基于多羧酸配体构筑的多孔配位聚合物的合成与质子传导和荧光特性研究

发布时间：2018-03-22 08:33

本文选题：金属-有机骨架　切入点：多孔配位聚合物　出处：《东北师范大学》2017年硕士论文　论文类型：学位论文

【摘要】：我们所生活的环境周围中充斥着形形色色的材料,它们不仅保障了我们的一切活动,同时,它们的发展也推动了整个社会的进步。多孔配位聚合物(PCPs)或金属—有机框架(MOFs)作为一类新型孔道材料,凭借着结构性质上的独特优势成为了近十几年来的研究热点。经过长期以及大量的研究发现,PCPs/MOFs材料的应用领域十分广泛,涉及到了人类生活的方方面面,比如,它们可作为应用于燃料电池的质子传导材料、存储能源气体的气体吸附性材料、医药领域的药物运输材料等等。在过去的十几年里,该类材料的研究和发展势如破竹,使得目前被报道的结构不同的PCPs/MOFs材料种类数以千计,显然,再继续对该类材料单纯的进行结构研究已经意义不大了。因此,针对PCPs/MOFs材料在实际生产和生活中的应用,我们首先最需要做的就是了解它的合成方法和最终得到的材料的结构和性能之间的关系。其最终目的就是为了能更好的实现定向设计和合成具有特定功能的PCPs/MOFs材料。本文分别利用羧酸和氮杂环配体作为有机建筑单元与d10过渡金属离子相链接,构筑了六例新型PCPs/MOFs材料,并且分别对他们的酸碱稳定性、固态荧光和质子传导的性质展开研究,具体内容如下所示:(一)在这部分中,我们采用水热扩散法,利用一种氮杂环配体tpy与Cd盐构筑了一例三维PCPs材料(PCP1)。经过对它的晶体结构进行分析可知,在PCP1结构的c轴方向上存在一维的开放孔道,并且孔道中存在大量的客体水分子,利用这一特征,我们对它进行了质子传导实验。实验是在相对湿度为97%,变温的条件下进行的。并且在97%的相对湿度,95℃的条件下测得它的导电率为1.81×10-5 Scm-1。这个实验结果表明了在较高的湿度环境中PCP1具有一定的质子传导能力。另外,我们还发现,PCP1的框架开始坍塌的温度为410℃,并且在p H为2-13的范围内以及一些常见有机溶剂中,PCP1都能保持很好的结构稳定性,因此,可以综合表述为PCP1存在很好的热稳定性和化学稳定性。[Cd_(0.5)(tpy)]·0.75H_2O(PCP1)tpy=2-(1H-1,2,4-Triazol-5-yl)pyrazine(二)我们利用氮杂多羧基配体(tda)分别和2,2′-联吡啶与1,10-邻菲罗啉运用混合配体实验方案,利用溶剂热方法,与Cd离子构筑了两例互为同构的MOFs材料(MOF1和MOF2)。该两例MOFs材料均是由一维链状结构通过多重的π-π堆积作用形成的三维的配位聚合物材料。我们对它们进行了稳定性的检测实验,实验结果表明MOF1和MOF2在p H=2-12的范围内以及常见有机溶剂中可以保持很好的稳定性,这显示这两例MOFs材料具有很好的化学稳定性。另外,通过热重分析发现,这两个同构的化合物在热稳定温度上有较小的差别,对比它们的结构可以发现,这个差别来自于第二配体之间所产生的π-π堆积作用。Cd(tda)(2,2′-Dipy) (MOF1)Cd(tda)(1,10-phen)(MOF2)tda=3,3'-(1H-1,2,4-triazole-3,5-diyl)dibenzoic acid2,2′-Dipy=2,2′-Dipyridyl1,10-phen=1,10-Phenanthroline monohydrate(三)我们选用一种三重对称的三齿羧酸配体tcpb分别与Zn离子,Co离子和Cd离子利用溶剂热合成的方法构筑了三例MOFs材料。其中MOF5是具有三重互穿结构的三维MOFs材料。另外两例则都(MOF3与MOF4)是二维的网状结构,并且经过结构分析发现MOF3与MOF4为同构结构。我们对这三例MOFs材料进行了固体荧光测试,发现其最大发射峰较纯有机配体的固体荧光的最大发射峰都出现了较大的红移现象。[Cd_(1.5)(tcpb)(DMF)(H_2O)] (MOF3)Co_(1.5)(tcpb)(DMF))2]·3DMF(MOF4)[Zn(Htcpb)(4,4'-bpy)_(0.5)]·1.5H_2O(MOF5)tcpb=1,3,5-tris(4-carbonylphenyloxy)benzene4,4'-bpy=4,4'-Dipyridyl
[Abstract]:The surrounding environment in which we live is filled with the materials of every hue, which not only ensure all activities, we at the same time, their development also promoted the progress of the whole society. Porous coordination polymer (PCPs) or metal organic framework (MOFs) as a new type of hole materials, with the unique advantages of structural properties which has become a research hotspot in recent years. After long-term research and found in large amount, application field of PCPs/MOFs material is very wide, involving all aspects of human life, for example, they can be used as proton conductive material used in fuel cells, gas adsorption materials stored energy gas, the field of medicine drug delivery materials and so on. In the past ten years, the research and development of this kind of materials like gangbusters, makes the structure currently being reported thousands of PCPs/MOFs materials of different kinds, obviously, Continue on this kind of materials are simple structure research has little significance. Therefore, the application of PCPs/MOFs material in the actual production and life, we first need to do is to understand the relationship between structure and properties of its synthetic methods and materials of the final. The final purpose is to realize the directional design the PCPs/MOFs has a specific function and synthetic material better. This paper uses carboxylic acid and heterocyclic ligands as unit of organic architecture and D10 transition metal ions are linked, constructed six cases of the new PCPs/MOFs material, and the pH stability of their research on properties of solid state fluorescence and proton conduction, the specific content is as follows: (a) in this part, we adopt the hot water diffusion method, using a Nitrogen Heterocyclic Ligands TPY and Cd to build a three-dimensional salt PCPs material (PCP1). After the The analysis of crystal structure, there are one-dimensional pores in the c direction on the PCP1 structure, and there are a large number of water molecules in the channels of the object, using this feature, we conducted a proton conducting experiment on it. The experiment is in the relative humidity of 97%, temperature conditions for relative humidity and in. 97%, the temperature of 95 DEG C measured its conductivity is 1.81 * 10-5 Scm-1. the experimental results show that in high humidity environment in PCP1 with proton conduction ability. In addition, we also found that the PCP1 framework began to collapse of the temperature is 410 DEG C, and in P H in the range of 2-13 and some of the common organic solvents, PCP1 can maintain good structural stability, therefore, can be expressed as PCP1.[Cd_ has excellent thermal and chemical stability of the (0.5) (TPY)] - 0.75H_2O (PCP1) tpy=2- (1H-1,2,4-Triazol-5-yl) pyrazine (two) we use the aza multicarboxyl ligand (TDA) and 2,2 '- bipyridine and Phenanthroline 1,10- using mixed ligand experiment, by solvothermal method, constructed the MOFs materials of two cases are isomorphic with Cd ions (MOF1 and MOF2). The two cases of MOFs materials are made one dimensional chain structure through multiple stacking interaction to form three-dimensional coordination polymer material. We conducted experiments of stability test for them, the experimental results show that MOF1 and MOF2 can keep good stability in the range of P and H=2-12 in common organic solvents, which showed that the two cases of MOFs with chemical materials good stability. In addition, found by thermogravimetric analysis, the isomorphism of two compounds have smaller differences in heat stable temperature, comparing their structures can be found, the difference generated by the second ligand stacking interaction between.Cd (TD A (2,2) -Dipy) (MOF1) Cd (TDA) (1,10-phen) (MOF2) tda=3,3'- (1H-1,2,4-triazole-3,5-diyl) dibenzoic acid2,2 '-Dipy=2,2' -Dipyridyl1,10-phen=1,10-Phenanthroline monohydrate (three) we selected three teeth ligands TCPB a three fold symmetry respectively with Zn ions, Co ions and Cd ions by solvothermal synthesis building three cases of MOFs. MOF5 is the material with three-dimensional MOFs material three interpenetrating structure. Another two cases were (MOF3 and MOF4) is a two-dimensional network structure, and through the structure analysis found that MOF3 and MOF4 are isomorphic structure. We carried out solid fluorescence test on three cases of the MOFs materials, find the maximum emission the solid fluorescence emission peak of the peak compared with the pure organic ligands are.[Cd_ redshift larger (1.5) (TCPB) (DMF) (H_2O)] (MOF3) Co_ (1.5) (TCPB) (DMF)) 2] 3DMF (MOF4) [Zn (Htcpb) (4,4'-bpy) (0.5 _)] 1.5H_2O (MOF5) tcpb=1,3,5-tris (4-carbonylphenyloxy) benzene4,4'-bpy=4,4'-Dipyridyl

【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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