Proton adsorption on metallic catalysts is a prerequisite for efficient hydrogen evolution reaction (HER). However, tuning proton adsorption without perturbing metallicity remains a challenge. A Schottky catalyst based on metal-semiconductor junction principles is presented. With metallic MoB, the introduction of n-type semiconductive g-C N induces a vigorous charge transfer across the MoB/g-C N Schottky junction, and increases the local electron density in MoB surface, confirmed by multiple spectroscopic techniques. This Schottky catalyst exhibits a superior HER activity with a low Tafel slope of 46 mV dec and a high exchange current density of 17 μA cm , which is far better than that of pristine MoB. First-principle calculations reveal that the Schottky contact dramatically lowers the kinetic barriers of both proton adsorption and reduction coordinates, therefore benefiting surface hydrogen generation.
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