Single-Crystalline Mo-Nanowire-Mediated Directional Growth of High-Index-Faceted MoNi Electrocatalyst for Ultralong-Term Alkaline Hydrogen Evolution

As appealing alternatives to noble-metal-based electrocatalysts for catalyzing hydrogen evolution reaction (HER) in alkali electrolyzers, earth-abundant MoNi-based catalysts have attracted intensive attention. Unfortunately, the exploration of MoNi-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 nanowire film serve as a free-standing cathode in alkaline solutions, it exhibit 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 the 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-day 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.