Jiang Liping, Fu Xiaolong, Jiang Jun, Li Jizhen, Xie Wuxi, Zhao Xitong, Guo Tao, Fan Xuezhong
Xi'an Modern Chemistry Research Institute, Xi'an 710065, China.
ACS Omega. 2022 Jul 12;7(29):25732-25740. doi: 10.1021/acsomega.2c03026. eCollection 2022 Jul 26.
Four ,-dimethylaminomethylferrocene polynitrogen catalysts were applied to the thermal decomposition of FOX-12, and their catalytic effect on FOX-12 was investigated by TG-DSC. The kinetic parameters and kinetic model of the mixed system were revealed by the Kissinger method, Freidman method, and combined kinetic analysis. The results showed that MAFcTAZ is the catalyst with the strongest effect on FOX-12, the decomposition peak temperature of FOX-12 is reduced, and the decomposition weight loss is higher than those for other catalysts, which prove that the decomposition of FOX-12 is more thorough under the catalysis of MAFcTAZ. The introduction of the four catalysts reduced the thermal decomposition peak temperature of FOX-12. MAFcTAZ was the most active catalyst for the decomposition of FOX-12, and the maximum heat release of catalyzing the decomposition of FOX-12 can reach 1236.76 J·g. The activation energy ( ) of FOX-12 decomposition decreased from 217.91 to 128.19, 137.85, 157.65, and 151.91 kJ·mol under the effect of MAFcNO, MAFcPA, MAFcNTO, and MAFcTAZ. The Freidman analysis illustrated that MAFcTAZ reduced the activation energy during the entire decomposition process of FOX-12. The physical model of the decomposition reaction of FOX-12 transformed from the random nucleation and two-dimensional growth of nuclei model (A2) to the random scission model (L2) in the presence of MAFcNO and two-dimensional diffusion (D2) under the effect of MAFcPA, MAFcNTO, and MAFcTAZ. By analyzing the molecular structures, MAFcTAZ has a higher iron content and nitrogen content, which are the essence of its excellent catalytic performance. From the perspective of interaction energy, the strong catalytic effect of MAFcTAZ is attributed to its large interaction energy with FOX-12 by energy decomposition analysis.
将四种二甲基氨基甲基二茂铁多氮催化剂应用于FOX-12的热分解反应，并通过TG-DSC研究了它们对FOX-12的催化作用。采用基辛格法、弗里德曼法和联合动力学分析揭示了混合体系的动力学参数和动力学模型。结果表明，MAFcTAZ是对FOX-12催化效果最强的催化剂，FOX-12的分解峰值温度降低，且分解失重高于其他催化剂，这证明在MAFcTAZ催化下FOX-12的分解更彻底。四种催化剂的引入均降低了FOX-12的热分解峰值温度。MAFcTAZ是分解FOX-12最具活性的催化剂，催化FOX-12分解的最大热释放量可达1236.76 J·g。在MAFcNO、MAFcPA、MAFcNTO和MAFcTAZ的作用下，FOX-12分解的活化能(E)从217.91降至128.19、137.85、157.65和151.91 kJ·mol。弗里德曼分析表明，MAFcTAZ在FOX-12的整个分解过程中降低了活化能。在MAFcNO存在下，FOX-12分解反应的物理模型从随机成核和二维核生长模型(A2)转变为随机断裂模型(L2)；在MAFcPA、MAFcNTO和MAFcTAZ的作用下转变为二维扩散模型(D2)。通过分析分子结构，MAFcTAZ具有较高的铁含量和氮含量，这是其优异催化性能的本质。从相互作用能的角度来看，通过能量分解分析，MAFcTAZ的强催化作用归因于其与FOX-12的大相互作用能。
