It is a great challenge to prepare non-noble metal electrocatalysts toward hydrogen evolution reaction (HER) with large current density. Synergistic electronic and morphological structures of the catalyst have been considered as an effective method to improve the catalytic performance, due to the enhanced intrinsic activity and enlarged accessible active sites. Herein, we present novel ternary Co_1−xV_xP nano-needle arrays with modulated electronic and morphological structures as an electrocatalyst for highly efficient HER in alkaline solution. The NF@Co_1−xV_xP catalyst shows a remarkable catalytic ability with low overpotentials of 46 and 226 mV at current densities of 10 and 400 mA cm⁻², respectively, as well as a small Tafel slope and superior stability. Combining the experimental and computational study, the excellent catalytic performance was attributed to the improved physical and chemical properties (conductivity and surface activity), large active surface area, and fast reaction kinetics. Furthermore, the assembled Co-V based electrolyzer (NF@Co_1−xV_x-HNNs(+)||NF@Co_1−xV_xP(−)) delivers small full-cell voltages of 1.58, 1.75, and 1.92 V at 10, 100, and 300 mA cm⁻², respectively. Our findings provide a systematic understanding on the V-incorporation strategy to promote highly efficient ternary electrocatalysts via synergistic control of morphology and electronic structures.

制备大电流密度的非贵金属电催化剂以进行析氢反应（HER）是一个巨大的挑战。由于增强的内在活性和扩大的可利用的活性位点，催化剂的协同电子和形态结构被认为是改善催化性能的有效方法。在这里，我们提出了具有调节的电子和形态结构的新型三元Co _{1- x} V _x P纳米针阵列，作为在碱性溶液中高效HER的电催化剂。NF @ Co _{1- x} V _x P催化剂显示出显着的催化能力，在10和400 mA cm ^-2的电流密度下具有46和226 mV的低过电势分别具有小的塔菲尔斜率和优越的稳定性。结合实验和计算研究，优异的催化性能归因于改善的物理和化学性质（电导率和表面活性），较大的活性表面积和快速的反应动力学。此外，组装好的基于Co-V的电解槽（NF @ Co _{1- x} V _x -HNNs（+）|| NF @ Co _{1- x} V _x P（-））可以提供1.58、1.75和1.85的小全电池电压，并且在10、100和300 mA cm ^-2时分别为1.92V。我们的研究结果提供了有关V-纳入战略系统的了解，以促进高效三元电催化剂通过 形态和电子结构的协同控制。