四唑基呋咱类HE-MOFs的分子设计、表征及性能研究

发布时间：2018-03-08 08:58

  本文选题：高能金属有机骨架化合物　切入点：3-氨基-4-(四唑-5-基)呋咱　出处：《中北大学》2017年硕士论文　论文类型：学位论文

【摘要】：高能金属有机骨架化合物(HE-MOFs)是近年来相当热门的一类新型材料,因为其具有体系稳定、结构可控、性能可修饰等多种性能优势,而且有着较高的密度、良好的热稳定性、卓越的机械强度和硬度等。故在含能材料领域有着很好的发展潜力和应用前景。本研究旨在探索新型低感的HE-MOFs,主要研究内容包括以下两个部分:第一,选择氮含量高(N%=64.05%)且配位能力强的3-氨基-4-(四唑-5-基)呋咱(HAFT)作为含能配体。以六配位的Cd作为中心金属离子,基于配位化学的理论进行分子设计并合成不同维度的HE-Cd-MOFs,通过缓慢溶剂挥发法培养得到了三种晶体:NH4AFT、[Cd(H2O)2(AFT)2]n和[Cd(N2H4)(AFT)2·0.7H2O]n。采用X-单晶衍射仪对三种单晶的晶体结构进行研究,在分子水平上明确了配体HAFT与金属离子Cd的配位方式,其中[Cd(H2O)2(AFT)2]n为2D平面结构,属于单斜晶系,空间群为P21/c,晶体密度高达2.252 g-cm-3;用双齿配位的N2H4去取代[Cd(H2O)2(AFT)2]n中的配位水分子以期得到更加复杂的HE-Cd-MOFs的晶体结构,但最终得到的[Cd(N2H4)(AFT)2·0.7H2O]n体结构表明,其为1D链状结构,也属于单斜晶系,空间群为C2/c,晶体密度为2.026g·cm-3,略低于[Cd(H2O)2(AFT)2]n。这是由于肼分子的键太短,只能在骨架内部将两个中心Cd离子连接起来。对所得HE-Cd-MOFs进行热分析,计算得到其非等温动力学参数、热爆炸临界温度及爆炸性能等综合参数,其中,[Cd(N2H4)(AFT)2·0.7H2O]n(Teo= 308.5℃)具有极好的热稳定性,这可能是由于在Cd2+和AFT-桥接成的链状结构间隙中N2H4再次将两个Cd2+中心离子连接起来,使得其结构更加稳固。第二,以具有六配位能力的Zn、Cu代替重金属元素Cd作为中心金属离子,进行分子设计以期得到绿色环保型的HE-Zn/Cu-MOFs。对其进行热分析研究,并计算其非等温动力学参数、热爆炸临界温度等参数。其中,HE-Zn-MOFs(TM=300.1℃)的热稳定性优于 HE-Cu-MOFs(Teo=256.8℃)。因此,以HAFT作为含能桥联配体合成的HE-MOFs既表现出了较好的热稳定性,又表现出较低的撞击感度(40J),并且可以通过分子设计合成不同维度的HE-MOFs,所以在追求高能量低感度的含能材料领域中具有较高的研究价值。
[Abstract]:HE-MOFs, a high energy organometallic skeleton compound, is a new kind of material which is very popular in recent years, because it has the advantages of stable system, controllable structure, modifiable performance, high density and good thermal stability. Because of its excellent mechanical strength and hardness, this study has great potential and application prospects in the field of energetic materials. This study aims to explore a new type of low sensitivity HE-MOFs, the main contents of which include the following two parts: first, The 3-amino-4-( tetrazole-5-yl) furazan (3-amino-4-furoxan) with a high nitrogen content of 64.05) was selected as the energetic ligand. The hexagonal CD was used as the central metal ion. Based on the theory of coordination chemistry, the molecular design and synthesis of HE-Cd-MOFs with different dimensions were carried out. Three kinds of crystals were obtained by slow solvent volatilization method. The crystal structures of the three crystals were studied by means of X- single crystal diffractometer, [Cd(H2O)2(AFT)2] n and [Cd(N2H4)(AFT)2 路0.7H2O] n. At the molecular level, the coordination mode of the ligand HAFT with the metal ion CD was clarified. [Cd(H2O)2(AFT)2] n is a 2D planar structure and belongs to monoclinic system. The space group is P21 / c and the crystal density is up to 2.252g-cm-3.The didentate coordination N2H4 is used to replace the coordination water molecule in [Cd(H2O)2(AFT)2] n in order to obtain the more complex crystal structure of HE-Cd-MOFs, but the resulting structure of [Cd(N2H4)(AFT)2 路0.7H2O] n shows that it is a 1D chain structure and belongs to monoclinic crystal system. The space group is C _ 2 / c, and the crystal density is 2.026 g 路cm ~ (-3), which is slightly lower than [Cd(H2O)2(AFT)2] n. This is because the bond of hydrazine molecule is so short that the two central CD ions can only be connected inside the skeleton. The thermal analysis of the obtained HE-Cd-MOFs is carried out and the non-isothermal kinetic parameters are calculated. The thermal explosion critical temperature and explosion properties, among which [Cd(N2H4)(AFT)2 路0.7H2O] nteo = 308.5 鈩，

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