基于荧光金属—有机骨架功能材料的可控合成及性能研究

发布时间：2018-07-03 09:29

本文选题：金属-有机骨架 + 发光　；参考：《东北师范大学》2017年博士论文

【摘要】：金属-有机骨架(MOFs)由于其在气体存储,选择性吸附分离,发光,药物传输和催化等方面的潜在应用,成为研究热点之一。其中,光功能MOFs材料引起极大关注。MOFs的发光可以通过有机配体和金属节点的选择得到调节,此外,大小和形状可调节的孔赋予它们负载客体发光体进入空腔的能力,从而为它们的发光性能提供了多样性。在过去的几年里,大量的光功能MOFs被报道并在荧光检测,光催化,非线性光学和生物医学成像等领域显示出潜在的应用。本文选用荧光基配体,结合运用混配体策略,设计合成了几例稳定的多孔的荧光MOFs。对合成的MOFs进行后处理引入镧系或其它发光体实现发光可调。引入稀土或荧光染料构筑发光MOFs复合材料进而用在对爆炸物和挥发性有机化合物的检测方面。依据三基色原理,将光色互补的发光体引入到发光的多孔的MOFs中,调节其含量实现白光发射,并将制备的白光材料应用于白光器件。1.成功构筑了一个稳定的多孔咔唑基MOF(NENU-522)。该荧光MOF在空气和酸碱水溶液中极其稳定,为负载Ln~(3+)实现荧光可调提供了条件。重要的是,调节封装的Eu~(3+)和Tb~(3+)的含量实现了白光发射。此外,Tb~(3+)@NENU-522被用作荧光传感器,对含有不同-NO2数目的爆炸物实现定性和定量的检测,对硝基苯,1,3-二硝基苯,和2,4,6-三硝基苯酚荧光完全淬灭的最低浓度分别为2000,1000,和80 ppm。同时Tb~(3+)@NENU-522传感器显示出高选择性和循环利用性。[Zn4O(L)_3(H_2O)_2]_3[Zn4O(L)_3]·xDMF(NENU-522)H_2L = 9H-carbazole-3,6-dicarboxylic acid2.成功合成了一个具有分子筛BCT拓扑的荧光MOF(NENU-519),它是极少的一例具有分子筛拓扑的两层互穿结构。阴离子骨架的NENU-519显示出选择性吸附阳离子染料的能力。此外,我们开发Rh6@NENU-519(Rh6=Rhodamine 6G)作为双发射传感器,把配体和染料发射峰强度的比值作为检测信号。根据配体与染料间不同的能量转移可以区分邻,间,对-二甲苯和乙苯的同分异构体。另外,Rh6@NENU-519能作为荧光开关检测不同的芳香性化合物,如苯、不同取代基取代的苯和吡啶。[(CH3)_2NH_2]_2[(Zn2O)L]·5DMF(NENU-519)H4L = tetrakis[4-(carboxyphenyl)oxamethyl]methane acid3.成功构筑了一个稳定的介孔蓝光发射的MOF(NENU-521)。NENU-521可以作为主体负载Alq3实现可调的荧光发射和高效的白光发射。Alq3@NENU-521复合材料具有优异的稳定性,白光发射的Alq3@NENU-521能作为有潜力的白光荧光粉应用于WLEDs。[(Zn4O)_3(TPA)4(TDA)_3(H_2O)6][(Zn4O)(TPA)_2]_2·12DMF(NENU-521)H_2TDA = thiophene-2,5-dicarboxylic acidH3TPA = 4,4',4''-nitrilotribenzoic acid4.合成了一个具有lon拓扑的阴离子骨架的荧光MOF(NENU-524),由可以看作双次级建筑单元的三角棱柱单元{Zn8(btca)6(2-NH_2-bdc)_3}构成。NENU-524具有永久性的孔道和优异的空气稳定性。通过离子交换过程可以将黄光发射的[Ir(ppy)_2(bpy)]~+成功封装进蓝光发射的NENU-524的孔道中。[Ir(ppy)_2(bpy)]~+@NENU-524([Ir(ppy)_2(bpy)]~+:3.86 wt%)能发出白光,CIE色坐标为(0.300,0.336),量子效率为15.2%。用制备的白光材料作为荧光粉组装的WLED发射出明亮的白光,该WLED能在空气中稳定使用一个月。[(CH3)_2NH_2]_2[Zn8(btca)6(2-NH_2-bdc)_3]·8DMF(NENU-524)H_2btca = benzotriazole-5-carboxylic acid 2-NH_2-H_2 bdc = 2-amino-1,4-benzenedicarboxylic acid
[Abstract]:Metal organic framework (MOFs) has become one of the hotspots of research because of its potential applications in gas storage, selective adsorption, separation, luminescence, drug transmission and catalysis. Among them, light functional MOFs materials can be regulated by the selection of organic ligands and metal nodes, and the size and shape can be adjusted. The pores of the node give them the ability to load the guest luminescent body into the cavity, thus providing diversity for their luminescence properties. In the past few years, a large number of optical functions have been reported and shown potential applications in the fields of fluorescence detection, photocatalysis, nonlinear optics and biomedical imaging. This paper uses fluorescence based ligands, combining with MOFs. Using the mixed ligand strategy, several stable porous fluorescent MOFs. were designed and synthesized for the synthesis of MOFs. The lanthanide or other luminescent bodies were introduced to realize luminescence. The rare earth or fluorescent dyes were introduced to construct the luminescent MOFs composite and then used in the detection of explosives and volatile organic compounds. Based on the three color principle, The light color complementary luminescence is introduced into the luminescent porous MOFs, adjusting its content to achieve white light emission, and applying the white light material to the white light device.1. to build a stable porous carbazole based MOF (NENU-522). The fluorescent MOF is extremely stable in the air and acid base water solution, and provides the adjustable fluorescence for the load Ln~ (3+). It is important that the content of the encapsulated Eu~ (3+) and Tb~ (3+) be controlled by white light emission. In addition, Tb~ (3+) @NENU-522 is used as a fluorescence sensor to achieve qualitative and quantitative detection of explosives containing different -NO2 numbers, and the lowest concentration of nitrobenzene, 1,3- two nitrobenzene, and 2,4,6- three nitrophenol is 2, respectively, and the lowest concentration of the fluorescence of 2,4,6- three nitrophenol is 2, respectively. 0001000, and 80 ppm., Tb~ (3+) @NENU-522 sensor shows high selectivity and cyclic utilization.[Zn4O (L) _3 (H_2O) _2]_3[Zn4O (L) _3] xDMF. Layer interpenetrating structure. The NENU-519 of the anionic skeleton shows the ability to selectively adsorb cationic dyes. In addition, we develop Rh6@NENU-519 (Rh6=Rhodamine 6G) as a dual emission sensor. The ratio of the ligand and dye emission peak intensity is used as a detection signal. According to the different energy transfer between the ligand and the dye, we can distinguish between the adjacent and the two. In addition, Rh6@NENU-519 can be used as a fluorescent switch to detect different aromatic compounds, such as benzene, different substituent substituents of benzene and pyridine. [(CH3) _2NH_2]_2[(Zn2O) L]. 5DMF (NENU-519) H4L = tetrakis[4- (carboxyphenyl) oxamethyl]methane constructs a stable mesoporous blue light emission. MOF (NENU-521).NENU-521 can be used as the main body load Alq3 to achieve adjustable fluorescence emission and high efficient white light emission.Alq3@NENU-521 composites with excellent stability. White light emitting Alq3@NENU-521 can be used as a potential white light phosphor for WLEDs.[(Zn4O) _3 (TPA) 4 (TDA) _3. DA = thiophene-2,5-dicarboxylic acidH3TPA = 4,4', 4''-nitrilotribenzoic acid4. syntheses a fluorescent MOF (NENU-524) with an anion skeleton with a lon topology, which is composed of a triangular prism unit of a dual secondary building unit, {Zn8 (BTCA) 6 (2-NH_2-bdc), which has a permanent pass and excellent air stability. The yellow emitting [Ir (PPy) _2 (bpy) + + can be successfully encapsulated into.[Ir (PPy) _2 (bpy)]~+@NENU-524 (bpy)]~+@NENU-524 (bpy)]~+@NENU-524 ([Ir (PPy)) in the NENU-524 channel of the blue light emission through the ion exchange process. With bright white light, the WLED can be used steadily for one month in the air. [(CH3) _2NH_2]_2[Zn8 (BTCA) 6 (2-NH_2-bdc) _3]. 8DMF (NENU-524) H_2btca = benzotriazole-5-carboxylic acid 2-NH_2-H_2
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB34

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