Jiang Yunjia, Wang Lingyao, Hu Jianbo, Krishna Rajamani, Chen Banglin, Zhang Yuanbin
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua, 321004, China.
Zhejiang Lab, Hangzhou, 311100, P. R. China.
Adv Mater. 2024 Mar;36(11):e2311140. doi: 10.1002/adma.202311140. Epub 2023 Dec 14.
Separating propyne/propadiene to produce pure propadiene is extremely challenging in industry due to their similar properties. Herein, a novel ZrF anion pillared cage-like metal-organic framework (termed as CuZrF -TPA) for highly efficient propyne/propadiene separation is reported. It exhibits high propyne capacity (177.4/188.6 cm /cm at 0.5/1.0 bar and 298 K), benchmark separation selectivity (6.0), and remarkable separation potential (5.7 mol L ) simultaneously. Record propadiene productivity (≈4.7 mol L ) is achieved through a single adsorption process in breakthrough experiments with excellent recycle stability even under humid conditions. Based on the structure of propyne-loaded single crystals, two binding sites are identified, including a major propyne trapping site at the windows and a minor binding site located in the large cages. Modelling studies further confirm that the contracted cage windows surrounded with rotating Lewis basic F atoms and aromatic rings are the optimal bonding sites to capture propyne with multiple hydrogen bonding and π···π interactions.
由于丙炔和丙二烯性质相似，在工业上分离丙炔/丙二烯以生产纯丙二烯极具挑战性。在此，报道了一种用于高效丙炔/丙二烯分离的新型ZrF 阴离子柱撑笼状金属有机框架（称为CuZrF -TPA）。它同时展现出高丙炔吸附量（在0.5/1.0 bar和298 K下为177.4/188.6 cm³/cm³）、基准分离选择性（6.0）和显著的分离潜力（5.7 mol/L）。在突破实验中，通过单次吸附过程实现了创纪录的丙二烯生产率（≈4.7 mol/L），即使在潮湿条件下也具有出色的循环稳定性。基于负载丙炔的单晶结构，确定了两个结合位点，包括窗口处的主要丙炔捕获位点和位于大笼子中的次要结合位点。建模研究进一步证实，被旋转的路易斯碱性F原子和芳香环包围的收缩笼窗口是通过多重氢键和π···π相互作用捕获丙炔的最佳结合位点。
