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Laterally nanostructured surfaces give rise to a new dimension ofunderstanding and improving electrochemical reactions. In this study, wepresent a peculiar mechanism appearing at a metal/insulator interface, whichcan significantly enhance the Hydrogen Evolution Reaction (HER) from waterreduction by altering the local reaction conditions in two ways: facilitatedadsorption of hydrogen on the metal catalyst surface and improved transfer ofions through the double layer. The mechanism is uncovered using electrodesconsisting of well-defined nanometer-sized metal arrays (Au, Cu, Pt) embeddedin an insulator layer (silicon nitride), varying various parameters of both theelectrode (size of the metal patches, catalyst material) and the electrolyte(cationic species, cation concentration, pH). In addition, simulations of theelectrochemical double layer are carried out, which support the elaboratedmechanism. Knowledge of this mechanism will enable new design principles fornovel composite electrocatalytic systems.

How Metal/Insulator Interfaces Enable the Enhancement of the Hydrogen Evolution Reaction Kinetics in Two Ways