Large-scale simulations of CO_(2) diffusion in metal-organic frameworks with open Cu sites

作     者：Tongan Yan Minman Tong Qingyuan Yang Dahuan Liu Yandong Guo Chongli Zhong Tongan Yan;Minman Tong;Qingyuan Yang;Dahuan Liu;Yandong Guo;Chongli Zhong

作者机构：State Key Laboratory of Organic-Inorganic CompositesBeijing University of Chemical TechnologyBeijing 100029China School of Chemistry and Materials ScienceJiangsu Normal UniversityXuzhou 221116China College of Mathematics ScienceBohai UniversityJinzhou 121013China State Key Laboratory of Separation Membranes and Membrane ProcessesTiangong UniversityTianjin 300387China 

出 版 物：《Chinese Journal of Chemical Engineering》 (中国化学工程学报（英文版）)

年 卷 期：2022年第35卷第2期

页      面：1-9页

核心收录：

学科分类：083002[工学-环境工程] 0830[工学-环境科学与工程（可授工学、理学、农学学位）] 08[工学] 0703[理学-化学] 0702[理学-物理学] 

基　　金：supported by National Key Research and Develop-ment Program of China(2016YFB0600901) the Natural Science Foundation of China(22038010,21878229,22078024 and 21978005). 

主　　题：Metal-organic frameworks Open Cusites Molecular simulations Carbon dioxide Diffusion 

摘      要：Understanding CO_(2) diffusion behavior in functional nanoporous materials is beneficial for improving the CO_(2) adsorption,separation,and conversion performances.However,it is a great challenge for studying the diffusion process in experiments.Herein,CO_(2) diffusion in 962 metal–organic frameworks(MOFs)with open Cu sites was systematically investigated by theoretical methods in the combination of molecular dynamic simulations and density functional theory(DFT)calculations.A specific force field was derived from DFT-D2 method combined with Grimme’s dispersion-corrected(D2)density functional to well describe the interaction energies between Cu and CO_(2).It is observed that the suitable topology is conductive to CO_(2) diffusion,and 2D-MOFs are more flexible in tuning and balancing the CO_(2) adsorption and diffusion behaviors than 3D-MOFs.In addition,analysis of diffusive trajectories and the residence times on different positions indicate that CO_(2) diffusion is mainly along with the frameworks in these MOFs,jumping from one strong adsorption site to another.It is also influenced by the electrostatic interaction of the frameworks.Therefore,the obtained information may provide useful guidance for the rational design and synthesis of MOFs with enhanced CO_(2) diffusion performance for specific applications.