He Minghui, Xia Fengjie, Xu Tingting, Gao Xiaoxia, Jiang Zhenzhen, Wang Xia, He Yabing
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua 321004, China.
Dalton Trans. 2019 Aug 14;48(30):11374-11381. doi: 10.1039/c9dt01778j. Epub 2019 Jul 8.
The design and construction of porous materials for high-efficient adsorption-based separation of CH from CH and CO is a fundamental goal in the chemical industry. In this work, a lactam-functionalized bent diisophthalate linker, 5,5'-(1-methylpyridin-2(1H)-one-3,5-diyl) diisophthalic acid, was judiciously designed and utilized to construct a dicopper paddlewheel-based MOF under solvothermal conditions. Single-crystal X-ray diffraction revealed that the resulting solid is a three-dimensional mfj-type network incorporating Lewis-acidic copper sites and accessible lactam groups as two different kinds of functional sites. Furthermore, gas adsorption studies indicated that the material exhibited great promise for CH/CH and CO/CH separations. In particular, compared to the unmodified parent compound, the resultant MOF exhibits 9.4% and 12.9% higher CH and CO uptake capacities and 48.0% and 28.3% higher CH/CH and CO/CH adsorption selectivities for the equimolar gas mixtures at 298 K and 1 atm, despite the lower specific surface area and pore volume. This work reported the first lactam-functionalized MOF displaying significantly enhanced adsorption of CO and CH over CH.
设计和构建用于从CH₄与CO₂中高效吸附分离CH₄的多孔材料是化学工业的一个基本目标。在这项工作中，一种内酰胺官能化的弯曲间苯二甲酸酯连接体，即5,5'-（1-甲基吡啶-2(1H)-酮-3,5-二基）间苯二甲酸，经过精心设计并用于在溶剂热条件下构建一种基于双铜桨轮的金属有机框架（MOF）。单晶X射线衍射表明，所得固体是一种三维mfj型网络，包含路易斯酸性铜位点和可及的内酰胺基团作为两种不同类型的功能位点。此外，气体吸附研究表明该材料在CH₄/CO₂和CO₂/CH₄分离方面展现出巨大潜力。特别是，与未改性的母体化合物相比，所得MOF在298 K和1 atm下对等摩尔气体混合物的CH₄和CO₂吸附容量分别高出9.4%和12.9%，CH₄/CO₂和CO₂/CH₄吸附选择性分别高出48.0%和28.3%，尽管其比表面积和孔体积较低。这项工作报道了首个对内酰胺进行官能化的MOF，其对CO₂和CH₄的吸附能力相对于CH₄有显著增强。
