The hydrogen evolution reaction was studied on various metallic polycrystalline and composite electrodes. Techniques used in the studies of the mechanism and kinetics of this reaction: steady-state polarization curves, potential step, potential relaxation in an open circuit and ac impedance were critically compared. In most cases the kinetics was determined using nonlinear least square approximation of the steady-state currents and charge transfer impedances. It was found that the hydrogen evolution proceeds through the Volmer-Heyrovsky reaction mechanism. Various electrode parameters characterizing electrode activities and surface roughness were determined. Comparison of intrinsic (per unit of real surface area) activities revealed that the main contribution to the electrode activity comes from the increase in the real surface area.
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