摘要
金属有机骨架材料与导电聚合物的复合已成为材料领域的研究热点,理论计算对于理解新型材料的微观结构和吸附机理起着不可或缺的作用。采用浸渍法使MIL-101吸附吡咯达到饱和,利用吡咯室温易挥发的特点,控制MIL-101/Py的干燥时间以调控MIL-101空腔中吡咯的含量。结合分子动力学模拟发现,负载量较低时,吡咯单体分布在MIL-101笼的边缘;随着负载量增加,逐渐向中心聚集;负载量过大时,吡咯单体难以进入。模拟辅助实验说明,在MIL-101中填充聚合物单体可以优化孔道结构,MOF/聚合物复合材料为基于孔径筛分效应的离子选择性分离奠定了基础。用DFT方法探索MIL-101与吡咯的相互作用,计算得到MIL-101中各部分对吡咯的吸附强弱顺序为:Cr_(3)O-O>Cr_(3)O-F>CH-π/NH-π>Cr_(3)O-Cr,且由吸附能判断,吡咯与MIL-101之间的吸附方式为物理吸附。
The composition of metal organic framework materials and conductive polymers has attracted much attention in the field of materials,and theoretical calculations play an indispensable role in understanding the micro-structure and adsorption mechanism of the new materials.The pyrrole adsorption onto MIL-101 was saturated by dipping method,and the drying time of MIL-101/Py was controlled to regulate the content of pyrrole in the cavity of MIL-101 by taking advantage of the volatile characteristics of pyrrole at room temperature.This lays the foundation for the precise design of MIL-101 aperture.Combined with molecular dynamics simulation,it is found that at low loading,pyrrole monomers are distributed on the edge of MIL-101 cage,and gradually aggregated towards the center as the loading increases,while it is difficult for pyrrole monomers to enter when the loading is too large.Simulation auxiliary experiments show that fill-ing of polymer monomers in MIL-101 can optimize the pore structure,and the MOF/polymer composite lays the foundation for ion-selective separation based on the pore size sieving effect.The interaction between MIL-101 and pyrrole was explored by DFT method.The order of the ad-sorption strength of each part in MIL-101 towards pyrrole is Cr_(3)O-O>Cr_(3)O-F>CH-π/NH-π>Cr_(3)O-Cr,and judged by the adsorption energy,the adsorption between pyrrole and MIL-101 is physical adsorption.
作者
延彩萍
安小伟
杜晓
郝晓刚
YAN Caiping;AN Xiaowei;DU Xiao;HAO Xiaogang(College of Chemical Engineering and Technology,Taiyuan University of Technology,Taiyuan 030024,China;College of Environmental Science and Engineering,Taiyuan University of Technology,Taiyuan 030024,China)
出处
《太原理工大学学报》
CAS
北大核心
2022年第3期466-473,共8页
Journal of Taiyuan University of Technology
基金
国家自然科学基金面上资助项目(22078017)。
关键词
金属有机骨架
吡咯
含量调控
分子动力学
量化计算
metal organic framework
pyrrole
content control
molecular dynamics
quanti-tative calculation
