Orbital Hybridization‐Mediated Decoupling of Electrocatalytic Functions for Paired CO2 Electrosynthesis

This study constructs a dual‐scale Ag‐based catalyst on CeO2 nanorods via a facet‐guided strategy. This catalyst can induce a cascaded orbital hybridization effect, which synergistically optimizes oxygen vacancy stability, CO desorption kinetics, and charge transfer efficiency. At a current density of 52.5 mA·cm−2, the Faradaic efficiency of dimethyl carbonate (DMC) reaches as high as 88.53%. 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 CeO2 {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 Ag1 (for CO2 activation) and metallic Agn sub‐nanoclusters (for electron transport). The resulting orbitally hybridized interface boosts oxygen vacancy (OV) 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 CO2, 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 CO2 valorization. This study constructs a dual-scale Ag-based catalyst on CeO 2 nanorods via a facet-guided strategy. This catalyst can induce a cascaded orbital hybridization effect, which synergistically optimizes oxygen vacancy stability, CO desorption kinetics, and charge transfer efficiency. At a current density of 52.5 mA·cm −2, the Faradaic efficiency of dimethyl carbonate (DMC) reaches as high as 88.53%. 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. Advanced Science, EarlyView.