Parameterizing Oriented External Electric Fields to Engineer Electronic Structure, Adsorption Properties, and CO Oxidation Kinetics on Nonprecious Co ₄ P ₄

Superhalogens, characterized by exceptionally high electron affinity (EA) and strong oxidizing capacity, play a critical role in energy conversion and catalysis. Conventional design strategies based on electron‐counting rules, however, offer limited tunability for continuous and precise modulation of electronic structure. Herein, we employ density functional theory to systematically investigate the influence of oriented external electric fields (OEEF) on the Co ₄ P ₄ cluster, with emphasis on electronic properties, small‐molecule adsorption, and CO oxidation. Our results reveal that OEEF elevates the cluster EA from non‐superhalogen to superhalogen levels while preserving its core–shell geometry, magnetic characteristics, and superatomic orbital arrangement. A polynomial relationship between OEEF intensity and EA enables geometrically noninvasive, precise regulation of electronic affinity. Directional OEEF further induces field‐strength‐dependent charge redistribution, thereby modulating active‐site distribution and reaction energetics to govern catalytic behavior. In CO oxidation, OEEF reversibly switches the cluster surface between activated and passivated states by tuning CO and O ₂ adsorption affinities, and reaction pathway analysis confirms systematic modulation of reaction barriers. This work introduces a novel strategy for synchronously optimizing electronic structure, molecular adsorption, and reaction kinetics through OEEF parameterization, thereby advancing the rational design of efficient nonprecious metal catalysts.