火炸药学报

为了探讨富勒烯(C₇₀)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C₇₀团簇分子的相互作用,分析了UDMH在C₇₀表面的吸附行为及分解路径,计算获得了UDMH在C₇₀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C₇₀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,C₇₀分子的加入并未改变UDMH分解的初始和次级反应位点,在与NO₂抽氢反应时表现为在NH₂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19.4kJ/mol、21.1kJ/mol,反应热分别降低了24.2kJ/mol和27kJ/mol。因此,C₇₀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(C₇₀)as a catalyst for the decomposition of unsymmetrical dimethylhydrazine(UDMH)propellants, the interactions between UDMH molecules and C₇₀ cluster molecules were conducted using the density functional theory(DFT). The adsorption behavior and decomposition path of UDMH on C₇₀ surface were analyzed. The activation energy and reaction heats of the hydrogen extraction reaction of UDMH in the presence of C₇₀ were calculated and obtained. The results show that UDMH molecules exhibit two adsorptin configurations on the surface of C₇₀, mainly undergoing physical adsorption with relatively low adsorption energy. The addition of C₇₀ molecules does not change the initial and secondary reaction site of UDMH decomposition, but exhibites sequential occurrence on the NH₂ groups during the hydrogen extraction reaction with NO₂. Compared with the decomposition of pure UDMH, the activation energy of the initial elementary reaction of UDMH decomposition in two adsorption configurations decrease by 19.4kJ/mol and 21.1kJ/mol, respectively, and the heat of reaction reduces by 24.2kJ/mol and 27kJ/mol, respectively. Therefore, C₇₀ has catalytic ability for the first two steps of UDMH decomposition, promoting the decomposition of UDMH.

引言
1 计算方法
2 结果与讨论
3 结论

图1 C70和UDMH的三维结构<br/>Fig.1 The three-dimensional structures of C70 and UDMH

图1 C70和UDMH的三维结构
Fig.1 The three-dimensional structures of C70 and UDMH

图2 两种不同C70-UDMH吸附优化构型<br/>Fig.2 Two different kinds of optimized conformations of C70-UDMH

图2 两种不同C70-UDMH吸附优化构型
Fig.2 Two different kinds of optimized conformations of C70-UDMH

图3 各个结构的局域态密度图像<br/>Fig.3 Local density of states of different structures

图3 各个结构的局域态密度图像
Fig.3 Local density of states of different structures

图4 UDMH分解的两步基元反应结构示意图<br/>Fig.4 Schematic diagram of two-step elementary reaction structure for UDMH decomposition

图4 UDMH分解的两步基元反应结构示意图
Fig.4 Schematic diagram of two-step elementary reaction structure for UDMH decomposition

图5 UDMH分解的两步基元反应的能量曲线<br/>Fig.5 Energetic profiles of two-step elementary reaction for UDMH decomposition

图5 UDMH分解的两步基元反应的能量曲线
Fig.5 Energetic profiles of two-step elementary reaction for UDMH decomposition

图6 两种吸附体系中UDMH分解的基元反应结构图<br/>Fig.6 The elementary reactions structuresdiagrams of UDMH decomposition in two adsorption systems

图6 两种吸附体系中UDMH分解的基元反应结构图
Fig.6 The elementary reactions structuresdiagrams of UDMH decomposition in two adsorption systems

图7 不同吸附构型UDMH分解的基元反应能量曲线<br/>Fig.7 Energetic curves of the elementary reactions for UDMH decomposition in different adsorption systems

图7 不同吸附构型UDMH分解的基元反应能量曲线
Fig.7 Energetic curves of the elementary reactions for UDMH decomposition in different adsorption systems

表1 纯UDMH体系以及两种C70体系中UDMH分解基元反应的活化能及反应热<br/>Table 1 Activation energies and heat of reaction of the elementary reactions for UDMH decomposition in the pure UDMH system and in two C70 systems

表1 纯UDMH体系以及两种C70体系中UDMH分解基元反应的活化能及反应热
Table 1 Activation energies and heat of reaction of the elementary reactions for UDMH decomposition in the pure UDMH system and in two C70 systems

图8 纯UDMH与C70-UDMH体系中前两步抽氢反应的能量曲线<br/>Fig.8 Energetic curves of the first two steps of hydrogen extraction reaction in the pure UDMH and C70-UDMH systemsC70

图8 纯UDMH与C70-UDMH体系中前两步抽氢反应的能量曲线
Fig.8 Energetic curves of the first two steps of hydrogen extraction reaction in the pure UDMH and C70-UDMH systemsC70

表2 纯UDMH、C70及两种吸附体系的Mulliken电荷<br/>Table 2 Mulliken charges of pure UDMH, C70 and two adsorption systems

表2 纯UDMH、C70及两种吸附体系的Mulliken电荷
Table 2 Mulliken charges of pure UDMH, C70 and two adsorption systems

表3 UDMH以及分解反应中间体中N原子与C70中一个C原子的距离<br/>Table 3 Distances between N atoms in UDMH and its decomposition reaction intermediates and one C atom in C70

表3 UDMH以及分解反应中间体中N原子与C70中一个C原子的距离
Table 3 Distances between N atoms in UDMH and its decomposition reaction intermediates and one C atom in C70

图9 (a～f)UDMH及其分解反应中间体; (g)、(h)测距时参考C70选定的C原子<br/>Fig.9 (a—f)UDMH and its intermediates of decomposition reactions; (g)、(h)C atoms selected with reference to C70 during ranging

图9 (a～f)UDMH及其分解反应中间体; (g)、(h)测距时参考C70选定的C原子
Fig.9 (a—f)UDMH and its intermediates of decomposition reactions; (g)、(h)C atoms selected with reference to C70 during ranging

表4 UDMH分解过程中部分化学键键长<br/>Table 4 Partial chemical bond lengths during UDMH decomposition process

表4 UDMH分解过程中部分化学键键长
Table 4 Partial chemical bond lengths during UDMH decomposition process

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备注

引言

1 计算方法

2 结果与讨论

3 结论

期刊信息

备注

引言

1 计算方法

2 结果与讨论

3 结 论

期刊信息

3 结论