It remains a challenge to explore economical, high-effective and long term stability electrocatalysts toward large-scale hydrogen production. This work utilizes surface engineering strategy to in-situ CoFe-Prussian Blue Analogues on NiCo-layered double hydroxides to obtain 3D hierarchical heterostructure precursor (NiCo–CoFe-PBA). After phosphatization, this precursor can be further transform into tri-metallic phosphide (NiCoP/CoFeP@NF) and directly act as efficient self-supported electrode for Water and Urea Electrolysis. Impressively, the obtained NiCoP/CoFeP@NF-12 (±) electrode shows excellent catalytic performance with only requires the cell voltage of 1.61 and 1.46 V to deliver 10 mA cm⁻² in overall water splitting and urea electrolysis, respectively, which benefiting from the porous Ni foam (NF) substrate, large catalytic activity area, remarkable mass/electron transfer property, the synergistic effect of components as well as superhydrophilicity and superaerophobicity of electrode surface. In addition, the experimental results also confirm that urea-assisted system has energy saving advantage superior than traditional water splitting in alkaline electrolyte. Moreover, the hierarchical strategy can also be introduced to the construction of other intricate composites for the utilization in energy conversion and storage.

探索经济、高效和长期稳定的电催化剂以实现大规模制氢仍然是一个挑战。这项工作利用表面工程策略在 NiCo 层状双氢氧化物上原位 CoFe-普鲁士蓝类似物，以获得 3D 分层异质结构前体（NiCo-CoFe-PBA）。磷化后，该前驱体可进一步转化为三金属磷化物（NiCoP/CoFeP@NF），并直接作为高效的水电解和尿素电解的自支撑电极。令人印象深刻的是，获得的 NiCoP/CoFeP@NF-12 (±) 电极显示出优异的催化性能，仅需 1.61 和 1.46 V 的电池电压即可提供 10 mA cm ^-2分别在整体水分解和尿素电解中，受益于多孔泡沫镍（NF）基材、大的催化活性面积、显着的传质/电子转移性能、组分的协同作用以及电极表面的超亲水性和超疏气性。此外，实验结果也证实尿素辅助系统在碱性电解液中具有优于传统水分解的节能优势。此外，分层策略也可以引入到其他复杂复合材料的构建中，以用于能量转换和存储。