论文部分内容阅读
用硫酸镍与碳酰肼(CHZ)反应,制备得到一种新型含能配合物[Ni(CHZ)3]SO4·3H2O,通过X射线单晶衍射,元素分析和傅立叶变换红外(FTIR)光谱对其进行了表征.晶体结构测试表明,该化合物晶体属于三斜晶系,P1空间群,a=0.85237(1)nm,b=0.90964(1)nm,c=1.22559(2)nm,β=96.731(2)°,V=0.8849(2)nm3,Z=2,Dc=1.798g·cm-3.在该配合物分子中,碳酰肼作为双齿配体,以羰基O原子和端基N原子与Ni2+离子发生配位,形成3个相互垂直的五元平面螯合环.在氢键、静电引力和范德华力的作用下,该配合物形成了复杂的三维网状结构.对碳酰肼分子进行了DFT-B3LYP/6-311+G**量化计算研究,得到其NBO电荷,从理论上说明碳酰肼的配位点是羰基O原子和端基N原子.采用DSC、TG-DTG和FTIR光谱技术对目标化合物的热分解机理进行了研究,并用Kissinger法和Ozawa-Doyle法对其热分解过程中两个放热峰的非等温反应动力学参数进行了计算.结果表明,该配合物具有较高的能量和良好的热稳定性.
A novel energetic complex [Ni (CHZ) 3] SO4 · 3H2O was prepared by the reaction of nickel sulfate with carbohydrazide (CHZ). XRD, elemental analysis and Fourier transform infrared spectroscopy (FTIR) The crystal structure of the compound belongs to triclinic system with a = 0.85237 (1) nm, b = 0.90964 (1) nm, c = 1.22559 (2) nm and β = 96.731 (2) °, V = 0.8849 (2) nm3, Z = 2, Dc = 1.798g · cm-3. In the complex molecule, the carbohydrazide acts as a bidentate ligand with carbonyl O atom and terminal N The atoms coordinate with Ni2 + ions to form three perpendicular five-membered chelating rings, which formed a complex three-dimensional network structure under the action of hydrogen bonding, electrostatic attraction and van der Waals forces. The calculation of the DFT-B3LYP / 6-311 + G ** quantification results in the NBO charge of the molecule, which theoretically shows that the coordination point of the carbonyl hydrazide is the carbonyl O atom and the terminal N atom. Using DSC, TG-DTG And FTIR spectroscopy were used to study the thermal decomposition mechanism of the target compounds. The Kissinger method and Ozawa-Doyle method were used to calculate the non-isothermal reaction kinetic parameters of the two exothermic peaks during the thermal decomposition process. The complex has high energy and good thermal stability.