官能团修饰的二维共价有机骨架中二氧化碳捕获与分离性能的理论计算  

Theoretical calculations of CO_(2) capture and separation by functional groups modified 2D covalent organic framework

作　　者：赵杰 张慧丽 鲁效庆 王兆杰 ZHAO Jie;ZHANG Huili;LU Xiaoqing;WANG Zhaojie(Pipe Network Group(Xinjiang)United Pipeline Co.,Ltd.,Urumqi 830000,China;School of Materials Science and Engineering,China University of Petroleum(East China),Qingdao,Shandong 266580,China)

机构地区：[1]管网集团(新疆)联合管道有限责任公司,乌鲁木齐830000 [2]中国石油大学(华东)材料科学与工程学院,青岛266580

出　　处：《无机化学学报》2025年第2期275-283,共9页Chinese Journal of Inorganic Chemistry

基　　金：管网集团(新疆)联合管道有限责任公司技术开发项目(No.GWXJLH22-2022-015)资助。

摘　　要：通过引入—OH、—NH2和—SO_(3)H极性官能团,设计了具有高比表面积、亚胺键连接的二维三聚茚酮基共价有机骨架(truxenone-based covalent organic frameworks,TRO-COFs),并通过巨正则蒙特卡洛(giant canonical Monte Carlo,GCMC)模拟和密度泛函理论(density functional theory,DFT)探究了298 K和0~1.0×10^(5)Pa条件下极性官能团对TRO-COFs的CO_(2)捕获性能的影响。结合能和内聚能的分析表明官能团引入后结构仍保持较高的稳定性。极性官能团的引入显著增强了TRO-COFs的CO_(2)吸附性能。CO_(2)吸附量大小顺序为TRO-COF-SO_(3)H>TRO-COF-NH2>TRO-COF-OH>TRO-COF-H。在298 K和1.0×10^(5)Pa条件下,TRO-COF-SO_(3)H表现出8.02 mmol·g^(-1)的CO_(2)吸附量及CO_(2)优于N_(2)和CH_(4)的选择性(37和26)。同时,通过径向分布函数和气体吸附密度分布也进一步说明了不同极性官能团对CO_(2)捕获与分离性能影响的差异。最后,从吸附热、范德瓦耳斯力和库仑相互作用等多个角度详细阐明了极性官能团的作用机制。By introducing polar functional groups such as—OH,—NH2,and—SO_(3)H,two-dimensional truxenonebased covalent organic frameworks(TRO-COFs)with high surface area and imine bond connections are designed.The influence of polar functional groups on the CO_(2)capture performance of TRO-COFs is explored using grand canonical Monte Carlo simulation(GCMC)and density functional theory(DFT)at 298 K and 0-1.0×10^(5)Pa.Analysis of binding energy and cohesive energy indicate that the functional groups modified TRO-COFs still maintain high structural stability.The introduction of functional groups significantly enhances the CO_(2)adsorption performance,with the order as follows:TRO-COF-SO_(3)H>TRO-COF-NH2>TRO-COF-OH>TRO-COF-H.Notably,TRO-COF-SO_(3)H exhibits the highest CO_(2)adsorption capacity of 8.02 mmol·g^(-1)with a selectivity of CO_(2)over N_(2)and CH_(4)at 298 K and 1.0×10^(5)Pa(37 and 26).Moreover,the different effects of functional groups on CO_(2)capture and separation are illustrated through the radial distribution function and adsorption density distribution.Finally,the modified mechanism of functional groups is elucidated from the heat of adsorption,van der Waals(vdW),and Coulomb interactions.

关 键 词：共价有机骨架 CO_(2)捕获与分离 密度泛函理论 巨正则蒙特卡洛 

分 类 号：TQ424[化学工程] X511[环境科学与工程—环境工程]