Solvent Engineering and Metal‐Doping Dual Effects Enable Morphology Precise Controlled MOF‐based Electrocatalysts for Highly Efficient Oxygen Evolution Reaction

Abstract Designing economically viable electrocatalysts with superior activity for the oxygen evolution reaction (OER) represents a critical challenge in advancing practical water electrolysis systems for renewable hydrogen generation. In this work, CoFe‐MOF(W) with a layered structure is created through synergistic modulation of a dual‐regulation mechanism combining solvent engineering with metal doping, exhibiting superior electrocatalytic performance, requiring merely 276 mV overpotential to reach a current density of 10 mA cm −2 while demonstrating fast kinetics with a 55 mV dec −1 Tafel slope. The experimental results indicated that the solvent engineering facilitated the inducing unsaturated coordination states that tailored morphology and exposed more active sites, meanwhile, Fe‐doping modulated the electronic structure of Co sites while introducing multimetal synergy for enhanced charge transfer, resulting in superior OER performance. Further mechanistic studies revealed that CoFe‐MOF(W) underwent surface reconstruction, generating Co(Fe)OOH is the true OER active species. Moreover, the density‐functional theory (DFT) calculations confirmed that Fe doping optimized * OH adsorption free energy, thus enhancing the OER kinetics. This work elucidates a new insight into solvent modulation and metal doping strategies for MOF‐based electrocatalysts to achieve efficient OER performance, which is potentially promising for applications in sustainable energy systems.