本文選題：金屬-有機(jī)網(wǎng)格 + 水分子傳感��； 參考：《東華理工大學(xué)》2017年碩士論文

【摘要】：材料,是人類物質(zhì)文明的先導(dǎo)和基礎(chǔ),是推動(dòng)社會(huì)發(fā)展的直接動(dòng)力,是開發(fā)新型能源和治理環(huán)境污染的重要保障。它在人類歷史發(fā)展的長(zhǎng)河中扮演著重要的角色,是人類生存和生活不可或缺的部分。傳感材料,作為功能材料的一大“分支”,受到研究者的廣泛關(guān)注。而無(wú)機(jī)-有機(jī)框架材料(metal-organic frameworks,MOFs)因其骨架的剛性、永久的孔性、結(jié)構(gòu)的多樣性以及同時(shí)兼?zhèn)涞母呋瘜W(xué)和熱穩(wěn)定性,成為了傳感材料中的“明日之星”。以溶劑化顯色和發(fā)光性能為主,包括干涉測(cè)量法,局域表面等離子體共振光譜法(LSPR)、石英晶體微量天平法(QCM)、表面聲波傳感(SAW)、微型懸臂梁傳感(MCL)、電化學(xué)阻抗法、膠體晶體(CC)等在內(nèi)的信號(hào)轉(zhuǎn)導(dǎo)方式可以滿足對(duì)不同的被分析物分子產(chǎn)生信號(hào)響應(yīng),而不用擔(dān)心MOFs材料的性質(zhì)和結(jié)構(gòu),在有機(jī)小分子、蒸汽和氣體、陰/陽(yáng)離子等研究領(lǐng)域取得了重大的進(jìn)展。鑒于此,本論文設(shè)計(jì)制備了兩例新型的配合物,并對(duì)它們進(jìn)行了結(jié)構(gòu)表征,熱穩(wěn)定性分析,水溶劑傳感,吸附性能以及其中一個(gè)發(fā)光配合物的熒光壽命,量子產(chǎn)率和另一個(gè)具有溶劑化顯色效應(yīng)的配合物的紫外-可見光譜光譜等研究,具體如下:通過(guò)混合溶劑熱的方法,1,3,5-均三苯甲酸配體和酰胺配體L1與金屬Zn(Ⅱ)通過(guò)自組裝制備出一例在b方向上具有一維螺旋結(jié)構(gòu)的六方配合物MOF-1。對(duì)其單晶結(jié)構(gòu)解析,結(jié)果顯示MOF-1存在兩種對(duì)映的手性結(jié)構(gòu),分別結(jié)晶在P6422和P6222兩種空間群,并互為外消旋體。Platon和Topos軟件計(jì)算MOF-1的溶劑占有率為32.8%且具有四重自穿插結(jié)構(gòu)。在外加的機(jī)械壓力下,能使原本信號(hào)不強(qiáng)的樣品可以經(jīng)研磨來(lái)提升其熒光強(qiáng)度、熒光壽命及量子產(chǎn)率。并且對(duì)不同有機(jī)溶劑中的含水量進(jìn)行分析,結(jié)果顯示研磨后的樣品能對(duì)不同濃度產(chǎn)生三種不同的熒光響應(yīng)機(jī)制:在較低濃度下,對(duì)水分子表現(xiàn)出隨濃度增加熒光強(qiáng)度增強(qiáng)的信號(hào)變化機(jī)制;在常規(guī)濃度下,對(duì)水分子表現(xiàn)出發(fā)射波長(zhǎng)隨濃度增加而紅移的信號(hào)變化機(jī)制;在較高濃度下,對(duì)水分子表現(xiàn)出隨濃度增加熒光信號(hào)猝滅的變化機(jī)制。另外對(duì)MOF-1的吸附性能研究發(fā)現(xiàn)研磨的樣品能通過(guò)水分子來(lái)調(diào)控對(duì)C2H2,C2H4,CO2吸附能力。通過(guò)水熱合成法,4,4'-聯(lián)吡啶和L2配體與金屬Co(Ⅱ)通過(guò)自組裝制備出一例水分子參與配位,具有一維螺旋結(jié)構(gòu)的六方配合物MOF-2。單晶結(jié)構(gòu)解析顯示MOF-2同樣存在兩種對(duì)映的手性構(gòu)型,分別結(jié)晶在P61和P65兩種空間群,并互為外消旋體。實(shí)驗(yàn)發(fā)現(xiàn),樣品在200℃真空熱處理下,容易失去配位水分子使金屬Co(Ⅱ)的配位數(shù)由6配位變成4配位,導(dǎo)致樣品表面顏色由粉色向藍(lán)紫色轉(zhuǎn)變。在吸附實(shí)驗(yàn)中,樣品僅對(duì)水分子具有較大的吸附能力,并且吸附水分子后樣品的顏色恢復(fù),由藍(lán)紫色重新變回粉色。而在水分子傳感研究中,發(fā)現(xiàn)MOF-2能對(duì)水分子產(chǎn)生典型的溶劑化顯色效應(yīng),并且對(duì)水分子有高的靈敏性,其檢測(cè)線可以低至10%以下。紫外-可見光譜解釋了MOF-2對(duì)水分子產(chǎn)生溶劑化顯示的機(jī)制:處于四面體環(huán)境中的Co(Ⅱ)會(huì)與吸附的水分子配位轉(zhuǎn)變成八面體的幾何構(gòu)型,伴隨著分裂能?0的升高,d電子躍遷所需要吸收的能量增大,因而波長(zhǎng)逐漸向短波方向,相對(duì)應(yīng)的MOF-2所呈現(xiàn)的顏色向長(zhǎng)波方向移動(dòng),所以吸附水分子后,樣品的顏色從較深的藍(lán)紫色逐漸恢復(fù)到較淡的粉色,表現(xiàn)出較為明顯的水分子顯色效應(yīng)。
[Abstract]:Material, the precursor and foundation of human material civilization, is the direct driving force for promoting social development and an important guarantee for the development of new energy and environmental pollution. It plays an important role in the long river of human history and is an indispensable part of human existence and life. Sensing materials, as a major "branch of functional materials" "Metal-organic frameworks (MOFs) has become a" tomorrow star "in sensing materials because of its rigid framework, permanent porosity, structural diversity, and simultaneous high chemical and thermal stability. Quantitative method, local surface plasmon resonance spectroscopy (LSPR), quartz crystal microbalance (QCM), surface acoustic wave sensing (SAW), micro cantilever Liang Chuangan (MCL), electrochemical impedance method, colloidal crystal (CC), etc. can satisfy the signal response to different molecules of the analyte, without fear of the properties of the MOFs material. And structure, great progress has been made in the field of organic small molecules, steam and gas, and anion / cation, and so on. In this paper, two new complexes are designed and prepared, and they are characterized by structure characterization, thermal stability analysis, water solvent sensing, adsorption properties, and the fluorescence lifetime of one of the luminescent complexes and quantum yield. The UV visible spectral spectra of the other complex with solvent color effect are studied as follows: 1,3,5- three benzoic acid ligands and amide ligands L1 and metal Zn (II) are prepared by self assembly through a mixed solvent heat method to prepare a single crystal junction of six square complexes with one dimensional spiral structure in the direction of B. The results show that there are two enantiomeric chiral structures in MOF-1, which crystallize in two space groups of P6422 and P6222 respectively, and each other for the external raceme.Platon and Topos software, the solvent occupancy of MOF-1 is 32.8% and it has a self insertion structure. Under the applied mechanical pressure, the samples of the original signal can be grinded by grinding. The fluorescence intensity, the fluorescence lifetime and the quantum yield are raised, and the water content in different organic solvents is analyzed. The results show that the samples after grinding can produce three different fluorescence response mechanisms to different concentrations. To the water molecules, the mechanism of the signal change of the emission wavelength with a red shift with the increase of concentration is shown. At a high concentration, the change mechanism of the fluorescence quenching with the concentration increases with the concentration of the water molecules. In addition, the adsorption properties of MOF-1 can be controlled by the water molecules to regulate the adsorption capacity of C2H2, C2H4, and CO2. Synthetic method, 4,4'- bipyridine and L2 ligand and metal Co (II) are prepared by self-assembly to prepare a case of water molecules to participate in coordination. The structure of MOF-2. single crystal structure of six party complex with one dimensional spiral structure shows that MOF-2 also has two enantiomeric chiral configurations, which crystallize in two space groups of P61 and P65, respectively. Under the vacuum heat treatment at 200 c, it is easy to lose the coordination water molecules to make the coordination number of metal Co (II) changed from 6 coordination to 4 coordination, which leads to the change of the color from pink to blue purple. In the adsorption experiment, the sample has a larger adsorption capacity for water molecules, and the color of the sample is restored after the adsorption of water molecules, and the color is changed from blue purple. In the water molecular sensing study, it is found that MOF-2 can produce a typical solvation effect on water molecules and have high sensitivity to water molecules, and the detection line can be as low as 10%. The UV visible spectrum explains the mechanism of MOF-2 to produce solvent display of water molecules: Co (II) in tetrahedral environment and adsorption The coordination of water molecules into the geometric configuration of the eight surface body, with the increase of the splitting energy 0, the energy absorbed by the d electron transition is increased, so the wavelength moves towards the short wave direction and the corresponding color of the corresponding MOF-2 moves towards the long wave direction, so the color of the sample is gradually recovered from the deeper blue purple to the lighter color after the adsorption of water molecules. The pink color shows a more obvious color effect of water molecules.

【學(xué)位授予單位】：東華理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4

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