Rational heterostructure-design in electrocatalysts represents a promising approach toward high performance in the electrocatalytic hydrogen evolution reaction (HER). In specific, optimizing the H adsorption behavior at the surface/interface of heterostructure is of key importance to improve the catalytic performance. Herein, we demonstrate the construction of a heterostructure from a well-defined oxygen-bridged Co/Mo heterometallic zeolitic imidazolate framework (MOZ) as an efficient electrocatalyst for HER. The optimized hybrid exhibits high catalytic activity and stability in electrolytes with a wide pH range. Detailed XPS, XAS and theoretical studies reveal that the regulation of metal species can tailor the lattice of Mo₂C within the hybrid and induce the formation of defect sites, which could not only induce surface charge transfer between the atoms and provide an additional active site, but also affect the H adsorption behavior at the interface of a heterostructure. This work provides an effective strategy to design a heterostructure with tailored active sites for energy conversion.

电催化剂中合理的异质结构设计代表了一种在电催化氢释放反应（HER）中实现高性能的有前途的方法。具体而言，优化异质结构的表面/界面处的H吸附行为对于提高催化性能至关重要。在这里，我们展示了由定义明确的氧桥联的Co / Mo杂金属沸石咪唑酸盐骨架（MOZ）作为HER的有效电催化剂的异质结构的构建。经过优化的杂化体在宽pH范围的电解质中显示出高催化活性和稳定性。详细的XPS，XAS和理论研究表明，金属物种的调节可以定制Mo ₂的晶格杂化物中的C并诱导缺陷位点的形成，这不仅可以诱导原子之间的表面电荷转移并提供额外的活性位点，还可以影响异质结构界面处的H吸附行为。这项工作提供了一种有效的策略来设计具有量身定制的能效转换能量的异质结构。