Triple Framework Isomerism and Efficient Ethane/Ethylene Separation of Single‐Crystal Covalent Organic Frameworks With 2D hcb Sheets
Abstract
ABSTRACT Constructing triple framework isomerism with atom‐resolution structures is of great significance but remains highly challenging for covalent organic frameworks (COFs). Herein, [3+3] imine condensation of 1,3,5‐trimethyl‐2,4,6‐tris(4‐aminophenyl)benzene with 1,3,5‐triethyl‐2,4,6‐tris(4‐formylphenyl)benzene affords three single‐crystal COF isomers composed of hcb nets. Their AB hcb stacking, double [2D+2D], and triple [2D+2D+2D] crossing entangled structures have been resolved by 3D electron diffraction. Among the three desolvated COFs, GZU‐4a exhibits the highest ethane uptake (100.7 cm 3 g −1 ) and ethane/ethylene selectivity (1.6), enabling one‐step production of high‐purity ethylene (>99.99%) in dynamic breakthrough experiments. The superior and inverse separation performance originates from its rigid non‐interpenetrated framework with optimized pore confinement for strengthened ethane binding. This work not only presents an unprecedented example of triple isomeric COFs with atom‐resolution structures from non‐interpenetration to inclined interpenetration of 2D nets, but also shows an inverse adsorption selectivity for ethane over ethylene, greatly enriching the diversity of COFs.
Article Details
Authors (12)
Baoqiu Yu
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering
Tonghai Wang
College of Chemistry
Yucheng Jin
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering
Zhongwei Liu
Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, School of Chemistry and Chemical Engineering
Qingmei Xu
Shangwei Yuan
Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, School of Chemistry and Chemical Engineering
Xin Xiao
Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, School of Chemistry and Chemical Engineering
Xu Ding
State Key Laboratory of Chemo/Bio-Sensing, College of Chemistry and Chemical Engineering
Hailong Wang
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering
Zhenjie Zhang
College of Chemistry, Frontiers Science Center for New Organic Matter
Banglin Chen
Jianzhuang Jiang
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering