The slow water dissociation is the rate-determining step that slows down the reaction rate in alkaline hydrogen evolution reaction (HER). Optimizing the surface electronic structure of the catalyst to lower the energy barrier of water dissociation and regulating the binding strength of adsorption intermediates are crucial strategy for boosting the catalytic performance of HER. In this study, RuO₂/BaRuO₃ (RBRO) heterostructures with abundant oxygen vacancies and lattice distortion were in-situ constructed under a low temperature via the thermal decomposition of gel-precursor. The RBRO heterostructures obtained at 550 °C exhibited the highest HER activity in 1 M KOH, showing an ultra-low overpotential of 16 mV at 10 mA cm⁻² and a Tafel slope of 33.37 mV dec⁻¹. Additionally, the material demonstrated remarkable durability, with only 25 mV of degradation in overpotential after 200 h of stability testing at 10 mA cm⁻². Density functional theory calculations revealed that the redistribution of charges at the heterojunction interface can optimize the binding energies of H* and OH* and effectively lower the energy barrier of water dissociation. This research offers novel perspectives on surpassing the water dissociation threshold of alkaline HER catalysts by means of a systematic design of heterogeneous interfaces.

缓慢的水解离是减慢碱性析氢反应 (HER) 反应速率的速率决定步骤。优化催化剂的表面电子结构以降低水解离的能垒并调节吸附中间体的结合强度是提高HER催化性能的关键策略。本研究通过凝胶前驱体的热分解在低温下原位构建了具有丰富氧空位和晶格畸变的RuO ₂ /BaRuO _{3 (RBRO)异质结构。}^{在550 °C下获得的RBRO异质结构在1 M KOH中表现出最高的HER活性，在10 mA cm -2}下表现出16 mV的超低过电势和33.37 mV dec ^-1的塔菲尔斜率。^{此外，该材料表现出卓越的耐用性，在10 mA cm -2}下进行200小时稳定性测试后，过电势仅下降25 mV 。密度泛函理论计算表明，异质结界面电荷的重新分布可以优化H*和OH*的结合能，有效降低水解离的能垒。这项研究为通过异质界面的系统设计超越碱性 HER 催化剂的水解离阈值提供了新的视角。