Alkaline hydrogen evolution reaction (HER) is a cornerstone for efficient green hydrogen production via anion exchange membrane water electrolysis (AEMWE), yet suffering from sluggish water dissociation kinetics. Ruthenium (Ru)-based catalysts exhibit Pt-like activity at a fraction of the cost, but their performance is hampered by excessive hydroxide accumulation on Ru sites, a consequence of their overly strong oxygen affinity and suboptimal d-band center. Herein, we reported a class of Mo/V-dual-tailored Ru metallic glass nanosheets (Mo/V-Ru NSs) to enable spatial segregation of water dissociation sites (on Mo/V) from hydrogen evolution sites (on Ru), achieving the acceleration of alkaline HER electrocatalysis. The optimized Mo/V-Ru NSs deliver outstanding alkaline HER performance, with overpotentials of 36 and 86 mV at 10 and 100 mA·cm⁻², respectively, outperforming pure Ru counterparts and commercial Pt/C. Remarkably, the Mo/V-Ru NSs-based AEMWE can achieve a high current density of 100 mA·cm⁻² at a low cell voltage of 1.68 V and exhibit excellent durability for over 120 h. In-situ Fourier transform infrared (FT-IR) spectroscopy elucidates the role of Mo and V in water adsorption and O–H bond cleavage, synergistically lowering the water dissociation barrier. Density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations confirm enhanced water adsorption on Mo/V sites and preferential Ru-H coordination, supporting the site-segregation mechanism.

The hydrogen evolution reaction (HER) of molybdenum disulfide (MoS₂) is limited in alkaline and acid solution because the active sites are on the finite edge with extended basal plane remaining inert. Herein, we activated the interfacial S sites by coupling with Ru nanoparticles on the inert basal plane of MoS₂ nanosheets. The density functional theory (DFT) calculation and experimental results show that the interfacial S electronic structure was modulated. And the results of ∆G_H* demonstrate that the adsorption of H on the MoS₂ was also optimized. With the advantage of interfacial S sites activation, the Ru-MoS₂ needs only overpotential of 110 and 98 mV to achieve 10 mA·cm^–2 in both 0.5 M H₂SO₄ and 1 M KOH solution, respectively. This strategy paves a new way for activating the basal plane of other transition metal sulfide electrocatalysts for improving the HER performance.