Making the hydrogen evolution reaction in polymer electrolyte membrane electrolysers even faster

Although the hydrogen evolution reaction (HER) is one of the fastest electrocatalytic reactions, modern polymer electrolyte membrane (PEM) electrolysers require larger platinum loadings (∼0.5-1.0 mg cm(-2)) than those in PEM fuel cell anodes and cathodes altogether (∼0.5 mg cm(-2)). Thus, catalyst optimization would help in substantially reducing the costs for hydrogen production using this technology. Here we show that the activity of platinum(111) electrodes towards HER is significantly enhanced with just monolayer amounts of copper. Positioning copper atoms into the subsurface layer of platinum weakens the surface binding of adsorbed H-intermediates and provides a twofold activity increase, surpassing the highest specific HER activities reported for acidic media under similar conditions, to the best of our knowledge. These improvements are rationalized using a simple model based on structure-sensitive hydrogen adsorption at platinum and copper-modified platinum surfaces. This model also solves a long-lasting puzzle in electrocatalysis, namely why polycrystalline platinum electrodes are more active than platinum(111) for the HER.