The extensive investigation regarding the active site of the Cu/ZnO/Al₂O₃ catalyst gradually recognizes the paramount importance of the oxygen vacancy in the hydrogenation of CO₂ to methanol. However, it is challenging to probe the nature of oxygen vacancy during methanol synthesis and understand its role in the enhancement of reactivity at the molecule level. Here, the inversed ZnO_1–x/Cu catalysts with abundant oxygen vacancies are prepared by simple ball milling. The interfacial transformations between ZnO_1–x and Cu during material preparation and reaction are elucidated by the correlations of geometrical and chemical states with mechanical energies. The dynamics of the oxygen vacancy during the reaction are revealed as well. The ZnO_1–x/Cu with more oxygen vacancy exhibits a superior CH₃OH productivity of 1.2 g_MeOH g^–1 h^–1 at 240 °C and a selectivity above 90%. The mechanistic studies reveal that oxygen vacancy promotes the activation of CO₂ to formate and significantly reduces the barrier of the hydrogenation from *HCOO to *H₂COO intermediates.

中文翻译：

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揭示 CO2 稳健合成甲醇过程中 ZnO1-x/Cu 中氧空位的动态

_{对Cu/ZnO/Al 2} O ₃催化剂活性位点的广泛研究逐渐认识到氧空位在CO ₂加氢制甲醇中的至关重要性。然而，探究甲醇合成过程中氧空位的性质并了解其在分子水平增强反应活性中的作用具有挑战性。在这里，通过简单的球磨制备了具有丰富氧空位的反相ZnO _{1– x /Cu催化剂。材料制备和反应过程中ZnO 1– x}和Cu之间的界面转变可以通过几何和化学状态与机械能的相关性来阐明。反应过程中氧空位的动态也被揭示。具有更多氧空位的ZnO _{1– x} /Cu表现出优异的CH ₃ OH生产率，在240 °C时为1.2 g _MeOH g ^–1 h ^–1，选择性高于90%。机理研究表明，氧空位促进CO ₂活化生成甲酸盐，并显着降低*HCOO加氢至*H ₂ COO中间体的障碍。