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在环氧氯丙烷与一氧化碳环加成反应过程中ZIF-67和ZIF-L沸石咪唑酯骨架特定晶面的浸出

Leaching in Specific Facets of ZIF-67 and ZIF-L Zeolitic Imidazolate Frameworks During the CO Cycloaddition with Epichlorohydrin.

作者信息

Delgado-Marín Jose J, Rendón-Patiño Alejandra, Velisoju Vijay Kumar, Kumar Gadde Sathish, Zambrano Naydu, Rueping Magnus, Gascón Jorge, Castaño Pedro, Narciso Javier, Ramos-Fernandez Enrique V

机构信息

Instituto de Materiales and Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Alicante, Apdo. 99, Alicante 03080, Spain.

KAUST Catalysis Center, Advanced Catalytic Materials, King Abdullah University of Science and Technology, Thuwal 23955, Saudi Arabia.

出版信息

Chem Mater. 2023 Jan 3;35(2):692-699. doi: 10.1021/acs.chemmater.2c03374. eCollection 2023 Jan 24.

Abstract

Zeolitic imidazolate frameworks (ZIFs) have been profusely used as catalysts for inserting CO into organic epoxides (i.e., epichlorohydrin) through cycloaddition. Here, we demonstrate that these materials suffer from irreversible degradation by leaching. To prove this, we performed the reactions and analyzed the final reaction mixtures by elemental analysis and the resulting materials by different microscopies. We found that the difference in catalytic activity between three ZIF-67 and one ZIF-L catalysts was related to the rate at which the materials degraded. Particularly, the {100} facet leaches faster than the others, regardless of the material used. The catalytic activity strongly depended on the amount of leached elements in the liquid phase since these species are extremely active. Our work points to the instability of these materials under relevant reaction conditions and the necessity of additional treatments to improve their stability.

摘要

沸石咪唑酯骨架材料(ZIFs)已被大量用作通过环加成将CO插入有机环氧化物(即环氧氯丙烷)的催化剂。在此,我们证明这些材料会因浸出而发生不可逆降解。为了证明这一点,我们进行了反应,并通过元素分析对最终反应混合物进行了分析,同时通过不同的显微镜技术对所得材料进行了分析。我们发现,三种ZIF-67催化剂和一种ZIF-L催化剂之间的催化活性差异与材料降解的速率有关。特别是,无论使用何种材料,{100}晶面的浸出速度都比其他晶面快。催化活性强烈依赖于液相中浸出元素的量,因为这些物种具有极高的活性。我们的工作表明这些材料在相关反应条件下的不稳定性,以及进行额外处理以提高其稳定性的必要性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e46/10373435/0306e1c24d09/cm2c03374_0010.jpg

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