含氮类配体MOFs和中空ZnO@ZIF-8复合材料的合成及其性质研究

发布时间：2018-05-04 08:13

  本文选题：金属有机框架材料 + 异金属　； 参考：《海南大学》2017年硕士论文

【摘要】：金属有机框架材料(Metal-organic frameworks = MOFs)是具有分子内孔隙的有机-无机杂化材料,由有机配体和金属单元通过配位自组装而形成的。MOFs材料具有大的比表面积,高的孔隙率,结构和功能具有多样性。所以近年来MOFs材料在气体吸附与分离、荧光性质、电化学性质、化学传感器等领域引起人们的广泛注度。因此新颖的MOFs的拓展合成及在材料方面的应用具有重要的意义。本学位论文主要研究成果如下:1.基于单一种类金属构筑两例新型金属有机框架材料。其一是以半刚性含氮羧酸类配体 5-(Bis-carboxymethyl-amino)-isophthalic acid(H4L1)与 MnCl2 在溶剂热条件下成功合成出一例化合物[Mn3(L1)2(H2O)6]·H2O(HNU-20),通过利用X-射线单晶衍射仪分析其结构表明HNU-20是以金属Mn的二核簇与配体H4L1形成二维层状结构,并通过氢键形成三维的超分子结构;其二是以半刚性含氮羧酸类配体5-bis(3-carbonyIbenzyl)-aminoisophthalic acid(H4L2),以及辅助配体 5-甲基四氮唑(5-Methyl-1H-tertazole=mtz)与Zn(OAc)2·2H2O在溶剂热条件下成功合成出一例化合物Zn2L2(mtz)2(HNU-21),通过X-射线单晶衍射仪分析其结果表明HNU-21具有三维孔道,孔隙率约为64.3%,若将Zn2+和配体简化后,整体结构为典型的4-连接sod的拓扑。最后探究其荧光性能,结果表明HNU-21对金属Fe3+有着良好的选择性识别作用,检测限可以达到10-4mol/L,并且HNU-21对6种爆炸物也有着不同程度的荧光识别作用,其中对2,4-二硝基苯酚的荧光识别能力最强,检测限可以达到10-3mol/L。2.基于异金属的两例金属有机框架材料。以半刚性含氮羧酸类配体5-bis(3-carbonyIbenzyl)-aminoisophthalic acid(H4L2)与 ZnCl2和 LiNO3,在溶剂热条件下成功合成出一例化合物ZnLi2L2(DMF)2(HNU-22);在HNU-22基础上,采用Co2+替换Zn2+,成功合成了 HNU-23。通过X-射线单晶衍射仪分析其结果表明,HNU-22和HNU-23是同构的,其结构是每个金属簇与8个配体连接,而每个配体连接4个金属簇,如果将金属簇和配体分别作为节点,则整体框架可简化为4,8-连接的拓扑,拓扑类型是flu,符号为{412.612.84}{46}2。最后探究HNU-22的荧光性能,结果表明HNU-22对金属Fe3+有着良好的识别作用,其检测限在10-3mol/L,并且HNU-22对爆炸物成份的2,4-二硝基苯酚也有着良好的荧光识别作用,检测限可以达到10-4mol/L。3.基于金属有机框架复合材料的合成及其性能探究。以中空ZnO为基底,在其表明生长ZIF-8,成功合成中空ZnO@ZIF-8复合材料。通过扫描电子显微镜(SEM),透射电子显微镜(TEM),X-射线粉末衍射(XRD)对所得的材料结构和微观形貌进行表征,并探究了其气敏性质。研究结果表明,中空ZnO@ZIF-8微球对乙醇的气敏性能有了明显的提高,可见ZIF-8负载到中空ZnO微球对乙醇检测灵敏度提高起到了重要作用。
[Abstract]:Metal-organic frameworks = MOFs) is an organic-inorganic hybrid material with intramolecular pores, which is formed by coordination self-assembly of organic ligands and metal units, and has large specific surface area and high porosity. The structure and function are diverse. In recent years, MOFs materials have been widely used in the fields of gas adsorption and separation, fluorescence properties, electrochemical properties, chemical sensors and so on. Therefore, the development and synthesis of novel MOFs and its applications in materials are of great significance. The main research results of this dissertation are as follows: 1. Two new organometallic frame materials were constructed based on a single type of metal. One is the synthesis of [Mn3(L1)2(H2O)6] H2O HNU-20 with semi-rigid carboxylic acid ligand 5-(Bis-carboxymethyl-amino)-isophthalic acido H4L _ 1) and MnCl2 under solvothermal conditions. The structure of [Mn3(L1)2(H2O)6] H _ 2O _ (HNU-20) has been analyzed by X-ray single crystal diffractometer. It shows that HNU-20 is a binuclear cluster and ligand of mn. H4L1 forms a two-dimensional layered structure. The three-dimensional supramolecular structure was formed by hydrogen bonding. The second is the successful synthesis of a compound Zn _ 2L _ 2K _ 2H _ NU _ (21) with semi-rigid nitrogen-containing carboxylic acid ligand 5-bis(3-carbonyIbenzyl)-aminoisophthalic acidine H _ 4L _ 2N _ 2 and auxiliary ligand 5-Methyl-1H-tertazoleine mtzt) and Zn(OAc)2 2H2O under solvothermal conditions. The results of X-ray single crystal diffractometer show that HNU-21 has a three-dimensional pore channel. The porosity is about 64.3. If Zn2 and ligands are simplified, the whole structure is a typical 4-connected sod topology. Finally, the fluorescence properties of HNU-21 were investigated. The results show that HNU-21 has a good selective recognition effect on metal Fe3, the detection limit can reach 10 ~ (-4) mol / L, and HNU-21 also has a different degree of fluorescence recognition to six kinds of explosives. Among them, the fluorescence recognition ability of 2o 4-dinitrophenol is the strongest, and the detection limit can reach 10 ~ (-3) mol / L ~ (-2). Two examples of organometallic frame materials based on different metals. A novel compound ZnLi2L2ODMFU 2HNU-22 was successfully synthesized from semi-rigid carboxylic acid ligand 5-bis(3-carbonyIbenzyl)-aminoisophthalic acido H4L2), ZnCl2 and Lino 3 under solvothermal conditions, and HNU-23 was successfully synthesized by replacing Zn2 with Co2 on the basis of HNU-22. The results of X-ray single crystal diffractometer show that HNU-22 and HNU-23 are isomorphic. The structure is that each metal cluster is connected with eight ligands, while each ligand is connected with four metal clusters, if the metal clusters and ligands are used as nodes, The whole frame can be simplified to the topology of 4n8- connection, the topology type is flu. the symbol is {412.612.84} {46} 2. Finally, the fluorescence properties of HNU-22 were investigated. The results show that HNU-22 can recognize metal Fe3 well, its detection limit is 10-3 mol / L, and HNU-22 also has a good fluorescence recognition effect on 2 ~ (- 4) -dinitrophenol of explosive component, the detection limit can reach 10 ~ (-4) mol / L ~ (-3). Synthesis and Properties of Organometallic frame Composites. Hollow ZnO composites were successfully synthesized by ZIF-8 growth on hollow ZnO substrate. The structure and microstructure of the materials were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the gas sensitivity of hollow ZnO@ZIF-8 microspheres to ethanol has been improved obviously. It is shown that ZIF-8 loaded hollow ZnO microspheres play an important role in improving the sensitivity of ethanol detection.
【学位授予单位】：海南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;TB33
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本文编号：1842277