Highly Reusable and Active Nanometal?Silicon-Nanowire Array Hybrid Catalysts for Hydrogenation

Article abstract of DOI:10.1002/ejic.202001006

Highly reusable and active silicon-nanowire-array-stabilized metal-nanoparticle (SiNA-MNP) catalysts are prepared for effective hydrogenation under mild conditions. Monometallic Pd (SiNA-Pd), platinum (SiNA-Pt), and rhodium (SiNA-Rh) nanoparticles are pre

Full text of DOI:10.1002/ejic.202001006

Communications
doi.org/10.1002/ejic.202001006
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Highly Reusable and Active NanometalÀ Silicon-Nanowire
Array Hybrid Catalysts for Hydrogenation
[a]
[a]
[b]
[a]
Heeyoel Baek, Takuma Sato, Yasuhiro Uozumi, and Yoichi M. A. Yamada*
Highly reusable and active silicon-nanowire-array-stabilized
metal-nanoparticle (SiNA-MNP) catalysts are prepared for
effective hydrogenation under mild conditions. Monometallic
Pd (SiNA-Pd), platinum (SiNA-Pt), and rhodium (SiNA-Rh) nano-
particles are prepared on silicon nanowire arrays by the silver-
nanoparticle-assisted chemical etching of silicon wafers with a
variety of metal precursors. Moreover, bimetallic PdÀ Rh (SiNA-
PdRh) and PdÀ Pt (SiNA-PdPt) nanoalloy catalysts are also
synthesized in one-pot processes in mixed-metal solutions
without any reducing agent, such as NaBH or H gas, and other
neous or successive chemical reduction of one or two different
metal precursors, which often requires the use of a reducing or
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stabilizing agent, such as NaBH , N H , H gas, or a polymer
4 2 2 2
[6]
(Figure 1a). It is worth noting that the selection of a suitable
support material and the development of an appropriate
preparation method can enhance the catalytic activity of
[7]
supported metal nanoparticles.
Silicon nanowire arrays (SiNAs) can be used as nano-
[8]
structure templates and as reducing agents suitable for the
reductive formation of metal nanoparticles without the need
4
2
external factors. The SiNA-MNP catalysts were characterized by
SEM/EDX, TEM, XAFS, XRD, and ICP-MS. Each catalyst was used
to hydrogenate trans-stilbene in a 0.1 MPa hydrogen atmos-
phere to assess catalytic activity. Moreover, the SiNA-PdPt and
SiNA-PdRh alloy catalysts are also robust and stable, with high
reusability numbers for hydrogenation.
for an additional reducing agent, such as NaBH
or H gas, or
4 2
other external factors (Figure 1b and Figure 1c). The hydrogen-
[9]
terminated surfaces of SiNA readily reduce metal ions, such as
Pd, Ag, and Rh to metal aggregates of various morphologies on
[10]
SiNA surfaces in solution at room temperature. We previously
reported the preparation of monometallic SiNA-MNP (SiNA-Pd
and SiNA-Rh) and its use in organic transformations, such as the
Mizoroki–Heck reaction, CÀ H arylations, and carboxylic acid
[11,12]
The catalytic hydrogenation of a carbon–carbon multiple bond
is a useful and versatile chemical conversion in the fine
decarboxylations.
In particular, SiNA-Pd was found to be
highly reusable (over 150 times) during hydrogenation while
maintaining its high activity. Moreover, we showed that the
palladium nanoparticles were immobilized on the surface of the
metallic silicon nanowire array through the formation of
palladium silicide (PdSi). Since this metal–support interaction is
very strong, this immobilization method, which involves metal-
supported agglomeration, improves the stability and reusability
of a heterogeneous catalyst, and resolves problems associated
with metal leaching from the support.
[1]
chemicals, pharmaceuticals, and food industries. The hydro-
genation reactions are carried out by molecular hydrogen in
the presence of a Pt, Fe, Ni, Rh, Co, Ru, or Pd catalyst on a solid
[2,3]
support, such as silica, activated carbon, or alumina.
How-
ever, heterogeneous catalysts that are highly reusable and
stable are still in demand. Discovering a simple and general
catalyst that can facilitate catalytic hydrogenation under mild
conditions remains a challenging but rewarding task.
To further improve their catalytic performance, catalysts are
often modified in a variety of ways. Particularly, the bimetalliza-
tion of a solid support not only provides unique reaction
properties, such as electrical and alloy synergism, but also
[4]
efficient catalytic activity. For example, among such bimetallic
or alloy catalysts, SiO -supported PdÀ Ni bimetallic catalysts
2
have attracted significant attention due to their remarkable
[5]
stabilities and high selectivities.
The conventional preparation of a heterogeneous metallic
catalyst typically involves electrodeposition and the simulta-
[
[
a] Dr. H. Baek, Dr. T. Sato, Dr. Y. M. A. Yamada
RIKEN Center for Sustainable Resource Science,
351-0198 Wako, Saitama, Japan
E-mail: ymayamada@riken.jp
b] Prof. Dr. Y. Uozumi
Institute for Molecular Science (IMS),
444-8787 Okazaki, Aichi, Japan
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/ejic.202001006
Figure 1. Schematic images showing the preparation of solid-supported
metal-nanoparticle catalysts.
Part of the “Supported Catalysts” Special Collection.
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Communications
doi.org/10.1002/ejic.202001006
Herein, we report the development of monometallic nano-
the reduction of each metal ion on the SiNA surface bearing
terminal hydrogens. Moreover, we also developed bimetallic
catalysts containing palladium-platinum (PdPt) and palladium-
rhodium (PdRh) nanoparticles. Bimetal-doped SiNA catalysts
were prepared by a one-pot process under similar conditions in
a mixture of metal precursors devoid of reducing agents, such
as H gas or NaBH , at room temperature.
The morphology of catalysts and the size of nanoparticles
on SiNA were determined by using cross-sectional scanning
electron microscopy (SEM) and transmission electron micro-
scopy (TEM). SEM images of sections of SiNA-Pd (Figure 3a),
SiNA-Pt (Figure 3d), and SiNA-Rh (Figure 3g) reveal nanowire
lengths and widths of approximately 5–10 μm and below
900 nm, respectively. Dispersion of metal atoms over the
catalyst surfaces was mapped with energy-dispersive X-ray
(EDX), and showed that Pd (Figure 3b), Pt (Figure 3e), and
Rh(Figure 3h) nanoparticles are located across the entire surface
of their respective SiNAs.
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particle composites located in SiNA nanostructures. In addition,
we developed a method for the preparation of durable
bimetallic nanoparticle catalysts on SiNA using a facile one-pot
metal-supported agglomeration process. All SiNA-MNPs cata-
lyze the hydrogenation of trans-stilbene under mild conditions
and can be reused many times without the loss of catalytic
activity. At the same time, we investigated the structures of the
Pd, Rh, and Pt species on the SiNAs by SEM/EDX, TEM, XAFS,
and XRD.
Toward an additive-free approach devoid of reducing
agents, we developed an alternative synthetic method that
uses the hydrogen-terminated surface of SiNA. This strategy
involves a simple one-pot process to prepare monometallic and
bimetallic nanoparticle-SiNAs at room temperature. A schematic
image of the experimental route used to prepare SiNA-MNPs is
shown in Figure 2. Initially, SiNA is prepared by the silver-
nanoparticle-assisted chemical etching of a p-type silicon wafer
in a mixture of hydrofluoric acid and hydrogen peroxide. The
metal nanoparticles are agglomerated into the SiNA through
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The SEM images of bimetallic SiNA-PdPt (Figure 4a) and
SiNA-PdRh (Figure 4e) also show similar well-defined nano-
Figure 2. A schematic image depicting the preparation of SiNA-MNP catalysts.
Figure 3. Cross-sectional SEM/EDX and TEM images of monometallic SiNA-
MNP: (a–c) SiNAÀ Pd, (d–f) SiNA-Pt, and (g–i) SiNA-Rh.
Figure 4. Cross-sectional SEM/EDX images and TEM images of bimetallic
SiNA-MNP catalysts: (a–d) SiNA-PdPt and (e–h) SiNA-PdRh.
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structures, with the presence of bimetallic PdPt and PdRh
nanoparticles on the SiNA surfaces confirmed by EDX images
Figure 4b, Figure 4c and Figure 4f, Figure 4g). The TEM images
of SiNA-Pd, -Pt, and -Rh reveal dispersed Pd, Pt, and Rh
nanoparticles with diameters of approximately 9–11 nm, 3–
spectrum of bimetallic SiNA-PdRh in R-space (Figure 5f) sug-
gests that the RhÀ metal bond is elongated compared to those
in Rh foil and monometallic SiNA-Rh, which indicates the
existence of PdÀ Rh solid-solution alloy nanoparticles. The fitted
data for the first coordination shell in R-space (1.9–2.8 Å) are
summarized in Table 1, which shows that the mean coordina-
tion number of each metal (Pd or Rh) in each catalyst sample
(SiNA-Pd, -Rh, or -PdRh) is lower than that of the face-centered
cubic-packed bulk metal (7.3–8.8 vs. 12). Most importantly, the
RhÀ M (M=Pd, Rh (3:1)) bond in SiNA-PdRh is clearly longer
(2.700 Å) than that in Rh foil (2.689 Å). XPS revealed that the Pt
4f7/2 binding energy of SiNA-PdPt (70.3 eV) is negatively shifted
compared to that of monometallic SiNA-Pt (70.5 eV), suggesting
charge transfer from Pd atoms to Pt atoms (Figure S1,
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(
4
nm, and 4–5 nm, respectively (Figure 3c, Figure 3f, Figure 3i),
while the TEM images of bimetallic SiNA-PdPt and SiNA-PdRh
show dispersed nanoparticles with diameters of approximately
7
–9 nm and 9–11 nm, respectively (Figure 4d and Figure 4h).
To investigate the chemical states of the nanoparticles,
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monometallic SiNA-Pd and SiNA-Rh, as well as bimetallic SiNA-
PdRh, were subjected to XAFS experiments at the Pd K-edge
(24.4 keV) and Rh K-edge (23.2 keV). By comparison with Pd and
Rh foil as reference materials, the XANES spectral features of the
catalyst samples on Pd (Figure 5a) and Rh (Figure 5d) clearly
reveal that both Pd and Rh are in their metallic zero-valence
oxidation states, while the catalyst samples show reduction in
extended X-Ray absorption fine structure (EXAFS) intensity in k-
space (Figure 5b (Pd) and Figure 5e (Rh)) and R-space (Figure 5c
[13]
Supporting Information).
Since distinguishing atomic species with close atomic
numbers ( Rh and 46Pd) is difficult by EXAFS, the structures and
4
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phase information of the metallic nanoparticles were further
investigated by XRD (Figure 6). Pd nanoparticles on SiNA exhibit
diffraction peaks at around 40.1° and 46.6° that are assigned to
the (111) and (200) planes, respectively, of the face-centered
cubic structure (fcc) of Pd (Figure 6, deep-green trace; PDF
00-0046-1043). The diffraction peak at 41.1° of the Rh nano-
(Pd) and 5f (Rh)), which strongly suggests that metallic Pd and
Rh nanoparticles are formed on the surface of the silicon
nanowire array through chemical reduction by the hydrogen-
terminated silicon surface. Furthermore, the Rh K-edge EXAFS
particles are assigned to the (111) crystalline plane of metallic
Rh (Figure 6, green trace; PDF 00-005-0685). Similarly, the main
(111) reflection of the formed PdRh is shifted along the 2θ axis
to 40.2°, and lies between the limits of pure Pd and Rh,
consistent with the formation of the PdRh alloy (Figure 6, red
[14]
trace). The diffractin peaks of PdPt bimetallic nanoparticles
on SiNA are observed between the limits of pure Pd and Pt
[15]
(
Figure S3, Supporting Information) . In addition, the remain-
ing intense reflections are ascribed to the silicon nanowire array
and the silicon substrate, which is due to the introduction of
the silicon wafer as the catalyst support. These data provide
evidence for the formation of PdRh and PdPt alloys.
We used ICP-MS to determine the nanoparticle loading on
SiNA, which revealed contents of 14.0 μmol/g, 6.07 μmol/g, and
4
.32 μmol/g on SiNA-Pd, -Pt, and -Rh, respectively. The actual
ratio between metals contents in bimetallic SiNA-PdPt and
Figure 5. XAFS data for SiNA-Pd, SiNA-Rh, and SiNA-PdRh. (a) Pd K-edge
XANES, (b) Pd K-edge EXAFS in k-space, (c) Pd K-edge EXAFS in R-space,
(
d) Rh K-edge XANES, (e) Rh K-edge EXAFS in k-space, (f) Rh K-edge in R-
À 1
space (k-range: 3–15 Å ).
[a]
Table 1. EXAFS fitting data.
[b]
[c]
Sample
Edge
N
R [Å]
σ2 [Å2]
R factor
[d
Pd foil
SiNA-Pd
SiNA-PdRh
Rh foil
SiNA-Rh
Pd-K
Pd-K
Pd-K
Rh-K
Rh-K
Rh-K
12 ]
2.742(3)
2.740(2)
2.739(2)
2.689(2)
2.685(3)
2.700(4)
0.006
0.006
0.007
0.005
0.006
0.007
0.002
0.001
0.002
0.002
0.002
0.004
[
e]
8.8(4)
7.9(5)
[
[
e,f]
e,f]
[d]
12
[e]
7.3(5)
8.4(8)
SiNA-PdRh
À 1
2
[
a] k-Range: 3–15 Å , R-range: 1.9–2.8 Å. S
0
is assumed to be 1. All spectra
were acquired at room temperature. [b] Mean coordination number of the
first coordination shell. [c] Pd(Rh)À Pd(Rh) distance. [d] The coordination
number of the bulk-metal foil is assumed to be 12. [e] Acquired in
fluorescence mode. [f] The ratio of Rh:Pd is ~1:3, based on ICP-MS.
Figure 6. XRD patterns of monometallic Pd, Rh, and bimetallic PdRh on SiNA.
Eur. J. Inorg. Chem. 2021, 708–712
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nd
rd
-
0
PdRh are 0.65:0.35 (11.2 μmol/g Pd+5.97μmol/g Pt) and
.81:0.19 (8.55 μmol/g Pd+1.996 μmol/g Rh).
gave bibenzyl in 95% (2 use) and 55% yield (3 use), with
significant loss of catalytic activity. On the other hand, both
bimetallic catalysts (SiNA-PdRh and -PdPt) exhibited no signifi-
cant loss of catalytic activity and were reusable over 50 times
with persistent catalyst activity observed (Figure 7). Cumulative
turnover numbers (TONs) were calculated by normalizing
bibenzyl conversion; the TONs of the catalysts are 29,100 (based
on total PdPt nanoparticle) and 12,375 (based on total PdRh
nanoparticle), respectively. The bimetallic nanoalloy catalysts
(SiNA-PdRh and -PdPt) were more durable and exhibited
greater catalytic activity when Pd was present, with higher
reusability numbers and significantly improved stabilities
observed.
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The catalytic performance of the SiNA-Pd, -Pt, -Rh, -PdPt,
and -PdRh catalysts was evaluated by hydrogenating trans-
stilbene (1) to bibenzyl (2) in EtOH at 70°C. The monometallic
SiNA-Pd and -Rh catalysts gave 2 in yields of up to 99%, while
the SiNA-Pt catalyst showed lower catalytic activity (70% yield
after 24 h). The bimetallic SiNA-PdPt and -PdRh catalysts
exhibited high catalytic activities over 24 h in 0.1 MPa of
hydrogen gas to deliver yields of 99% (Scheme 1).
To further evaluate the catalytic performance of the
catalysts, they were subjected to reusability testing under
similar conditions to those described above. Monometallic
SiNA-Pd showed high hydrogenation activity (Figure 7); how-
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In summary, we successfully prepared monometallic SiNA-
Pd, SiNA-Rh, and SiNA-Pt catalysts by the confined metal
etching of silicon nanowire arrays with Ag nanoparticles.
Moreover, PdRh and PdPt alloy catalysts were also synthesized
on SiNA through a simple one-pot process in mixed-metal
solutions without any external factors. The prepared catalysts
were used to catalytically hydrogenate trans-stilbene under
hydrogen and then reused. SiNA-Pd and the SiNA-PdPt and
SiNA-PdRh nanoalloy catalysts were catalytically stable com-
pared to the other monometallic catalysts (SiNA-Pt and -Rh).
Moreover, they were reused more than 50 times without
significant loss of catalytic activity. The method described
herein provides a simple approach to the synthesis of highly
stable and robust alloy or monometallic catalysts on silicon
supports; we believe that it will be useful when designing new
powerful catalytic systems for green and sustainable organic
reaction applications.
nd
ever, SiNA-Pt showed poor reusability with yields of 63% (2
use) and 51% (3 use). In addition, the SiNA-Rh catalyst also
rd
Scheme 1. Hydrogenation of trans-stilbene with SiNA-MNP catalysts.
Experimental Section
Catalytic hydrogenation with the SiNA-MNP catalysts
Each SiNA-MNP catalyst (0.0006 mmol Pd, 0.0006 mmol Pt,
0
.0005 mmol Rh, 0.0006 mmol PdRh, or 0.00085 mmol PdPt) and
trans-stilbene (0.5 mmol) in ethanol (2 mL) were added to a 10-mL
glass vessel and stirred under H (0.1 MPa, balloon) at 70°C for 24 h
2
using a vortex mixer with a temperature controller. After cooling to
room temperature, the reaction mixture was analyzed by GC (HP-1)
with dodecane as the internal standard to determine the yield. The
catalyst was easily recovered using tweezers, washed with ethanol,
acetone, and H O, and then dried under a flow of N for the next
2
2
reaction.
Acknowledgements
We would like to thank Dr. Tetsuo Honma (JASRI) for assistance
with the hard X-ray XAFS experiments and Dr. Aiko Nakao for X-
ray spectroscopy assistance (RIKEN, Japan). We would also like to
thank Mr. Daishi Inoue (CEMS, RIKEN) for SEM/EDX assistance, Mr.
Kiyohiro Adachi (CEMS, RIKEN) for XRD assistance, Prof. Go
Hamasaka (Institute for Molecular Science) and Ms. Tomoko
Kikitsu (CEMS, RIKEN) for TEM assistance. We gratefully acknowl-
edge financial support from JST ACT-C (no. JPMJCR12ZC), JST
ACCEL (no. JPMJAC1401), the JSPS (nos. 24550126, 20655035, and
Figure 7. Reusability testing of the SiNA-MNP catalysts.
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Conflict of Interest
The authors declare no conflict of interest.
[
[
Keywords: Alloys · Heterogeneous catalysis · Hydrogenation ·
Metal agglomeration · Reusability · Silicon-nanowire arrays
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Manuscript received: October 30, 2020
Revised manuscript received: January 5, 2021
Accepted manuscript online: January 14, 2021
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