Porous covalent organic framework liquid for boosting CO_(2)adsorption and catalysis via dynamically expanding effect  

作　　者：Zi-Ao Chen Lei Zou Rong Cao Yuan-Biao Huang 

机构地区：[1]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [2]University of Chinese Academy of Sciences,Beijing 100049,China [3]Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou 350108,China

出　　处：《National Science Review》2025年第3期350-362,共13页国家科学评论(英文版)

基　　金：supported by the National Key Research and Development Program of China(2023YFA1507904 and 2021YFA1501500);the National Natural Science Foundation of China(NSFC)(U22A20436,22071245,22033008 and 22220102005);the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ103)。

摘　　要：The features of intrinsic porosit y and fluidit y endow porous liquids(PLs)with unique properties and performance but the preparation of PLs remains challenging due to the difficulty in liquefying and keeping porous features at the same time.Herein,we develop a stepwise surface functionalization and ion exchange strategy to achieve a rare example of flexible covalent organic framework(COF)-based PL(COF-PLs).By coating the outer surface of the judiciously selected three-dimensional flexible COF-301 with an imidazolium salt corona,followed by liquefaction using the anion canopy potassium poly(ethylene glycol)sulfonate(PEGS)via electrostatic interactions,a flexible PL,COF-301-PL,can be obtained.Theoretical calculations and CO_(2)adsorption experiments reveal that the cavities of COF-301-PL undergo dynamic adjustments in response to changes in CO_(2)pressure.The dynamic expansion effect can not only provide additional gas adsorption capacity(7.04 mmol/g at 40 bar)but also facilitate the mass transfer of gas molecules during the catalytic process.Consequently,COF-301-PL exhibits superior catalytic efficiency for the conversion of CO_(2)into cyclic carbonate by a factor of 24 and 17 compared to those of PEGS and COF-301 solid counterpart,respectively.The optimization of substrate adsorption and mass transfer conditions consequently improves the overall efficiency of catalytic reactions.This work offers a new perspective on the preparation of PLs and their great potential application for gas adsorption and catalysis.

关 键 词：covalent organic frameworks porous liquids breathing effect CO_(2)adsorption cycloaddition reactions 

分 类 号：O643.3[理学—物理化学] O64[理学—化学]