多孔有机骨架材料的合成及性能研究

发布时间：2018-04-24 12:48

本文选题：多孔有机聚合物 + 配位聚合物　；参考：《山东理工大学》2017年硕士论文

【摘要】：多孔有机骨架材料(Porous Organic Frameworks,POFs)由于其较大的比表面积和可调节功能化,合成方法多样等优点受到广大科学研究者广泛关注。在近二十年间,具有多孔性质的结晶态的多孔配位聚合物(Porous Coordination Polymer,PCPs),以及一种通过共价键连接而形成的多孔有机聚合物材料(Porous Organic Polymers,POPs)成为了科学家们的研究热点,也为多孔材料的研究开辟了另一个崭新的领域。目前,配位聚合物材料和多孔有机聚合物材料已经被广泛的应用于催化、离子传感、气体存储、气体分离、光催化、电池及超级电容器、离子交换、质子传导以及药物传输释放等领域。本论文中首先合成了多孔有机聚合物的模型化合物P,在模型化合物的基础上成功合成了新型的多孔有机聚合物。其次,采用带有修饰基团的有机配体作为次级构筑单元,通过溶剂热法合成了新型的荧光配位聚合物材料。首先,合成了1,3,5-三醛基均苯三酚,将其与萘酰亚胺衍生物通过希夫碱反应合成出了多孔有机聚合物的模型化合物P,并采用核磁共振氢谱和元素分析对其结构进行表征,并且研究了模型化合物P作为荧光离子探针的性质。结果表明,在DMSO溶液中,化合物P对Fe~(2+)和Cu~(2+)同时表现出荧光淬灭现象,并且P的荧光淬灭程度与溶液中Fe~(2+)离子浓度呈线性关系;另外,化合物P与Fe~(2+)离子形成金属复合物P-Fe,该复合物的荧光能够高选择性的被阴离子H_2PO_4~-增强,溶液的荧光强度随着H_2PO_4~-浓度的增加而线性增加,即P-Fe可以通过“关-开”模式选择性的荧光传感H_2PO_4~-离子,金属复合物P-Fe对H_2PO_4~-的检出限为1.897×10-7mol/L。其次,基于模型化合物P的结构和性质,我们通过调整萘酰亚胺衍生物的结构,成功得到了多孔有机聚合物,命名为POP-1(Porous Organic Polymers 1),我们采用粉末X射线衍射,氮气吸附,热重分析对其进行了表征,并且研究了POP-1作为催化剂光降解染料罗丹明B的性质。研究发现,POP-1对罗丹明B具有较高的催化活性,在经过三次重复的催化反应后,其活性基本没有下降,并且自然光条件下仍然可以高效的催化降解RhB。另外,对POP-1的光催化实验过程进行了动力学研究,实验结果表明温度的升高有利于光催化反应的进行,降解反应的活化能为82.37 kJ/mol。最后,利用含有氨基活性基团的2-氨基对苯二甲酸与2,2?-联吡啶作为有机配体,与金属镉制备出一种多孔的配位聚合物1。X射线粉末衍射(XRD)、元素分析以及热重分析(TGA)对其进行表征,并对其性质进行研究。实验发现,配位聚合物1具有作为荧光探针检测Cu~(2+)以及小分子环己烷的性质。
[Abstract]:Porous Organic frameworks (POFs) has attracted wide attention due to its large specific surface area, adjustable functionalization and various synthesis methods. In the last two decades, porous Coordination polymeric PCPs, a crystalline porous coordination polymer, and a kind of porous organic polymer material, Porous Organic PolymersPOPss, have become the focus of scientists. It also opens up another new field for the study of porous materials. At present, coordination polymer materials and porous organic polymer materials have been widely used in catalysis, ion sensing, gas storage, gas separation, photocatalysis, batteries and supercapacitors, ion exchange, Proton conduction and drug transport and release and other fields. In this paper, we first synthesized the porous organic polymer model compound, and based on the model compound, we successfully synthesized a new porous organic polymer. Secondly, novel fluorescent coordination polymer materials were synthesized by solvothermal method using organic ligands with modified groups as secondary building units. Firstly, the model compound P of porous organic polymer was synthesized by Schiff base reaction, and the structure of the model compound was characterized by nuclear magnetic resonance (NMR) and elemental analysis. The properties of the model compound P as a fluorescent ion probe were also studied. The results show that in DMSO solution, compound P exhibits fluorescence quenching phenomenon for both Fe~(2) and Cu~(2, and the fluorescence quenching degree of P is linearly related to the concentration of Fe~(2) ions in the solution, in addition, there is a linear relationship between the fluorescence quenching degree of P and the concentration of Fe~(2 ion in the solution. Compound P and Fe~(2) ions form a metal complex P-Fe.The fluorescence of the complex can be enhanced by highly selective anionic H2PO4-, and the fluorescence intensity of the solution increases linearly with the increase of H2PO4- concentration. That is to say, P-Fe can detect H2PO4- ion through "turn-on" mode selective fluorescence sensing, and metal complex P-Fe has a detection limit of 1.897 脳 10 ~ (-7) mol 路L ~ (-1) for H _ 2PO _ (4). Secondly, based on the structure and properties of model compound P, we successfully obtained the porous organic polymer, named POP-1(Porous Organic Polymers 1, by adjusting the structure of naphthalimide derivatives. We used powder X-ray diffraction and nitrogen adsorption. It was characterized by thermogravimetric analysis and the photodegradation of Rhodamine B by POP-1 as catalyst was studied. It was found that POP-1 had high catalytic activity for Rhodamine B, and after three repeated catalytic reactions, the activity of POP-1 did not decrease and RhB could be degraded efficiently under natural light condition. In addition, the kinetics of photocatalytic reaction of POP-1 was studied. The experimental results showed that the increase of temperature was beneficial to the photocatalytic reaction, and the activation energy of the degradation reaction was 82.37 kJ / mol. Finally, a porous coordination polymer, XRDX, characterized by elemental analysis and thermogravimetric analysis (TGA), was prepared by using 2-aminoterephthalic acid and 2Aminoterephthalic acid as organic ligands and cadmium as organic ligands, respectively, by X-ray powder diffraction (XRD), elemental analysis and thermogravimetric analysis (TGA). And its properties are studied. It is found that the coordination polymer 1 has the properties of detecting Cu~(2 as a fluorescent probe and cyclohexane as a small molecule.
【学位授予单位】：山东理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;TB383.4

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