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吡啶在Ti、Zr、N掺杂石墨烯表面吸附的理论研究

王聚财 唐克 孙潇镝 洪新

王聚财, 唐克, 孙潇镝, 洪新. 吡啶在Ti、Zr、N掺杂石墨烯表面吸附的理论研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60440-8
引用本文: 王聚财, 唐克, 孙潇镝, 洪新. 吡啶在Ti、Zr、N掺杂石墨烯表面吸附的理论研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60440-8
WANG Jucai, TANG Ke, SUN Xiaodi, HONG Xin. Theoretical calculations of pyridine adsorption on the surfaces of Ti, Zr, N doped graphene[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60440-8
Citation: WANG Jucai, TANG Ke, SUN Xiaodi, HONG Xin. Theoretical calculations of pyridine adsorption on the surfaces of Ti, Zr, N doped graphene[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60440-8

吡啶在Ti、Zr、N掺杂石墨烯表面吸附的理论研究

doi: 10.1016/S1872-5813(24)60440-8
基金项目: 辽宁省自然科学基金(2019-ZD-0699)和辽宁省教育厅基本科研项目揭榜挂帅服务地方项目(JYTMS20230835)资助
详细信息
    通讯作者:

    E-mail: tangke0001@163.com

  • 中图分类号: TE626

Theoretical calculations of pyridine adsorption on the surfaces of Ti, Zr, N doped graphene

Funds: The project was supported by the Science and Technology Program of Liaoning Provincial (2019-ZD-0699) and Liaoning Provincial Department of Education basic research projects (JYTMS20230835).
  • 摘要: 采用密度泛函方法,研究了Ti、Zr和N掺杂及本征石墨烯对柴油中典型碱性氮化物吡啶的吸附行为,讨论了相应的吸附能、吸附构型、马利肯电荷转移、差分电荷密度和态密度。结果表明,金属Ti、Zr掺杂能显著增强吡啶在石墨烯表面的吸附能,非金属N掺杂可略微增加吡啶和石墨烯表面间的吸附能。吡啶在不同原子修饰的石墨烯表面的吸附能大小顺序为Ti掺杂石墨烯>Zr掺杂石墨烯>N掺杂石墨烯>本征石墨烯,吡啶可与Ti、Zr掺杂石墨烯发生N−Ti、N−Zr和π−π作用,与N掺杂石墨烯、本征石墨烯发生N−N、C−N和π−π作用。进一步分析发现,吡啶和金属Ti、Zr掺杂石墨烯表面存在明显的电子转移和化学键的形成,而和非金属N掺杂石墨烯及本征石墨烯间并无化学键形成。吡啶与Ti、Zr掺杂石墨烯发生化学吸附,与N掺杂石墨烯、本征石墨烯发生物理吸附。吡啶更稳定的吸附在Ti、Zr掺杂石墨烯表面。
  • 图  1  Ti、Zr、N掺杂及本征石墨烯表面的球棍模型

    Figure  1  Ball and stick model of Ti, Zr or N-doped and intrinsic graphene(Ti, Zr, N, C atoms are represented by incanus, green, blue, grey, respectively)

    图  2  本征及掺杂石墨烯的态密度

    Figure  2  Density of states (DOS) of the Ti, Zr or N-doped and intrinsic graphene

    图  3  吡啶垂直吸附在各石墨烯表面的吸附构型

    Figure  3  Adsorption configuration of pyridine perpendicular adsorption on Ti, Zr or N-doped and intrinsic graphene(Ti, Zr, N, C and H atoms are represented by incanus, green, blue, grey and white, respectively)

    图  4  吡啶环平行吸附在各石墨烯表面的吸附构型

    Figure  4  Adsorption configuration of pyridine parallel(ring) adsorption on Ti, Zr or N-doped and intrinsic graphene(Ti, Zr, N, C and H atoms are represented by incanus, green, blue, grey and white, respectively)

    图  5  吡啶氮平行吸附在各石墨烯表面的吸附构型

    Figure  5  Adsorption configuration of pyridine-nitrogen atom parallel adsorption on Ti, Zr or N-doped and intrinsic graphene surfaces (Ti,Zr, N, C and H atoms are represented by incanus, green, blue, grey and white, respectively)

    图  6  吡啶吸附在各石墨烯表面吸附前后的态密度

    Figure  6  Total density of states of Ti, Zr or N-doped and intrinsic graphene and pyridine adsorption

    图  7  吡啶吸附在各石墨烯表面体系中吸附位点分波态密度

    Figure  7  Partial density of states of the pyridine-nitrogen atom and Ti, Zr, N and C in adsorption system

    图  8  吡啶吸附在各石墨烯表面的电子密度

    Figure  8  Isosurface of electron density of pyridine adsorption on Ti, Zr or N-doped and intrinsic graphene (Ti, Zr, N, C and H atoms are represented by incanus, green, blue, grey and white, respectively)

    图  9  吡啶吸附在各石墨烯表面的差分电荷密度

    Figure  9  Isosurface of differential charge density of pyridine adsorption on Ti, Zr or N-doped and intrinsic graphene (Ti, Zr, N, C and H atoms are represented by incanus, green, blue, grey and white, respectively)

    表  1  各石墨烯表面的几何参数

    Table  1  Geometrical parameters of the Ti, Zr or N-doped and intrinsic graphene

    Doped graphenes Bond length dC−x/nm Bond angle ∠C−X−C/(°)
    Ti-doped graphenes 0.1775−0.1778 119.905−120.048
    Zr-doped graphenes 0.1869−0.1871 119.836−120.082
    N-doped graphenes 0.1409−0.1411 119.997−120.006
    intrinsic graphenes 0.1420 120
    下载: 导出CSV

    表  2  吡啶在各石墨烯表面上三种吸附构型的吸附能

    Table  2  Adsorption energy of pyridine adsorption on Ti, Zr or N-doped and intrinsic graphene

    Adsorption structure Energy/eV
    Ti-doped graphenes Zr-doped graphenes N-doped graphenes Intrinsic graphenes
    Vertical −1.857 −1.590 −0.499 −0.374
    Parallel(ring) −1.854 −1.583 −0.767 −0.736
    Parallel(N) −2.034 −1.853 −0.734 −0.672
    下载: 导出CSV

    表  3  吡啶在各石墨烯表面吸附前后吡啶的马利肯电荷布居

    Table  3  Mulliken charge of pyridine adsorption on Ti, Zr or N-doped and intrinsic graphene

    Atom or mole cule Before adsorption/e After adsorption (Ti-GR)/e After adsorption (Zr-GR)/e After adsorption (N-GR)/e After adsorption (GR)/e
    s-orbital electron p-orbital electron mulliken population s-orbital electron p-orbital electron mulliken population s-orbital electron p-orbital electron mulliken population s-orbital electron p-orbital electron mulliken population s-orbital electron p-orbital electron mulliken population
    C1 1.242 2.8 −0.042 1.236 2.819 −0.056 1.23 2.823 −0.053 1.242 2.798 −0.041 1.242 2.799 −0.04
    C2 1.242 2.834 −0.076 1.237 2.865 −0.101 1.23 2.867 −0.096 1.246 2.832 −0.076 1.245 2.832 −0.08
    C3 1.205 2.738 0.057 1.195 2.685 0.121 1.184 2.687 0.129 1.21 2.73 0.06 1.21 2.731 0.058
    N 1.59 3.705 −0.295 1.603 3.908 −0.511 1.602 3.929 −0.531 1.59 3.732 −0.322 1.591 3.709 −0.3
    C5 1.205 2.738 0.057 1.194 2.676 0.13 1.184 2.691 0.125 1.21 2.728 0.062 1.21 2.73 0.059
    C6 1.242 2.834 −0.076 1.237 2.865 −0.102 1.23 2.866 −0.095 1.246 2.832 −0.076 1.245 2.832 −0.08
    H7 0.923 0 0.077 0.87 0 0.13 0.876 0 0.124 0.918 0 0.082 0.921 0 0.079
    H8 0.925 0 0.075 0.868 0 0.132 0.874 0 0.126 0.92 0 0.08 0.923 0 0.077
    H9 0.925 0 0.075 0.859 0 0.141 0.872 0 0.128 0.917 0 0.083 0.921 0 0.079
    H10 0.925 0 0.075 0.854 0 0.146 0.872 0 0.128 0.918 0 0.082 0.922 0 0.078
    H11 0.925 0 0.075 0.868 0 0.132 0.874 0 0.126 0.92 0 0.08 0.923 0 0.077
    py 12.349 17.649 0.002 12.021 17.818 0.162 12.03 17.863 0.111 12.337 17.652 0.014 12.353 17.633 0.01
    下载: 导出CSV

    表  4  吡啶在各石墨烯表面吸附前后各石墨烯的马利肯电荷布居

    Table  4  Mulliken charge of Ti, Zr or N-doped and intrinsic graphene of pyridine before and after adsorption

    Atom or
    molecule
    Before adsorption/e After adsorption/e
    s-orbital electron p-orbital electron d-orbital electron mulliken population s-orbital electron p-orbital electron d-orbital electron mulliken population
    Ti 2.616 6.135 2.824 0.425 2.658 6.384 2.625 0.333
    Zr 2.471 6.015 2.786 0.728 2.747 6.317 2.394 0.541
    N 1.551 3.907 −0.458 1.542 3.87 −0.412
    C 1.301 2.699 0 1.302 2.665 0.032
    Ti-GR 0 −0.160
    Zr-GR 0 −0.109
    N-GR 0 −0.012
    GR 0 −0.008
    下载: 导出CSV
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  • 收稿日期:  2023-11-26
  • 修回日期:  2024-02-08
  • 录用日期:  2024-03-04
  • 网络出版日期:  2024-04-03

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