Supporting Information

How to Reliably Report the Overpotential of an Electrocatalyst

Siqi Niu, Siwei Li*, Yunchen Du, Xijiang Han and Ping Xu*

MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and
Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology,
Harbin 150001, China

Corresponding author:
* pxu@hit.edu.cn (P.X.)
* lsw_hit@sina.com (S.L.)

Experimental Section
The potential was referred to RHE by calibrating the reference electrode with
Pt foil (Aldrich) as both the working and the counter electrodes in a sealed
standard three-electrode. Saturate the electrolyte with high-purity hydrogen for
at least half an hour before performing electrode calibration. Cyclic
voltammograms (CV) were performed at the scan rate of 1 mV/s and the average
of the two inter-conversion point values was taken to be the thermodynamic
potential for the hydrogen evolution reaction. To investigate the influence of
temperature on the correction values of the electrodes, a thermostatic water bath
was used to precisely control the temperature of the electrolyte at 20, 25 and 30
oC, respectively.

Additional Figures and Tables

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Figure S1. (a) Single cycle CV curves of Hg/HgO electrode calibration in 0.1 M KOH at different
temperature, (b) The enlarged view of (a).

Figure S2. (a) Single cycle CV curves of Hg/HgO electrode calibration in 1 M KOH at different
temperature, (b) The enlarged view of (a).

Figure S3. (a) Single cycle CV curves of Hg/Hg2Cl2 electrode calibration in 0.1 M H2SO4 at
different temperature, (b) The enlarged view of (a).

Figure S4. (a) Single cycle CV curves of Hg/Hg2Cl2 electrode calibration in 0.5 M H2SO4 at
different temperature, (b) The enlarged view of (a).

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Figure S5. (a) Single cycle CV curves of Ag/AgCl electrode calibration in 0.1 M Na2SO4 at
different temperature, (b) The enlarged view of (a).

Figure S6. Temperature-dependent RHE calibrated potentials of the Hg/HgO, Ag/AgCl, and
Hg/Hg2Cl2 reference electrodes.

Figure S7. (a) Single cycle CV curves of Hg/HgO electrode calibration in 1 M KOH on the 1st,
3rd, 5th, 7th, and 10th day, respectively, (b) The enlarged view of (a).

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Figure S8. (a) Single cycle CV curves of Hg/Hg2Cl2 electrode calibration in 0.5 M H2SO4 on the
1st, 3rd, 5th, 7th, and 10th day, respectively, (b) The enlarged view of (a).

Figure S9. (a) Single cycle CV curves of Ag/AgCl electrode calibration in 0.1 M Na2SO4 on the
1st, 3rd, 5th, 7th, and 10th day, respectively, (b) The enlarged view of (a).

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Table S1. The specific correction values for three reference electrodes in different
electrolytes at various temperature. The potential values are referenced to
reversible hydrogen electrode.

Reference Temperature
Electrolyte 1st (V) 2nd (V) 3rd (V)
Electrode (oC)

20 0.898 0.897 0.899

0.1 M KOH 25 0.894 0.894 0.893

30 0.893 0.892 0.892

Hg/HgO
20 0.930 0.931 0.932
1 M KOH 25 0.927 0.927 0.927

30 0.925 0.926 0.927

20 0.301 0.301 0.301

0.1 M
H2SO4 25 0.298 0.299 0.299

30 0.293 0.295 0.294

Hg/Hg2Cl2
20 0.269 0.267 0.268
0.5 M
H2SO4 25 0.259 0.261 0.260

30 0.257 0.258 0.258

20 0.709 0.710 0.710

0.1 M
Ag/AgCl 25 0.707 0.705 0.705
Na2SO4
30 0.703 0.705 0.704

Table S2. The practical pH values and the theoretical values of different
electrolytes.
Electrolyte Measured pH value Theoretical pH value

0.1 M KOH 12.64 13

1 M KOH 13.65 14

0.1 M H2SO4 0.80 0.7

0.5 M H2SO4 0.26 0

0.1 M Na2SO4 5.46 7

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