Alkali metal cations change the hydrogen evolution reaction mechanisms at Pt electrodes in alkaline media

The effects of seemingly inert alkali metal (AM) cations on the electrocatalytic activity of electrode materials towards reactions essential for energy provision have become the emphasis of substantial research efforts in recent years. The hydrogen and oxygen evolution reactions during alkaline water electrolysis and the oxygen electro-reduction taking place in fuel cells are of particular importance. There is no universal theory explaining all the details of the AM cation effect in electrocatalysis. For example, it remains unclear how “spectator” AM-cations can change the kinetics of electrocatalytic reactions often more significantly than the modifications of the electrode structure and composition. This situation originates partly from a lack of systematic experimental and theoretical studies of this phenomenon. The present work exploits impedance spectroscopy to investigate the influence of the AM cations on the mechanism of the hydrogen evolution reaction at Pt microelectrodes. The activity follows the trend: Li+≥Na+>K+>Cs+, where the highest activity corresponds to 0.1 ​M LiOH electrolytes at low overpotentials. We demonstrate that the nature of the AM cations also changes the relative contribution of the Volmer–Heyrovsky and Volmer–Tafel mechanisms to the overall reaction, with the former being more important for LiOH electrolytes. Our density functional theory-based thermodynamics and molecular dynamics calculations support these findings.