Indirect identification of Hads relaxation on different metals by electrochemical impedance spectroscopy

For the hydrogen evolution reaction, the coverage rate of the electrode surface by adsorbed hydrogen is generally difficult to evidence especially in presence of bubbles. In the present paper, a parallel competing reaction was incorporated to the interface by the addition of ferricyanide to a NaOH solution. This reaction was supposed to take place on the free electrode surface and allowed the relaxation of adsorbed hydrogen to be identified. Models taking into account hydrogen evolution, hydrogen absorption, and ferricyanide reduction were proposed. Three metals were tested: platinum, iron, and palladium, which absorb hydrogen in very different quantities. In these conditions, low frequency loops related to the Hads surface coverage appeared in the electrochemical impedance diagrams, whose properties depend on the tested metal. Very good agreement was found between the experimental data and model predictions.