<b>A Ce-CuZn catalyst with abundant </b><b>Cu/Zn-O</b>_{<strong>V</strong>}<b>-Ce</b><b> active sites for CO</b>_{<strong>2</strong>}<b> hydrogenation to methanol</b>

CO₂ hydrogenation to chemicals and fuels is a significant approach for achieving carbon neutrality. It is essential to rationally design the chemical structure and catalytic active sites towards the development of efficient catalysts. Here we show a Ce-CuZn catalyst with enriched Cu/Zn-O_V-Ce active sites fabricated through the atomic-level substitution of Cu and Zn into Ce-MOF precursor. The Ce-CuZn catalyst exhibits a high methanol selectivity of 71.1% and a space-time yield of methanol up to 400.3 g·kg_cat^-1·h^-1 with excellent stability for 170 h at 260 °C, comparable to that of the state-of-the-art CuZnAl catalysts. Controlled experiments and DFT calculations confirm that the incorporation of Cu and Zn into CeO₂ with abundant oxygen vacancies can facilitate H₂ dissociation energetically and thus improve CO₂ hydrogenation over the Ce-CuZn catalyst via formate intermediates. This work offers an atomic-level design strategy for constructing efficient multi-metal catalysts for methanol synthesis through control of active sites.二氧化碳加氢制备化学品与燃料是实现碳中和的重要路径。合理设计催化剂的化学结构与催化活性位点，对于开发高效催化剂至关重要。本工作报道了一种富含Cu/Zn-氧空位（O_V）-Ce活性位点的Ce-CuZn催化剂，通过将铜与锌原子级取代掺入铈基金属有机框架（Ce-Metal-Organic Framework, Ce-MOF）前驱体制得。该Ce-CuZn催化剂展现出71.1%的高甲醇选择性，甲醇时空产率最高可达400.3 g·kg_cat⁻¹·h⁻¹，且在260℃下可稳定运行170小时，性能可与当前顶尖的CuZnAl催化剂相媲美。对照实验与密度泛函理论（Density Functional Theory, DFT）计算证实，将铜与锌掺入富含氧空位的二氧化铈（CeO₂）中，可从能量层面促进氢气解离，进而通过甲酸酯中间体路径提升Ce-CuZn催化剂上的二氧化碳加氢性能。本工作通过调控活性位点，为构建用于甲醇合成的高效多金属催化剂提供了一种原子级别的设计策略。