With regard to green chemistry and sustainable development, the fixation of CO₂ into epoxides to form cyclic carbonates is an attractive and promising pathway for CO₂ utilization. Metal oxides, renowned as promising eco-friendly catalysts for industrial production, are often undervalued in terms of their impact on the CO₂ addition reaction. In this work, we successfully developed ZnO nanoplates with (002) surfaces and ZnO nanorods with (100) surfaces via morphology-oriented regulation to explore the effect of crystal faces on CO₂ cycloaddition. The quantitative data obtained from electron paramagnetic resonance spectroscopy indicated that the concentration of oxygen vacancies on the ZnO nanoplate surfaces was more than twice that on the ZnO nanorod surfaces. Density functional theory calculations suggested that the (002) surfaces have lower adsorption energies for CO₂ and epichlorohydrin than the (100) surfaces. As a result, the yield of cyclochloropropene carbonate on the ZnO nanoplates (64.7%) was much greater than that on the ZnO nanorods (42.3%). Further evaluation of the reused catalysts revealed that the decrease in the oxygen vacancy concentration was the primary factor contributing to the decrease in catalytic performance. Based on these findings, a possible catalytic mechanism for CO₂ cycloaddition with epichlorohydrin was proposed. This work provides a new idea for the controllable preparation of high-performance ZnO catalysts for the synthesis of cyclic carbonates from CO₂ and epoxides.

就绿色化学和可持续发展而言，将CO ₂固定在环氧化物中形成环状碳酸酯是一种有吸引力且有前景的CO ₂利用途径。金属氧化物被誉为有前景的工业生产环保催化剂，但其对CO ₂加成反应的影响往往被低估。本工作中，我们通过形貌定向调控，成功开发了（002）面ZnO纳米片和（100）面ZnO纳米棒，探讨晶面对CO ₂环加成反应的影响。电子顺磁共振波谱获得的定量数据表明，ZnO纳米板表面的氧空位浓度是ZnO纳米棒表面的两倍以上。密度泛函理论计算表明，(002)表面对CO ₂和环氧氯丙烷的吸附能比(100)表面低。结果，ZnO纳米片上环氯丙烯碳酸酯的产率（64.7%）远高于ZnO纳米棒上的产率（42.3%）。对重复使用的催化剂的进一步评估表明，氧空位浓度的降低是导致催化性能下降的主要原因。基于这些发现，提出了CO ₂与环氧氯丙烷环加成的可能催化机制。该工作为可控制备高性能ZnO催化剂用于CO ₂与环氧化物合成环状碳酸酯提供了新思路。