Ni and Co Active Site Transition and Competition in Fluorine‐Doped NiCo(OH)2 LDH Electrocatalysts for Oxygen Evolution Reaction

The oxygen evolution reaction (OER) performance of NiCo LDH electrocatalysts can be improved through fluorine doping. The roles of Ni and Co active sites in such catalysts remain ambiguous and controversial. In addressing the issue, this study draws upon the molecular orbital theory and proposes the active center competitive mechanism between Ni and Co. The doped F‐atoms can directly impact the valence state of metal atoms or exert an indirect influence through the dehydrogenation, thereby modulating the active center. As the F‐atoms are progressively aggregate, the eg orbitals of Ni and Co transition from e2g to e1g, and subsequently to e0g. The corresponding valence state elevates from +2 to +3, and then to +4, signifying an initial increase followed by a subsequent decrease in the electrocatalytic performance. Furthermore, a series of F‐NiCo LDH catalysts are synthesized to verify the eg orbital occupancy analysis, and the catalytic OER overpotentials are 303, 243, 240, and 246 mV at the current density of 10 mA cm−2, respectively, which coincides well with the theoretical prediction. This investigation not only provides novel mechanistic insights into the transition and competition of Ni and Co in F‐NiCo LDH catalysts but also establishes a foundation for the design of high‐performance catalysts. The active center competitive mechanism in F‐NiCo LDH for OER from the points of view of both eg orbital and the valence.