Smart metal–metal oxide heterointerface construction holds promising potentials to endow an efficient electron redistribution for electrochemical CO₂ reduction reaction (CO₂RR). 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 CO₂RR 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 CeO₂ nanorods (Ag/O_V-CeO₂) for CO₂RR, and it was found that the oxygen vacancy-driven heterointerface could effectively promote CO₂RR 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 CO₂RR to CO.

中文翻译：

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氧空位驱动的异质界面打破了电催化二氧化碳还原中间体的线性比例关系


智能金属-金属氧化物异质界面结构具有为电化学CO ₂ 还原反应（CO ₂ RR）提供有效电子重新分布的广阔潜力。然而，受固有的线性比例关系的抑制，竞争中间体的结合能会由于电子能级的变化而同时变化，使得很难专门定制目标中间体和最终CO的结合能 ₂ 纳米棒（Ag/O _V -CeO ₂ ）上以捕获CO ₂ RR转化为CO，其中-0.9时最大CO法拉第效率（FE）为96.3%在流通池内以 390 mV 的低过电势实现了 V 和超过 62.3% 的令人印象深刻的高 CO FE。实验和计算结果共同表明，氧空位驱动的异质界面电荷溢出赋予了Ag最佳的电子结构，并引入了*COOH独有的额外吸附位点，这超出了线性比例关系，增强了与*COOH的结合能不阻碍 *CO 解吸，从而实现有效的 CO ₂ RR 为 CO。