The difficulty of synthesizing uniform atomically precise active sites limits our ability to engineer increasingly more active heterogeneous catalysts for the hydrogenation of CO₂ to methanol. Here we design Cu/ZrO_x clusters on MgO with near atomic precision for CO₂ hydrogenation using a liquid-phase atomic layer deposition method. The controlled cluster structure modulates the binding strength of CO₂ and moderately stabilizes monodentate formate—an essential reaction intermediate for methanol production. We achieved a methanol selectivity of 100 and 76.7% at 200 and 250 °C, respectively and a methanol productivity that was one to two orders of magnitude higher than when the same catalysts were prepared by impregnation. Ab initio computations show that Cu/ZrO_x clusters can tune the oxidation of Zr, which controls the stability of reaction intermediates on the catalyst. Our approach demonstrates the potential of precise atomic control of catalytic clusters to improve catalytic productivity.

合成均匀原子精确活性位点的难度限制了我们设计越来越活跃的非均相催化剂的能力，用于将 CO₂ 加氢成甲醇。在这里，我们使用液相原子层沉积方法以接近原子的精度在 MgO 上设计了用于 CO₂ 氢化的 Cu/ZrO_x 团簇。受控的团簇结构可调节 CO₂ 的结合强度，并适度稳定单齿甲酸盐——甲醇生产的重要反应中间体。我们在 200 °C 和 250 °C 下分别实现了 100% 和 76.7% 的甲醇选择性，甲醇生产率比通过浸渍制备相同催化剂时高出 1 到 2 个数量级。从头计算表明，Cu/ZrO_x 团簇可以调节 Zr 的氧化，从而控制催化剂上反应中间体的稳定性。我们的方法展示了对催化团簇进行精确原子控制以提高催化生产率的潜力。