Orbital Hybridization‐Mediated Decoupling of Electrocatalytic Functions for Paired CO 2 Electrosynthesis

ABSTRACT The intrinsic trade‐offs between activity, selectivity, and stability pose a fundamental challenge in electrocatalyst design. Here, we address these challenges by constructing a dual‐scale catalytic architecture where traditionally competing functions are decoupled and optimized simultaneously. Our approach is guided by the unique orbital hybridization landscape of CeO 2 110 facets, predicted by density functional theory (DFT) to confer a moderate Ag adsorption energy (−4. 11 eV), to construct an electronically coupled interface of atomically dispersed Ag 1 (for CO 2 activation) and metallic Ag n sub‐nanoclusters (for electron transport). The resulting orbitally hybridized interface boosts oxygen vacancy (O V) density by 1. 84‐fold and reduces charge‐transfer resistance by 58%. When deployed in a membrane‐free paired electrolyzer, this catalyst enables direct dialkyl carbonate synthesis from CO 2, achieving 88. 53% Faradaic efficiency (FE) for dimethyl carbonate (DMC) at an industrial current density of 52. 5 mA·cm −2 with 20 h stability, a performance competitive with the state‐of‐the‐art. The versatility of this morphology‐governed orbital hybridization strategy is further demonstrated by the selective production of diethyl carbonate (DEC). This work establishes a rational design principle that controls catalytic synergy through crystallographically defined orbital interactions, offering a promising approach to address persistent trade‐offs in electrocatalysis for CO 2 valorization.