LAUSR

As appealing alternatives to noble metal-based electrocatalysts for catalyzing hydrogen evolution reaction (HER) in alkali-electrolyzers, earth-abundant Mo-Ni-based catalysts have attracted intensive attentions. Unfortunately, the exploration of Mo-Ni-based electrocatalysts with superior intrinsic activity and ultralong-term stability still remains a grand challenge. Here, ultralong high-index faceted Mo@MoNi core-shell nanowires were topochemically synthesized through the thermal reduction of Mo@NiMoO4 core-shell nanowires, where single-crystalline Mo support facilitates the topological transformation of NiMoO4 into high-index faceted MoNi. When the as-achieved Mo@MoNi core-shell nanowires serve as a free-standing cathode in alkaline solutions, it exhibits a remarkably decreased HER overpotential of 18 mV at 10 mA cm-2 and a Tafel slope of ~33 mV dec-1, which are much lower than those for state-of-the-art earth-abundant electrocatalysts and even commercial Pt/C. Experimental and theoretical investigations reveal that the exposed high-index (331) facets of MoNi can considerably reduce the energy barriers of initial water dissociation and subsequent hydrogen combination steps, which synergistically accelerates the sluggish alkaline HER kinetics. Significantly, after a 70-days HER operation, the overpotential of Mo@MoNi electrocatalysts at 10 mA cm-2 decreases by only 4 mV. Therefore, this work sheds a bright light on the rational design of high-performance HER electrocatalysts and their practical utilization for alkaline electrolyzers.