Dong Wen-Shuai, Cao Wen-Li, Tariq Qamar-Un-Nisa, Wu Xiao-Wei, Hu Yong, Zhang Chao, Zhang Jian-Guo
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, P. R. China.
Dalton Trans. 2022 Jun 27;51(25):9894-9904. doi: 10.1039/d2dt00593j.
Two bimetallic complexes of 4-hydroxy-3,5-dinitropyrazole, [KMn(DNPO)(HO)]·2HO (BMEP-1) and [KZn(DNPO)(HO)] (BMEP-2), were synthesized and characterized by IR spectroscopy and elemental analysis. The crystal structures of BMEP-1 and BMEP-2 were determined by single-crystal X-ray diffraction. It is noteworthy that these complexes presented different metal-organic frameworks. The thermal behaviors of BMEP-1 and BMEP-2 were investigated by differential scanning calorimetry and thermogravimetric analysis measurements. These bimetallic complexes exhibited high thermal stability (348.0 °C and 331.0 °C) due to their large coordination bonds and three-dimensional interconnected structure. The catalytic performances of BMEP-1 and BMEP-2 on the thermal decomposition of ammonium perchlorate were investigated by TGA-DSC, TGA-FTIR, and non-isothermal kinetic analyses. The results showed that BMEP-1 and BMEP-2 exhibited excellent catalytic performance in the thermal decomposition of ammonium perchlorate. Notably, there was only a single exothermic peak at 302.6 °C and 318.6 °C, and the activation energy values of ammonium perchlorate decreased to 123.88 kJ mol and 128.43 kJ mol, respectively. TGA-FTIR results showed that BMEP-1 and BMEP-2, as effective components of catalysis, will promote the production of HO, NO, NO, and HCl in advance, during the thermal decomposition of ammonium perchlorate. BMEP-1 and BMEP-2 are expected to be two candidate additives for the catalytic decomposition of ammonium perchlorate in composite solid propellants.
合成了4-羟基-3,5-二硝基吡唑的两种双金属配合物[KMn(DNPO)(H₂O)]·2H₂O(BMEP-1)和[KZn(DNPO)(H₂O)](BMEP-2),并通过红外光谱和元素分析对其进行了表征。通过单晶X射线衍射测定了BMEP-1和BMEP-2的晶体结构。值得注意的是,这些配合物呈现出不同的金属有机骨架。通过差示扫描量热法和热重分析测量研究了BMEP-1和BMEP-2的热行为。由于其较大的配位键和三维互连结构,这些双金属配合物表现出高热稳定性(348.0℃和331.0℃)。通过TGA-DSC、TGA-FTIR和非等温动力学分析研究了BMEP-1和BMEP-2对高氯酸铵热分解的催化性能。结果表明,BMEP-1和BMEP-2在高氯酸铵热分解中表现出优异的催化性能。值得注意的是,在302.6℃和318.6℃仅出现一个放热峰,高氯酸铵的活化能值分别降至123.88 kJ·mol⁻¹和128.43 kJ·mol⁻¹。TGA-FTIR结果表明,BMEP-1和BMEP-2作为有效的催化成分,在高氯酸铵热分解过程中会提前促进HO、NO、NO₂和HCl的产生。BMEP-1和BMEP-2有望成为复合固体推进剂中高氯酸铵催化分解的两种候选添加剂。