本文選題：金屬有機(jī)框架材料 + 異金屬�。� 參考：《海南大學(xué)》2017年碩士論文

【摘要】：金屬有機(jī)框架材料(Metal-organic frameworks = MOFs)是具有分子內(nèi)孔隙的有機(jī)-無機(jī)雜化材料,由有機(jī)配體和金屬單元通過配位自組裝而形成的。MOFs材料具有大的比表面積,高的孔隙率,結(jié)構(gòu)和功能具有多樣性。所以近年來MOFs材料在氣體吸附與分離、熒光性質(zhì)、電化學(xué)性質(zhì)、化學(xué)傳感器等領(lǐng)域引起人們的廣泛注度。因此新穎的MOFs的拓展合成及在材料方面的應(yīng)用具有重要的意義。本學(xué)位論文主要研究成果如下:1.基于單一種類金屬構(gòu)筑兩例新型金屬有機(jī)框架材料。其一是以半剛性含氮羧酸類配體 5-(Bis-carboxymethyl-amino)-isophthalic acid(H4L1)與 MnCl2 在溶劑熱條件下成功合成出一例化合物[Mn3(L1)2(H2O)6]·H2O(HNU-20),通過利用X-射線單晶衍射儀分析其結(jié)構(gòu)表明HNU-20是以金屬M(fèi)n的二核簇與配體H4L1形成二維層狀結(jié)構(gòu),并通過氫鍵形成三維的超分子結(jié)構(gòu);其二是以半剛性含氮羧酸類配體5-bis(3-carbonyIbenzyl)-aminoisophthalic acid(H4L2),以及輔助配體 5-甲基四氮唑(5-Methyl-1H-tertazole=mtz)與Zn(OAc)2·2H2O在溶劑熱條件下成功合成出一例化合物Zn2L2(mtz)2(HNU-21),通過X-射線單晶衍射儀分析其結(jié)果表明HNU-21具有三維孔道,孔隙率約為64.3%,若將Zn2+和配體簡化后,整體結(jié)構(gòu)為典型的4-連接sod的拓?fù)洹Ｗ詈筇骄科錈晒庑阅?結(jié)果表明HNU-21對(duì)金屬Fe3+有著良好的選擇性識(shí)別作用,檢測(cè)限可以達(dá)到10-4mol/L,并且HNU-21對(duì)6種爆炸物也有著不同程度的熒光識(shí)別作用,其中對(duì)2,4-二硝基苯酚的熒光識(shí)別能力最強(qiáng),檢測(cè)限可以達(dá)到10-3mol/L。2.基于異金屬的兩例金屬有機(jī)框架材料。以半剛性含氮羧酸類配體5-bis(3-carbonyIbenzyl)-aminoisophthalic acid(H4L2)與 ZnCl2和 LiNO3,在溶劑熱條件下成功合成出一例化合物ZnLi2L2(DMF)2(HNU-22);在HNU-22基礎(chǔ)上,采用Co2+替換Zn2+,成功合成了 HNU-23。通過X-射線單晶衍射儀分析其結(jié)果表明,HNU-22和HNU-23是同構(gòu)的,其結(jié)構(gòu)是每個(gè)金屬簇與8個(gè)配體連接,而每個(gè)配體連接4個(gè)金屬簇,如果將金屬簇和配體分別作為節(jié)點(diǎn),則整體框架可簡化為4,8-連接的拓?fù)?拓?fù)漕愋褪莊lu,符號(hào)為{412.612.84}{46}2。最后探究HNU-22的熒光性能,結(jié)果表明HNU-22對(duì)金屬Fe3+有著良好的識(shí)別作用,其檢測(cè)限在10-3mol/L,并且HNU-22對(duì)爆炸物成份的2,4-二硝基苯酚也有著良好的熒光識(shí)別作用,檢測(cè)限可以達(dá)到10-4mol/L。3.基于金屬有機(jī)框架復(fù)合材料的合成及其性能探究。以中空ZnO為基底,在其表明生長ZIF-8,成功合成中空ZnO@ZIF-8復(fù)合材料。通過掃描電子顯微鏡(SEM),透射電子顯微鏡(TEM),X-射線粉末衍射(XRD)對(duì)所得的材料結(jié)構(gòu)和微觀形貌進(jìn)行表征,并探究了其氣敏性質(zhì)。研究結(jié)果表明,中空ZnO@ZIF-8微球?qū)σ掖嫉臍饷粜阅苡辛嗣黠@的提高,可見ZIF-8負(fù)載到中空ZnO微球?qū)σ掖紮z測(cè)靈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.
【學(xué)位授予單位】：海南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4;TB33
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本文編號(hào)：1842277