Importing Atomic Rare‐Earth Sites to Activate Lattice Oxygen of Spinel Oxides for Electrocatalytic Oxygen Evolution

Spinel oxides have emerged as highly active catalysts for the oxygen evolution reaction (OER). Owing to covalency competition, the OER process on spinel oxides often follows an arduous adsorbate evolution mechanism (AEM) pathway. Herein, we propose a novel rare-earth sites substitution strategy to tune the lattice oxygen redox of spinel oxides and bypass the AEM scaling relationship limitation. Taking NiCo₂O₄ as a model, the incorporation of Ce into the octahedral site induces the formation of Ce-O-M (M=Ni, Co) bridge, which triggers charge redistribution within NiCo₂O₄. The developed Ce-NiCo₂O₄ exhibits remarkable OER activity with a low overpotential, satisfactory electrochemical stability, and good practicability in anion-exchange membrane water electrolyzer. Theoretical analyses reveal that OER on Ce-NiCo₂O₄ surface follows a more favorable lattice oxygen mechanism (LOM) pathway and non-concerted proton-electron transfers compared to pure NiCo₂O₄, as also verified by pH-dependent behavior and in situ Raman analysis. The ¹⁸O-labeled electrochemical mass spectrometry provides direct evidence that the oxygen released during the OER originates from the lattice oxygen of Ce-NiCo₂O₄. We discover that electron delocalization of Ce 4f states triggers charge redistribution in NiCo₂O₄ through the Ce-O-M bridge, favoring antibonding state occupation of Ni-O bonding in [Ce-O-Ni] unit site, thereby activating lattice oxygen redox of NiCo₂O₄ in OER. This work provides a new perspective for designing highly active spinel oxides for OER and offers significant insights into the rare-earth-enhanced LOM mechanism.