Engineering copper-based catalysts that favour high-value alcohols is desired in view of the energy density, ready transport and established use of these liquid fuels. In the design of catalysts, much progress has been made to target the C–C coupling step; whereas comparatively little effort has been expended to target post-C–C coupling reaction intermediates. Here we report a class of core–shell vacancy engineering catalysts that utilize sulfur atoms in the nanoparticle core and copper vacancies in the shell to achieve efficient electrochemical CO₂ reduction to propanol and ethanol. These catalysts shift selectivity away from the competing ethylene reaction and towards liquid alcohols. We increase the alcohol-to-ethylene ratio more than sixfold compared with bare-copper nanoparticles, highlighting an alternative approach to electroproduce alcohols instead of alkenes. We achieve a C₂₊ alcohol production rate of 126 ± 5 mA cm⁻² with a selectivity of 32 ± 1% Faradaic efficiency.

考虑到这些液体燃料的能量密度，易于运输和确定的用途，需要有利于高价值醇的工程铜基催化剂。在催化剂的设计中，以CC偶联步骤为目标已经取得了很大进展。而针对CC后偶联反应中间体的投入相对较少。在这里，我们报告了一类核-壳空位工程催化剂，它们利用纳米颗粒核中的硫原子和壳中的铜空位来实现有效的电化学CO ₂还原为丙醇和乙醇。这些催化剂使选择性从竞争的乙烯反应转向液体醇。与裸铜纳米颗粒相比，我们将醇/乙烯比提高了六倍以上，从而突出了一种替代方法，可以电生成醇而不是烯烃。我们实现了126±5 mA cm ^-2的C ₂₊醇生产率，选择性为32±1％法拉第效率。