Exploring nonprecious electrocatalysts for water splitting with high efficiency and durability is critically important. Herein, bimetallic phosphides are encapsulated into graphitized carbon to construct a C@NiCoP composite nanoarray using bimetallic metal-organic framework (MOF) as a self-sacrificial template. The resulting C@NiCoP exhibits superior performance for pH-universal electrocatalytic hydrogen evolution reaction (HER), particularly representing a low overpotential of 46.3 mV at 10 mA cm⁻² and Tafel slope of 44.1 mV dec⁻¹ in alkaline media. The structural characterizations combined with theoretical calculation demonstrate that tailored electronic structure from bimetal atoms and the synergistic effect with graphitized carbon layer could jointly optimize the adsorption ability of hydrogen on active sites in HER process, and enhance the electrical conductivity as well. In addition, the carbon layer served as a protecting shell also prevents highly dispersed NiCoP components from agglomeration and/or loss in harsh media, finally improving the durability. This work thus provides a new insight into optimizing activity and stability of pH-universal electrocatalysts by the nanostructural design and electronic structure modulation.

探索非贵重的电分解水高效电催化剂至关重要。在此，将双金属磷化物封装到石墨化碳中，以双金属金属有机骨架（MOF）作为自我牺牲模板来构建C @ NiCoP复合纳米阵列。所得的C @ NiCoP对pH值通用的电催化氢析出反应（HER）表现出优异的性能，特别是在10 mA cm ^-2下的低过电势为46.3 mV，Tafel斜率为44.1 mV dec ^-1在碱性介质中。结构表征与理论计算相结合表明，由双金属原子定制的电子结构以及与石墨化碳层的协同效应可以共同优化HER过程中氢在活性位点上的吸附能力，并同时提高电导率。另外，作为保护壳的碳层还可以防止高度分散的NiCoP组分在苛刻的介质中结块和/或损失，最终提高了耐用性。因此，这项工作为通过纳米结构设计和电子结构调节优化pH通用型电催化剂的活性和稳定性提供了新的见识。