biostudies-literatureUnknown18(1)Zhou YElucidating the structure-activity relationship between the electronic structure of catalytic active sites and oxygen evolution reaction (OER) activity at the orbital level is critical yet challenging in lithium-oxygen (Li-O₂) batteries. Herein, employing frontier molecular orbital theory, we designed a Pt-based catalyst as a model cathode to investigate the influence of frontier orbital interactions between the Pt d_z² orbital and the 5σ orbital of LiO₂ on the OER activity. Specifically, compared to the pure Pt catalyst, the d_z²-d_z² orbital coupling between low-electronegativity Fe and Pt in PtFe catalyst induces predominant electron transfer from Fe to the d_z² frontier orbital of Nano-micro letters257https://www.ebi.ac.uk/biostudies/studies/S-EPMC12913837biostudies-literatureEngineering PtFe/LiO<sub>2</sub> Frontier Orbital Interaction in Li-O<sub>2</sub> Batteries.PMC12913837Yang HLi JLiu KFeng DChen HHong GZhou YZhu ALiu YZhang TYao YLin DXue PLuan CYin KfalseEngineering PtFe/LiO<sub>2</sub> Frontier Orbital Interaction in Li-O<sub>2</sub> Batteries.Elucidating the structure-activity relationship between the electronic structure of catalytic active sites and oxygen evolution reaction (OER) activity at the orbital level is critical yet challenging in lithium-oxygen (Li-O₂) batteries. Herein, employing frontier molecular orbital theory, we designed a Pt-based catalyst as a model cathode to investigate the influence of frontier orbital interactions between the Pt d_z² orbital and the 5σ orbital of LiO₂ on the OER activity. Specifically, compared to the pure Pt catalyst, the d_z²-d_z² orbital coupling between low-electronegativity Fe and Pt in PtFe catalyst induces predominant electron transfer from Fe to the d_z² frontier orbital of 2026-01-01T00:00:00Z2026 Feb2026-07-16T06:49:48.091Z2026-07-09T10:40:53.139ZS-EPMC129138374170318610.1007/s40820-026-02085-z