Plasma-Assisted Synthesis of Monodispersed and Robust Ruthenium Ultrafine Nanocatalysts for Organosilane Oxidation and Oxygen Evolution Reactions

Article abstract of DOI:10.1002/cctc.201700809

We report a facile and general approach for preparing ultrafine ruthenium nanocatalysts by using a plasma-assisted synthesis at <100 °C. The resulting Ru nanoparticles are monodispersed (typical size 2 nm) and remain that way upon loading onto carbon and TiO₂ supports. This gives robust catalysts with excellent activities in both organosilane oxidation and the oxygen evolution reaction.

Full text of DOI:10.1002/cctc.201700809

DOI: 10.1002/cctc.201700809
Communications
Plasma-Assisted Synthesis of Monodispersed and Robust
Ruthenium Ultrafine Nanocatalysts for Organosilane
Oxidation and Oxygen Evolution Reactions
Edwin S. Gnanakumar,[a] Wesley Ng,[a] Bilge Cos¸kuner Filiz,[a] Gadi Rothenberg,[a]
Sheng Wang,[b] Hualong Xu,[b] Laura Pastor-Pꢀrez,[c] M. Mercedes Pastor-Blas,[c]
Antonio Sepffllveda-Escribano,[c] Ning Yan,*[a] and N. Raveendran Shiju*[a]
We report a facile and general approach for preparing ultrafine
ruthenium nanocatalysts by using a plasma-assisted synthesis
at <1008C. The resulting Ru nanoparticles are monodispersed
(typical size 2 nm) and remain that way upon loading onto
carbon and TiO2 supports. This gives robust catalysts with ex-
cellent activities in both organosilane oxidation and the
oxygen evolution reaction.
One way to avoid these problems is by using plasma-assist-
ed synthesis.[18,19] This method produces nanoparticles and
metal-supported catalysts from metal precursors.[18,20,21] Some
of the supported catalysts prepared by the plasma-assisted
synthesis method are Au/Y-zeolite,[22] Pt/Y-zeolite,[22] Pt/g-
Al2O3,[23] Co/g-Al2O3,[23] Ni/g-Al2O3,[24] Pt/Al2O3-CeO2,[25] Co/C,[26]
and Fe/C.[26] This method is simple, quick, and compatible with
impregnation processes.[27] However, these thermal plasma
techniques do not always give good control of the particle
size.[28] In these processes, the nanoparticles undergo rapid ag-
glomeration because of the high temperatures, which may
result in broad particle-size distributions.[28]
Heterogeneous catalysts often consist of small metal particles
dispersed on supports.[1–4] Although many methods have been
proposed for their synthesis,[5–7] the most common approach
involves impregnating the support with a metal precursor so-
lution, followed by thermal decomposition and reduction at a
relatively high temperature.[8–10] The problem is that these
steps often cause sintering and/or agglomeration.[2–4,11] More-
over, many “too-small-to-be-stable” nanoparticles form through
the Ostwald ripening mechanism.[12] The result is a broad parti-
cle-size distribution, which lowers catalyst performance.[10,13–15]
Alternatively, one can use strong reducing agents, such as
sodium borohydride and hydrazine, to convert the precursors
into the corresponding metals, but many of these reductants
are corrosive and/or toxic and can cause further problems
downstream.[16,17] Hence, most of today’s syntheses of mono-
dispersed nanocrystals are based on colloidal chemical synthet-
ic procedures involving the use of capping agents and spacers,
which hamper large-scale applications.
Herein, we report a cold plasma-assisted approach for the
preparation of supported ruthenium catalysts.[27–30] This
method has excellent support compatibility (we used carbon
as well as titania supports), which enables the synthesis of
monodispersed and ultrafine Ru nanoparticles. Cold plasma
synthesis is solvent-free and ligand-free, giving high-purity
nanoparticles. We tested these catalysts in two representative
yet different reactions: organosilane oxidation and the oxygen
evolution reaction (OER). Previous organosilane oxidations
were performed mainly by using metals such as gold,[31–36] pal-
ladium,[8,32] platinum,[37] and rhodium.[38] The costs of these
metals are 38, 24, 31, and 285 $gꢀ1, respectively (January
2017).[39] Although ruthenium is much cheaper (1.3 $OZTꢀ1), it
has rarely been used for silane oxidation. The OER is the rate-
determining step in many important energy-related processes
such as water splitting, reversible metal–air batteries, and fuel
cells.[40,41] Ruthenium oxide (RuO2) is one of the best-perform-
ing OER catalysts to date.[42–44] Thus, we decided to focus on
Ru catalysts, and in both reactions the catalysts showed high
activity and stability.
[a] Dr. E. S. Gnanakumar, W. Ng, Dr. B. Cos¸kuner Filiz, Prof. Dr. G. Rothenberg,
Dr. N. Yan, Dr. N. R. Shiju
Van’t Hoff Institute for Molecular Sciences
University of Amsterdam
Figure 1 illustrates the facile preparation procedures for the
carbon-supported 5 wt% Ru catalyst (denoted hereafter as Ru-
Plasma) by a cold plasma synthesis (detailed experimental pro-
cedures are included in the Supporting Information). The low-
temperature process (<1008C) gave ultrafine and monodis-
persed Ru nanoparticles on the support. Conversely, conven-
tional calcination requires at least 4008C to decompose the
RuCl3 precursor (see the coupled thermogravimetric and differ-
ential scanning calorimetric analyses in Figure S2 in the Sup-
porting Information). Combined with sequential reduction in
H2, it causes the agglomeration of the Ru nanoparticles.
P.O. Box 94157, 1090GD Amsterdam (The Netherlands)
E-mail: n.yan@uva.nl
n.r.shiju@uva.nl
[b] S. Wang, Prof. Dr. H. Xu
Shanghai Key Lab of Molecular Catalysis and
Innovative Materials, Department of Chemistry
Fudan University
Shanghai 200433 (P.R. China)
[c] L. Pastor-Pꢀrez, Prof. Dr. M. M. Pastor-Blas, Prof. Dr. A. Sepffllveda-Escribano
Departamento de Química Inorgµnica,
Instituto Universitario de Materiales de Alicante
Universidad de Alicante
Ap. 99, E-03080 Alicante (Spain)
The powder X-ray diffraction (XRD) pattern of Ru-Plasma in
Figure 2a confirms the complete decomposition of RuCl3 and
Supporting Information for this article can be found under:
https://doi.org/10.1002/cctc.201700809.
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Thanks to the plasma treatment, Ru-Plasma has a highly uni-
form particle-size distribution. Figure 2d,e shows that nearly
all of the Ru nanoparticles have dimensions between 1 and
2 nm. In contrast, the Ru particle-size distribution in commer-
cial Ru-Conv is much wider (see Figure 2 f,g). There are many
too-small (<1 nm, blue arrow) and too-large (>5 nm, yellow
arrow) Ru nanoparticles that reduce performance (more TEM
results of Ru-Plasma are included in the Supporting Informa-
tion). This confirms the hypothesis of sintering by Ostwald rip-
ening: the small particles become even smaller as the big ones
grow bigger, a “big-fish-eat-small-fish” effect.[12] In addition, Ru-
Plasma has a higher specific surface area (1298 m2 gꢀ1) than
Ru-Conv (713 m2 gꢀ1) according to standard N2 adsorption
measurements, due to its finer nanostructure.
Figure 1. A comparison of the workflows for the preparation of supported
Ru catalysts by conventional calcination–reduction and plasma-assisted syn-
thesis.
the formation of metallic Ru after plasma treatment. By com-
paring with the pattern of commercial 5 wt% Ru on carbon
(denoted hereafter as Ru-Conv), we attribute the broad peaks
at 2q=24.0 and 43.58 to carbon (graphite) and the tiny peaks
from 2q=38.4 to 448 to metallic Ru.[45] X-ray photoelectron
spectroscopy (XPS) also reveals the effectiveness of the plasma
synthesis. Indeed, overlapping of the C1s and Ru3d core levels
poses a challenge upon analyzing the spectrum in Figure 2b,
particularly at low Ru loadings. Nonetheless, there is a clear
binding-energy shift in the Ru3d5/2 peak relative to its position
in the sample before plasma treatment, which implies a de-
crease in the Ru oxidation state (see inset).[46,47] We also stud-
ied the crystal structure of Ru-Plasma through high- resolution
transmission electron microscopy (HRTEM). Figure 2c shows
the atom-resolved micrographs of two Ru compound particles;
the 2.3 Š d spacing indicates the (100) plane of metallic Ru
crystal.[48,49]
Ru-Plasma showed excellent activity and stability in a
number of chemical and electrochemical reactions. We initially
performed organosilane oxidation to organosilanol by using
water as an oxidant under ambient conditions (see Scheme 1
and Table 1). Our catalyst produced organosilanols selectively.
H2 gas was the sole byproduct, and no disiloxanes were ob-
served, unlike conventional approaches.[31–38,50–53] The reported
reactions were conducted at high temperature and/or under
an O2 atmosphere, and the turnover number (TON) was not
usually higher than 20.[32,36] With dimethylphenylsilane as the
model substrate, our Ru-Plasma catalyst showed a turnover fre-
quency (TOF) of 29 minꢀ1 at room temperature. Conversely,
Ru-Conv showed a TOF of only 6 minꢀ1 (see Table 1, entry 4),
which reflects the presence of less-active sites. At 408C, the
TOF increased to 44 minꢀ1 with the Ru-Plasma catalyst, even
though we doubled the silane/Ru molar ratio to 2637 (Table 1,
Figure 2. a) XRD patterns of Ru-Plasma and Ru-Conv. b) Deconvoluted X-ray photoelectron spectra of the C1s and Ru3d core levels. A and B in the inset com-
pare the fitted envelopes in the region of Ru3d5 for Ru-Plasma before and after plasma treatment. c) HRTEM micrograph of Ru nanoparticles on carbon. TEM
images of the d) Ru-Plasma and f) Ru-Conv catalysts and e,g) the corresponding particle-size distribution plots.
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attributed to the hydrolysis of Ru [Eq. (1)],[55] in agreement
with the formation of metallic Ru after plasma treatment.
RuþH2O $ RuOHþHþþeꢀ
ð1Þ
Figure 3 shows the 20 cycle CV curves of Ru-Plasma and Ru-
Conv in oxygen-saturated electrolyte from 0.8 to 1.58 V versus
the reversible hydrogen electrode (RHE) (overpotential, h=
0.3 V). Apparently, Ru-Conv suffered instant oxidation at ap-
proximately 1.51 V versus RHE in the first cycle (see the anodic
Scheme 1. Oxidation of organosilane to silanol with water by using support-
ed Ru catalysts.
Table 1. Organosilane oxidation to silanol by using supported Ru cata-
lysts.[a]
Entry
Catalyst
Substrate
Conv.
[%]
T
TON
TOF
[minꢀ1
]
[min]
1
2
3
Ru-Plasma Me2PhSiH (1a)
Ru-Plasma Me2PhSiH (1a)
Ru-Plasma Me2PhSiH (1a)
>99
45
60
1318 29
2637 44
5274 38
>99[b]
>99[b] 140
4
5
6
7
8
9
10
Ru-Conv
Me2PhSiH (1a)
>99
>99
>99
>99
>99
>99
0
210
30
50
25
20
1318
6
Ru-Plasma Ph3SiH (1b)
Ru-Plasma MePh2SiH (1c)
Ru-Plasma PhMeSiH2 (1d)
Ru-Plasma Et3SiH (1e)
Ru-Plasma Ph2SiH2 (1 f)
500 17
500 10
500 20
500 25
500 14.3
35
180
none
Me2PhSiH (1a)
100
0
[a] Reaction conditions: catalyst (25 mg), H2O (2mL, as oxidant), acetone
(5 mL), 258C. [b] Reaction was performed at 408C.
entry 2). The reaction proceeded to complete conversion even
at a higher silane/Ru ratio of 5274 with a TOF of 37.7 minꢀ1
(Table 1, entry 3).
Ru-Plasma was also active for the oxidation of other organo-
silanes (Table 1, entries 5–9). Control experiments confirmed
that no reaction took place in the absence of the catalyst or
only with the carbon support. The selectivity to silanol was
>99%. No disiloxane was detected, ruling out silanol conden-
sation. Interestingly, the spent Ru-Plasma catalyst retained high
activity and selectivity after three consecutive runs, indicating
its stability (see the TEM image of the spent catalyst in the
Supporting Information). We then prepared titania-supported
Ru catalysts by the same synthesis route. These also had mon-
odispersed Ru nanoparticles and showed excellent activity in
organosilane oxidation reactions (see the Supporting Informa-
tion for details), which suggests good support compatibility of
the new synthesis approach.
A new catalyst synthesis protocol is much more useful if it
can be applied to different reaction scenarios. We therefore ex-
amined the performance of the Ru-Plasma catalyst in the elec-
trochemical oxygen evolution reaction. However, the “too-
small” Ru nanoparticles corroded if the OER potential was ap-
Figure 3. 20 cycle CV plots of the a) Ru-Conv and b) Ru-Plasma catalysts in
O2-saturated 0.05m H2SO4 from 0.8 to 1.58 V vs. RHE. c) A comparison of the
OER LSV curves for the Ru-Conv and Ru-Plasma catalysts after CV cycling.
The scan rate was 10 mVsꢀ1, the rotating speed of the rotating disc elec-
trode was 1600 rpm, and iR correction was applied; the inset shows the
mass activity of both catalysts at h=0.25 V.
2ꢀ
plied (RuO4 was soluble in the reaction medium).[42,54] Thus,
careful control of the nanostructure of the catalyst is impor-
tant. Figure S6 shows the cyclic voltammetry (CV) curve of Ru-
Plasma in 0.05m deoxygenated H2SO4. The redox peaks were
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versely, this was not observed on Ru-Plasma; gradual current
degradation was owing to the accumulation of oxygen bub-
bles that blocked the working electrode. We then ran linear
sweep voltammetry (LSV) while rotating the electrode at a
scan rate of 10 mVsꢀ1 to study the OER activity as well as the
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itself is an excellent OER catalyst. At h=0.25 V, the mass activi-
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that of Ru-Conv and better than that of most 5 wt% Ru cata-
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moved, the Ru-Conv catalyst showed more significant per-
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reflect the good structural stability of Ru-Plasma, which can
sustain more Ru nanoparticles (active sites) than Ru-Conv after
applying OER potentials. A broad peak at approximately 1.54 V
in the LSV curve of the Ru-Conv sample might be related to
the oxidation of Ru nanoparticles. We also performed several
cycles of LSV for the Ru-Plasma catalyst, which showed repro-
ducibility and thus stability (see the Supporting Information).
In summary, our results show that plasma treatment effec-
tively decomposes RuCl3 to Ru nanoparticles under near-ambi-
ent conditions. The resulting metal particles on both carbon
and TiO2 supports were ultrafine and monodispersed. In partic-
ular, the Ru-Plasma catalyst demonstrated significantly higher
activity and stability in both organosilane oxidation and the
oxygen evolution reaction than the catalyst made by the con-
ventional method. As we showed, the method could be ap-
plied successfully for multiple supports, indicating its general
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N.R.S. and E.S.G. acknowledge financial support from the NWO
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Chemistry
of
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University
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Amsterdam,
http://suschem.uva.nl
Keywords: nanostructures · oxidation · plasma chemistry ·
ruthenium · supported catalysts
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Manuscript received: May 16, 2017
Revised manuscript received: July 17, 2017
Accepted manuscript online: July 17, 2017
Version of record online: && &&, 0000
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E. S. Gnanakumar, W. Ng,
B. Co¸skuner Filiz, G. Rothenberg, S. Wang,
H. Xu, L. Pastor-Pꢀrez, M. M. Pastor-Blas,
A. Sepffllveda-Escribano, N. Yan,*
N. R. Shiju*
&& – &&
Plasma-Assisted Synthesis of
Monodispersed and Robust
Ruthenium Ultrafine Nanocatalysts for
Organosilane Oxidation and Oxygen
Evolution Reactions
Out in the cold: Supported ruthenium
catalysts prepared by a novel cold
plasma-assisted approach show excel-
lent activity in two representative yet
different reactions: organosilane oxida-
tion and oxygen evolution.
&
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