A Grafting Hydrogen‐bonded Organic Framework for Benchmark Selectivity of C2H2/CO2 Separation under Ambient Conditions

Abstract

Reticular chemistry and pore engineering have garnered significant advancements in metal‐organic frameworks and covalent organic frameworks, leveraging robust metal‐coordination and covalent bonds. However, these achievements remain elusive in hydrogen‐bonded organic frameworks, hindered by their inherent weakness in hydrogen bonding. Herein, we strategically manipulate the porosity of hydrogen‐bonded frameworks through a grafting approach, culminating in the synthesis of two isomorphic HOFs, HOF‐FJU‐99 and HOF‐FJU‐100, with distinct pore environments. Remarkably, HOF‐FJU‐100, with its microporous architecture, not only showcases exceptional stability but also achieves unparalleled separation efficiency and ultrahigh selectivity for C2H2/CO2 mixtures (50/50, v/v) under ambient conditions. Its IAST selectivity value of 201 stands as a benchmark, towering over all previously reported HOFs. The pore of HOF‐FJU‐100 boasts an electrostatic potential highly favourable for C2H2 adsorption, as evidenced by single crystal X‐ray diffraction analysis revealing multiple hydrogen bonding interactions between C2H2 molecules and the framework. In situ gas‐carrier powder X‐ray diffraction analysis underscores the adaptability of pore structure, dynamically adjusting its orientation in response to C2H2, thereby enabling a highly efficient and specific separation of C2H2/CO2 mixtures through specific adsorptive interactions.