Developing bifunctional electrocatalysts with high performance that are easily available, low-cost, and long-term stable is challenging. Interface engineering and vacancy engineering are two effective methods for constructing excellent catalysts. Based on the integration of these two strategies, a heterostructured catalyst with abundant oxygen vacancies was built via electrodeposition. The as-prepared catalyst, V_O-Co(OH)₂/CoN, had long-term stability in alkaline electrolyte and demonstrated excellent bifunctional activity with low overpotentials of 52 mV for the hydrogen evolution reaction and 206 mV for the oxygen evolution reaction at 10 mA cm⁻². The electrolytic cell constructed by V_O-Co(OH)₂/CoN only required a cell potential of 1.518 V at 10 mA cm⁻². According to both the results of experiments and density functional theory computations, the outstanding bifunctional activity of V_O-Co(OH)₂/CoN is attributed to the synergistic effect of heterointerface and oxygen vacancies. A Co atom and an oxygen vacancy formed an active Co-vacancy pair near the heterointerface, which synergistically boosted water splitting by changing the reaction path. Oxygen vacancy not only participated in catalysis as an active site, but also effectively adjusted the electron densities to improve the catalyst conductivity. Our work is vital to guide the design of highperformance catalysts and understand the catalytic mechanism.

开发易于获得、低成本和长期稳定的高性能双功能电催化剂具有挑战性。界面工程和空位工程是构建优良催化剂的两种有效方法。基于这两种策略的整合，通过电沉积构建了具有丰富氧空位的异质结构催化剂。所制备的催化剂 V _O -Co(OH) ₂ /CoN 在碱性电解质中具有长期稳定性，并表现出优异的双功能活性，析氢反应的过电位低至 52 mV，析氧反应的过电位低至 206 mV 10 毫安厘米^-2。_{V O} -Co(OH) ₂构成的电解池^{/CoN 在 10 mA cm -2}下仅需要 1.518 V 的电池电势。根据实验和密度泛函理论计算的结果，V _O -Co(OH) ₂ /CoN 出色的双功能活性归因于异质界面和氧空位的协同作用。Co原子和氧空位在异质界面附近形成活性Co-空位对，通过改变反应路径协同促进水分解。氧空位不仅作为活性位点参与催化，还能有效调节电子密度，提高催化剂的电导率。我们的工作对于指导高性能催化剂的设计和理解催化机理至关重要。