Constructing bifunctional non-precious metal electrocatalysts is necessary for effective overall water splitting (OWS), but challenging. Herein, a novel hybrid nanostructure of ZIF-67/MIL-88(Fe, Ni), denoted as Co-M-Fe/Ni(x) (x represents the mass of ZIF-67), was successfully synthesized by hydrothermal and in-situ growth method, and showed a highly efficient and stable bifunctionality of both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline electrolyte. The Co-M-Fe/Ni(150) exhibited excellent OER performance with a low overpotential of 269 mV and 149 mV @ 10 mA cm⁻² for OER and HER in 1 mol L⁻¹ KOH, respectively. With Co-M-Fe/Ni(150) as cathode and anode, the integrated OWS device had achieved low potential of 1.52 V @ 10 mA cm⁻², exhibiting its excellent performance of OWS. Based on the results of experiments, ZIF-67 and MIL-88(Fe, Ni), as metal-organic frameworks (MOFs), which have a large specific surface area, uniform distribution of porous structures facilitates charge transmission, promoting the penetration of electrolytes, and improves electron transfer rate. The mechanism of the superior electrocatalytic performance of Co-M-Fe/Ni(150) may be attributed to the synergy of ZIF-67 and MIL-88(Fe, Ni). This work provides guidance for the rational design or optimization of non-noble composites for energy conversion.

构建双功能非贵金属电催化剂对于有效的全水分解 (OWS) 是必要的，但具有挑战性。在此，通过水热法成功合成了一种新型杂化纳米结构 ZIF-67/MIL-88(Fe, Ni)，表示为 Co-M-Fe/Ni(x)（x 代表 ZIF-67 的质量） -原位生长方法，并在碱性电解质中显示出高效稳定的析氢反应（HER）和析氧反应（OER）双功能。Co-M-Fe/Ni(150) 表现出优异的 OER 性能，在 1 mol L ^-1 KOH中 OER 和 HER 的过电位分别为 269 mV 和 149 mV @ 10 mA cm ^{-2 。}以 Co-M-Fe/Ni(150) 为阴极和阳极，集成 OWS 器件实现了 1.52 V @ 10 mA cm ^{−2的低电势}，展示了其出色的OWS性能。根据实验结果，ZIF-67和MIL-88(Fe, Ni)作为金属有机骨架材料(MOFs)，具有较大的比表面积，均匀分布的多孔结构有利于电荷传输，促进电解质，并提高电子传输速率。Co-M-Fe/Ni(150) 优异电催化性能的机制可能归因于 ZIF-67 和 MIL-88(Fe, Ni) 的协同作用。这项工作为用于能量转换的非贵金属复合材料的合理设计或优化提供了指导。