Tuning the High-Pressure Phase Behaviour of Highly Compressible Zeolitic Imidazolate Frameworks: From Discontinuous to Continuous Pore Closure by Linker Substitution.
Tuning the High-Pressure Phase Behaviour of Highly Compressible Zeolitic Imidazolate Frameworks: From Discontinuous to Continuous Pore Closure by Linker Substitution.
复制标题
DOI：
10.1002/anie.202117565
复制
发表时间：
2022-05-16
影响因子：
16.6
通讯作者：
Henke, Sebastian
中科院分区：
文献类型：
--
作者：
Song, Jianbo;Pallach, Roman;Frentzel-Beyme, Louis;Kolodzeiski, Pascal;Kieslich, Gregor;Vervoorts, Pia;Hobday, Claire L.;Henke, Sebastian
关键词：
介绍了化学成分为 M(im)2−x (bim)x 的 ZIF-62 族柔性沸石咪唑酯骨架 (ZIF) 的高压行为 (M2+=Zn2+, Co2+; im−=咪唑酯; bim−=苯并咪唑酯, 0.02≤x≤0.37)。高压粉末 X 射线衍射表明，在高达 4000 bar 的静水压力下，材料可逆地从开孔 (op) 收缩到闭孔 (cp) 相。依次增加 bim− 分数 (x) 会增强框架，导致 op 到 cp 相变的阈值压力增加，而整个转变过程中的总体积收缩会减少。最重要的是，当 x≥0.35 时，典型的不连续 op 到 cp 跃迁（一阶）变为不寻常的连续跃迁（二阶）。这使得可以通过调节压力来连续微调材料的空隙体积和孔径，从而为 MOF 在压力可切换设备、膜和执行器中开辟新的可能性。调整不同咪唑酯连接体的比例可以调节一系列沸石咪唑酯骨架（ZIF）从一级到二级的高压开孔到闭孔相变。二阶相变允许通过调节机械压力来微调骨架材料的孔隙结构。
The high‐pressure behaviour of flexible zeolitic imidazolate frameworks (ZIFs) of the ZIF‐62 family with the chemical composition M(im)2−x (bim)x is presented (M2+=Zn2+, Co2+; im−=imidazolate; bim−=benzimidazolate, 0.02≤x≤0.37). High‐pressure powder X‐ray diffraction shows that the materials contract reversibly from an open pore ( op ) to a closed pore ( cp ) phase under a hydrostatic pressure of up to 4000 bar. Sequentially increasing the bim− fraction (x) reinforces the framework, leading to an increased threshold pressure for the op ‐to‐ cp phase transition, while the total volume contraction across the transition decreases. Most importantly, the typical discontinuous op ‐to‐ cp transition (first order) changes to an unusual continuous transition (second order) for x≥0.35. This allows finetuning of the void volume and the pore size of the material continuously by adjusting the pressure, thus opening new possibilities for MOFs in pressure‐switchable devices, membranes, and actuators. Adjusting the ratio of different imidazolate linkers modulates a high‐pressure open‐pore to closed‐pore phase transition of a series of zeolitic imidazolate frameworks (ZIFs) from first order to second order. The second‐order phase transition allows finetuning the pore structure of the framework material by regulation of the mechanical pressure.
登录
查看更多内容
影响因子：
19
作者：
Henke, Sebastian;Schneemann, Andreas;Fischer, Roland A.
通讯作者：
Fischer, Roland A.
晶体趋于作用：金属有机框架CUK-1作为压力驱动的分子弹簧。
影响因子：
8.4
作者：
Iacomi P;Lee JS;Vanduyfhuys L;Cho KH;Fertey P;Wieme J;Granier D;Maurin G;Van Speybroeck V;Chang JS;Yot PG
通讯作者：
Yot PG
影响因子：
16.6
作者：
Chanut, Nicolas;Ghoufi, Aziz;Llewellyn, Philip L.
通讯作者：
Llewellyn, Philip L.
影响因子：
56.9
作者：
Banerjee, Rahul;Phan, Anh;Yaghi, Omar M.
通讯作者：
Yaghi, Omar M.
影响因子：
8.6
作者：
Coudert, Francois-Xavier
通讯作者：
Coudert, Francois-Xavier