Abstract Developing highly efficient heterogeneous catalysts for cycloaddition of CO 2 and epoxides to produce cyclic carbonates is promising but challenging. In this work, a novel three-dimensional metal organic framework (MOF) with cylinder pore systems and unsaturated Zn sites has been demonstrated as potent candidate in CO 2 fixation at mild and solvent-free conditions. The Zn(atz)(bdc) 0.5 , where atz = aminotriazole and H 2 bdc = terephthalic, exhibits microporous nature that can regulate the catalytic interaction of active centers and substrates. The structure stability has been systematically investigated and proven to be sufficient for practical application. Furthermore, the cooperative effects of porosity, CO 2 binding affinity, activation centers, and synergism with co-catalyst have been deeply investigated. Moreover, high propylene epoxide conversion (97%) and selectivity (> 99%) have been achieved at mild conditions (60 °C and 1 MPa) with excellent cycle stability. Owing to the well-defined pore system, an obvious substrates selectivity has been clearly observed. A possible catalytic mechanism has been proposed and verified by DFT calculations. Furthermore, the prepared Zn-MOF can also be used as an efficient heterogeneous catalyst for the reaction of epoxides with alcohols to produce β-alkoxy alcohol. Graphic Abstract

中文翻译：

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稳定的锌基金属-有机骨架作为温和条件下二氧化碳环加成和醇解的有效催化剂

摘要 开发用于 CO 2 和环氧化物环加成以生产环状碳酸酯的高效多相催化剂是有前景的，但具有挑战性。在这项工作中，具有圆柱孔系统和不饱和锌位点的新型三维金属有机骨架 (MOF) 已被证明是在温和和无溶剂条件下固定 CO 2 的有效候选者。Zn(atz)(bdc) 0.5 ，其中atz = 氨基三唑和H 2 bdc = 对苯二甲酸，表现出微孔性质，可以调节活性中心和底物的催化相互作用。结构稳定性已被系统地研究并证明足以用于实际应用。此外，已经深入研究了孔隙率、CO 2 结合亲和力、活化中心以及与助催化剂的协同作用的协同效应。而且，在温和条件（60 °C 和 1 MPa）下实现了高环氧丙烷转化率 (97%) 和选择性 (> 99%)，并具有出色的循环稳定性。由于定义明确的孔系统，已经清楚地观察到明显的底物选择性。已经提出并通过 DFT 计算验证了一种可能的催化机制。此外，所制备的Zn-MOF还可用作环氧化物与醇反应生成β-烷氧基醇的有效多相催化剂。图形摘要 所制备的Zn-MOF还可用作环氧化物与醇反应生成β-烷氧基醇的高效多相催化剂。图形摘要 所制备的Zn-MOF还可用作环氧化物与醇反应生成β-烷氧基醇的高效多相催化剂。图形摘要