一种新型阴离子型金属有机框架微孔材料的制备及其超声法快速合成研究  

Fabrication of Anionic-Pillared Metal Organic Frameworks and the Study of Rapid Synthesis Through Ultrasonic Method

作　　者：张付昭 许文莉 李良军 赵学波[1] 张奎同 邢涛 Zhang Fuzhao;Xu Wenli;Li Liangjun;Zhao Xuebo;Zhang Kuitong;Xing Tao(College of New Energy,China University of Petroleum(East China),Shandong,266580;Shandong Energy Group Co.,Ltd.,Shandong,250014)

机构地区：[1]中国石油大学(华东)新能源学院,山东266580 [2]山东能源集团,山东250014

出　　处：《当代化工研究》2022年第20期55-57,共3页Modern Chemical Research

基　　金：山东省重大科技创新工程项目“氢能技术-工业副产氢能利用与纯化技术研究与应用”(项目编号:2020CXGC010402);山东省自然科学基金项目“基于MOF的仿生分级超结构的构筑及气体分离性能的研究”(项目编号:ZR2021MB084)。

摘　　要：本研究揭示了一种新型的合成方法——超声法在快速合成阴离子型金属有机框架(MOF)材料方面的应用。采用扩散法制备了一种新型的阴离子型MOF材料:CuTaOF_(5)-bpy(其中,bpy为4,4-联吡啶)的单晶,并利用超声法在15min内快速合成了粉末样品。X-射线单晶衍射结果显示,该材料为4,4-联吡啶、Cu^(2+)和阴离子TaOF_(5)^(2-)自组装而成的阴离子柱撑型微孔MOF材料。通过超声快速合成法制备的粉末样品与单晶具有一致的晶体结构,且具有优异的结晶性。随着超声时间的延长,样品的结晶性呈现出先增强后减弱的趋势,在15min时具有最高的结晶性。气体吸附结果表明,超声快速合成法合成的样品与单晶样品具有相近的CO_(2)吸附性能。巨正则蒙特卡洛(GCMC)模拟结果显示,阴离子TaOF_(5)^(2-)为CO_(2)的优先吸附位点,说明阴离子的引入有利于增强MOF材料对CO_(2)的吸附能力。This study revealed the application of ultrasonic method in the rapid preparation of anionic metal-organic frameworks(MOFs).The single-crystal of a new type of anionic metal organic framework:CuTaOF_(5)-bpy(in which,bpy is 4,4-bipyridine)was prepared by diffusion method,and the powder-like sample was prepared through an ultrasonic method in 15 minutes.Single-crystal X-ray diffraction revealed that this MOF is a microporous anionic three-dimensional MOF self-assembled by 4,4-bipyridine,Cu^(2+) and anion TaOF_(5)^(2-).And the powder sample prepared by the ultrasonic method possess the same crystal structure with the single crystal and excellent crystallinity.When prolonging the ultrasonic time,the crystallinity of the sample showed a tendency to increase first and then decrease,with the highest crystallinity at 15 minutes.CO_(2)adsorption experiments show that the sample synthesized by the ultrasonic method has the same pore structure as well as the similar CO_(2)adsorption performance with the single crystal sample.Grand canonical Monte Carlo(GCMC)simulation results show that the TaOF_(5)^(2-)anions are the preferential adsorption site for CO_(2),indicating that the introduction of anions is beneficial to enhance the CO_(2)adsorption in MOFs.

关 键 词：金属-有机框架材料 阴离子柱撑体 超声合成 二氧化碳捕获 蒙特卡洛模拟 

分 类 号：O611.4[理学—无机化学]