Closed‐Shell Polarization Gating Governs Selective Hydrogen Peroxide Electrosynthesis

ABSTRACT Selective hydrogen peroxide (H 2 O 2 ) electrosynthesis via the two‐electron oxygen reduction reaction (2e − ORR) is intrinsically constrained by the entanglement between molecular activation and bond cleavage, which simultaneously triggers O═O scission and hydrogen evolution. Here we introduce Closed‐Shell Polarization Gating (CPG) as a general electronic‐structure paradigm for decoupling activation from dissociation in 2e − ORR. Within this framework, deeply buried d 10 states attenuate metal‐oxygen covalency and convert adsorption from bond‐activation‐driven chemistry to polarization‐regulated coordination. This closed‐shell configuration enforces end‐on O 2 adsorption, selectively stabilizes *OOH through interfacial polarization and hydrogen bonding, and suppresses O═O bond cleavage, thereby electronically programming the reaction pathway. High‐throughput density functional theory (DFT) screening identifies representative d 10 single‐atom centers (Zn and Cd) positioned near the apex of the 2e − ORR volcano. Guided by theory, a Zn‐based single‐atom catalyst delivers high H 2 O 2 selectivity consistent with theoretical predictions. Constant‐potential ab initio molecular dynamics (CP‐AIMD) simulations further reveal that the polarization‐gated regime persists dynamically under electrochemical bias and explicit solvation. By establishing closed‐shell polarization as a pathway‐selective gating mechanism, this work advances a general electronic principle for programming selective electrocatalytic pathways beyond H 2 O 2 synthesis.