The synergistic achievement of heteroatom doping, defect engineering and appropriate structural design is efficient to adjust and boost the catalytic performance of catalysts yet challenging. Herein, P-doped NiS₂ hierarchical architectures with sulfur vacancies are synthesized via a Prussian-blue-analogue-sacrificed strategy followed by a phosphidation process. By modulation of phosphorus (P) doping and sulfur vacancies, the optimal catalyst manifests outstanding electrocatalytic activities, affording low overpotentials of 73 mV at 10 mA cm⁻² for hydrogen evolution reaction (HER), and 255 mV at 20 mA cm⁻² for oxygen evolution reaction (OER), respectively. Density functional theory calculations certify that the P dopant not only serves as the new active sites, but also activates the electrochemical activity of neighboring Ni and S sites. Moreover, the synergistcs effect of P-doping with sulfur vacancies further improve electrochemical activities of HER and OER by optimizing the hydrogen (ΔG_H*) and oxygen-containing intermediates (OH*, O* and OOH*) adsorption free energy. This finding provides a directive strategy to design efficient non-noble metal catalysts for energy conversion and storage.

杂原子掺杂，缺陷工程和适当的结构设计的协同成就对于调节和提高催化剂的催化性能是有效的，但仍具有挑战性。在此，通过普鲁士蓝-类似物-牺牲的策略，接着进行磷化过程，合成具有硫空位的P-掺杂的NiS ₂分级结构。通过调节磷（P）掺杂和硫空位，最佳催化剂表现出出色的电催化活性，在10 mA cm ^-2的低氢电离反应（HER）处提供73 mV的低电势，在20 mA cm ^{-2的情况下提供}255 mV的低电势。分别用于放氧反应（OER）。密度泛函理论计算证明，P掺杂剂不仅充当了新的活性位，而且还激活了相邻的Ni和S位的电化学活性。此外，通过优化氢（ΔGH _*）和含氧中间体（OH *，O *和OOH *）的吸附自由能，P掺杂与硫空位的协同效应进一步提高了HER和OER的电化学活性。这一发现为设计用于能量转化和存储的高效非贵金属催化剂提供了指导性策略。