智能金属-金属氧化物异质界面结构具有广阔的潜力,可以为电化学CO2还原反应(CO2RR)提供有效的电子再分布。然而,受到内在线性缩放关系的抑制,由于电子能级的变化,竞争性中间体的结合能将同时发生变化,这使得很难专门为目标中间体和最终的CO2RR性能定制结合能。尽管如此,创建对目标中间体具有选择性的特定吸附位点可能会破坏线性缩放关系。为了验证它,Ag纳米团簇锚定在富含氧空位的CeO2纳米棒(Ag/OV-CeO2)上,用于CO2RR,发现氧空位驱动的异质界面可以有效地促进CO2RR在整个电势窗口中转化为CO,其中在流动池内390mV的低超电势下,在-0.9V时的最大CO法拉第效率(FE)为96.3%,而令人印象深刻的高COFE超过62.3%。实验和计算结果共同表明,氧空位驱动的异界面电荷溢出赋予了Ag的最佳电子结构,并引入了仅可识别*COOH的额外吸附位点,which,除了线性缩放关系之外,提高了对*COOH的结合能,而不阻碍*CO解吸,从而导致有效的CO2RR对CO。
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/OV-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.