Copper-based catalysts for the hydrogenation of CO₂ to methanol have attracted much interest. The complex nature of these catalysts, however, renders the elucidation of their structure–activity properties difficult. Here we report a copper-based catalyst with isolated active copper sites for the hydrogenation of CO₂ to methanol. It is revealed that the single-atom Cu–Zr catalyst with Cu₁–O₃ units contributes solely to methanol synthesis around 180 °C, while the presence of small copper clusters or nanoparticles with Cu–Cu structural patterns are responsible for forming the CO by-product. Furthermore, the gradual migration of Cu₁–O₃ units with a quasiplanar structure to the catalyst surface is observed during the catalytic process and accelerates CO₂ hydrogenation. The highly active, isolated copper sites and the distinguishable structural pattern identified here extend the horizon of single-atom catalysts for applications in thermal catalytic CO₂ hydrogenation and could guide the further design of high-performance copper-based catalysts to meet industrial demand.

_{用于CO 2}加氢制甲醇的铜基催化剂引起了极大的兴趣。然而，这些催化剂的复杂性使其难以阐明其结构-活性特性。在这里，我们报告了一种具有分离的活性铜位点的铜基催化剂，用于将 CO ₂氢化为甲醇。结果表明，具有 Cu ₁ -O ₃单元的单原子 Cu-Zr 催化剂仅有助于在 180 °C 左右合成甲醇，而具有 Cu-Cu 结构模式的小铜簇或纳米粒子的存在则负责形成 CO副产品。此外，Cu ₁ –O _{3的逐渐迁移}在催化过程中观察到在催化剂表面具有准平面结构的单元并加速CO ₂加氢。此处确定的高活性、孤立的铜位点和可区分的结构模式扩展了单原子催化剂在热催化 CO ₂加氢中的应用范围，并可以指导高性能铜基催化剂的进一步设计以满足工业需求。