Kinetics of the cathodic evolution of hydrogen on alloys of the MoxW1–xSi2 system in an alkaline electrolyte
The kinetics and mechanism of the hydrogen evolution reaction on alloys of the MoxW1-xSi2 system (x = 1.0; 0.68; 0.41; 0) in a 1.0 M NaOH solution have been studied by the methods of polarization and impedance measurements. The cathodic polarization curves of silicides were characterized by the Tafel plots with constants a and b, equal to 0.47–0.49 and 0.068–0.076 V, respectively. The impedance spectra of MoxW1-xSi2 electrodes in the Tafel region are a combination of a capacitive semicircle with a displaced centre at high frequencies and an inductive arc at low frequencies. In the region of the highest frequencies on the impedance plots a straight-line section with a slope slightly higher than 45º was recorded, indicating
the presence of pores in the surface layer of the electrodes.
To describe the hydrogen evolution reaction on silicides an equivalent electrical circuit was used, the Faraday impedance of which consisted of series-connected charge transfer resistance R1 and a parallel R2C2-chain (at R2 < 0, C2 < 0), which corresponded to the atomic hydrogen adsorption on the electrode surface. The impedance of the double layer capacitance was modelled by the constant phase element CPE1.
The results of polarization and impedance measurements for the investigated silicides were in satisfactory agreement with the discharge – electrochemical desorption mechanism, in which both stages are irreversible and have unequal transfer coefficients. The limiting stage is the electrochemical desorption. The Langmuir isotherm for adsorbed atomic hydrogen was fulfilled. It was concluded that MoxW1-xSi2 alloys in an alkaline electrolyte are promising electrode materials that are active in the electrolytic hydrogen evolution reaction.
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