采用密度泛函理论(DFT)方法,基于立方体构筑单元(—B4N4O12—)理论设计得到了5种新型高连通性硼氮共价有机骨架(BN-COFs)材料。对5种材料结构进行理论表征,并采用巨正则蒙特卡罗(GCMC)方法模拟研究了250K、298K和350K(K=273.15℃)温度下材料对甲烷(CH4)的吸附性能。结果表明:5种材料中BN-COF-5对CH4的吸附性能最佳,在250K、298K和350K下的最大CH4吸附量分别为237.41cm3(STP)/cm3、177.76cm3(STP)/cm3和117.86cm3(STP)/cm3,最大工作容量(298K,65bar→5bar)为119.46cm3(STP)/cm3。CH4分子在骨架中的质心密度分布结果表明,CH4的最佳吸附位点处于(—B4N4O12—)团簇以及线性配体形成的角落附近。所设计的高连通性BN-COFs具有良好的CH4吸附性能,可为实验上研究开发新型CH4吸附剂提供一定的理论参考。
By using density functional theory (DFT) method,five novel high connectivity boron-nitrogen covalent organic framework (BN-COFs) materials were designed based on the cube building unit (—B4N4O12—).The structures of the five materials were characterized theoretically.The adsorption properties of the materials for methane (CH4) at 250K,298K and 350K were simulated and investigated by using grand canonical Monte Carlo (GCMC) method.The results showed that BN-COF-5 had the best adsorption performance for CH4 among the five materials.The maximum CH4 adsorption capacities at 250K,298K and 350K were 237.41cm3(STP)/cm3,177.76cm3(STP)/cm3 and 117.86cm3(STP)/cm3,respectively.The maximum working capacity (298K,65bar→5bar) was 119.46cm3(STP)/cm3.The centroid density distribution of CH4 molecules in the skeleton revealed that the optimal adsorption site for CH4 was near the corner where the (—B4N4O12—) cluster and linear ligand were formed.The high connectivity BN-COFs designed in this study had good CH4 adsorption performance,which could provide a theoretical reference for the experimental research and development of new CH4 adsorbents.
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