Ln-MOFs的合成及作为荧光探针在选择性检测苦味酸的应用
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摘要
随着对国土安全和水体环境的重视,利用化学传感器检测爆炸物、硝基苯等物质的方法成为了热点话题,具有荧光发光性能的金属有机骨架(MOF)被认为是一种潜在的探针材料。为合成具有荧光发光性能的MOF传感材料,选用具有共轭结构的三齿有机配体4,4’,4"-(1,3,5-三嗪2,4,6-三苯基)甲酸(H3TATB)和镧系金属Tb2O3进行配位,构筑了一种微孔的新型镧系金属有机框架材料{Tb-MOF[Tb2(TATB)2(DMF)2(H2O)2](1)}。通过单晶X射线衍射分析,X射线粉末衍射(PXRD),以及荧光光谱等方法研究配合物的结构和荧光性能。结果表明,Tb3+与羧基配位彼此相连形成一维链,通过配体进一步的连接构筑成三维框架。更重要的是该MOF材料在多种溶剂中具有荧光发光性能,并对苦味酸(PA)表现出高选择性和敏锐的荧光淬灭响应,且经洗涤后可以重复使用,有良好的循环使用性。
The use of chemical sensors to detect substances such as explosives and nitrobenzene has been a hot topic,with the emphasis on land security and water environment. The metal-organic framework(MOF) which has fluorescence luminescence is considered as a potential probe material. In order to obtain a novel sensor material,microporous lanthanide metal-organic framework {Tb-MOF[Tb2(TATB)2(DMF)2(H2 O)2](1)} has been constructed by organic ligand4,4',4"-s-triazine-2,4,6-triyltribenzoic acid(H3 TATB) and Tb2 O3. The structures and fluorescence properties were characterized by single-crystal X-ray diffraction analyses,powder X-ray diffraction(PXRD) and fluorescence spectra.This compound has a 1 D chain structure because Tb3 +coordinated with carboxyl,and further connected to be a 3 D framework through ligands. More importantly, the luminescence properties of the MOF in different kinds of solvent have been investigated. The luminescence studies revealed that the MOF exhibited high sensitivity and fast luminescence quenching response towards picric acid(PA). Finally,the MOF can be regenerated by washing which exhibited excellent recyclability.
The use of chemical sensors to detect substances such as explosives and nitrobenzene has been a hot topic,with the emphasis on land security and water environment. The metal-organic framework(MOF) which has fluorescence luminescence is considered as a potential probe material. In order to obtain a novel sensor material,microporous lanthanide metal-organic framework {Tb-MOF[Tb2(TATB)2(DMF)2(H2 O)2](1)} has been constructed by organic ligand4,4',4"-s-triazine-2,4,6-triyltribenzoic acid(H3 TATB) and Tb2 O3. The structures and fluorescence properties were characterized by single-crystal X-ray diffraction analyses,powder X-ray diffraction(PXRD) and fluorescence spectra.This compound has a 1 D chain structure because Tb3 +coordinated with carboxyl,and further connected to be a 3 D framework through ligands. More importantly, the luminescence properties of the MOF in different kinds of solvent have been investigated. The luminescence studies revealed that the MOF exhibited high sensitivity and fast luminescence quenching response towards picric acid(PA). Finally,the MOF can be regenerated by washing which exhibited excellent recyclability.
引文
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[3] Germain M E,Knapp M J. Optical explosives detection:From color changes to fluorescence turn-on[J].Chemical Society Reviews, 2009, 38(9):2543-2555.
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[6] Hou X G,Wu Y,Cao H T,et al. A cationic iridium(III)complex with aggregation-induced emission(AIE)properties for highly selective detection of explosives[J].Chemical Communications,2014,50(45):6031-6034.
[7] Nagarkar S S,Joarder B,Chaudhari A K,et al.Highly Selective Detection of Nitro Explosives by a Luminescent Metal-Organic Framework[J].Angewandte Chemie,2013,52(10):2881-2885.
[8] Ying W,La A,Yu D,et al. Novel Signal-Amplifying Fluorescent Nanofibers for Naked-Eye-Based Ultrasensitive Detection of Buried Explosives and Explosive Vapors[J].Advanced Functional Materials,2012,22(17):3547-3555.
[9] Ye J,Zhao L,Bogale R F,et al. Highly Selective Detection of 2,4,6-Trinitrophenol and Cu(2+)Ion Based on a Fluorescent Cadmium-Pamoate Metal-Organic Framework[J].Chemistry,2015,21(5):2029-2037.
[10] Wollin K M,Dieter H H. Toxicological Guidelines for Monocyclic Nitro-,Amino-and Aminonitroaromatics,Nitramines,and Nitrate Esters in Drinking Water[J].Archives of Environmental Contamination&Toxicology,2005,49(1):18-26.
[11] Shi Z Q,Guo Z J,Zheng H G. Two luminescent Zn(II)metal-organic frameworks for exceptionally selective detection of picric acid explosives[J].Chemical Communications,2015,51(39):8300-8303.
[12]周贺,何兴权.介孔氮掺杂碳材料应用于氧还原催化剂[J].长春理工大学学报:自然科学版,2018,41(03):60-63.
[13] Hu X L,Qin C,Wang X L,et al. A luminescent dye@MOF as a dual-emitting platform for sensing explosives[J].Chemical Communications,2015,51(99):17521-17524.
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[15] Gong Y N,Jiang L,Lu T B. A highly stable dynamic fluorescent metal-organic framework for selective sensing of nitroaromatic explosives[J].Chemical Communications, 2013, 49(94):11113-11115.
[16] Li Y,Zhang S,Song D. A luminescent metal-organic framework as a turn-on sensor for DMF vapor[J].Angewandte Chemie International Edition,2013,52(2):710-713.
[17] Yu Y,Ma J P,Dong Y B. Luminescent humidity sensors based on porous Ln3+-MOFs[J].Crystengcomm,2012,14(21):7157-7160.
[18] Weber I T,Melo A J de,Lucena M A,et al.High photoluminescent metal-organic frameworks as optical markers for the identification of gunshot residues[J].Analytical Chemistry,2011,83(12):4720-4723.
[19] Xu H,Liu F,Cui Y,et al. A luminescent nanoscale metal-organic framework for sensing of nitroaromatic explosives[J].Chemical Communications,2011,47(11):3153-3155.
[20] Li H,Shi W,Zhao K,et al. Highly selective sorption and luminescent sensing of small molecules demonstrated in a multifunctional lanthanide microporous metal-organic framework containing 1D honeycomb-type channels[J].Chemistry,2013,19(10):3358-3365.
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