CATHODIC HYDROGEN EVOLUTION ON IRON DISILICIDE. II. ACIDIC SOLUTION

The kinetics of hydrogen evolution reaction on FeSi2-electrode in 0.5 M H2SO4 solution has been studied using methods of polarization and impedance measurements. With the help of diagnostic criteria for the hydrogen evolution reaction mechanisms based on the analysis of the dependence of the parameters of the equivalent electric circuit on overvoltage, it was established that the reaction of hydrogen evolution on iron disilicide in the sulfuric acid solution proceeds along the discharge - electrochemical desorption route, where desorption is the rate-determining stage. Both stages are irreversible, the transfer coefficients α of the stages are equal, simultaneously the hydrogen absorption reaction by the electrode material proceeds in the kinetic mode (in the whole investigated range of potentials). It was found that the adsorption of atomic hydrogen is described by the equation of the Langmuir isotherm. The influence of thin oxide film on the hydrogen evolution kinetics is noted. The influence of various methods of modifying of the surface of FeSi2-electrode on the kinetics and mechanism of the cathodic process has been studied. It was found that the modification of the disilicide surface by hydrogenation at a current density of i = 30 mA/cm2, an anodic etching in 0.5 M H2SO4 at the potential E = 0.4 V relative to the standard hydrogen electrode, an anodic etching in 1.0 M NaOH at the potential E = 0.1 V, chemical etching in 5.0 M NaOH at 70 °C reduce the overvoltage of hydrogen evolution, but the mechanism of the cathodic process does not change as a result of the electrode modification. Reduction of the overvoltage of hydrogen evolution on iron disilicide is due to the action of two factors: the development of the surface and the change in the composition of the surface layer of the electrode. It has been concluded that FeSi2 in the sulfuric acid solution is a promising electrode material that exhibits activity in the electrolytic hydrogen evolution reaction.

CATHODIC HYDROGEN EVOLUTION ON IRON DISILICIDE. I. ALKALINE SOLUTION

The kinetics of hydrogen evolution reaction on FeSi2-electrode in 1.0 M NaOH solution has been studied using methods of polarization and impedance measurements. With the help of diagnostic criteria for the hydrogen evolution reaction mechanisms based on the analysis of the dependence of the parameters of the equivalent electric circuit on overvoltage, it was established that the reaction of hydrogen evolution on iron disilicide in the alkaline electrolyte proceeds along the discharge - electrochemical desorption route, where desorption is the rate-determining stage. Both stages are irreversible, the transfer coefficients of the stages are equal (α1 = α2 = α), simultaneously the hydrogen absorption reaction by the electrode material proceeds in the diffusion mode (in the whole investigated range of potentials). It was found that the adsorption of atomic hydrogen is described by the equation of the Langmuir isotherm. The influence of various methods of modifying of the surface of FeSi2-electrode on the kinetics and mechanism of the cathodic process has been studied. It was found that the modification of the disilicide surface by hydrogenation at a current density of i = 30 mA/cm2, an anodic etching in 0.5 M H2SO4 at the potential E = 0.4 V relative to the standard hydrogen electrode, an anodic etching in 1.0 M NaOH at the potential E = 0.1 V, chemical etching in 5.0 M NaOH at 70 °C reduce the overvoltage of hydrogen evolution, but the mechanism of the cathodic process does not change as a result of the modification. Reduction of the overvoltage of hydrogen evolution on iron disilicide is due to the action of two factors: the development of the surface and the change in the composition of the surface layer of the electrode. It has been concluded that FeSi2 in the alkaline electrolyte is a promising electrode material that exhibits activity in the electrolytic hydrogen evolution reaction.