The kinetics of hydrogen evolution reaction on cobalt monosilicide CoSi in potassium hydroxide solution was studied using methods of polarization and impedance measurements. Electrochemical impedance of CoSi was studied in 1 M KOH at 21-22 °C in the range of potentials of hydrogen evolution. Solutions were prepared from high-purity reagents and de-ionized water (Milli-Q). The working solutions were de-aerated with hydrogen (purity 99.999 %). Cobalt silicide was prepared from silicon (99.99 % purity) and electrolytic cobalt (99.98 % purity) by Czochralski method (pulling from the melt at speed of 0.4 mm/min). Electrodes were cut using electric-spark method. The working electrode surface was 0.4 – 0.6 cm2. Before measurements, the working electrode surface was abraded with emery papers of 1000 and 2000, cleaned with ethanol and washed in the working solution. Electrochemical measurements were carried out in three-electrode electrochemical cell with cathodic and anodic compartments separated with a porous glass diaphragm. Potentials Е were changed from low to high cathodic polarisations and vice versa. Before recording an impedance spectrum at each potential value, the electrode was polarised under potentiostatic conditions until constant value of current was reached. The electrode potentials are given with respect to the SHE. Impedance measurements were carried out using FRA Solartron and potentiostat Solartron 1280 (Solartron Analytical) in the frequency range from 10 kHz to 0.01 Hz (10 points per decade). The alternating signal amplitude was 10 mV. The CorrWare2, ZPlot2 and ZView2 software (Scribner Associates, Inc.) was used for measuring and processing the impedance data. In 1 М KOH polarization curve for CoSi-electrode has Tafel plot with the slope bk = 0.113 V. Earlier it was established that b for Со2Ѕі and CoSi2 at these conditions were 0.123 and 0.105 V, respectively, while b for Co was equal to 0.144 V. Tafel slope for cobalt monosilicide is less than Co, i.e. the difference between the current densities on the silicide and cobalt increases with increasing in cathodic polarization. At a constant electrode potential E, the current density i for CoSi is higher than for Co (at E = -1.2 V the value of i for CoSi is equal to 1.58 mA/cm2, and for Co i = 0.32 mA/cm2). Nyquist diagrams consist of the combination of capacitive semicircle at high frequencies and an inductive arc at low frequencies. Impedance spectra of cobalt silicide can not be accurately described by a simple equivalent circuit consisting of parallel-connected charge transfer resistance and the double layer capacitance. In order to describe the behavior of CoSi - electrode in 1 M KOH solution in the range of investigated potentials the equivalent circuit was used which was obtained in several works as a model of two-stage process with the adsorption of intermediate substances, in particular for hydrogen evolution reaction. In order to analyze the impedance data we used the diagnostic criteria for hydrogen evolution reaction mechanisms, based on the dependence of equivalent circuit elements on the overvoltage and OH- ions concentration, which were previously proposed. Determination of the kinetic parameters (rate constants and transfer coefficients) of hydrogen evolution reaction steps on the basis of the impedance data has been considered. Hydrogen evolution reaction on CoSi electrode in alkaline solution is discussed using the proposed criteria. It has been shown that hydrogen evolution reaction on CoSi in potassium hydroxide solution proceeds through the Volmer-Heyrovsky route with Heyrovsky reaction as the rate-determining and with the Langmuir isotherm for hydrogen adsorption. Forcitation:Shamsutdinov A.Sh., Shein A.B. Cathodic hydrogen evolution on cobalt monosilicide in potassium hydroxide solution. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 10. P. 9-15
Extracting the kinetic parameters of the hydrogen evolution reaction at Pt in acidic media by means of dynamic multi-frequency analysis