密度泛函理论研究富勒烯C_(70)对偏二甲肼与NO_(2)的抽氢反应机制  

Density Functional Theory Study on the Hydrogen Extraction Reaction Mechanism of Unsymmetrical Dimethylhydrazine with NO_(2)Affected by Fullerenes C_(70)

作　　者：赵子航 慕晓刚 王生辉 马海霞[1,2] ZHAO Zi-hang;MU Xiao-gang;WANG Sheng-hui;MA Hai-xia(School of Chemical Engineering,Northwest University/Xi′an Key Laboratory of Special Energetic Materials,Xi′an 710069,China;Rocket Force University of Engineering,Xi′an 710025,China)

机构地区：[1]西北大学化工学院/西安市特种能源材料重点实验室,陕西西安710069 [2]火箭军工程大学,陕西西安710025

出　　处：《火炸药学报》2024年第3期237-244,I0004,共9页Chinese Journal of Explosives & Propellants

基　　金：陕西省重点科技创新团队计划项目(No.2022TD-33)。

摘　　要：为了探讨富勒烯(C_(70))作为催化剂用于偏二甲肼(UDMH)推进剂分解的可行性,采用密度泛函理论(DFT)研究了UDMH分子与C_(70)团簇分子的相互作用,分析了UDMH在C_(70)表面的吸附行为及分解路径,计算获得了UDMH在C_(70)存在时发生抽氢反应的活化能和反应热。结果表明,UDMH分子在C_(70)表面表现为两种吸附构型,主要发生物理吸附且吸附能较小,C_(70)分子的加入并未改变UDMH分解的初始和次级反应位点,在与NO_(2)抽氢反应时表现为在NH _(2)基团上依次发生。与纯UDMH分解相比,A、B两种吸附构型中UDMH分解初始基元反应的反应活化能分别下降了19.4 kJ/mol、21.1 kJ/mol,反应热分别降低了24.2 kJ/mol和27 kJ/mol。因此,C_(70)对于UDMH分解的前两步反应具有催化能力,能够促进UDMH的分解。To explore the feasibility of using fullerenes(C_(70))as a catalyst for the decomposition of unsymmetrical dimethylhydrazine(UDMH)propellants,the interactions between UDMH molecules and C_(70)cluster molecules were conducted using the density functional theory(DFT).The adsorption behavior and decomposition path of UDMH on C_(70)surface were analyzed.The activation energy and reaction heats of the hydrogen extraction reaction of UDMH in the presence of C_(70)were calculated and obtained.The results show that UDMH molecules exhibit two adsorptin configurations on the surface of C_(70),mainly undergoing physical adsorption with relatively low adsorption energy.The addition of C_(70)molecules does not change the initial and secondary reaction site of UDMH decomposition,but exhibites sequential occurrence on the NH _(2) groups during the hydrogen extraction reaction with NO_(2).Compared with the decomposition of pure UDMH,the activation energy of the initial elementary reaction of UDMH decomposition in two adsorption configurations decrease by 19.4 kJ/mol and 21.1 kJ/mol,respectively,and the heat of reaction reduces by 24.2 kJ/mol and 27 kJ/mol,respectively.Therefore,C_(70)has catalytic ability for the first two steps of UDMH decomposition,promoting the decomposition of UDMH.

关 键 词：量子化学 富勒烯C_(70) 偏二甲肼 UDMH 密度泛函理论 DFT 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O641[理学—物理化学]