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重质有机资源热解过程中自由基诱导反应的密度泛函理论研究

毕山松 郭啸晋 王波 徐祥 赵丽凤 刘清雅

毕山松, 郭啸晋, 王波, 徐祥, 赵丽凤, 刘清雅. 重质有机资源热解过程中自由基诱导反应的密度泛函理论研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60067-1
引用本文: 毕山松, 郭啸晋, 王波, 徐祥, 赵丽凤, 刘清雅. 重质有机资源热解过程中自由基诱导反应的密度泛函理论研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60067-1
BI Shan-song, GUO Xiao-jin, WANG Bo, XU Xiang, ZHAO Li-feng, LIU Qing-ya. A DFT simulation on induction reactions involved radicals during pyrolysis of heavy organics[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60067-1
Citation: BI Shan-song, GUO Xiao-jin, WANG Bo, XU Xiang, ZHAO Li-feng, LIU Qing-ya. A DFT simulation on induction reactions involved radicals during pyrolysis of heavy organics[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60067-1

重质有机资源热解过程中自由基诱导反应的密度泛函理论研究

doi: 10.1016/S1872-5813(21)60067-1
基金项目: 国家重点研发计划(2016YFB0600302)资助
详细信息
    作者简介:

    毕山松:bishansong@iet.cn

    通讯作者:

    Tel:+86-135-8165-0241,E-mail:guoxiaojin@iet.cn

  • 中图分类号: TQ511

A DFT simulation on induction reactions involved radicals during pyrolysis of heavy organics

Funds: The project was supported by the National Key R&D Program of China (2016YFB0600302)
  • 摘要: 以重质有机资源热解过程中的自由基反应为背景,为了探究自由基对共价键的诱导作用及其对共价键解离能的影响,采用基于密度泛函理论的研究方法,选择ωB97XD/6-31G**级别在Gaussian 09程序上对·CH3、·OH和·H分别诱导七类共价键反应过程的能量进行了理论计算。结果表明,空间位阻效应对自由基诱导反应能垒的影响占主要地位,共价键种类的影响相对次要;不存在·OH和·H的同基团诱导交换反应时,·OH诱导能垒比·H的高约40 kJ/mol,·CH3比·OH、·H的诱导能垒分别高约为50、90 kJ/mol;存在·OH或·H的同基团诱导交换反应时,会导致能垒约有70 kJ/mol的提高,在计算时应判断诱导反应的具体情况并加以修正。可以利用上述值估算不同共价键诱导反应的能垒。
  • 图  1  五种方法的计算耗时与计算精度

    Figure  1.  The calculation time and accuracy of five methods

    图  2  自由基诱导共价键的能量变化示意图

    Figure  2.  Schematic diagram of the free energy change of induction reaction between covalent bond and radical

    图  3  ·CH3诱导七种共价键的能量变化

    Figure  3.  Free energy change of seven covalent bonds induced by ·CH3

    (a): Cal−Cal; (b): Cal−Car; (c): Cal−H; (d): Car−H; (e): Cal−O;(f): Car−O; (g): O−H

    图  4  ·OH诱导七种共价键的能量变化

    Figure  4.  The free energy change of seven covalent bonds induced by ·OH

    (a): Cal−Cal; (b): Cal−Car; (c): Cal−H; (d): Car−H; (e): Cal−O; (f): Car−O; (g): O−H

    图  5  ·H诱导七种共价键的能量变化

    Figure  5.  The free energy change of seven covalent bonds induced by ·H

    (a): Cal−Cal; (b): Cal−Car; (c): Cal−H; (d): Car−H; (e): Cal−O; (f): Car−O; (g): O−H

    表  1  与自由基发生诱导反应的共价键

    Table  1.   The covalent bonds induced by free radicals

    Cal−Cal Bond
    CH3-CH3CH3-C2H5
    CH3-CH2PhCH3-CH2CH=CH2
    CH3-CH2OHHOCH2-C2H5
    HOCH2-CH2OHCH3-CH2OCH3
    Cal−Car Bond
    C2H5-C2H3CH3-Ph
    C2H5-PhnC3H7-Ph
    HOCH2-Ph
    Cal−H Bond
    H-CH3H-C2H5
    H-CH2C2H5
    (H-CH2-cyclopropane)

    (cyclobutene)

    (cyclopentane)

    (cyclohexane)
    H-CH2OH
    H-CH2CH=CH2
    Car−H Bond
    H-CH=CH2H-CH=CHCH3
    H-PhH-C(OH)=CH2

    (naphthalene-αH)

    (naphthalene-βH)
    Cal−O Bond
    HO-CH3HO-C2H5
    HO-CH2C2H5HO-CH2CH2OH
    HO-CH2PhCH3-OCH3
    C2H5-OC2H5CH3-OC2H5
    CH3-OPhC3H7-OC2H3
    Car−O Bond
    HO-PhC3H7O-C2H3
    CH3O-PhC2H5O-Ph
    O−H Bond
    H-OCH3H-OC2H5
    H-OCH2C2H5H-OCH(CH3)2
    H-OPhH-OCH2Ph
    H-OPhOH(p)H-OPhCH3(p)
    下载: 导出CSV

    表  2  ·CH3诱导七种共价键的能垒范围和Gibbs能变化

    Table  2.   Range of energy barrier and the change of delta G of seven covalent bonds induced by ·CH3

    Bonds REB/(kJ·mol−1RDG/(kJ·mol−1
    Cal−Cal277.7−320.1(−64.7)−0.0
    Cal−Car322.7−351.334.4−59.5
    Cal−H108.7−149.5(−80.4)−0.0
    Car−H123.7−146.110.7−38.2
    Cal−O220.6−296.8133.9−0.0
    Car−O311.4−347.845.0−75.1
    O−H100.1−125.7(−95.6)−11.8
    下载: 导出CSV

    表  3  ·OH诱导七种共价键的能垒范围和Gibbs能变化

    Table  3.   The range of energy barrier and the change of delta G of seven covalent bonds induced by ·OH

    BondsREB/(kJ·mol−1RDG/(kJ·mol−1
    Cal−Cal227.8−264.2(−88.3)−(−23.6)
    Cal−Car270.8−295.2(−7.6)−35.9
    Cal−H63.8−92.9(−136.0)−(−55.5)
    Car−H82.5−92.8(−44.8)−(−17.4)
    Cal−O205.8−325.0ROH: 120.2−161.5
    R1OR2: (−157.5)−(−65.1)
    Car−O325.5−370.1200.2−243.7
    O−H53.6−73.6(−151.5)−(−67.3)
    下载: 导出CSV

    表  4  ·H诱导七种共价键的能垒范围和Gibbs能变化

    Table  4.   The range of energy barrier and the change of delta G of seven covalent bonds induced by ·H

    BondsREB/(kJ·mol−1RDG/(kJ·mol−1
    Cal−Cal207.1−238.2−152.8− −88.1
    Cal−Car235.9−265.2−43.8− −28.6
    Cal−H84.2−107.3−95.6− −15.2
    Car−H110.6−125.2−4.5−23.0
    Cal−O169.0−226.0−221.9− −104.9
    Car−O207.8−238.2−102.4− −44.8
    O−H82.5−105.9−142.8− −27.0
    下载: 导出CSV

    表  5  共价键的键解离能及诱导反应能垒

    Table  5.   The BDEs and the energy barriers of the induction reaction

    Types of the covalenceBDEs/(kJ·mol−1Energy barriers/(kJ·mol−1
    C−C BondCal−Cal·CH3·OH·H
    CH3-CH3377.4302.7260.1219.2
    CH3-C2H5370.3308.1261.2224.7
    CH3-CH2OH364.8301.6250.5219.7
    HOCH2-C2H5356.9320.1252.0237.1
    HOCH2-CH2OH358.2316.2227.8238.2
    CH3-CH2OCH3363.2277.7253.9207.1
    CH3-CH2C2H3317.6290.1245.8213.7
    CH3-CH2Ph319.7293.7250.1216.7
    Cal−Car
    C2H5-C2H3418.4338.1286.6254.6
    CH3-Ph426.8322.7284.5235.9
    C2H5-Ph419.2348.2295.2260.2
    nC3H7-Ph421.7351.3293.7261.8
    HOCH2-Ph413.4342.3270.8265.2
    C−H BondCal−H
    H-CH3439.3125.670.7102.8
    H-C2H5420.5122.166.893.6
    H−CH2C2H5422.2149.577.1106.2
    H−CH2-cyclopropane407.5137.485.5107.3
    cyclobutane405.0127.378.997.5
    cyclopentane400.0139.292.9106.9
    cyclohexane(chair form)416.3126.973.298.1
    H−CH2CH=CH2369.0108.763.884.2
    H−CH2OH401.9120.578.694.0
    Car−H
    H−CH=CH2465.3140.387.6117.4
    H−C(CH3)=CH2464.8134.482.5110.6
    H−C(OH)=CH2400.0123.783.4112.7
    H-Ph472.2144.490.9124.3
    naphthalene(αH)469.4146.192.8125.2
    naphthalene(βH)468.2143.491.3124.3
    C−O BondCal−O
    HO-CH3384.9268.6297.2180.5
    HO-C2H5391.2268.1290.3182.2
    HO-CH2C2H5392.0267.5293.6180.3
    HO-CH2Ph340.2244.2263.4169.0
    Cal−O·CH3·OH·H
    HO-CH2CH2OH338.9269.4294.1181.7
    CH3-OCH3349.8276.2253.3205.8
    CH3-OC2H5348.1274.8249.3204.9
    C2H5-OC2H5355.6296.8259.1226.0
    CH3-OPh268.6233.0205.8173.8
    C3H7-OC2H3274.1286.8238.4241.2
    Car−O
    HO-Ph463.6311.4355.0216.9
    C3H7O-C2H3431.0347.8370.1237.2
    C−O BondCH3O-Ph416.7315.5325.1207.8
    C2H5O-Ph416.7316.6337.6209.4
    O−H BondH-OCH3437.7110.372.1105.1
    H-OC2H5438.1119.073.6105.9
    H-OCH2C2H5432.6117.872.8104.1
    H-OC(CH3)2442.3112.665.898.6
    H-OCH2Ph425.5118.372.7105.3
    H-OCH=CH2355.6107.567.4104.1
    H-OPh368.2125.767.9104.3
    H-OPhCH3(p)374.0106.469.0104.5
    H-OPhOH(p)352.0100.164.595.6
    下载: 导出CSV
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  • 收稿日期:  2020-12-31
  • 修回日期:  2021-01-26
  • 网络出版日期:  2021-03-30

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