Qin Xiaohan, Shen Simin, Xu Mengling, Xu Wangfu, Huang Kun, Zhang Xiang-Yu
Institute of Applied Chemistry, Precise Synthesis and Function Development Key Laboratory of Sichuan Province, School of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, China.
Inorg Chem. 2025 Jul 7;64(26):13499-13506. doi: 10.1021/acs.inorgchem.5c02137. Epub 2025 Jun 25.
Developing lanthanide metal-organic frameworks (Ln-MOFs) for catalyzing CO into chemicals is significant due to their luminescence instead of catalysis. In this work, three isostructural Ln-MOFs (Eu-MOF, Ga-MOF, and Tb-MOF) have been hydrothermally synthesized based on 4,4'-(quinoxaline-2,3-diyl)dibenzoic acid (Hqda). Structural analyses indicate that these new MOFs show the same coordination mode with a two-dimensional, porous, and 4-connected net. The investigation of their performances in catalyzing CO conversion shows that they can efficiently catalyze the conversion of CO with epoxides to produce cyclic carbonates under solvent-free and atmospheric conditions with up to 99% conversion. Meanwhile, the catalysts show good recyclability and broad substrate adaptability. Besides, the previously reported Hqda-based Ln-MOF (Eu-MOF-1) with a different coordination mode exhibits similar catalytic activity toward the above reaction. The catalytic data mainly suggest that these isostructural Ln-MOFs show comparably catalytic activity, revealing that the nodes (Eu, Tb, and Ga) and coordination mode have a slight effect on catalytic activity in the CO coupling reaction with epoxides. Further, these Ln-MOFs have been used for promoting the one-pot "oxidative carboxylation" from olefins and CO to produce cyclic carbonates by the TBHP/Ln-MOF/TBAB composite, achieving over 80% yield under atmospheric conditions.
开发用于将一氧化碳催化转化为化学品的镧系金属有机框架（Ln-MOFs）具有重要意义，因为它们具有发光性能而非催化性能。在这项工作中，基于4,4'-（喹喔啉-2,3-二基）二苯甲酸（Hqda）水热合成了三种同构的Ln-MOFs（Eu-MOF、Ga-MOF和Tb-MOF）。结构分析表明，这些新型MOFs具有相同的配位模式，形成二维、多孔且具有4连接节点的网络。对它们催化一氧化碳转化性能的研究表明，在无溶剂和常压条件下，它们能有效地催化一氧化碳与环氧化物转化生成环状碳酸酯，转化率高达99%。同时，催化剂表现出良好的可回收性和广泛的底物适应性。此外，先前报道的具有不同配位模式的基于Hqda的Ln-MOF（Eu-MOF-1）对上述反应表现出相似的催化活性。催化数据主要表明，这些同构的Ln-MOFs表现出相当的催化活性，这表明节点（Eu、Tb和Ga）和配位模式对与环氧化物的一氧化碳偶联反应中的催化活性影响较小。此外，这些Ln-MOFs已被用于通过TBHP/Ln-MOF/TBAB复合材料促进烯烃和一氧化碳的一锅法“氧化羧化”反应以生成环状碳酸酯，在常压条件下产率超过80%。
