Theoretical Calculations of Pyridine Adsorption on the Surfaces of Ti, Zr, N Doped Graphene
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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。Abstract: The removal of nitrides from diesel fuel has important significance for the environment and human health. The adsorption behaviour of Ti, Zr and N-doped and intrinsic graphene on pyridine, a typical basic nitride in diesel fuel, has been investigated by density functional methods in this paper. the corresponding adsorption energy, adsorption configurations, Mulliken charge transfer, differential charge density, and density of states were discussed. The results show that metal Ti and Zr doping can significantly enhance the adsorption energy between pyridine and graphene surfaces, and non-metal N doping can slightly increase the adsorption energy between pyridine and graphene surfaces. The magnitude of the adsorption energy of pyridine on the surface of graphene modified with different atoms was in the order of Ti doped graphene > Zr doped graphene > N doped graphene > intrinsic graphene, Pyridine could undergo N-Ti, N-Zr and π-π interactions with Ti and Zr doped graphene, and N-N, C-N and π-π interactions with N doped graphene and intrinsic graphene. Further analysis reveals that there are obvious electron transfer and chemical bond formation between pyridine and metallic Ti, Zr-doped graphene surfaces, while there is no chemical bond formation with non-metallic N-doped graphene and intrinsic graphene. Chemical adsorption interaction of pyridine with Ti, Zr-doped graphene, physical adsorption interaction with N-doped graphene and intrinsic graphene. Pyridine was more stable adsorption on the surface of Ti Zr-doped graphene.
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Key words:
- graphene /
- dope /
- adsorption /
- denitrification /
- simulation /
- surface
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表 1 各石墨烯表面的几何参数
Table 1 Geometrical parameters of the intrinsic and Ti, Zr, N doped graphenes
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 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 intrinsic and Ti、Zr、N doped graphenes
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 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 of pyridine before and after adsorption on intrinsic and Ti、Zr、N doped graphenes
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 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 intrinsic and Ti、Zr、N doped graphenes of pyridine before and after adsorption on intrinsic and Ti、Zr、N doped graphenes
Atom or
moleculeBefore 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 -
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