Heterostructured Bimetallic MOF‐on‐MOF Architectures for Efficient Oxygen Evolution Reaction

Electron modulation presents a captivating approach to fabricate efficient electrocatalysts for the oxygen evolution reaction (OER), yet it remains a challenging undertaking. In this study, an effective strategy is proposed to regulate the electronic structure of metal–organic frameworks (MOFs) by the construction of MOF‐on‐MOF heterogeneous architectures. As a representative heterogeneous architectures, MOF‐74 on MOF‐274 hybrids are in situ prepared on 3D metal substrates (NiFe alloy foam (NFF)) via a two‐step self‐assembly method, resulting in MOF‐(74 + 274)@NFF. Through a combination of spectroscopic and theory calculation, the successful modulation of the electronic property of MOF‐(74 + 274)@NFF is unveiled. This modulation arises from the phase conjugation of the two MOFs and the synergistic effect of the multimetallic centers (Ni and Fe). Consequently, MOF‐(74 + 274)@NFF exhibits excellent OER activity, displaying ultralow overpotentials of 198 and 223 mV at a current density of 10 mA cm−2 in the 1.0 and 0.1 M KOH solutions, respectively. This work paves the way for manipulating the electronic structure of electrocatalysts to enhance their catalytic activity. The metal–organic framework based heterogeneous electrocatalysts (MOF‐on‐MOF) can facilitate electron transfer at the dual‐MOF interface. In addition, the synergistic effect between Ni and Fe sites can promote electronic structure reconfiguration of active sites. Based on the above strategies for modulating the electronic structure of MOF‐based electrocatalysts, MOF‐(74 + 274)@NFF with optimal electronic structure exhibits superior oxygen evolution reaction (OER) performance.