Yu Chunlong, He Xinglei, Gong Chenxu, Li Jingheng, Ye Ke-Yin
Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou 350108, China.
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China.
Inorg Chem. 2025 Apr 14;64(14):6977-6986. doi: 10.1021/acs.inorgchem.5c00235. Epub 2025 Mar 29.
Well-defined metal-organic frameworks (MOFs) provide an attractive platform for catalysis. Understanding the intrinsic structure-activity relationship of MOFs helps guide the design of novel catalysts. In this work, a new three-dimensional (3D) Mn(salen)-based MOF () with strong adsorption capacity and high selectivity for CO was synthesized. Through sequential demetallization and remetallization, the flexible tailoring of the metal centers was realized to obtain a series of remetallized MOFs (; M = Mn, Co, Cu, Ni, V). Among them, was proved to be the most active catalyst for the cycloaddition of CO and epoxides. Mechanistic studies reveal that displays a high CO affinity and Lewis acidity. In addition, kinetic studies suggest that has a lower activation energy than the original MOF () and demetallized MOF (). Remarkably, could be reused five times without affecting its catalytic activity.
结构明确的金属有机框架（MOF）为催化提供了一个有吸引力的平台。了解MOF的内在结构-活性关系有助于指导新型催化剂的设计。在这项工作中，合成了一种对CO具有强吸附能力和高选择性的新型三维（3D）基于Mn（salen）的MOF（）。通过顺序脱金属和再金属化，实现了金属中心的灵活剪裁，以获得一系列再金属化的MOF（；M = Mn、Co、Cu、Ni、V）。其中，被证明是CO与环氧化物环加成反应中最具活性的催化剂。机理研究表明，显示出高CO亲和力和路易斯酸性。此外，动力学研究表明，比原始MOF（）和脱金属MOF（）具有更低的活化能。值得注意的是，可以重复使用五次而不影响其催化活性。
