Pore Modulation of Hydrogen-Bonded Organic Frameworks for Efficient Separation of Propylene.
Pore Modulation of Hydrogen-Bonded Organic Frameworks for Efficient Separation of Propylene.
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用于高效分离丙烯的氢键有机框架的孔隙调节。
DOI：
10.1002/anie.202308579
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发表时间：
2023
影响因子：
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通讯作者：
Banglin Chen
中科院分区：
文献类型：
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作者：
Youlie Cai;Junkuo Gao;Jing;Puxu Liu;Yanchun Zheng;Wei Zhou;Hui;Libo Li;Rui‐Biao Lin;Banglin Chen
开发结合功能位点、尺寸控制和存储能力以捕获气体分子的氢键有机框架（HOF）是一项新颖且具有挑战性的事业。然而，缺乏有效的策略来调整氢键网络以实现高性能 HOF。在这里，通过将结构导向剂（SDAs）引入四（4-羧基苯基）卟啉（TCPP）的氢键网络中，获得了一系列具有不同孔结构的HOF-ZSTU-M（M = 1、2和3）。这些 HOF 具有独特的空间配置，孔道范围从离散到连续多维。单晶 X 射线衍射 (SCXRD) 分析揭示了以 SDA 为主的氢键模型的罕见多样性。 HOF-ZSTU-2通过多个羧基与铵（NH4+）形成强层状氢键网络，具有适合选择性捕获丙烯（C3H6）的一维“珍珠链”通道。在 298 K 和 1 bar 下，HOF-ZSTU-2 的 C3H6 存储密度达到 0.6 kg L-1，代表最好的 C3H6 存储材料之一，同时提供 12.2 的丙烯/丙烷 (C3H6/C3H8) 选择性。理论计算和原位 SCXRD 详细分析了 C3H6 在珍珠链通道中不同位置的结合强度。动态突破性测试证实HOF-ZSTU-2可以有效地将C3H6从多种混合物中分离出来。
Developing hydrogen-bonded organic frameworks (HOFs) that combine functional sites, size control, and storage capability for targeting gas molecule capture is a novel and challenging venture. However, there is a lack of effective strategies to tune the hydrogen-bonded network to achieve high-performance HOFs. Here, a series of HOFs termed as HOF-ZSTU-M (M = 1, 2, and 3) with different pore structures are obtained by introducing structure-directing agents (SDAs) into the hydrogen-bonding network of tetrakis (4-carboxyphenyl) porphyrin (TCPP). These HOFs have distinct space configurations with pore channels ranging from discrete to continuous multi-dimensional. Single-crystal X-ray diffraction (SCXRD) analysis reveals a rare diversity of hydrogen-bonding models dominated by SDAs. HOF-ZSTU-2, which forms a strong layered hydrogen-bonding network with ammonium (NH4+) through multiple carboxyl groups, has a suitable 1D "pearl-chain" channel for the selective capture of propylene (C3H6). At 298 K and 1 bar, the C3H6 storage density of HOF-ZSTU-2 reaches 0.6 kg L-1, representing one of the best C3H6 storage materials, while offering a propylene/propane (C3H6/C3H8) selectivity of 12.2. Theoretical calculations and in-situ SCXRD provide a detailed analysis of the binding strength of C3H6 at different locations in the pearl-chain channel. Dynamic breakthrough tests confirm that HOF-ZSTU-2 can effectively separate C3H6 from multi-mixtures.