Supporting Information

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, University of Science
and Technology of China, Hefei, Anhui 230026, China
‡
Department of Physics, University of Science and Technology of China, Hefei, Anhui 230026,
China
§
Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui
230026, China
&
Department of Chemistry, Tsinghua University, Beijing 100084, China
||
State Key Lab of Organic-Inorganic Composites, Beijing University of Chemical Technology,
Beijing100029, China
#
National Synchrotron Radiation Laboratory (NSRL), University of Science and Technology of
China, Hefei, Anhui 230029, China

Corresponding Author

*hongxun@ustc.edu.cn

*bjiangch@ustc.edu.cn

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Experimental Section

Materials: All materials were obtained from commercial suppliers and used without further

purification. Palladium chloride (PdCl2, Pd 59.0%) were purchased from Alfa Aesar. Ruthenium

acetylacetonate (Ru(acac)3, %) was purchased from Aldrich. Poly(vinyl pyrrolidone) (PVP,

K30) and commercial Pd/C catalyst (20% metal) were purchased from Sinopharm Chemical

Reagent Co., Ltd (Ourchem). Sodium iodide (NaI) and Benzyl alcohol were purchased from

Sinopharm Chemical Reagent Co., Ltd (Shanghai, China). Deionized (DI) water obtained from

Milli-Q System (Millipore, Billerica, MA) was used in all our experiments. Commercial Ru/C

catalyst (20% metal) and Pt/C catalyst (20% metal) were purchased from Aladdin.

Synthesis of the Pd nanorods: The Pd nanorods were synthesized similarly to the previously

reported method 1. In a typical synthesis, PdCl2 (0.1mmol, 17.7 mg), PVP (800 mg), and NaI (2

mmol, 300 mg) were dissolved in 12mL DI water under ultrasonic for at least 30 min, and then

transferred to a Teflon-lined stainless-steel autoclave with a capacity of 20 mL. The mixture was

heated from room temperature to 200°C within 20 min and kept for 2 h. After cooling down to

room temperature, the final products were separated by centrifugation and purified by an

ethanol-acetone mixture to remove excess PVP molecules. The purified Pd NRs were dispersed

in 4 mL benzyl alcohol.

Synthesis of the Mesoporous Pd@Ru nanorods: In a typical synthesis, Ru(acac)3 (0.025 mmol,

10.0 mg) and PVP(100 mg) were dissolved in 5mL benzyl alcohol and mixed with 2mL Pd NRs.

The mixture was completely dispersed under ultrasonic for at least 30 min and kept at 200oC for

12h in a Teflon-lined stainless-steel autoclave with a capacity of 20 mL. After cooling down to

room temperature, the final products were separated by centrifugation and purified by an

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ethanol-acetone mixture to remove excess PVP molecules. In addition, the control samples were

prepared with the Ru(acac)3 content varied from 10 mg to 2 mg.

Electrochemical measurements: All the electrochemical experiments were conducted on an

electrochemical Workstation (CHI 760E) in a three-electrode system in 1.0 M KOH solution and

0.5 M H2SO4 solution at room temperature. Samples were deposited on the glassy carbon

electrode (GCE, 0.196 cm2 in area) and used as the working electrode. Ag/AgCl electrode was

used as the reference electrode and a graphite rod was used as the counter electrode. 1 mg

catalyst and 4 mg carbon black (Cabot Vulcan XC-72) were dispersed in 1 mL of ethanol/Nafion

(v/v = 19:1) by sonication for 30 min. Then, 10 µL well-dispersed catalyst was deposited on the

glassy carbon electrode and dried naturally. The HER was conducted in both N2-saturated 1.0 M

KOH and 0.5 M H2SO4 solutions with a scan rate of 5 mV s−1 at 1600 rpm on rotating electrode.

All potentials were referenced to a reversible hydrogen electrode (RHE) with IR correction. R

was measured by electrochemical impedance spectroscopy (EIS) and referred to the Ohmic

resistance, which results from the electrolyte/contact resistance. EIS measurements were carried

out from 100 kHz to 0.1 Hz on a rotation electrode at 1600 rpm. The extraction of

electrochemical parameters was performed using Nova software.

ECSA measurements: The ECSA of the catalyst has been already proved could be calculated by

Cu under-potential deposition (UPD) method (J. Mater. Chem. 2012, 22, 5197-5204;

Electrochimica Acta 2016, 188, 472-479). The ECSAs of solid Pd@Ru NRs and mesoporous

Pd@Ru NRs were calculated by integrating the charge associated with oxidation of Cu (on the

surface of catalyst by Cu UPD) in electrolyte containing 50 mM CuSO4 and 50 mM H2SO4, by

assuming a charge of 420 µC/cm2. The tests were conducted on the same electrochemical

Workstation (CHI 760E) except that a Pt rod was used as the counter electrode. 1 mg catalyst

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and 4 mg carbon black (Cabot Vulcan XC-72) were dispersed in 1 mL of ethanol/Nafion (v/v =

19:1) by sonication for 30 min. Then, 20 µL well-dispersed catalysts were deposited on the

glassy carbon electrode and dried naturally. A background electrolyte was 50 mM H2SO4. The

Cu UPD was carried out in 50 mM H2SO4, containing 50 mM CuSO4 by applying 0.1V (vs

Ag/AgCl). DI watter was used for the measurement and the solutions were purged with N2. The

loading of catalyst was 0.02mgPd+Ru (0.102 mgPd+Rucm-2). Cu UPD measurements were carried

out over a potential range from 0.05v to 0.8V, at scan rate of 5mV/s.

Characterization: Transmission electron microscopy (TEM) was carried out on a Hitachi H-

7650 transmission electron microscope at an acceleration voltage of 100 kV, and the high-angle

annular dark-field scanning TEM (HAADF-STEM), EDX elemental mapping were operated by a

JEOL JEM-2010 LaB6 high resolution transmission electron microscope operated at 200 kV.

The scanning electron microscope (SEM) was performed on JSM-6700F SEM. Powder X-ray

diffraction patterns of samples were recorded on a Rigaku Miniflex-600 operating at 40 kV

voltage and 15 mA current with Cu Kα radiation (λ = 0.15406 nm). The synchrotron radiation

photoemission spectroscopy (SRPES) spectra were measured with photon energies of 400 eV

and 1486.6 eV at the BL11U beamline in the National Synchrotron Radiation Laboratory (NSRL)

in Hefei, China.

Computation methods and models.

Density functional theory (DFT)2,3 implemented in Vienna Ab Initio Simulation Package (VASP)

was used to compute the molecule-metal interactions. Revised-Perdew-Burke-Ernzerhof (RPBE)

functional4 within the generalized gradient approximation (GGA) was throughout employed. A

plane-wave basis set was employed to expand the electronic wave-functions with a kinetic

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energy cutoff of 400 eV and the projected-augmented-wave (PAW)5 method was used to

describe the interaction between the valence electrons and ionic core. Spin polarization was

included in all cases. These slabs all consist of a periodic 2×2 unit cell with four layers (1/4 ML)

and the two bottom layers of the slab were fixed while the top two layers were allowed relax.

The Brillouin-zone integration was performed using a 5×5×1 k-point Monkhorst-Pack grid.6 The

optimized lattice parameters for Pd, Pt,and Ru are a = 3.95 Å, a = 3.95Å and a = b = 2.74 Å, c =

4.31 Å, respectively, which compare well with experimental values a=3.89 Å for Pd, a=3.92 Å

for Pt, a=b=2.71 Å,c=4.28 Å for Ru).7 The thickness of vacuum is set to be 15 Å to avoid

artificial interaction between vertically repeated slabs.

The HER is a classical example of a two-electron transfer reaction.In the alkaline solution, the

Volmer step is limited by the dissociation of water, a lower dissociation barrier would facilitate

the HER. As a result, we computed the water dissociation free energy barrier ∆GB , which can be

generally expressed as,

∆GB = ∆EB + ∆EZPE − T ∆Svib , (S1)

where ∆EB is the activation energy for water dissociation:

∆E B = ETS − EH 2 O* , (S2)

∆EZPE represents the difference in the zero point energy between adsorbed H2O and transition

state. In addition, vibrational entropies of the adsorbed water and the transition state could be

determined by vibrational frequencies ν i ,8

S = R∑
i
{ hν i kT
exp ( hν i kT ) −1 }
− ln 1 − exp ( −hν i kT )  , (S3)

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including the Planck constant h, the Boltzmann constant k, and the ideal gas constant R.

Supporting Figures

Figure S1. The histograms of width distribution of (a) Pd NRs, (b) solid Pd@Ru NRs, and (c)
porous Pd@Ru NRs. Black curve represents Gaussian fit. The average widths for Pd NRs, solid
Pd@Ru NRs, and porous Pd@Ru NRs are17.0 nm, 28.0 nm and 25.5 nm, respectively.

Figure S2. The histograms of diameter distribution of (a) polygonal cavities, (b) pinholes. Black
curve represents Gaussian fit. The average diameters for polygonal cavities and pinholes are 20.3
nm and 3.0 nm, respectively.

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Figure S3. (a) The atomic resolution HAADF-STEM image of a mesoporous Pd@Ru NR. (b-g)
the corresponding FFT patterns in different areas marked in red and yellow squares in (a),
respectively.

Figure S4. Schematic illustration for the formation of the mesoporous Pd@Ru NRs.

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Figure S5. EDX line scans of (a) solid and (b) mesoporous Pd@Ru. Inset: STEM image of (a)
solid and (b) mesoporous Pd@Ru.

Figure S6. TEM image of mesoporous Pd@Ru NRs after acid treatment (HNO3, 15h). Peaks
appear in XRD pattern (inset), corresponding to the reflections of hcp Ru (PDF#06-0663).

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Figure S7. The histogram of the atomic ratios (Ru:Pd) of the solid Pd@Ru NRs (2h) and
mesoporous Pd@Ru NRs (12h) with photon energies of 400 eV and 1486.6 eV, respectively.

Figure S8. Voltammetry curves for Cu UPD (red line) on (a) solid Pd@Ru NRs and (b)
mesoporousPd@Ru NRs in N2-saturated solution containing 50mM H2SO4 and 50mM CuSO4,
the blue lines was the baseline voltammetry curve for catalysts in 50mM H2SO4.

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Figure S9. Nyquist plots of (a) solid Pd@Ru NRs, (b) mesoporousPd@Ru NRs, and (c) Pt/C.
(inset is the equivalent circuit used to fit an experimental curve). The RCT of solid Pd@Ru NRs,
mesoporousPd@Ru NRs, and Pt/C is 39.6, 12.9,and 25.3Ω, respectively, which shows that the
mesoporousPd@Ru NRs have superior charge transfer capability.

Figure S10. TEM image of the porous Pd@Ru NRs after the hydrogen evolution reaction for 10h.
The ICP data shows that the Ru/Pd ratio is 1.82 which similar to the 1.7 before test. The slight
change might come from the dissolution of Pd in electrolyte.

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Figure S11. Polarization curves of porous Pd@Ru NRs, solid Pd@Ru NRs, Pd/C, Ru/C and Pt/C
electrocatalyst in 0.5 M H2SO4 solution.

Figure S12. Tafel plots obtained from the polarization curves of porous Pd@Ru NRs and Pt/C
electrocatalyst in 1.0 M KOH and 0.5 M H2SO4 solution.

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Figure S13. HER mass activity of porous Pd@Ru NRs, Pd/C, Ru/C and commercial Pt/C
(normalized by mass of Pd and Ru; at - 0.06 V) in both acid and alkaline media.

Figure S14. (a) Durability test of porous Pd@Ru NRs in 0.5 M H2SO4 and 1.0 M KOH, (b) Pt/C

in 0.5 M H2SO4.

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Supporting Tables
Catalysts Electrolyte Loading Substrate Current Overpotential Tafel slope Ref
amount density （mV） （mVdec-1）
(mg/cm2) (mA—cm-2)

Mesoporous Pd@Ru 1.0 M KOH 0.05 GCE 10 30 30 This

NRs work
37(normalized
by ECSA)

Solid Pd@Ru NRs 1.0 M KOH 0.05 GCE 10 76 48 This

59(normalized work
by ECSA)

Ru/C2N 1.0 M KOH 0.285 RDE 10 17 38 9

Au-Ru NWs 1.0 M KOH 0.08 GCE 10 50 30.8 10

Ni3N/Pt 1.0 M KOH 2.0 Ni mesh 10 50 36.5 11

Ru/C3N4 0.1 M KOH 0.204 GCE 10 79 N/A 8

Table S1. Summary of some recently reported representative HER electrocatalysts in alkaline
electrolytes.

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