Research Article

Cite This: ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX www.acsami.org

Mesoporous Pd@Ru Core−Shell Nanorods for Hydrogen Evolution

Reaction in Alkaline Solution
Yiqi Luo,†,‡ Xuan Luo,§ Geng Wu,† Zhijun Li,† Guanzhong Wang,‡ Bin Jiang,*,§ Yanmin Hu,†
Tingting Chao,† Huanxin Ju,# Junfa Zhu,# Zhongbin Zhuang,⊥ Yuen Wu,† Xun Hong,*,†
and Yadong Li†,∥
†
Center of Advanced Nanocatalysis (CAN) and Department of Chemistry, ‡Department of Physics, and §Department of Chemical
Physics, University of Science and Technology of China, Hefei, Anhui 230026, China
∥
Department of Chemistry, Tsinghua University, Beijing 100084, China
⊥
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State Key Lab of Organic−Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
#
National Synchrotron Radiation Laboratory (NSRL), University of Science and Technology of China, Hefei, Anhui 230029, China
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*
S Supporting Information

ABSTRACT: The activity and stability of bimetallic nano-

catalysts strongly depend on their structures, compositions,
and interfaces. Here, we report the synthesis of mesoporous
Pd@Ru core−shell bimetallic nanorods composed of face-
centered cubic Pd and hexagonal close-packed Ru. The
nanorods have two types of cavities with diameters of 3.0 ±
0.9 and 20.3 ± 8.1 nm. The mutual diffusion process between
Ru and Pd is characterized by the high-angle annular dark-
field scanning transmission electron microscopy, energy-
dispersive X-ray spectroscopy mapping, and the synchrotron
radiation photoemission spectroscopy measurements. The
mesoporous Pd@Ru nanorods exhibit superior catalytic performance and stability for hydrogen evolution reactions
(overpotentials of 30 mV at 10 mA·cm−2 in 1.0 M KOH solution and 37 mV at 10 mA·cm−2 in 0.5 M H2SO4 solution).
KEYWORDS: electrocatalysis, ruthenium, mesoporous, core−shell, element diffusion

■ INTRODUCTION
Hydrogen evolution reaction (HER) is a crucial step in
electrochemical water splitting which is utilized as a clean and
sustainable approach for hydrogen production.1,2 It is of great
importance to develop efficient electrocatalysts to improve the
sluggish kinetics for HER, especially in alkaline solution with
inferior proton concentration.3 Although a series of electro-
catalysts with excellent HER activities in alkaline solution have
been reported,3−7 issues associated with the activity and
stability remain not fully solved. For example, Pt-based
nanocatalysts, which were reported to be the most competitive
electrocatalysts in terms of reaction efficiency, still suffer from
high cost and low stability in alkaline media.8 Indeed, the HER
kinetics is limited by an additional water dissociation process in
alkaline solution3 and hence largely determined by the Gibbs
free-energy barrier ΔGB of catalysts.9−13 As a result, it is
essential to design better HER catalysts from the perspective of
the hydrogen binding energy and the energy barrier for water
dissociation.14 Ruthenium, an alternative noble metal with a
similar bond strength with hydrogen compared to platinum,15
has attracted much attention as an efficient catalyst for
HER.8,9,16,17 For example, Ru nanoparticles supported on a
nitrogenated holey two-dimensional carbon exhibited excep-
tional performance and stability in both alkaline and acidic
solutions.8 On the other hand, bimetallic nanostructures have
shown dramatic improvement compared to their monometallic
counterparts because of their electronic interplay and strain
effects.18−23 More recently, Ru nanorods (NRs) supported on
4H/face-centered cubic (fcc) Au nanowires exhibited excellent
electrocatalytic performance toward the HER in alkaline
media.16 Therefore, rational design of Ru-based biemtallic
catalysts may generate effective HER catalysts.
The electrochemical activities and stabilities of bimetallic
catalysts depend on their size, morphology, structure, and
composition.16,17,24,25 Particularly, the rational control of
porous structure20,26,27 and composition28−31 of bimetallic
nanocatalysts are significant in improving the catalytic
efficiency to economize precious metals.32 Controllable
synthesis of the porous structure has been utilized to increase
the surface-to-mass ratio of nanocatalysts, expose abundant
active catalytic sites, and facilitate mass transport during the
electrocatalytic reaction.33,34 Moreover, the properties of
bimetallic nanocatalysts may be tuned by varying their
composition and atomic ordering.28,31 Therefore, it offers
Received: June 14, 2018
Accepted: September 13, 2018
Published: September 13, 2018

© XXXX American Chemical Society A DOI: 10.1021/acsami.8b09988

ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces
additional probabilities to controllable synthesis of Ru-based
bimetallic nanocatalysts for HER.
Herein, we utilize palladium NRs (Pd NRs)35 as a seed to
synthesize the Pd@Ru core−shell NRs. Then, the mesoporous
nanostructure was obtained by a further diffusion process. The
mesoporous Pd@Ru core−shell NRs exhibit excellent HER
performance particularly in alkaline solutions. In a typical
synthesis, Pd NRs were obtained as reported35 by heating the
mixture [0.1 mmol PdCl2, 2 mmol NaI, 800 mg of
poly(vinylpyrrolidone) (PVP), 12 mL of deionized water]
from room temperature to 200 °C for 30 min and kept for 2 h.
The separated and purified products together with ruthenium
acetylacetonate (Ru(acac)3, 20.0 mg) and PVP (200 mg) were
dissolved in 14 mL of benzyl alcohol. The mixture was
completely dispersed under ultrasonic for 30 min and kept at
200 °C for 12 h in a Teflon-lined stainless-steel autoclave.
The mesoporous structure of the obtained NRs was
confirmed by the transmission electron microscopy (TEM)
image (Figure 1a) and high-angle annular dark-field scanning
Figure 1. (a) TEM image of the mesoporous Pd@Ru NRs. (b,c)
HAADF−STEM image of a mesoporous Pd@Ru NR. The pinholes
are marked by blue arrows in (c). (d) Atomic resolution HAADF−
STEM image of a mesoporous Pd@Ru NR. (e,f) Corresponding FFT
patterns in different areas marked in red-dashed squares in (d).
TEM (HAADF−STEM) images (Figure 1b,c). In Figure 1a,
the NRs have a relatively uniform diameter of 25.5 ± 2.6 nm
(Figure S1) with a rough surface and a porous nanostructure.
Figure 1b shows that polygonal cavities with a diameter of 20.3
± 8.1 nm (Figure S2) formed periodically along the NRs.
Moreover, pinholes with a diameter of 3.0 ± 0.9 nm (Figure
S2) were marked by blue arrows in the high-magnified
HAADF−STEM images (Figure 1c). The mesoporous NRs
exhibit two different crystal structures, with the lattice fringes
of 0.207 and 0.223 nm, corresponding to the {101} plane of
Ru and the {111} plane of Pd, respectively (Figure 1d). Fast
B DOI: 10.1021/acsami.8b09988
Research Article
Fourier transform (FFT) patterns clearly show the hexagonal
close-packed (hcp) phase of Ru (Figure 1e) and the fcc phase
of Pd (Figure 1f), and these heterostructures contain abundant
interfaces (Figures 1d and S3).
To confirm the formation mechanism of the mesoporous
Pd@Ru NRs, a time-dependent reaction process was
investigated. The scheme for the formation of mesoporous
Pd@Ru core−shell NRs is shown in Figure S3. The Pd NRs
with a uniform diameter of 17.0 ± 0.7 nm (Figures 2a and S1)
changed to solid Pd@Ru core−shell NRs with an diameter of
28.0 ± 2.5 nm after the reaction proceeded for 2 h (Figures 2b
and S1). Mesoporous NRs, with a diameter of 25.5 ± 2.6 nm,
were obtained after a reaction time of 12 h (Figures 2c and
S1). Figure 2d,e shows the HAADF−HRTEM image and the
corresponding elemental mapping image of the solid Pd@Ru
core−shell NRs, revealing the uniform distribution of Ru on
the surface of the solid Pd core. In contrast, Figure 2f,g
illustrates the feature of the mesoporous Pd@Ru core−shell
NRs, which are composed of a porous Pd core and a inward
expanded distribution of Ru, thus demonstrating the inward
diffusion of Ru and the outward diffusion of Pd. The energy-
dispersive X-ray line scans of the mesoporous Pd@Ru NR
(Figure S5) indicated that the catalysts have core−shell
structures. Moreover, after the further acid treatment by
moving the Pd core using nitrate acid (Figure S6), the porous
Ru nanotubes were obtained.
Figure 2h displays the X-ray diffraction (XRD) patterns of
the Pd@Ru NRs after the reaction times of 2, 6, and 12 h.
Three pronounced reflection peaks appear at 2θ = 40.01°,
46.31°, and 68.05°, corresponding to the fcc Pd(111), (200),
and (220) reflections, respectively. With increasing the
reaction time, the XRD pattern shows another three reflection
peaks at 2θ = 38.39°, 42.15°, and 44.01°, corresponding to the
hcp Ru(100), (002), and (101) reflections, respectively. It
reveals that the mesoporous Pd@Ru NRs are composed of
mixed Pd (fcc) and Ru (hcp) phases.
The synchrotron radiation photoemission spectroscopy
(SRPES) spectra of Pd 3d and Ru 3d were measured with
photon energies of 400 and 1486.6 eV, respectively (Figure 2i).
As shown in Figure 2i, peaks at 340.3 and 335.0 eV can be
assigned to Pd 3d3/2 and Pd 3d5/2 of the metallic Pd0,
respectively. The Ru 3d3/2 signals overlap with the C 1s signals
from PVP around 285 eV, and the component of Ru could be
obtained by spectrum decomposition. The peaks at 280.1 eV
are associated with Ru 3d5/2 of metallic Ru0 (Figure 2i). The
peak areas were calibrated by the beam flux and photo-
ionization cross section at the corresponding photon energy.
As shown in Figure S7, the Ru/Pd ratios of solid Pd@Ru NRs
at photon energies of 400 and 1486.6 eV are 27.06 and 10.56,
respectively, illustrating that the Ru atoms are enriched on the
surface. In contrast, the Ru/Pd ratios of mesoporous Pd@Ru
NRs at photon energies of 400 and 1486.6 eV are 3.46 and
2.72, respectively. The Ru/Pd ratio decreased when the
reaction time changes from 2 to 12 h, indicating the inward
diffusion of Ru and the outward diffusion of Pd.
The electrocatalytic performance of the mesoporous Pd@Ru
NR electrocatalyst was evaluated and compared to the solid
Pd@Ru NRs, commercial Ru/C, Pd/C, and Pt/C electro-
catalysts under alkaline conditions (Figure 3a). The polar-
ization curves of the five electrocatalysts recorded in 1.0 M
KOH solution show an increasing trend in the HER activity
(on the overpotential basis) in the following order: Pd/C <
Ru/C < solid Pd@Ru NRs < Pt/C < mesoporous Pd@Ru NRs
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces Research Article

Figure 2. (a−c) TEM images of the Pd NRs, solid Pd@Ru NRs, and mesoporous Pd@Ru NRs, respectively. (d,e) HAADF−HRTEM image and
the corresponding elemental mapping image of the solid Pd@Ru NR. (f,g) HAADF−HRTEM image and the corresponding elemental mapping
image of the mesoporous Pd@Ru NR. (h) XRD patterns of the mesoporous Pd@Ru NRs during the reaction times of 2, 6, and 12 h, respectively.
(i) Pd 3d (left) and Ru 3d (right) SRPES spectra of the solid Pd@Ru NRs (2 h) and mesoporous Pd@Ru NRs (12 h) with photon energies of 400
and 1486.6 eV, respectively.

(Figure 3a). In addition, the overpotential required to drive a
current density of 10 mA·cm−2 is 30 mV for the porous Pd@
Ru NRs, which is superior to Pt/C (50 mV). Remarkably, the
resulting Tafel slope of mesoporous Pd@Ru NRs is measured
to be 30 mV dec−1, which is even lower than that of
commercial Pt/C (45 mV dec−1) and solid Pd@Ru NRs (48
mV dec−1). A smaller Tafel slope signifies a more favorable
kinetics toward electrochemical HER. Moreover, in compar-
ison with various representative noble metal HER electro-
catalysts in alkaline solution reported in recent years (Table
S1), the mesoporous Pd@Ru NRs exhibit a competitive
overpotential (Figure 3d). The mass current density (based on
the mass of precious metals) of the mesoporous Pd@Ru NRs
reaches 722.9 A g−1 at −0.06 V (Figure 3c), much higher than
that of Pt/C (315.3 A g−1), solid Pd@Ru NRs (117.6 A g−1),
Ru/C (75.3 A g−1), and Pd/C (6.7 A g−1). In addition, The
ECSAs of solid Pd@Ru NRs and mesoporous Pd@Ru NRs
were calculated to be 10.95 and 29.05 m2/g by the Cu UPD
method (Figure S8), and the overpotentials normalized by the
ECSA (at 10 mA·cm−2) are 59 and 37 mV (Table S1). The
mesoporous structures exhibit superior charge-transfer capa-
bility which is confirmed by electrochemical impedance
spectroscopy measurements (Figure S9). The accelerated
durability test demonstrates its exceptional stability, with a
smaller negative shift of the HER polarization after 3000
continuous potential cycles than Pt/C (Figure 3e). No
C DOI: 10.1021/acsami.8b09988
observable change can be noticed for the mesoporous Pd@
Ru NRs prior to and after the electrocatalytic reaction (Figure
S10). Furthermore, the durability of the mesoporous Pd@Ru
NRs was also evaluated by the chronoamperometry measure-
ment. As shown in Figure 3f, the current density of the
mesoporous Pd@Ru NRs showed a feeble decrease after 12 h,
indicating the superior electrocatalytic stability. In addition, the
electrocatalytic performance of the mesoporous Pd@Ru NRs
under acid conditions was also carried out in 0.5 M H2SO4
solution. The catalytic activity of the mesoporous Pd@Ru NRs
is comparable to that of Pt/C in acid solution and shows
superior HER performance than those of Ru/C and Pd/C
(Figure S11). The overpotential required to drive a current
density of 10 mA·cm−2 is 37 mV for the mesoporous Pd@Ru
NRs. The Tafel slope of mesoporous Pd@Ru NRs is 33 mV
dec−1 in acid media (Figure S12). The comparisons of HER
mass activity and stability of the mesoporous Pd@Ru NRs in
different media are shown in Figures S13 and S14, respectively.
In order to further understand the difference in activity
among these nanomaterials and the origin of the high HER
activity of the Pd@Ru NRs in alkaline environments, density
functional theory (DFT) calculations were performed in terms
of the thermodynamics and kinetics of HER on various metal
surfaces (Figure 4). For pure metal electrodes, single-crystal
slab models with the most commonly used facets were
selected, that is, Pd(111), Ru(0001), and Pt(111). In addition,
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces Research Article

Figure 3. (a) Polarization curves of mesoporous Pd@Ru NRs, solid Pd@Ru NRs, Pd/C, Ru/C, and Pt/C electrocatalysts in 1.0 M KOH solution.
(b) Tafel plots obtained from the polarization curves in (a). (c) HER mass activity of mesoporous Pd@Ru NRs, solid Pd@Ru NRs, Pd/C, Ru/C,
and commercial Pt/C (normalized by mass of Pd and Ru; at −0.06 V vs RHE). (d) Overpotential of porous Pd@Ru NRs and solid Pd@Ru NRs at
10 mA·cm−2 in 1.0 M KOH solution compared with some recently reported HER electrocatalysts. (e) Durability test of mesoporous Pd@Ru NRs
and commercial Pt/C in 1.0 M KOH. (f) Chronoamperometry measurement of the porous Pd@Ru NRs at a potential of −31 mV (vs RHE) for 12
h.

reaction (Had + H2O + e− → OH− + H2). The dissociation of

Figure 4. Gibbs free-energy diagram for water activation in HER on
different surfaces. Inset pictures show the Volmer reaction on the Ru/
Pd(111) site.
experimental characterization suggests the uniform distribution
of Ru on the surface of solid Pd core. Theoretically, we assume
a representative model, with a monolayer of Ru deposited on
the Pd(111) substrate, denoted as Ru/Pd(111).
In the alkaline solution, the HER is according to the
equation: 4H2O + 4e− → 2H2 + 4OH−, which containing the
Volmer reaction (H2O + e− → OH− + Had) and Heyrovsky
D DOI: 10.1021/acsami.8b09988
water producing H* and OH− becomes essential in the HER
because of the very low proton concentration.9,12 The
dissociation barrier is the kinetic bottleneck for alkaline-
based HER. For pure metals, our calculated results show that
Pt(111) is most favorable for water dissociation with a Gibbs
free-energy barrier ΔGB = 0.91 eV, followed by Ru(0001) with
ΔGB = 0.93 eV and Pd(111) with ΔGB = 1.52 eV. This result
supports in the alkaline solution the best and worst
performance of Pt/C and Pd/C, while a moderate activity of
Ru/C. For the Pd@Ru NRs, Ru/Pd(111) is found to be quite
similar or even more efficient to Pt(111) in water activation. As
a result, the Ru/Pd(111) site with ΔGB = 0.84 eV is expected
to be very active for HER in the alkaline solution, in general
accord with the experimental findings on the better perform-
ance of the Pd@Ru NRs than the commercial Pt/C. Because
surface structures analogous to Ru/Pd(111) could be largely
exposed in the Pd@Ru NRs in experimental conditions, the
extraordinary efficiency of this novel HER catalyst in alkaline
solutions can be attributed to the multiple active sites created
by this core−shell structure.
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces
■ CONCLUSIONS
In summary, we reported the preparation of mesoporous Pd@
Ru NRs composed of fcc Pd and hcp Ru. Two types of cavities
constituted the unique mesoporous structures of the catalysts,
and abundant metal interfaces were produced in the
interdiffusion process. Electrochemical tests demonstrate that
this mesoporous bimetallic catalyst possesses excellent HER
catalytic activity with the overpotential of 30 mV at 10 mA·
cm−2 in 1.0 M KOH solution and extremely high mass activity
of 722.9 A g−1 at −0.06 V. DFT calculations reveal that the
alkaline-based HER activity of the catalyst is enhanced by the
Ru/Pd(111)-like structures at the interface. We believe that
the scheme for the synthesis of mesoporous Pd@Ru NRs by
further manipulation of mutual diffusion of elements would
open up a new avenue for the design of multifarious bimetallic
catalysts.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.8b09988.
More materials characterization; electrochemical meas-
urements; and computational results (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: bjiangch@ustc.edu.cn (B.J.).
*E-mail: hongxun@ustc.edu.cn (X.H.).
ORCID
Bin Jiang: 0000-0003-2696-5436
Junfa Zhu: 0000-0003-0888-4261
Zhongbin Zhuang: 0000-0001-7187-1266
Yuen Wu: 0000-0001-9524-2843
Xun Hong: 0000-0003-2784-2868
Yadong Li: 0000-0003-1544-1127
Author Contributions
Y.L. and X.L. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Key R&D Program
of China (2017YFA0700104), National Natural Science
Foundation of China (21571169, 21521091, 21390393,
U1463202, 91645202, 21722306, and 21573203), Fundamen-
tal Research Funds for the Central Universities
(WK2060190081), China Ministry of Science and Technology
under Contract of 2016YFA (0202801), Youth Innovation
Promotion Association of the Chinese Academy of Science
(2018494), and Young Elite Scientists Sponsorship Program
by CAST (2016QNRC001). We thank the BL11U in NSRL
for SRPES measurements and Supercomputing Center of
USTC for high-performance computing services.
■
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F DOI: 10.1021/acsami.8b09988
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX