Structural Engineering of Co‐Metal–Organic Frameworks via Ce Incorporation for Improved Oxygen Evolution

Abstract The rational design of metal–organic framework (MOF)‐based electrocatalysts plays a key role in achieving high‐efficiency oxygen evolution reaction (OER). Herein, a synergetic morphology and electronic structure engineering strategy are proposed to design a Co‐MOF nanoflower grown on carbon paper via rare‐earth cerium doping (CoCe‐MOF/CP). Compared with Co‐MOF/CP, the developed CoCe‐MOF/CP exhibited superior OER performance with a low overpotential of 267 mV at 10 mA cm −2 and outstanding long‐term stability over 100 h. Theoretical calculations show that the unique 4f valence electron structure of Ce induced charge redistribution of the Co‐MOF surface through the strong Co 3d‐O 2p‐Ce 4f orbital electronic coupling below the Fermi level. Ce‐doped plays a key role in the engineering of the electronic states of the Co sites to endow them with the optimal free energy landscape for enhanced OER catalytic activity. This work provides new insights into comprehending the RE‐enhanced mechanism of electrocatalysis and provides an effective strategy for the design of MOF‐based electrocatalysts.