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A self-supported silver electrode was prepared by plasma spraying and used for catalysing the hydrogen evolution reaction. Thanks to the non-equilibrium synthetic conditions, the silver catalyst exposes high-energy (200) crystal planes, which enhance the adsorption of hydrogen and improve the intrinsic catalytic activity. As a result, the silver catalyst delivers an overpotential of 349 mV at 10 mA cm−2, which was much lower than those of Ag foil (742 mV) and commercial Ag powder (657 mV). This work provides a new idea of preparing active electrocatalysts by traditional processes. [ABSTRACT FROM AUTHOR]