Geometric Structure and Electronic Polarization Synergistically Boost Hydrogen-Evolution Kinetics in Alkaline Medium.

Efficient electrocatalysts for the hydrogen evolution reaction (HER) are significant for the utilization of hydrogen as a fuel, particularly under alkaline conditions. However, the sluggish kinetics of HER remains a challenge. Here we demonstrate an efficient HER catalyst comprising Ru and AgCl nanoparticles anchored on Ag nanowires (Ru/AgCl@Ag), which delivers a low overpotential of 12 mV at 10 mA cm(-2) and a Tafel slope of 38 mV decade(-1). A high mass activity of 214 mA mg(-1) at an overpotential of 25 mV and a long-term durability in 1.0 M KOH are observed. In combination with computational simulations, we find that the high electronegativity of chlorine in AgCl and d-band electrons from Ru synergistically destabilize the water molecule and modulate H adsorption/desorption on the surface of Ru/AgCl@Ag, respectively. This work opens a promising avenue for the facile design and application of highly active and stable composite electrocatalysts toward water splitting.