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

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

辽宁工业大学化学与环境工程学院, 辽宁锦州 121001

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

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E-mail: tangke0001@163.com

中图分类号: TE626
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出版历程
- 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
- 刊出日期: 2024-08-01

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

School of Chemical and Environmental Engineering, Liaoning University of Technology, Jinzhou 121001, China

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

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。
- 石墨烯 /
- 掺杂 /
- 吸附 /
- 脱氮 /
- 模拟 /
- 表面
Abstract: In this paper, the adsorption behavior of pyridine, a typical basic nitrogen compound in diesel oil, on Ti-doped, Zr-doped, N-doped and intrinsic graphene has been investigated by density functional methods. The corresponding adsorption energy, adsorption configurations, Mulliken charge transfer, differential charge density and density of states were discussed. The results show that doping graphene with metal atoms such as Ti or Zr can significantly obviously enhance the adsorption energy between pyridine and graphene surfaces, while non-metal N doping has a relatively minor effect. The magnitude of the adsorption energy of pyridine on the surfaces of graphene modified with different atoms follows the order: Ti-doped>Zr-doped>N-doped>intrinsic graphene. Pyridine interacts with Ti- or Zr-doped graphene through N−Ti, N−Zr and π−π interactions, while with N-doped and intrinsic graphene, it interacts via N−N, C−N and π−π interactions. There are significant electron transfer and chemical bond formation between pyridine and metal-doped (Ti, Zr) graphene surfaces, indicating chemical adsorption. However, there is no chemical bond formation with non-metal N-doped graphene and intrinsic graphene, suggesting physical adsorption in these cases. Overall, pyridine exhibits more stable adsorption on the surfaces of Ti, Zr-doped graphene.
- graphene /
- dope /
- adsorption /
- denitrification /
- simulation /
- surfaces

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FIG. 3304. FIG. 3304.

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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)

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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

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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)

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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)

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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)

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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

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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

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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)

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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)

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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 d_C−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

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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
Adsorption structure	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

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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 molecule	Before adsorption/e			After adsorption (Ti-GR)/e			After adsorption (Zr-GR)/e			After adsorption (N-GR)/e			After adsorption (GR)/e
Atom or molecule	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

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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
Atom or molecule	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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