Revealing Elusive Intermediates of Platinum Cathodic Corrosion through DFT Simulations

Cathodic corrosion of metals discovered more than 120 years ago remains a poorly understood electrochemical process. It is believed that the corrosion intermediates formed during cathodic polarization are extremely short-lived species because of their high reactivity. Together with the concurrent vigorous hydrogen evolution, this makes it challenging to investigate the reaction mechanism and detect the intermediates experimentally. From a computational standpoint, the process also presents a serious challenge as it occurs at rather low negative potentials in concentrated alkaline solutions. Here, we use density-functional-theory calculations to elucidate the identity of reaction intermediates and their reactivity at the Pt(111)/electrolyte interface. By controlling the electrode potential in an experimentally relevant region through constant Fermi-level molecular dynamics, we reveal the formation of alkali cation-stabilized Pt hydrides as intermediates of cathodic corrosion. The results also suggest that the found Pt anions could discharge at the interface to produce H₂ by reacting with either surface-bound hydrogen species or solution water molecules.