Oxygen Vacancy-Driven Heterointerface Breaks the Linear-Scaling Relationship of Intermediates toward Electrocatalytic CO₂ Reduction

Smart metal–metal oxide heterointerface construction holds promising potentials to endow an efficient electron redistribution for electrochemical CO 2 reduction reaction (CO 2 RR). However, inhibited by the intrinsic linear-scaling relationship, the binding energies of competitive intermediates will simultaneously change due to the shifts of electronic energy level, making it difficult to exclusively tailor the binding energies to target intermediates and the final CO 2 RR performance. Nonetheless, creating specific adsorption sites selective for target intermediates probably breaks the linear-scaling relationship. To verify it, Ag nanoclusters were anchored onto oxygen vacancy-rich CeO 2 nanorods (Ag/O V -CeO 2 ) for CO 2 RR, and it was found that the oxygen vacancy-driven heterointerface could effectively promote CO 2 RR to CO across the entire potential window, where a maximum CO Faraday efficiency (FE) of 96.3% at −0.9 V and an impressively high CO FE of over 62.3% were achieved at a low overpotential of 390 mV within a flow cell. The experimental and computational results collectively suggested that the oxygen vacancy-driven heterointerfacial charge spillover conferred an optimal electronic structure of Ag and introduced additional adsorption sites exclusively recognizable for *COOH, which, beyond the linear-scaling relationship, enhanced the binding energy to *COOH without hindering *CO desorption, thus resulting in the efficient CO 2 RR to CO.