柔軟な多孔性結晶を舞台としたドナー／アクセプター配列の動的制御

柔性多孔晶体中供体/受体排列的动态控制

• 批准号: 15F15339
• 负责人: 佐藤 弘志
• 金额: $ 1.47万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2015
• 资助国家: 日本
• 起止时间: 2015-11-09 至 2018-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15F15339/
• 关键词: 多孔体; 結晶; 構造変化; porous materials; metal-organic frameworks; radical; 細孔; 電荷移動

The exfoliation of two-dimensional (2D) materials such as graphite, layered transition metal dichalcogenides, layered double hydroxides and layered boron nitrides, has been demonstrated to give rise to extraordinary thermoelectric, catalytic, or separation properties. On the other hand, related studies of layered porous materi-als such as MOFs are comparatively less explored. While the top-down approach has been employed to exfoliate MOF nanosheets for ultrathin membranes, there still lacks an effective protocol to selectively obtain nanosheets of desired thickness and number of layers. We synthesized two 2D Cu(II) kagome MOFs, and explored the unique and reversible expansion phenomenon of the former in polar aprotic solvents and observed an unprecedented intermediate state with a bilayer structure. During the investigation of the stepwise and reversible expansion of a 2D metal-organic framework (MOF) in polar aprotic solvents, we discovered a unique bilayer intermediate state that has not been observed in other MOFs. More interestingly, exfoliation initiated from the intermediate and the fully expanded states led to the formation of double and single layer nanostructures, respectively, providing a new strategy for the selective preparation of ultrathin nanosheets from MOFs.

已经证明，二维（2D）材料（例如石墨，分层的过渡金属二分法，分层的双氢氧化物和分层硝酸盐）的去角质已被证明会引起非凡的热电，催化或分离特性。另一方面，对分层多孔材料（例如MOF）的相关研究的探索较少。虽然自上而下的方法已被用来去角质MOF纳米片以用于超薄膜，但仍然缺乏有效的方案来选择性地获得所需厚度和层数的纳米片。我们合成了两个2d Cu（ii）Kagome MOF，并探索了前者在极性催化溶剂中的独特而可逆的膨胀现象，并观察到具有双层结构的前所未有的中间状态。在对极性质子溶剂中2D金属有机框架（MOF）的逐步膨胀和可逆膨胀的研究期间，我们发现了在其他MOF中尚未观察到的独特双层中间状态。更有趣的是，从中间和完全扩展的状态开始的去角质导致了双层纳米结构的形成，为从MOFS选择性准备超薄纳米片的选择提供了新的策略。