高氯酸铵热分解机理的密度泛函理论研究

doi:10.6023/A23020056

摘要/Abstract

深入理解高氯酸铵的热分解机理, 对于优化固体推进剂配方设计十分重要. 我们采用对称破缺密度泛函方法 (BS-UB3LYP/6-311＋G(d,p)), 对高氯酸铵的热分解机理进行了系统的梳理和深入研究. 首先, 高氯酸铵通过质子转移, 生成HClO₄和NH₃, 从吸附态进入气相. 进而高氯酸的Cl—OH键均裂, 生成羟基自由基•OH和三氧化氯自由基•ClO₃, 它们优先和NH₃反应, 生成•NH₂. •NH₂和HClO₄反应生成•ClO₄自由基, 进而和NH₃反应生成H₂NO, 再被自由基物种拔H生成NO. NO和•OH反应生成NO₂, 和•NH₂及•OH反应生成N₂O. 这些产物与诸多实验观测结果一致.

关键词: 高氯酸铵, 热分解机理, broken-symmetry density functional theory (BS-UDFT), 开壳层单重态双自由基, 固体推进剂

The thermal decomposition characteristics of ammonium perchlorate (AP) have a great influence on the performance of solid propellant. Although a large number of mechanistic studies have been published over the past few decades, there is no unified understanding of the decomposition yet, and the overall mechanism pathway is still unclear. In the present work, the thermal decomposition pathways of AP were studied systematically using broken-symmetry density functional theory method (BS-UB3LYP/6-311＋G(d,p). This method can describe the homo-cleavage process of covalent bond well, and locate the transition state with singlet-diradical characteristics. Compared with typical multireference method, broken- symmetry density functional theory (BS-UDFT) can give good results and is much faster, and therefore is highly convenient for practical application. The results show that, the overall thermal decomposition pathway under the experimental conditions is initiated by the proton transfer between NH₄⁺ cation and ClO₄⁻ anion, leading to neutral NH₃ and HClO₄ molecules, which are absorbed on the AP surface and then escape to the gas phase. The second important step is the homolytic cleavage of the Cl—OH bond in HClO₄. The energy barrier is 67.5 kJ/mol under 620 K. Then, •OH radical and •ClO₃ radical react with NH₃ molecule, yielding •NH₂ radical. Then the •NH₂ radical react with HClO₄, leading to •ClO₄ radical, which reacts with NH₃, leading to the oxidized species H₂NO. The radical species, such as •OH, •NH₂, •ClO and so on, abstract the H atom of H₂NO, yielding NO. NO reacts with •OH radical, leading to NO₂; NO reacts with •NH₂ radical and •OH radical, leading to N₂O. These products are consistent well with the experimental observations. Due to the complexity of the mechanisms, some strategies are used in this study: firstly, we concentrate on the reaction pathways of active species and the NH₃ and HClO₄ molecules, which exist in large amount; secondly, more reaction pathways involving the newly formed active species are considered.

Key words: ammonium perchlorate, thermal decomposition mechanism, broken-symmetry density functional theory (BS-UDFT), open-shell singlet diradical, solid propellant

引用此文

杨洁, 凌琳, 李玉学, 吕龙. 高氯酸铵热分解机理的密度泛函理论研究[J]. 化学学报, 2023, 81(4): 328-337.

Jie Yang, Lin Ling, Yuxue Li, Long Lu. Density Functional Theory Study on Thermal Decomposition Mechanisms of Ammonium Perchlorate[J]. Acta Chimica Sinica, 2023, 81(4): 328-337.

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图/表 18

图1. 高氯酸铵的热分解机理. a: 吸附态; g: 气态

Figure 1. The possible thermal decomposition mechanisms of ammonium perchlorate (AP). a: adsorption state; g: gaseous state

图2. 高氯酸铵的可能分解机理

Figure 2. The possible thermal decomposition mechanisms of ammonium perchlorate (AP)

图3. Path-b: AP的电子转移机理

Figure 3. Path-b: the electron transfer mechanism of AP

图4. Path-b: 高氯酸铵的质子转移过程. 能量单位: kJ/mol; 键长单位: nm

Figure 4. Path-b: the proton transfer process of ammonium perchlorate. Energies are in kJ/mol, and selected bond lengths are in nanometer (nm)

图5. Path-b中重要结构的几何构型. 键长单位: nm

Figure 5. Some optimized geometry structures on Path-b. The selected bond lengths are in nanometer (nm)

图6. Path-c: 高氯酸的热分解反应路径. 能量单位: kJ/mol; 键长单位: nm

Figure 6. Path-c: the thermal decomposition pathways of perchloric acid. Energies are in kJ/mol, and selected bond lengths are in nanometer (nm)

图7. Path-c上关键过渡态的结构和自旋密度分布图

Figure 7. The optimized structure of the transition states of Path-c and their spin density distribution

图8. Path-d和Path-e: 脱水机理的反应路径. 键长单位: nm

Figure 8. Path-d and Path-e: the pathway of dehydration mechanism. The selected bond lengths are in nanometer (nm)

图9. Path-f: ?OH自由基和NH3的反应路径. 键长单位: nm

Figure 9. Path-f: the reaction pathway of ?OH and NH3. The selected bond lengths are in nanometer (nm)

图10. Path-h: ?OH自由基和HClO4的反应路径. 键长单位: nm

Figure 10. Path-h: the reaction pathway of ?OH and HClO4. The selected bond lengths are in nanometer (nm)

图11. Path-g和Path-g': ?ClO3自由基和NH3的反应路径. 键长单位: nm

Figure 11. Path-g and Path-g': the reaction pathways of ?ClO3 and NH3. The selected bond lengths are in nanometer (nm)

图12. Path-i: ?ClO3和HClO4的反应路径. 键长单位: nm

Figure 12. Path-i: the reaction pathway of ?ClO3 and HClO4. The selected bond lengths are in nanometer (nm)

图13. Path-j: ?NH2自由基和HClO4的反应路径. 键长单位: nm

Figure 13. Path-j: the reaction pathway of ?NH2 and HClO4. The selected bond lengths are in nanometer (nm)

图14. Path-k~Path-m: 生成?NO的可能反应路径. 键长单位: nm

Figure 14. Path-k~Path-m: possible reaction pathways of ?NO formation. The selected bond lengths are in nanometer (nm)

图15. Path-n: 生成?NO2的可能反应路径. 键长单位: nm

Figure 15. Path-n: possible reaction pathways of ?NO2 formation. The selected bond lengths are in nanometer (nm)

图16. Path-n和Path-p: 生成N2O的可能反应路径. 键长单位: nm

Figure 16. Path-n and Path-p: possible reaction pathways of N2O formation. The selected bond lengths are in nanometer (nm)

图17. Path-q~Path-s: 生成N2的可能反应路径. 键长单位: nm

Figure 17. Path-q~Path-s: possible reaction pathways of N2 formation. The selected bond lengths are in nanometer (nm)

图18. 高氯酸铵总体分解机理的可能路径

Figure 18. The overall thermal decomposition mechanisms of ammonium perchlorate

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