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低温等离子体作用下亮氨酸转化路径的密度泛函理论研究

李月慧 李先春 孟繁锐 王晴 王焕然 葛玉洁

李月慧, 李先春, 孟繁锐, 王晴, 王焕然, 葛玉洁. 低温等离子体作用下亮氨酸转化路径的密度泛函理论研究[J]. 燃料化学学报(中英文), 2021, 49(2): 247-256. doi: 10.19906/j.cnki.JFCT.2021038
引用本文: 李月慧, 李先春, 孟繁锐, 王晴, 王焕然, 葛玉洁. 低温等离子体作用下亮氨酸转化路径的密度泛函理论研究[J]. 燃料化学学报(中英文), 2021, 49(2): 247-256. doi: 10.19906/j.cnki.JFCT.2021038
LI Yue-hui, LI Xian-chun, MENG Fan-rui, WANG Qing, WANG Huan-ran, GE Yu-jie. Density functional theory study on the conversion path of leucine by non-thermal plasma[J]. Journal of Fuel Chemistry and Technology, 2021, 49(2): 247-256. doi: 10.19906/j.cnki.JFCT.2021038
Citation: LI Yue-hui, LI Xian-chun, MENG Fan-rui, WANG Qing, WANG Huan-ran, GE Yu-jie. Density functional theory study on the conversion path of leucine by non-thermal plasma[J]. Journal of Fuel Chemistry and Technology, 2021, 49(2): 247-256. doi: 10.19906/j.cnki.JFCT.2021038

低温等离子体作用下亮氨酸转化路径的密度泛函理论研究

doi: 10.19906/j.cnki.JFCT.2021038
基金项目: 国家重点联合基金项目(U1910215)资助
详细信息
    作者简介:

    李先春:Tel:15141212188,Email:xianchunli@ustl.edu.cn

    通讯作者:

    E-mail:xianchunli@ustl.edu.cn

  • 中图分类号: X705

Density functional theory study on the conversion path of leucine by non-thermal plasma

Funds: The project was supported by the National Kay Joint Foundation of China (U1910215)
  • 摘要: 目前低温等离子体技术在处理固体废弃物方面已得到广泛关注,本研究基于密度泛函理论(DFT),在B3LYP/6-31G (d, p) 的水平上模拟计算了污泥中蛋白质模型化合物亮氨酸(LEU)在低温等离子体中的转化路径,包括脱氨优先机理、脱羧优先机理、其余C−C键断裂优先机理等七条主要路径。结果表明,亮氨酸易脱除氨基、羧基生成C5H10,再进一步分解成小分子烃。产物CO2来自羧基;生成CO的反应势垒相对较高,但CO2易在等离子体中被电离成CO从而提高CO的产量;小自由基的相互结合及其他小分子的分解生成CH4和H2。所有路径所需的能量均在低温等离子体高能电子能量的最大值范围内。
  • 图  1  亮氨酸的初步分解路径及其分子构型

    (a): deamination priority mechanisms; (b): decarboxylation priority mechanisms; (c): the remaining C−C bond breaking priority mechanisms

    Figure  1  Leucine preliminary decomposition pathway and its molecular configuration

    图  2  反应过程中键的演化

    Figure  2  Evolution of the selected bonds in the reaction

    图  3  脱NH3优先机理反应路径

    Figure  3  Reaction pathway of NH3 removal priority mechanism

    图  4  C5H9OH反应路径

    Figure  4  Reaction pathway of C5H9OH

    图  5  脱NH2·优先机理反应路径

    Figure  5  Reaction pathway of NH2·removal priority mechanism

    图  6  1-C6H11O2·和2-C6H11O2·的前线轨道

    Figure  6  Front-line orbits of 1-C6H11O2·and 2-C6H11O2·

    图  7  脱CO2优先机理反应路径

    Figure  7  Pathway of CO2 removal priority mechanism

    图  8  脱COOH·优先机理反应路径

    Figure  8  Pathway of COOH·removal priority mechanism

    图  9  C5H10反应路径

    Figure  9  Reaction pathway of C5H9 decomposition

    图  10  C5H9·, C4H6·反应路径

    Figure  10  Reaction pathway of C5H9·, C4H6·

    图  11  脱CH3·优先机理反应路径

    Figure  11  Reaction pathway of CH3·removal priority mechanism

    图  12  C1,2键优先断裂反应路径

    Figure  12  Reaction pathway of C1, 2 bond priority break

    图  13  CH3NO的反应路径

    Figure  13  Reaction pathway of CH3NO decomposition

    图  14  C4H10的反应路径

    Figure  14  Reaction pathway of C4H10

    图  15  i-C3H7的反应路径

    Figure  15  Reaction pathway of i-C3H7

    图  16  C(1)−H(9)和C(7)−H(9)键演变与能量关系

    Figure  16  Relationship between C(1)−H(9) and C(7)−H(9) bond evolution and the located energy

    图  17  C2−4键断裂优先机理反应路径

    Figure  17  Reaction pathway of C2−4 bond break in priority

    图  18  亮氨酸的反应路径图

    Figure  18  Reaction pathway of leucine

    表  1  生成小分子烃的反应焓

    Table  1  Reaction enthalpies of the formation of Small molecule hydrocarbon

    ReactionsThis work/(kJ·mol−1)References/(kJ·mol−1)
    CH3. + H.→CH4−430.9−434.7[22],−438.5[31]a
    C2H3. + H.→C2H4−459.9−453.5[22],−454.8[32]a
    CH3. + CH3.→C2H6−349.5−361.1[22],−366.1[33]a
    C2H5. + H.→C2H6−421.7−414.2[22],−410.9[31]a
    a: experiment result
    下载: 导出CSV
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  • 收稿日期:  2020-10-10
  • 修回日期:  2020-11-20
  • 刊出日期:  2021-02-08

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