Bonneau Mickaele, Lavenn Christophe, Zheng Jia-Jia, Legrand Alexandre, Ogawa Tomofumi, Sugimoto Kunihisa, Coudert Francois-Xavier, Reau Regis, Sakaki Shigeyoshi, Otake Ken-Ichi, Kitagawa Susumu
Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Sakyo-ku, Japan.
Air Liquide Laboratories, Innovation Campus Tokyo, Yokosuka, Japan.
Nat Chem. 2022 Jul;14(7):816-822. doi: 10.1038/s41557-022-00928-x. Epub 2022 Apr 21.
The safe storage of flammable gases, such as acetylene, is essential for current industrial purposes. However, the narrow pressure (P) and temperature range required for the industrial use of pure acetylene (100 < P < 200 kPa at 298 K) and its explosive behaviour at higher pressures make its storage and release challenging. Flexible metal-organic frameworks that exhibit a gated adsorption/desorption behaviour-in which guest uptake and release occur above threshold pressures, usually accompanied by framework deformations-have shown promise as storage adsorbents. Herein, the pressures for gas uptake and release of a series of zinc-based mixed-ligand catenated metal-organic frameworks were controlled by decorating its ligands with two different functional groups and changing their ratio. This affects the deformation energy of the framework, which in turn controls the gated behaviour. The materials offer good performances for acetylene storage with a usable capacity of ~90 v/v (77% of the overall amount) at 298 K and under a practical pressure range (100-150 kPa).
乙炔等易燃气体的安全储存对于当前工业用途至关重要。然而,纯乙炔工业使用所需的狭窄压力(P)和温度范围(298 K时100<P<200 kPa)以及其在较高压力下的爆炸行为使其储存和释放具有挑战性。具有门控吸附/解吸行为(客体的吸收和释放在阈值压力以上发生,通常伴随着骨架变形)的柔性金属有机骨架已显示出作为储存吸附剂的潜力。在此,通过用两种不同官能团修饰一系列锌基混合配体连锁金属有机骨架的配体并改变它们的比例,来控制气体吸收和释放的压力。这会影响骨架的变形能,进而控制门控行为。这些材料在298 K和实际压力范围(100 - 150 kPa)下具有良好的乙炔储存性能,可用容量约为90 v/v(占总量的77%)。