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基于密度泛函理论的CO2对NO异相还原影响的机理研究

周赛 刘虎 于鹏飞 车得福

周赛, 刘虎, 于鹏飞, 车得福. 基于密度泛函理论的CO2对NO异相还原影响的机理研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60088-9
引用本文: 周赛, 刘虎, 于鹏飞, 车得福. 基于密度泛函理论的CO2对NO异相还原影响的机理研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60088-9
ZHOU Sai, LIU Hu, YU Peng-fei, CHE De-fu. Application of density functional theory on the NO-char heterogeneous reduction mechanism in the presence of CO2[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60088-9
Citation: ZHOU Sai, LIU Hu, YU Peng-fei, CHE De-fu. Application of density functional theory on the NO-char heterogeneous reduction mechanism in the presence of CO2[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60088-9

基于密度泛函理论的CO2对NO异相还原影响的机理研究

doi: 10.1016/S1872-5813(21)60088-9
基金项目: 中国博士后科学基金(2018M633507)和陕西省自然科学基础研究计划(2020JQ-063)资助
详细信息
    通讯作者:

    Tel:15389251896,E-mail:epeliuhu@mail.xjtu.edu.cn

  • 中图分类号: TQ534.9

Application of density functional theory on the NO-char heterogeneous reduction mechanism in the presence of CO2

Funds: The project was supported by the Postdoctoral Research Foundation of China (2018M633507) and Natural Science Basic Research Plan in Shaanxi Province of China (2020JQ-063)
  • 摘要: 为深入理解CO2对NO异相还原的影响,本研究基于密度泛函理论,对CO2参与下的煤焦-NO异相还原反应机理进行研究,并选取armchair苯环模型模拟焦炭表面。结构优化采用B3LYP-D3/6-31G(d)方法,单点能计算采用B3LYP-D3/def2-TZVP方法。研究表明,CO2吸附后形成的羰基与吸附态NO反应生成CO2,继而CO2脱附为后续NO吸附及N2脱附提供邻近的碳活性位点。热力学研究表明,无CO2参与条件下,反应放热853.9 kJ/mol,决速步能垒为297.0 kJ/mol;CO2参与条件下,反应放出593.7 kJ/mol的热量,决速步能垒为214.1 kJ/mol。动力学研究表明,在298.15–1800 K的温度下,CO2参与条件下的反应速率常数大于无CO2参与条件下的反应速率常数。综合热力学和动力学研究结果发现,CO2对NO的异相还原反应具有促进作用。
  • 图  1  Armchair焦炭模型

    Figure  1  Armchair edge model

    图  2  煤焦-NO异相还原路径的反应势能面

    Figure  2  Potential energy surface of NO heterogeneous reduction

    图  3  煤焦-NO异相还原反应的各驻点结构(键长:Å)

    Figure  3  Structures of stagnation points of NO heterogeneous reduction (bond length: Å)

    图  4  CO2吸附构型与能量

    Figure  4  Adsorption configuration and energy of CO2

    图  5  CO2参与NO异相还原路径的反应势能面

    Figure  5  Potential energy surface of NO heterogeneous reduction with the participation of CO2

    图  6  CO2参与NO异相还原反应的各驻点结构(键长:Å)

    Figure  6  Structures of stagnation points of NO heterogeneous reduction with the participation of CO2 (bond length: Å)

    图  7  经典过渡态理论得到的反应速率常数

    Figure  7  Rate constant k calculated from cTST

    表  1  拟合所得动力学反应参数

    Table  1  Fitted kinetic parameters of Arrhenius expressions

    ReactionA/s−1Ea/(kJ·mol−1
    IM4→IM5+CO22.06 × 1015228.8
    IM3→IM41.83 × 1015311.5
    下载: 导出CSV
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  • 收稿日期:  2021-02-05
  • 修回日期:  2021-04-02
  • 网络出版日期:  2021-04-22

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