Mechanism and kinetics of the hydrogen evolution reaction

Hydrogen evolution reaction, HER, is the simplest electrocatalytic reaction. With development of renewable energy sources electrolytic production of hydrogen becomes an alternative way of hydrogen production for internal combustion engines and fuel cells. HER proceeds through the Volmer, Heyrovsky and Tafel reaction mechanism. The formal kinetics of HER is described briefly in many books but detailed description is only found in research papers. In this review detailed kinetic description of HER is presented for stationary measurements, electrochemical impedance spectroscopy, open circuit potential decay and current step techniques. It is illustrated by examples and limitations of the determination of kinetic parameters are discussed. Finally, experimental conditions necessary for obtaining good experimental data are presented.