An Interfacial View of Cation Effects on Electrocatalysis Systems

Abstract The identity of alkali metal cations in the electrolyte of electrocatalysis systems has been recently introduced as a crucial factor to tailor the kinetics and Faradaic efficiency of many electrocatalytic reactions. In this Minireview, we have summarized the recent advances in the molecular‐level understanding of cation effects on relevant electrocatalytic processes such as hydrogen evolution (HER), oxygen evolution (OER), and CO 2 electroreduction (CO 2 RR) reactions. The discussion covers the effects of electrolyte cations on interfacial electric fields, structural organization of interfacial water molecules, blocking the catalytic active sites, stabilization or destabilization of intermediates, and interfacial pHs. These cation‐induced interfacial phenomena have been reported to impact the performance (activity, selectivity, and stability) of electrochemical reactions collaboratively or independently. We describe that although there is almost a general agreement on the relationship between the size of alkali cations and the activities of HER, OER, and CO 2 RR, however, the mechanism by which the performance of these electrocatalytic reactions is influenced by alkali metal cations is still in debate.