本文選題：高能金屬有機(jī)骨架化合物　切入點(diǎn)：3-氨基-4-(四唑-5-基)呋咱　出處：《中北大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：高能金屬有機(jī)骨架化合物(HE-MOFs)是近年來(lái)相當(dāng)熱門的一類新型材料,因?yàn)槠渚哂畜w系穩(wěn)定、結(jié)構(gòu)可控、性能可修飾等多種性能優(yōu)勢(shì),而且有著較高的密度、良好的熱穩(wěn)定性、卓越的機(jī)械強(qiáng)度和硬度等。故在含能材料領(lǐng)域有著很好的發(fā)展?jié)摿蛻?yīng)用前景。本研究旨在探索新型低感的HE-MOFs,主要研究?jī)?nèi)容包括以下兩個(gè)部分:第一,選擇氮含量高(N%=64.05%)且配位能力強(qiáng)的3-氨基-4-(四唑-5-基)呋咱(HAFT)作為含能配體。以六配位的Cd作為中心金屬離子,基于配位化學(xué)的理論進(jìn)行分子設(shè)計(jì)并合成不同維度的HE-Cd-MOFs,通過(guò)緩慢溶劑揮發(fā)法培養(yǎng)得到了三種晶體:NH4AFT、[Cd(H2O)2(AFT)2]n和[Cd(N2H4)(AFT)2·0.7H2O]n。采用X-單晶衍射儀對(duì)三種單晶的晶體結(jié)構(gòu)進(jìn)行研究,在分子水平上明確了配體HAFT與金屬離子Cd的配位方式,其中[Cd(H2O)2(AFT)2]n為2D平面結(jié)構(gòu),屬于單斜晶系,空間群為P21/c,晶體密度高達(dá)2.252 g-cm-3;用雙齒配位的N2H4去取代[Cd(H2O)2(AFT)2]n中的配位水分子以期得到更加復(fù)雜的HE-Cd-MOFs的晶體結(jié)構(gòu),但最終得到的[Cd(N2H4)(AFT)2·0.7H2O]n體結(jié)構(gòu)表明,其為1D鏈狀結(jié)構(gòu),也屬于單斜晶系,空間群為C2/c,晶體密度為2.026g·cm-3,略低于[Cd(H2O)2(AFT)2]n。這是由于肼分子的鍵太短,只能在骨架內(nèi)部將兩個(gè)中心Cd離子連接起來(lái)。對(duì)所得HE-Cd-MOFs進(jìn)行熱分析,計(jì)算得到其非等溫動(dòng)力學(xué)參數(shù)、熱爆炸臨界溫度及爆炸性能等綜合參數(shù),其中,[Cd(N2H4)(AFT)2·0.7H2O]n(Teo= 308.5℃)具有極好的熱穩(wěn)定性,這可能是由于在Cd2+和AFT-橋接成的鏈狀結(jié)構(gòu)間隙中N2H4再次將兩個(gè)Cd2+中心離子連接起來(lái),使得其結(jié)構(gòu)更加穩(wěn)固。第二,以具有六配位能力的Zn、Cu代替重金屬元素Cd作為中心金屬離子,進(jìn)行分子設(shè)計(jì)以期得到綠色環(huán)保型的HE-Zn/Cu-MOFs。對(duì)其進(jìn)行熱分析研究,并計(jì)算其非等溫動(dòng)力學(xué)參數(shù)、熱爆炸臨界溫度等參數(shù)。其中,HE-Zn-MOFs(TM=300.1℃)的熱穩(wěn)定性優(yōu)于 HE-Cu-MOFs(Teo=256.8℃)。因此,以HAFT作為含能橋聯(lián)配體合成的HE-MOFs既表現(xiàn)出了較好的熱穩(wěn)定性,又表現(xiàn)出較低的撞擊感度(40J),并且可以通過(guò)分子設(shè)計(jì)合成不同維度的HE-MOFs,所以在追求高能量低感度的含能材料領(lǐng)域中具有較高的研究?jī)r(jià)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，

本文編號(hào)：1583223