Using clean electricity to convert carbon dioxide (CO₂), an earth abundant carbon feedstock, to high-energy fuels is a fascinating energy strategy for a sustainable future. However, high yield of multi-carbon products remains a grand challenge. Herein, we show that trimeric metal clusters anchored on nitrogen doped porous carbon materials possess remarkable activity and selectivity for C₂–C₃ hydrocarbons and alcohols. By comprehensive ab initio calculations on 3d, 4d and 5d transition metal trimers, we for the first time illuminate their specialty for catalyzing this tough reaction. These spatially confined triatomic metal centers are capable of simultaneous fixation of plural CO₂ molecules, provide exclusive reaction channels that sterically and electronically facilitate C–C coupling, and have tunable selectivity by mediating the cluster-substrate interaction. The catalytic mechanism and structure-activity relationship are uncovered for these sub-nano clusters with robust stability. These results provide important knowledge for atomically precise design of novel catalysts for direct conversion of CO₂ to high-energy fuels and high-value chemicals.

使用清洁的电能转换成二氧化碳（CO ₂），地球丰富的碳原料，以高能量燃料是一个可持续发展的未来一个迷人的能源战略。然而，高收率的多碳产品仍然是一个巨大的挑战。在这里，我们表明锚固在氮掺杂的多孔碳材料上的三聚体金属簇对C ₂ -C ₃烃和醇具有显着的活性和选择性。通过对3 d，4 d和5 d的从头算起的全面计算过渡金属三聚体，我们首次展示了其催化这种艰难反应的专长。这些空间受限的三原子金属中心能够同时固定多个CO ₂分子，提供排他的反应通道，在空间和电子方面促进CC偶联，并通过介导簇-底物相互作用具有可调的选择性。这些具有稳定稳定性的亚纳米簇的催化机理和构效关系没有发现。这些结果为原子催化剂精确设计新颖的催化剂提供了重要的知识，该催化剂可将CO ₂直接转化为高能燃料和高价值化学品。