Liang Jun, Chen Rui-Ping, Wang Xiu-Yun, Liu Tao-Tao, Wang Xu-Sheng, Huang Yuan-Biao, Cao Rong
State Key Laboratory of Structural Chemistry , Fujian Institute of Research on the Structure of Matter , University of Chinese Academy of Sciences Fujian , Fuzhou , 350002 , P. R. China . Email:
Department of Chemistry , College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , P. R. China.
Chem Sci. 2017 Feb 1;8(2):1570-1575. doi: 10.1039/c6sc04357g. Epub 2016 Nov 2.
A bifunctional imidazolium functionalized zirconium metal-organic framework (Zr-MOF), (I)Meim-UiO-66 (), was successfully prepared from the imidazole-containing Zr-MOF Im-UiO-66 () by a post-synthetic modification (PSM) method. It was found that the crystal size and pore features of the imidazole-containing could be tuned at the nanoscale. The bifunctional MOF , containing Brønsted acid sites and iodide ions, was shown to be an efficient and recyclable heterogeneous catalyst for the cycloaddition of carbon dioxide (CO) with epoxides, without the use of any co-catalyst, at ambient pressure. The solvent-free synthesis of the cyclic carbonate from CO and an epoxide was monitored by Fourier transform infrared spectroscopy (FT-IR) and an acid/base synergistic catalysis mechanism was proposed. We hope that our strategy provides an effective approach for the introduction of functional -heterocyclic groups into MOFs for potential applications.
通过后合成修饰（PSM）方法，成功地从含咪唑的锆基金属有机框架（Zr-MOF）Im-UiO-66（ ）制备了双功能咪唑鎓官能化锆基金属有机框架（Zr-MOF），(I)Meim-UiO-66（ ）。研究发现，含咪唑的Zr-MOF的晶体尺寸和孔特征可在纳米尺度上进行调控。含布朗斯特酸位点和碘离子的双功能金属有机框架（MOF） 被证明是一种高效且可回收的多相催化剂，用于二氧化碳（CO₂）与环氧化物的环加成反应，在常压下无需使用任何助催化剂。通过傅里叶变换红外光谱（FT-IR）监测了由CO₂和环氧化物无溶剂合成环状碳酸酯的过程，并提出了一种酸碱协同催化机理。我们希望我们的策略为将功能性杂环基团引入金属有机框架以实现潜在应用提供一种有效的方法。
