Electrochemical conversion of CO₂ into liquid fuels, powered by renewable electricity, offers one means to address the need for the storage of intermittent renewable energy. Here we present a cooperative catalyst design of molecule–metal catalyst interfaces with the goal of producing a reaction-intermediate-rich local environment, which improves the electrosynthesis of ethanol from CO₂ and H₂O. We implement the strategy by functionalizing the copper surface with a family of porphyrin-based metallic complexes that catalyse CO₂ to CO. Using density functional theory calculations, and in situ Raman and operando X-ray absorption spectroscopies, we find that the high concentration of local CO facilitates carbon–carbon coupling and steers the reaction pathway towards ethanol. We report a CO₂-to-ethanol Faradaic efficiency of 41% and a partial current density of 124 mA cm⁻² at −0.82 V versus the reversible hydrogen electrode. We integrate the catalyst into a membrane electrode assembly-based system and achieve an overall energy efficiency of 13%.

由可再生电力驱动的将CO ₂电化学转化为液体燃料，提供了一种解决间歇性可再生能源存储需求的方法。在这里，我们提出了分子-金属催化剂界面的协同催化剂设计，目的是产生一个富含反应中间体的局部环境，从而改善了由CO ₂和H ₂ O乙醇的电合成。我们通过功能化铜表面来实施该策略带有一族基于卟啉的金属配合物，可催化CO ₂使用密度泛函理论计算以及原位拉曼光谱和操作X射线吸收光谱法，我们发现高浓度的局部CO促进了碳-碳偶联，并引导反应路径向乙醇转化。我们报道了相对于可逆氢电极，CO ₂转化为乙醇的法拉第效率为41％，在-0.82 V时的部分电流密度为124 mA cm ^-2。我们将催化剂整合到基于膜电极组件的系统中，实现了13％的整体能源效率。