Wang Yujie, Liu Yaozu, Li Hui, Guan Xinyu, Xue Ming, Yan Yushan, Valtchev Valentin, Qiu Shilun, Fang Qianrong
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry , Jilin University , Changchun 130012 , People's Republic of China.
Department of Chemical and Biomolecular Engineering, Center for Catalytic Science and Technology , University of Delaware , Newark , Delaware 19716 , United States.
J Am Chem Soc. 2020 Feb 26;142(8):3736-3741. doi: 10.1021/jacs.0c00560. Epub 2020 Feb 17.
The development of three-dimensional (3D) covalent organic frameworks (COFs) with large pores and high surface areas is of great importance for various applications. However, it remains a major challenge due to the frequent structural interpenetration and pore collapse after the removal of guest species situated in the pores. Herein, we report for the first time a series of 3D mesoporous COFs through a general method of steric hindrance engineering. By placing methoxy and methyl groups strategically on the monomers, we can obtain non-interpenetrated 3D COFs of diamondoid structures with permanent mesopores (up to 26.5 Å) and high surface areas (>3000 m g), which are far superior to those of reported conventional COFs with the same topology. This work thus opens a new avenue to create 3D large-pore COFs for potential applications in adsorption and separation of large inorganic, organic, and biological molecules.
开发具有大孔和高比表面积的三维（3D）共价有机框架（COF）对于各种应用至关重要。然而，由于去除孔中客体物种后频繁出现结构互穿和孔坍塌，这仍然是一个重大挑战。在此，我们首次通过空间位阻工程的通用方法报道了一系列3D介孔COF。通过在单体上策略性地放置甲氧基和甲基，我们可以获得具有永久介孔（高达26.5 Å）和高比表面积（>3000 m²/g）的类金刚石结构的非互穿3D COF，这远远优于具有相同拓扑结构的已报道传统COF。因此，这项工作为创建用于吸附和分离大型无机、有机和生物分子的3D大孔COF开辟了一条新途径。
