Structural‐Insensitive Descriptors N_s,p Based on M‐N₄‐OH Active Entity for Predicting and Enhancing ORR Activity in 3d Transition Metal Catalysts

Abstract The development of high‐performance ORR catalysts is challenged by the understanding how the delocalized electrons in s‐ and p‐orbitals influence oxygen intermediate adsorption and overall catalytic performance. To address these challenges, the from active unit to bulk catalyst (FAUC) design strategy is employed to investigate the roles of s‐ and p‐orbitals in ORR activity. Specifically, six M‐N₄‐OH (M = V, Cr, Mn, Fe, Co, and Ni) catalyst systems are constructed and analyzed using density functional theory (DFT), this study reveals that, compared to d‐orbitals, the delocalized electrons in the s‐ and p‐orbitals (N_s,p) exhibit a significant volcano relationship with ORR activity. This superior predictive capability arises from the weaker dependence of s‐ and p‐orbitals on the local coordination environment. Additionally, a structure‐activity relationship is established where shortening M─O and M─N bond lengths significantly increases N_s,p. Through modification strategies such as doping and loading, the Co─N bond lengths are regulated in Co‐N₄‐OH‐C, resulting in shorter bonds and increased N_s,p, which shifted ORR catalytic activity closer to the volcano peak. These findings validate the N_s,p descriptor's rationality and universality across various 3d transition metals, providing new insights for the design of high‐performance ORR catalysts.