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Ligand Functionalization in Zirconium‐Based Metal‐Organic Frameworks for Enhanced Carbon Dioxide Fixation
Advanced Sustainable Systems ( IF 6.5 ) Pub Date : 2020-06-17 , DOI: 10.1002/adsu.202000098
Xiaodong Sun 1, 2 , Litong Shi 1 , Haijun Hu 1 , Hongwei Huang 3 , Tianyi Ma 2
Affiliation  

Ligand functionalization has always been considered as an effective method for regulating the catalytic activity of the metal‐organic frameworks (MOFs) materials. Herein, three stable zirconium‐based MOFs (Zr‐MOFs), constructed by the 10‐connected Zr6 cluster and different groups‐decorated V‐shaped ligands (H2L), are successfully synthesized through a facile ligand functionalization method. Subsequently, three isostructural Zr‐MOFs, including the parent structure Zr(H2L), amino‐decorated Zr(H2L) (NH2‐Zr(H2L)), and fluorine and amino bi‐decorated Zr(H2L) (F‐NH2‐Zr(H2L)), are employed as the platform for systematically investigating the effect of Lewis basic groups on the CO2 adsorption and separation behavior, more importantly the CO2 chemical fixation. Benefitting from the decorated Lewis basic groups, not only the CO2 adsorption enthalpy and selectivity over CH4 of NH2‐Zr(H2L) and F‐NH2‐Zr(H2L) are improved, but also their catalytic activities for cycloaddition of CO2 to form cyclic carbonates are significantly enhanced. Among them, F‐NH2‐Zr(H2L) exhibits the most effective performance for cycloaddition of CO2 and styrene epoxide, which can be attributed to the strong polarization between the CO2 molecule and the framework of F‐NH2‐Zr(H2L). Under a mild condition, the yield of F‐NH2‐Zr(H2L) for cycloaddition of CO2 with styrene epoxide can reach up to 97%, which surpasses most of the reported MOFs‐based catalysts.

中文翻译:

锆基金属有机骨架中的配体官能化,用于增强二氧化碳固定

配体官能化一直被认为是调节金属有机骨架(MOFs)材料催化活性的有效方法。在此,通过简便的配体官能化方法成功合成了由10个连接的Zr 6簇和不同基团装饰的V型配体(H 2 L)构成的三个稳定的基于锆的MOF(Zr-MOF)。随后,三个同构的Zr-MOF,包括母体结构Zr(H 2 L),氨基修饰的Zr(H 2 L)(NH 2‐ Zr(H 2 L))以及氟和氨基双修饰Zr(H)2 L)(F-NH 2 -Zr(H 2L)),用作系统研究Lewis碱性基团对CO 2吸附和分离行为(更重要的是CO 2化学固定)影响的平台。得益于修饰的路易斯碱性基团,不仅改善了NH 2 -Zr(H 2 L)和F-NH 2 -Zr(H 2 L)的CO 2吸附焓和对CH 4的选择性,而且还提高了它们的催化活性。用于环加成CO 2以形成环状碳酸酯的反应显着增强。其中,F-NH 2 -Zr(H 2 L)对CO的环加成反应最有效2和苯乙烯环氧化合物,这可以归因于CO 2分子与F-NH 2 -Zr(H 2 L)骨架之间的强极化作用。在温和的条件下,CO 2与苯乙烯环氧化物环加成反应的F-NH 2 -Zr(H 2 L)产率可达到97%,超过了大多数已报道的基于MOFs的催化剂。
更新日期:2020-06-17
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