Promoting Subordinate, Efficient Ruthenium Sites with Interstitial Silicon for Pt-Like Electrocatalytic Activity

Article abstract of DOI:10.1002/anie.201906394

The fundamental understanding and rational manipulation of catalytic site preference at extended solid surfaces is crucial in the search for advanced catalysts. Herein we find that the Ru top sites at metallic ruthenium surface have efficient Pt-like activity for the hydrogen evolution reaction (HER), but they are subordinate to their adjacent, less active Ru₃-hollow sites due to the stronger hydrogen-binding ability of the latter. We also present an interstitial incorporation strategy for the promotion of the Ru top sites from subordinate to dominant character, while maintaining Pt-like catalytic activity. Our combined theoretical and experimental studies further identify intermetallic RuSi as a highly active, non-Pt material for catalyzing the HER, because of its suitable electronic structure governed by a good balance of ligand and strain effects.

Full text of DOI:10.1002/anie.201906394

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Accepted Article
Title: Unmasking of recessive, efficient ruthenium sites with interstitial
silicon for Pt-like electrocatalytic activity
Authors: Hui Chen, Xuan Ai, Wang Liu, Zhoubing Xie, Weiqiang Feng,
Wei Chen, and Xiaoxin Zou
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201906394
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10.1002/anie.201906394
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Unmasking of recessive, efficient ruthenium sites with interstitial
silicon for Pt-like electrocatalytic activity
Hui Chen,[a],# Xuan Ai,[a],# Wang Liu,[a] Zhoubing Xie,[a] Weiqiang Feng,[b] Wei Chen,[c] Xiaoxin Zou*,[a]
Abstract: The fundamental understanding and rational manipulation
of catalytic site preference at extended solid surfaces is crucial in our
efforts to search for advanced catalysts. Herein we find that the Ru
top sites at metallic ruthenium surface have efficient Pt-like activity
for the hydrogen evolution reaction (HER), but they are relatively
recessive to their adjacent, less active Ru3-hollow sites due to the
stronger hydrogen-binding ability of the latter. We also present an
interstitial incorporation strategy for the transformation of the Ru top
sites from recessiveness to dominance, while maintaining Pt-like
catalytic activity. Our joint theoretical and experimental studies
further identify RuSi intermetallic as a highly active, non-Pt material
for catalyzing the HER, because of its suitable electronic structure
governed by a good balance of ligand and strain effects.
suitable hydrogen adsorption properties. While a number of
inexpensive materials are identified as promising alternatives to
expensive Pt catalysts,[5] most of them still exhibit catalytic
activity much lower than Pt. Very recently, despite the metallic
Ru catalyst with an intrinsically moderate HER activity, a few of
Ru-based nanomaterials,[6] especially those coupling with
nanocarbons, are shown to give remarkable HER activity close
to the Pt catalysts. However, it remains unclear what changes of
Ru-based catalytic sites occur behind the activity enhancement,
and a general guiding principle for engineering Ru-based
catalytic sites is also not available.
Herein, we present a joint theoretical and experimental study
that reveals the importance of catalytic site preference in
catalytic activity for HER of Ru-based catalysts. We find that
although the Ru top sites at metallic Ru surface have Pt-like
catalytic activity for HER, they are recessive to the adjacent, less
active Ru3-hollow sites. By incorporating appropriate interstitial
atoms to form intermetallics, we can unmask the recessive,
efficient Ru top sites, generating novel non-Pt HER catalyst with
Pt-like activity.
The in-depth understanding of characteristics of catalytic
sites at extended solid surfaces is instructive for rational catalyst
design. The Sabatier principle presents a general qualitative
rule: for an optimal catalyst there is a moderate bond strength
between catalytic site and key intermediate.[1] That is, a good
catalyst should bind the key intermediate to its catalytic site
strongly enough to activate it, yet not too strongly to enable
desorption of the product. Benefiting from the progress in
density functional theory (DFT) calculations, adsorption energy
of reaction intermediate can be used to quantitatively describe
the bond strength and thereby to evaluate catalytic activity of
each surface site.[2] At a complex, extended solid surface, there
are usually several types of possible catalytic sites with different
adsorption properties (also known as catalytic site diversity). The
most stable adsorption sites are the most favorable ones for
catalysis, and their activities more closely reflect the real activity
of catalyst (also known as catalytic site dominance).[3] Thus, for
a given catalytic site to be a desirable one, it is better to possess
a
moderate ability to bind the key intermediate, while
Figure 1. a) The stable H adsorption sites and b) their calculated ΔGH* on the
Ru(0001) surface. c) Schematic illustration of interstitial incorporation strategy
for transformation of Ru top sites from recessiveness to dominance. d) The
stable H adsorption sites and e) their calculated ΔGH* on the RuSi(110)
surface. f) ΔGH* at various hydrogen coverages for h1 site on the Ru(0001)
surface, Ru top site on the RuSi(110) surface and Pt top site on the Pt(111)
surface.
simultaneously being dominant to other adjacent sites.
To demonstrate this idea, we chose HER electrocatalysis as
a model reaction, which is involved in many renewable energy-
related technologies. The adsorption free energy of atomic
hydrogen (ΔGH*) is proven to be a reliable descriptor for
quantifying the aforementioned bond strength and thereby
evaluating the HER activity of a given catalytic site.[4] For an
optimum HER catalyst, its catalytic sites should have near-zero
ΔGH* value. The benchmark catalyst Pt is such a material with
DFT calculations are conducted to evaluate the
H
adsorption properties and HER activities of the possible catalytic
sites on the Ru(0001) surface (Figure S1 and Table S1 in
Supporting Information (SI)), a representative model surface of
metallic Ru.[7] The results (Figure 1a) show that the stable H
adsorption sites on the Ru(0001) surface include Ru top site and
two types of Ru3-hollow sites (i.e., h1 and h2 sites). Figures 1b
and S2 in SI further reveal that the Ru top site has a near-zero
ΔGH* (-0.07 eV), whereas the Ru3-hollow sites give largely
negative ΔGH* values of around -0.45 eV. This indicates that
despite its high Pt-like catalytic activity for HER, the Ru top site
is relatively recessive because the adjacent Ru3-hollow sites as
its rival sites are energetically more favorable for hydrogen
adsorption.
[a]
Dr. H. Chen, X. Ai, W. Liu, Z. Xie, Prof. X. Zou
State Key Laboratory of Inorganic Synthesis and Preparative
Chemistry, College of Chemistry, Jilin University, Changchun
130012, China; E-mail: xxzou@jlu.edu.cn
[b]
[c]
W. Feng
College of Materials Science and Engineering, Jilin University,
Changchun 130012, China
Prof. W. Chen
Laboratory of Theoretical and Computational Chemistry, Institute of
Theoretical Chemistry, Jilin University, Changchun 130023, China
# These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
In order to transform the highly active Ru top site from
recessiveness to dominance, we present an interstitial
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10.1002/anie.201906394
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incorporation strategy to eliminate the Ru3-hollow sites (Figure
1c). Silicon is found to be an appropriate interstitial atom by
constructing CsCl-type RuSi intermetallic structure. The (110)
surface of RuSi is the most exposed surfaces (Figure S3 and
Table S2 in SI) and accounts for the largest surface proportion
of 85% within the Wulff construction (Figure S4 in SI). Hence,
the RuSi(110) surface was studied for further DFT calculations
(Figure S5 and Table S3 in SI). As shown in Figure 1d, the Ru
atoms are isolated by the neighboring Si atoms, with the Ru3-
hollow site disappearing. The stable H adsorption sites on the
RuSi(110) surface include two top sites (Ru and Si top sites) and
two bridge sites (b1 and b2 sites). Among these catalytic sites
(Figure 1e), the Ru top site on the RuSi(110) surface is found to
be the most favorable site (or dominant site) for hydrogen
adsorption, whilst maintaining the near-zero ΔGH* or Pt-like
catalytic activity.
Figure 1f presents the comparison of ΔGH* values at the
preferred adsorption sites on RuSi(110), Ru(0001) as well as
Pt(111) surfaces (the model surface of Pt) under different H*
coverages (θH*). The result shows, the absolute values of ΔGH*
for the RuSi(110) surface are close to zero over the entire θH*
range, and they are smaller than those for the Ru(0001) and
Pt(111) surfaces. This result further suggests that RuSi should
be a very competitive, non-Pt material for catalyzing the HER.
activity. Figures 2b and 2c show a good linear corrolation
between ΔGH* value at the Ru top site and the d-band center,
and an inverse relationship between d-band center and d-band
width, the two key characters of electronic structure (Figure S6
and Table S9 in SI). As the d-band center downs away the
Fermi level (Figure 2b, inset), the antibonding states become
more occupied, resulting in weaker H adsorption and smaller
ΔGH value. Among the six RuX intermetallics, RuSi exhibits the
∗
most negative d-band center and near-zero ΔGH* at Ru top site.
Next, we attribute the modification of electronic properties in
RuX to a combination of strain and ligand effects.[8] On one hand,
the incorporation of interstitial atoms in Ru can generate
chemical strains and thereby result in the expansion of crystal
lattice. All the six RuX intermetallics have much larger Ru-Ru
bond lengths than matallic Ru (2.73 Å) and the Ru-Ru bond
lengths increase in the order: RuSi < RuGe < RuSn and RuAl <
RuGa < RuIn (Figure 2d). This variation is similar with the trend
in electronic structure (Figure 2c). This result implies that the
tensile strain, which can decrease the metal d-orbital overlap
and lead to a narrower band width and a more positive d-band
center, is a significant factor responsible for the modification of
electronic properties. On the other hand, orbital hybrization
between Ru and X atoms (termed the ligand effect) is another
significant factor can modify the electronic structure. The ligand
effect always results in a broadening of the metal d-band and a
more negative d-band center.
The much negative d-band center of RuSi can be explained
by the fact that among the six RuX intermatellics (Figure 2d and
Table S10 in SI), for RuSi the smallest expansion in Ru-Ru bond
length gives rise to the weakest strain effect, and simutinously,
the shortest Ru-X bond length means the strongest orbital
hybrization between Ru and X atoms (or ligand effect). The
orbital hybrization between Ru and Si atoms for RuSi is studied
by its density of the states (DOS) and the crystal orbital
Hamiltonian population (COHP) for Ru-Si bond (Figure 2e). The
results reveal that there are the DOS overlap and the bonding
between Ru 3d orbital and Si 2s-2p obitals. Overall, the above
results imply that the good balance of strain and ligand effects
render RuSi suitable electronic structure and thus a near-zero
ΔGH* value at Ru top site.
Inspired by the theoretical results, we synthesized the RuSi
material and then investigated its electrocatalytic activity for the
HER. The phase-pure RuSi sample traditionally had to be
synthesized by the direct reaction of ruthenium–silicon powders
at high pressure (> 7.8 GPa).[9] Here, we present the synthesis
of phase-pure RuSi nanoparticles without high pressure by
employing a magnesiothermic reduction reaction with RuCl3, Si
and Mg as the starting materials (see experimental details in SI).
The formation of RuSi under relatively mild conditions is mainly
because the new route significantly lowers the reaction enthalpy
in comparison with the traditional element reaction route (Figure
S7 in SI). This method can also be extended to obtain the other
Ru-Si phase Ru2Si3 (Figures S8 and S9 in SI).
The X-ray diffraction (XRD) pattern of the as-synthesized
sample confirms that the material contains single-phase RuSi
(Figure 3a). Scanning electron microscopy (SEM) image (Figure
3b) reveals that the material is composed of RuSi nanoparticles
of 100-200 nm in size. Elemental mapping images (Figure 3c)
show that the Ru and Si elements are homogeneously
Figure 2. a) Calculated ΔGH* at the stable H adsorption sites on the RuX(110)
surfaces. The inset gives stable H adsorption sites on the RuX(110) surfaces.
b) Relationship between ΔGH* at Ru top site and Ru d-band center. The inset
explains how the variation of d-band center affects H adsorption energy. c)
The d-band center and corresponding d-band width of the RuX(110) surfaces.
d) The Ru-Ru and Ru-X bond lengths of the six RuX intermetallics. e)
Calculated DOS of the RuSi(110) surface and COHP of Ru-Si bond.
To further understand the role of Si interstitial atom, a family
of six CsCl-type RuX intermetallics (X = Si, Ge, Sn, Al, Ga and
In) are investigated (Tables S3-S8 in SI). Figure 2a presents the
stable H adsorption sites on the RuX(110) surfaces and their
corresponding ΔGH* values. The results show that: (i) the RuX
intermetallics (X = Si, Ge and Sn) have energetically favourable
adsorption at the Ru top site, with RuSi exhibiting the most
optimal ΔGH* value; (ii) The ΔGH* absolute values at the Ru top
site periodically increase in the order: RuSi < RuGe < RuSn and
RuAl < RuGa < RuIn. These results indicate that besides the
local geometric structure of Ru catalytic site, its electronic
structure should also be crucial for realizing efficient catalytic
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10.1002/anie.201906394
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distributed over the entire nanoparticles. In high-resolution
transmission electron microscopy (HRTEM) image (Figures 3d),
the interplanar distances of 0.29 nm and 0.21 nm can be
assigned to the (001) and (110) crystallographic planes of RuSi,
respectively. The angle of 90o between the two planes is
consistent with the theoretical value. This result, coupled with
the corresponding fast Fourier transform image (Figures 3d,
inset), suggests that the exposed facet is {110}.
Figure 4. a) Ru 3d XPS spectra of RuSi, RuO2 and Ru. b) Si 2p XPS spectra
of RuSi, SiO2 and Si. c) XANES spectra at the Ru K-edge of RuSi, RuO2 and
Ru. Inset is the partially enlarged detail of Figure 4c. d) Fourier transforms of
the EXAFS spectra of RuSi, RuO2 and Ru. Note that the Fourier transforms
are not corrected for phase shift, so that the peak positions in Figure 4d are
shorter than the actual bond lengths.
Next, the electrocatalytic activity of RuSi toward HER in
acidic solution is studied (see Experimental Section and Figure
S11 in SI). For comparative purpose, metallic Ru and Pt
nanoparticles (Figures S12-13, SI) are also synthesized and
their catalytic activities are evaluated under the same conditions.
Figure 5a shows the polarization curves for the HER over RuSi,
Ru, Pt and Si. While Si is inactive for HER, metallic Ru has a
moderate catalytic activity. Contrary to Si and Ru, RuSi exhibits
a remarkable catalytic activity toward HER, which is comparable
to that of Pt and much better than that of Ru. In particular, RuSi
Figure 3. a) XRD pattern, b) SEM image, c) STEM image and the
corresponding elemental mapping images, and d) HRTEM image of RuSi.
Inset shows the corresponding fast Fourier transform image. The standard
diffraction pattern for RuSi (red line) is also included in Figure 3a.
The RuSi is further characterized by X-ray photoelectron
spectroscopy (XPS) and X-ray absorption spectroscopy (XAS).
XPS analysis presents that the surface atomic ratio of Ru and Si
is close to 1:1. Figure 4a shows Ru 3d XPS spectra for RuSi and
the reference samples (RuO2 and Ru), and Figure 4b shows Si
2p XPS spectra for RuSi and the reference samples (SiO2 and
Si). The Ru 3d XPS peaks for RuSi exhibit a shift toward lower
binding energy relative to those of metallic Ru, while the Si 2p
XPS peak of RuSi shows a significant shift toward higher binding
energy relative to that of Si. These results demonstrate that Ru
atom is negatively charged and Si atom is positively charged in
RuSi. The electron-richness of Ru atom in RuSi is also
confirmed by X-ray absorption near-edge structure (XANES)
spectra of Ru K-edge, which shows that the energy of
absorption edge of RuSi is slightly lower than that of metallic Ru
(Figure 4c). The charge states of Ru and Si in RuSi are also
examined by Bader charge analysis, which reveals that 0.8
electrons (|e|) transfer from Si atom to Ru atom. Although the
charges on Ru atom for RuSi and metallic Ru are different, the
transferred charges from Ru atom to adsorbed H atom are
almost the same (Figure S10 in SI).
−2
requires an overpotential of 19 mV at 10 mA cmgeo current
density (normalized by geometric area of the electrode). It is
worth noting that RuSi also has a catalytic activity similar to the
commercial 20 wt.% Pt/C catalyst (Figure S14, SI). In addition to
high activity, RuSi enables good catalytic and structural stability
during the HER (Figures S15 and S16, SI). Moreover, RuSi
gives nearly 100 % faradaic efficiency during the HER (Figure
S17 in SI), suggesting that the observed current can be
exclusively attributed to the HER during electrocatalysis.
The specific activities of RuSi, Ru and Pt are further
compared by normalizing the measured currents with respect to
electrochemical surface areas (ECSAs). Figure 5b shows the
comparison of the ECSAs of three materials and their specific
activities, evaluated by overpotential required at 0.1 mA
−2
cmECSA current density. This comparison reveals that their
specific activities follow almost the same trend with their
geometric area-normalized activities. The above results overall
demonstrate, RuSi is a highly active, non-Pt material with Pt-like
electroactivity for the HER.
Figure 5c shows the Tafel plots for RuSi, Ru and Pt. RuSi
displays a small Tafel slope of 28.9 mV dec−1, which is
comparable to that of Pt (30.2 mV dec−1) and much smaller than
that of Ru (73.6 mV dec−1). This suggests the rapid HER
catalytic kinetics in the presence of RuSi. Additionally, the Tafel
slope for RuSi suggests that the hydrogen evolution over this
material should occur via a Volmer-Tafel mechanism, in which
Figure 4d shows the comparison of Fourier transform of
extended X-ray absorption fine structure (EXAFS) at Ru K-edge
of three Ru-containing samples. There are two prominent peaks
for RuSi, which correspond to the Ru-Si bond and Ru-Ru bond,
respectively. The Ru-Ru bond distance is longer than the Ru-Si
bond distance in RuSi, and it is also longer than the Ru-Ru bond
distance in metallic Ru. These results are consistent with their
crystallographic data (Table S10, SI).
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the recombination of two adsorbed H atoms (H* + H* → H2) is
rate-determining step.[10] Such a Volmer-Tafel mechanism on the
RuSi(110) surface is also studied theoretically. Figure 5d
presents three typical steps: (i) two H atoms prefer to adsorbing
on adjacent Ru top sites with H-H distance of 2.91 Å. (ii) The two
H atoms form a transition state (TS) with H-H distance of 0.87 Å.
(iii) A H2 molecule forms and desorbs from the RuSi surface.
The calculated activation energy (0.75 eV) for the Tafel reaction
on RuSi(110) surface is a little lower than that on the Pt(111)
surface (0.85 eV).[11] The result further suggests that RuSi is an
efficient catalyst for HER.
and the China Postdoctoral Science Foundation (Grant No.
2018M641771). W. Chen acknowledges the financial support
from NSFC (21673093), Science and Technology Research
Program of Education Department of Jilin Province
(JJKH20190121KJ), Jilin Province Science and Technology
Development Plan (20170101175JC). We thank NSFC
(21621001) and the 111 Project (B17020) for financial support.
We thank the beamline BL14W (Shanghai Synchrotron
Radiation Facility) for the XAS measurements.
Keywords: site preference • hydrogen evolution reaction •
electrocatalysis • electronic structure • non-Pt catalysts
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required at a current density of 0.1 mA cm−2 (normalized by ECSAs) in 0.5 M
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In conclusion, we have demonstrated the importance of
manipulation of catalytic site preference for rational design of
advanced catalysts, with Ru-based HER electrocatalyst as a
model material system. We have also demonstrated that RuSi
efficiently catalyzes the HER with Pt-like activity, due to the
exposure of highly active Ru top sites.
[7]
[8]
Acknowledgements
X. Zou acknowledges the financial support from National Key
R&D Program of China, Grant No. 2017YFA0207800, the
National Natural Science Foundation of China (NSFC) Grant No.
21771079, Jilin Province Science and Technology Development
Plan 20170101141JC, Program for JLU Science and
Technology Innovative Research Team (JLUSTIRT) and Fok
Ying Tung Education Foundation, Grant No. 161011. H. Chen
acknowledges the financial support from the Postdoctoral
Innovative Talent Support Program (Grant No. BX20180120)
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10.1002/anie.201906394
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COMMUNICATION
Entry for Table of Contents (ToC)
COMMUNICATION
The importance of manipulation of
catalytic site preference for rational
design of advanced catalysts, with Ru-
based HER electrocatalyst as a model
material system, is demonstrated.
RuSi is identified as Pt-like HER
electrocatalyst, due to the dominant
change of efficient Ru top sites.
Hui Chen, Xuan Ai, Wang Liu, Zhoubing
Xie, Weiqiang Feng, Wei Chen, and
Xiaoxin Zou*
Page No. – Page No.
Unmasking of recessive, efficient
ruthenium sites with interstitial
silicon for Pt-like electrocatalytic
activity
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