Fe元素及点缺陷对焦炭表面NH<sub>3</sub>异相吸附的影响:密度泛函理论研究

李焕龙; 金晶; 侯封校; 王永贞; 翟中媛; 赵冰

Fe元素及点缺陷对焦炭表面NH₃异相吸附的影响:密度泛函理论研究

李焕龙^{1, 2},
金晶^{1, 2, ,},
侯封校^{1, 2},
王永贞^{1, 2},
翟中媛^{1, 2},
赵冰^{1, 2}

1.
上海理工大学能源与动力工程学院, 上海 200093
2.
上海理工大学协同创新研究院, 上海 200093

基金项目:

十三五国家科技支撑项目 2017YFF0209800

详细信息

中图分类号: TK16
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- 被引次数: 0
出版历程
- 收稿日期: 2018-07-17
- 修回日期: 2018-09-27
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-12-10

Effect of Fe and point deficiency on adsorption behavior of NH₃ on coke surface: A density functional theory study

LI Huan-long^{1, 2},
JIN Jing^{1, 2
, ,},
HOU Feng-xiao^{1, 2},
WANG Yong-zhen^{1, 2},
ZHAI Zhong-yuan^{1, 2},
ZHAO Bing^{1, 2}

1.
Department of Energy and Power Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China
2.
Collaborative Innovation Research Institute, University of Shanghai for Science and Technology, Shanghai 200093, China

Funds:

Thirteenth Five-Year″ Plan for Science & Technology Support of China 2017YFF0209800

More Information

Corresponding author: JIN Jing, Tel: +86-21-55277768, E-mail: alicejin001@163.com

摘要

摘要: 采用密度泛函理论，并使用具有周期性边界条件的石墨烯模型近似模拟焦炭表面，研究了Fe原子修饰及点缺陷对NH₃在焦炭表面异相吸附的影响。计算结果表明，NH₃分子在点缺陷石墨烯表面的吸附属于物理吸附，结合能为-0.381 eV；NH₃分子吸附在Fe修饰的完整石墨烯表面属于化学吸附，吸附能为-1.442 eV；Fe原子修饰及点缺陷单独存在下NH₃的吸附能均大于NH₃在完整石墨烯表面的吸附（吸附能为-0.190 eV）。此外，Fe原子修饰与点缺陷共存对NH₃的吸附具有协同作用，结合能达到-3.538 eV，明显大于两者单独存在下NH₃的吸附能之和，综合分析Mulliken布居数与态密度，Fe原子与石墨烯表面、NH₃分子之间有更多地电荷转移，可以解释两者共存对NH₃吸附协同促进的原因。
- 密度泛函理论 /
- 焦炭 /
- NH₃ /
- Fe /
- 点缺陷 /
- 吸附
Abstract: Effect of Fe and point deficiency on adsorption behavior of NH₃ on coke surface was studied using density functional theory and graphene model with periodic boundary conditions. The results show that the adsorption of NH₃ on surface of point-defective graphene belongs to physical adsorption with binding energy of -0.381 eV. The adsorption of NH₃ on surface of Fe-modified-graphene belongs to chemical adsorption with energy of -1.442 eV. The adsorption energy of NH₃ in the presence of Fe atom or point defect is greater than that of NH₃ on the surface of intact graphene. In addition, coexistence of Fe atom and point defect has a synergistic effect on adsorption of NH₃ with binding energy of -3.538 eV, which is much higher than the sum of adsorption energy of NH₃ in the presence of the two alone. There is more charge transferring among Fe atom, graphene surface and NH₃ molecule, which can explain the synergistic effect of coexistence of Fe and point defect.
- density functional theory /
- char /
- NH₃ /
- Fe /
- point-deficiency /
- adsorption

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图 1 点缺陷石墨烯表面与完整石墨烯表面

Figure 1 Surface of defect graphene and intact grapheme

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图 2 Fe修饰的点缺陷石墨烯表面的俯视图与侧视图

Figure 2 Top view and side view of Fe modified defect graphene surface

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图 3 Fe修饰的完整石墨烯表面的俯视图与侧视图

Figure 3 Top view and side view of Fe-modified intact graphene surface

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图 4 NH₃在石墨烯表面吸附的俯视图与侧视图

Figure 4 Top and side views of NH₃ adsorption on graphene surface

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图 5 差分电荷密度图

Figure 5 The deformation electron density

(a): adsorption of NH₃ on defective surface; (b): adsorption of NH₃ on intact graphene surface with Fe; (c): adsorption of NH₃ on defective graphene surface with Fe atom; (d): intact graphene surface; (e): defective surface

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图 6 NH₃在石墨烯表面吸附的PDOS

Figure 6 PDOS of NH₃ on graphene surface

(a): NH₃-Dgra; (b): NH₃-Gra

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图 7 NH₃在Fe修饰的完整石墨烯表面吸附的俯视图与侧视图

Figure 7 Top and side views of adsorption of NH₃ on Fe-modified intact graphene

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图 8 NH₃在Fe修饰的完整石墨烯表面吸附的PDOS

Figure 8 PDOS of adsorption of NH₃ on Fe-modified intact graphene surface

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图 9 NH₃分子在Fe修饰的缺陷石墨烯表面吸附的俯视图与侧视图

Figure 9 Top and side views of adsorption of NH₃ on Fe-modified defect graphene surface

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图 10 NH₃在Fe修饰的缺陷石墨烯表面吸附的PDOS

Figure 10 PDOS of adsorption of NH₃ on Fe-modified defect graphene surface

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表 1 石墨烯晶胞晶格常数

Table 1 The lattice constants of graphene cell

	a/nm	b/nm	c/nm	d/nm
Calculated value	0.2452	0.2452	0.6873	0.1416
Experimental value	0.2460	0.2460	0.6800	0.1420^[28]
Deviation /%	0.33	0.33	1.07	0.28

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表 2 Fe在石墨烯表面的结合能与NH₃在不同石墨烯表面的吸附能

Table 2 Binding energy of Fe on surface of graphene and adsorption energy of NH₃ on different graphene surfaces

	Total/eV	NH₃/eV	Gra/eV	Dgra/eV	Fe/eV	E_B/eV	E_B^*/eV
Fe+Gra	-37060.621	-	-33165.088	-	-3894.255	-1.279	-
Fe+Dgra	-36022.865	-	-	-32120.718	-3894.255	-7.891	-
NH₃+Gra	-34703.083	-1537.8045	-33165.088	-	-	-0.190	0-(-0.17)^{[29, 30]}
NH₃+Dgra	-33658.904	-1537.8045	-	-32120.718	-	-0.381	-0.24^[31]
NH₃+Fe+Gra	-38599.868	-1537.8045	-33165.088	-	-3894.255	-1.442	-
NH₃+Fe+Dgra	-37564.207	-1537.8045	-	-32120.718	-3894.255	-3.538	-

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表 3 不同吸附体系下的原子间距

Table 3 Interatomic distance in different adsorption systems

	Interatomic distance /nm
	d_C-C	d_Fe-N	d_Fe-C	d_Fe-H	d_N-H	d_N-C	d_H-C
NH₃+Dgra	0.2491	-	-	-	0.1023	0.3452	0.3080
NH₃+Fe+Gra	0.1438	0.2078	0.2165	0.2629	0.1024	-	-
NH₃+Fe+Dgra	0.2637	0.2036	0.1772	0.2592	0.1025	-	-

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表 4 NH₃在不同石墨烯表面吸附的Mulliken布居数

Table 4 Mulliken population of NH₃ adsorbed on different graphene surfaces

	Mulliken population /e
	Fe	N	H	C1	C2	C3	C4	C5	C6
NH₃₊Gra	-	-0.462	0.151	-0.002	-0.001	-0.002	-0.003	-0.001	-0.002
NH₃	-	-0.470	0.157	-	-	-	-	-	-
NH₃+Dgra	-	-0.489	0.176	-0.068	-0.064	-0.061	-	-	-
NH₃+Fe+Gra	0.136	-0.550	0.153	-0.013	-0.013	-0.016	-0.014	-0.015	-0.014
NH₃+Fe+Dgra	-0.209	-0.884	0.288	-0.014	-0.018	-0.020	-	-	-

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Fe元素及点缺陷对焦炭表面NH₃异相吸附的影响:密度泛函理论研究

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Effect of Fe and point deficiency on adsorption behavior of NH₃ on coke surface: A density functional theory study

Corresponding author: JIN Jing, Tel: +86-21-55277768, E-mail: alicejin001@163.com

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2023年《燃料化学学报（中英文）》评优结果公布！

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Fe元素及点缺陷对焦炭表面NH3异相吸附的影响:密度泛函理论研究

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Effect of Fe and point deficiency on adsorption behavior of NH3 on coke surface: A density functional theory study

Corresponding author: JIN Jing, Tel: +86-21-55277768, E-mail: alicejin001@163.com

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2023年《燃料化学学报（中英文）》评优结果公布！

Fe元素及点缺陷对焦炭表面NH₃异相吸附的影响:密度泛函理论研究

Effect of Fe and point deficiency on adsorption behavior of NH₃ on coke surface: A density functional theory study