) becomes slightly larger and new peaks
corresponding to Cu2+ species show up (2p3/2: 932.14 eV for Cu,
932.26 eV for Cu/WO2.72; 2p1/2: 952.05 eV for Cu, 952.48 eV for
Cu/WO2.72), indicating the decrease of surface electron density on
Cu NPs (Figure 2A). The change is similar to what was reported.32
Correspondingly, the binding energies of W4f in Cu/WO2.72 show
negative shifts compared with free WO2.72 NRs, suggesting the
possible negative charge transfer from Cu NPs to WO2.72 NRs. We
further studied the surface electrochemistry of Cu/WO2.72 in
CH2Cl2 by cyclic voltammograms (Figures S5). Compared to those
in the Cu/C, Cu NPs in the Cu/WO2.72 structure are more difficult
to be oxidized while the oxidized Cu NPs are also more difficult to
be reduced due to the electron polarization from Cu to WO2.72
,
which is consistent with what is concluded in the XPS data
analysis. The XPS spectra of Cu/SiO2 or Cu/C are identical with
that of free Cu NPs, indicating that there is no charge transfer
between Cu NPs and SiO2 or C support.
Table 1. Hydrogenation of 3-nitrostyrene with different Cu-based
catalysts.
Entry
Cat.
Yield / %
Time /
h
A
>99
98
95
0
B
0
C
0
1
2
3
4
5
6
Cu/WO2.72
Cu/SiO2
Cu/C
1.5
2.5
3
0
2
5
0
CuNi/SiO2
CuPd/SiO2
None
0
>99
>99
3
1.5
1.5
1.5
Figure 2. XPS spectra of (A) Cu 2p of Cu NPs and Cu/WO2.72 and
0
0
(B) W 4f of WO2.72 NRs and Cu/WO2.72
.
1
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Reaction conditions: 3-nitrostyrene (1 mmol), Cu-based catalysts (6
mole % Cu), ethanol (10 ml), AB (3 mmol), 298 K. Complete conversion
was observed in the cases of 1-5. Conversion and yields were determined
by GC-MS using dodecane as an internal standard.
We first tested the AB hydrogen evolution reaction in ethanol
solution catalyzed by Cu NPs deposited on different supports at 298
K (Figure S6). The Cu/WO2.72 is much more active than Cu/SiO2
and Cu/C due likely to the increased affinity of Cu+ to AB, and
33
WO2.72 to “H” in the Cu/WO2.72 structure.31,
Moreover,
Cu/WO2.72 demonstrates a superb stability for AB ethanolysis
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Finally, we conducted stability tests of Cu NPs catalysts in the
Materials and experimental methods, Figures S1–S11, and Tables
1
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3
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5
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7
8
reaction solution leading to chemoselective hydrogenation of 3-
nitrostyrene. The catalysts were recovered by simple centrifugation
followed by washing with water/ethanol. The Cu/C suffers a huge
loss in both activity and selectivity during the cycles (Figure S9).
The Cu NPs on carbon support were seen heavily aggregated on the
C surface after the fourth catalytic reaction (Figure S10), similar to
what have been observed.37-38 The Cu/SiO2 shows an improved
stability due to the stronger binding between Cu NPs and SiO2,
similar to the case of Ni/SiO2 for AB hydrolysis,34 but is still not as
robust as the Cu/WO2.72, which is the most stable catalyst,
maintaining its initial activity and selectivity after six catalytic
cycles (Figure 3) without showing any noticeable morphology
change (Figure S11). This stability test further confirms that strong
interfacial interaction between Cu NPs and WO2.72 is essential to
activate and stabilize Cu NPs for their active and selective
hydrogenation of nitrostyrene to vinylamine.
S1–S3.
AUTHOR INFORMATION
Corresponding Author
*ssun@brown.edu
*ysyu@hit.edu.cn
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Author Contributions
M.S and H.L contributed equally to this study.
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Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
This work was supported in part by the U.S. Army Research
Laboratory and the U.S. Army Research Office under grant
W911NF-15-1-0147, and by the Office of Vice President of
Research of Brown University. M.M. is supported by the National
Science Foundation Graduate Research Fellowship, under Grant
No. 1644760.
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