Xue Han, Xu Hailong, Song Xuedan, Chen Miaomiao, Wang Xinkui, Ji Min, Wang Min
School of Chemistry, Dalian University of Technology Dalian 116024, P. R. China.
BYD Auto Industry Co. Ltd., Shenzhen, Guangdong 518119, China.
Inorg Chem. 2024 Aug 26;63(34):16011-16017. doi: 10.1021/acs.inorgchem.4c02470. Epub 2024 Aug 15.
A porous metal-organic framework (MOF)-based frustrated Lewis pairs (FLPs) were prepared via a ligand replacement strategy to generate organic linker defects in zirconium-based MOF (MOF-808), thereby exposing Zr sites as Lewis acid. Due to the rigid features of the MOF skeleton, the unsaturated metal cluster and the adjacent lattice oxygen (Lewis bases) are in sterically hindered positions, which formed FLP sites with efficient H activation ability. This porous heterogeneous FLP catalyst [MOF-808-OH (15%)] exhibits high performance styrene hydrogenation to ethylbenzene with 99% yield. The high structural stability and reusability enabled the catalyst to maintain an over 98% activity after five cycles. This work provides a defect modulation strategy to prepare MOF-based solid FLP catalysts.
通过配体置换策略制备了一种基于多孔金属有机框架(MOF)的受阻路易斯酸碱对(FLP),以在锆基金属有机框架(MOF-808)中产生有机连接体缺陷,从而将Zr位点暴露为路易斯酸。由于MOF骨架的刚性特征,不饱和金属簇和相邻的晶格氧(路易斯碱)处于空间位阻位置,形成了具有高效H活化能力的FLP位点。这种多孔非均相FLP催化剂[MOF-808-OH(15%)]在苯乙烯加氢制乙苯反应中表现出高性能,产率达99%。高结构稳定性和可重复使用性使该催化剂在五个循环后仍能保持超过98%的活性。这项工作提供了一种缺陷调控策略来制备基于MOF的固体FLP催化剂。