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基于炔丙基与丁二炔生成第一个碳环的反应机理研究

张韦 宁硕 毛仕迪 杨喜历 陈朝辉 孟丽苹

张韦, 宁硕, 毛仕迪, 杨喜历, 陈朝辉, 孟丽苹. 基于炔丙基与丁二炔生成第一个碳环的反应机理研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60054-9
引用本文: 张韦, 宁硕, 毛仕迪, 杨喜历, 陈朝辉, 孟丽苹. 基于炔丙基与丁二炔生成第一个碳环的反应机理研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60054-9
ZHANG Wei, NING Shuo, MAO Shi-di, YANG Xi-li, CHEN Zhao-hui, Meng Li-ping. Study of the reaction mechanism based on the formation of the first carbocyclic ring from propargyl and diacetylene[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60054-9
Citation: ZHANG Wei, NING Shuo, MAO Shi-di, YANG Xi-li, CHEN Zhao-hui, Meng Li-ping. Study of the reaction mechanism based on the formation of the first carbocyclic ring from propargyl and diacetylene[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60054-9

基于炔丙基与丁二炔生成第一个碳环的反应机理研究

doi: 10.1016/S1872-5813(22)60054-9
基金项目: 国家自然科学基金(52166007)资助
详细信息
    通讯作者:

    E-mail: chenzhaohuiok@sina.com

  • 中图分类号: TQ517.1

Study of the reaction mechanism based on the formation of the first carbocyclic ring from propargyl and diacetylene

Funds: The project was supported by the National Natural Science Foundation of China (52166007).
  • 摘要: 第一碳环的形成是多环芳烃(PAHs)生成的关键速率控制步,探明第一碳环的生成机理对抑制PAHs生成至关重要。为探究第一碳环的生长过程,本文利用平均局部离子化能(ALIE)和静电势(ESP)预测反应发生的位点,基于密度泛函(DFT)方法和过渡态理论(TST),计算炔丙基(C3H3) + 丁二炔(C4H2)生成第一碳环的反应路径与化学动力学参数。结果表明:C3H3与C4H2加成反应形成五、六和七元环分子,其中五元环形成速率最快,六元环最慢。在第一碳环的生成过程中,H转移和闭环反应所需的活化能较大、反应速率缓慢,其决定了第一碳环的生长速率。各碳环上的H转移反应速率取决于碳环上的C原子数量,其中五元环最快,而六元环最慢。本研究完善了碳氢燃料燃烧过程中第一碳环生成的反应动力学和热力学数据,可为PAHs的生成及预测提供有力的理论依据。
  • 图  1  C3H3与C4H2的反应位点预测图(青色为C原子,白色为H原子)

    Figure  1  prediction of reaction sites of C3H3 and C4H2 (cyan is C atom, white is H atom)

    图  2  (a)C3H3(C1) + C4H2反应路径中反应物、产物、中间体和过渡态的几何构型;(b)C3H3(C1) + C4H2势能面(黑色表示路径1,绿色表示路径2,红色表示路径3)

    Figure  2  (a) geometry of reactants, products, intermediates and transition states in C3H3(C1) + C4H2 reaction path; (b) PES of C3H3(C1) + C4H2 (Black line is path 4, green line is path 5, and red line is path 6)

    图  3  (a)C3H3(C2) + C4H2反应路径中反应物、产物、中间体和过渡态的几何构型;(b)C3H3(C2) + C4H2势能面(红色表示路径4,黑色表示路径5,绿色表示路径6)

    Figure  3  geometry of reactants, products, intermediates and transition states in C3H3(C2) + C4H2 reaction path; (b) PES of C3H3(C2) + C4H2 (Green line is path 4, red line is path 5, and black line is path 6)

    图  4  关键反应速率

    Figure  4  rate of key elementary reactions

    图  5  6条路径的反应速率

    Figure  5  reaction rate of six paths

    表  1  由阿伦尼乌斯方程拟合的速率参数

    Table  1  Rate parameters by fitting the Arrhenius equation

    Reactionk(500)k(1500)k(2500)AnE
    C3H3(C1) + C4H2→CS13.0973E061.2206E094.0579E092.805E10−0.0237.46
    CS1→CS22.8566E034.8296E085.4526E091.342E110.0574.75
    CS2→CS37.7582E012.3325E098.3308E101.378E110.57103.32
    CS1→CS44.9170E−085.8639E041.6256E071.355E100.20172.13
    CS4→CS51.0545E−051.6020E075.1514E096.002E100.73169.96
    CS1→CS67.6005E−146.5020E043.0616E085.844E100.88251.26
    CS6→CS74.0193E107.3702E111.3944E124.624E110.2416.41
    CS7→CS85.7392E−031.0107E077.5059E081.074E110.17131.69
    C3H3(C2) + C4H2→CS94.5684E043.9849E082.5000E092.739E100.0456.38
    CS9→CS105.0747E093.8822E119.2917E112.525E120.0426.76
    CS10→CS111.4792E−046.0596E055.2423E071.909E100.09137.54
    CS11→CS121.8028E−032.2416E072.7569E098.041E090.73140.05
    CS10→CS138.5499E−101.0388E061.2311E092.239E110.64212.34
    CS13→CS141.8763E−161.1286E024.2175E054.182E100.10254.87
    CS14→CS151.3840E062.3066E101.7325E113.174E110.2858.65
    CS15→CS34.1674E038.6816E091.8110E111.566E110.5686.80
    CS10→CS162.4647E−109.4006E035.1025E062.479E100.11194.45
    CS16→CS52.2706E−035.2238E081.5198E117.397E081.62152.21
    下载: 导出CSV

    表  2  重要反应活化能计算值与文献值对比

    Table  2  The calculated values of important reaction activation energy compared with literature values

    /Calculated value /kJ/molLiterature value /kJ/mol
    C3H3(C1) + C4H235.035.1[33],37.2[14]
    C3H3(C2) + C4H244.144.7[33],39.8[14]
    H-transfer of six membered rings173.6,184.2186.0[32]
    H-transfer of five membered rings106.2,86.5106.8[13]
    下载: 导出CSV
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  • 收稿日期:  2022-06-11
  • 录用日期:  2022-07-08
  • 修回日期:  2022-07-06
  • 网络出版日期:  2022-07-28

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