Promoting Surface Reconstruction in Spinel Oxides via Tetrahedral‐Octahedral Phase Boundary Construction for Efficient Oxygen Evolution

Abstract Understanding the origin of surface reconstruction is crucial for developing highly efficient lattice oxygen oxidation mechanism (LOM) based spinel oxides. Traditionally, the reconstruction has been achieved through electrochemical procedures, such as cyclic voltammetry (CV), linear sweep voltammetry (LSV). In this work, we found that the surface reconstruction in LOM‐based CoFe 0.25 Al 1.75 O 4 catalyst was an irreversible oxygen redox chemical reaction. And a lower oxygen vacancy formation energy ( E O‐V ) could benefit the combination of the activated lattice oxygen atoms with adsorbed water molecular. Motivated by this finding, a strategy of phase boundary construction from Co tetrahedral to octahedral was employed to decrease E O‐V in CoFe 0.25 Al 1.75 O 4 . The results showed that as the Co octahedral occupancy ratio rose to 64 %, a 3.5 nm‐thick reconstructed layer formed on the catalyst surface with a 158 mV decrease in overpotential. Further experiments indicated that the coexistence of tetrahedral‐octahedral (O−T) phase would result in lattice mismatch, promoting non‐bonding oxygen states and lowering E O‐V . Then more active lattice oxygen combined with H 2 O molecules to generate hydroxide ions (OH − ), followed by soluble cation leaching, which enhanced the reconstruction process. This work provided new insights into the relationship between the intrinsic structure of pre‐catalysts and surface reconstruction in LOM‐based spinel electrocatalysts.