煤层气在含Al, Si, P和S煤结构模型上吸附的密度泛函理论研究

doi:10.7503/cjcu20150134

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (9): 1786.doi: 10.7503/cjcu20150134

煤层气在含Al, Si, P和S煤结构模型上吸附的密度泛函理论研究

何旭¹, 刘晓强¹, 何冰², 王晗光³, 刘旭东¹, 田之悦¹, 储伟⁴, 薛英¹()

1. 四川大学化学学院, 成都 610064
2. 成都师范学院化学生命科学学院, 成都 611130
3. 四川农业大学理学院, 雅安 625014
4. 四川大学化学工程学院, 成都 610065

收稿日期:2015-02-06 出版日期:2015-09-10 发布日期:2015-08-21
作者简介:联系人简介: 薛英, 女, 博士, 教授, 博士生导师. 主要从事计算化学研究. E-mail:yxue@scu.edu.cn
基金资助:
国家重点基础研究发展规划项目(批准号: 2011CB201202)和国家自然科学基金(批准号: 21173151, J1103315)资助

Coalbed Methane Adsorption on Al-, Si-, P- and S-containing Coal Models Predicted by Density Functional Theory^†

HE Xu¹, LIU Xiaoqiang¹, HE Bing², WANG Hanguang³, LIU Xudong¹, TIAN Zhiyue¹, CHU Wei⁴, XUE Ying^1,^*()

1. College of Chemistry, Sichuan University, Chengdu 610064, China
2. College of Chemistry and Life Science, Chengdu Normal University, Chengdu 611130, China
3. College of Science, Sichuan Agriculture University, Ya'an 625014, China
4. College of Chemical Engineering, Sichuan University, Chengdu 610065, China

Received:2015-02-06 Online:2015-09-10 Published:2015-08-21
Contact: XUE Ying E-mail:yxue@scu.edu.cn
Supported by:
† Supported by the National Basic Research Program of China(No.2011CB201202)and the National Natural Science Foundation of China(Nos.21173151, J1103315)

摘要/Abstract

摘要：

Al, Si, P和S掺杂石墨烯(X-Graphene, X-Gr, X=Al, Si, P和S)可用来代表具有结构异性的煤结构模型. 通过自旋极化的密度泛函理论(DFT)方法, 研究了煤层气(Coalbed methane, CBM, 主要成分为CH₄, CO₂和H₂O) 在煤结构模型X-Gr上的吸附, 并讨论了相应的吸附能、吸附平衡距离、 Mulliken电荷转移、电荷密度差分图和态密度. 结果表明, 含Al 和Si的煤结构模型对CBM的吸附较强, 而CBM在P和S煤结构模型的吸附为弱的物理吸附. CBM在X-Gr煤结构模型上的吸附作用随着掺杂元素非金属性的增强而减弱, 即Al-Gr>Si-Gr>P-Gr>S-Gr. 煤层气中 CO₂ 和 H₂O 吸附在煤炭表面的能力强于CH₄, 可以通过注入 CO₂ 和 H₂O 到煤层中促进 CH₄的开采. 此外, 含Al和Si煤结构与煤层气之间较强的相互作用表明其可以作为CH₄, CO₂和H₂O的气体传感器.

关键词: 煤层气, 煤结构模型, 掺杂, 吸附, 密度泛函理论

Abstract:

Al-, Si-, P- and S-doped graphenes(X-Gr, X=Al, Si, P and S) were used to represent the surface models of coal with the structural heterogeneity. Based on the spin-polarized density-functional theory, coalbed methane(CBM, the main components are CH₄, CO₂ and H₂O) adsorption on X-Gr was investigated and the corresponding adsorption energy, adsorption equilibrium distance, Mulliken charge, charge density differences and density of states were well discussed. The result show that Al- and Si-Gr are sensitive to CBM, whereas CBM adsorptions on P- and S-Gr are found to be physical adsorption. In brief, the interactions between CBM and X-Gr are slightly depend on the orientations of CBM gas molecules and the metallicity of the dopants in Gr. The higher adsorption energy, the higher metallicity of the dopants becomes, namely Al-Gr>Si-Gr>P-Gr>S-Gr. Through systematical and theoretical analysis, we found that CO₂ and H₂O were easy to adsorb on surface models of coal than CH₄. Hence, injection of CO₂ or H₂O in coal seams could enhance CH₄ recovery. In addition, we suggest that Al- and Si-Gr could be a good gas sensors for CBM because of the higher interactions between Al-/Si-Gr and CBM.

Key words: Coalbed methane, Coal model, Doping, Adsorption, Density functional theory

中图分类号:

O641

TrendMD:

何旭, 刘晓强, 何冰, 王晗光, 刘旭东, 田之悦, 储伟, 薛英. 煤层气在含Al, Si, P和S煤结构模型上吸附的密度泛函理论研究. 高等学校化学学报, 2015, 36(9): 1786.

HE Xu, LIU Xiaoqiang, HE Bing, WANG Hanguang, LIU Xudong, TIAN Zhiyue, CHU Wei, XUE Ying. Coalbed Methane Adsorption on Al-, Si-, P- and S-containing Coal Models Predicted by Density Functional Theory^†. Chem. J. Chinese Universities, 2015, 36(9): 1786.

图/表 7

Fig.1 5×5×1 Graphene and X-Gr in calculation(A) Three adsorption sites for Gr, namely, B(the midpoint of a carbon-carbon bond), C(the center of a hexagon) and T(above a carbon atom); (B) the structure of X-Gr, the colorized atom(Al, Si, P, S), h: the distance between the doped atom and Gr plane, (B1) top view, (B2) side view; (C) the adsorption configuration of CH4, CO2, and H2O; (D) the adsorption sites of CH4, CO2, and H2O on X-Gr, d: the distance between the doped atom and Gs.

Fig.2 Optimized partial geometrical structures of X-Gr (A) Al-Gr; (B) Si-Gr; (C) P-Gr; (D) S-Gr.

Table 1 Geometrical parameters of the Gr/X-Gr, including the calculated lattice constants(a), the embossment height(h) of doped atoms, dX—C(X=C, Al, Si, P, S ), formation and cohesive energies of Gr/X-Gr

System	a/nm	h/nm	d_X—C/nm	ΔE_f/(kJ·mol^-1)	ΔE_c/(kJ·mol^-1)
Gr	0.245	0	0.141		834.6
Ref.	0.244^[36]	0^[36]	0.141^[36]		849.1^[39]
Expt.	0.246^[36]	0^[36]	0.142^[36]	-	762.2^[40]
Al-Gr	1.226	0.169	0.184	1026.6	814.3
Ref.		0.176^[37]	0.185^[36,37]	970.6^[38]	-
Si-Gr	1.226	0.142	0.174	722.7	820.10
Ref.		0.146^[32,37]	0.176^[37]	715.0^[32]	-
P-Gr	1.224	0.137	0.175	688.9	821.1
Ref.		0.146^[38]	0.177^[38]	683.1^[38]	-
S-Gr	1.224	0.124	0.174	863.5	818.2
Ref.		0.110^[36]	0.174^[36]	807.6^[32]	-

Fig.3 Most favored adsorption configuration and electronic density difference images of CH4 on X-Gr(A) Al-Gr; (B) Si-Gr; (C) P-Gr; (D) S-Gr.

Fig.4 Most favored adsorption energies of Gs (CH4, CO2, H2O) on X-Gr

Fig.5 Partial density of states(PDOS) of X-Gr(A) Al-Gr; (B) Si-Gr; (C) P-Gr; (D) S-Gr. a. s; b. p; c. Cs; d. Cp.

Fig.6 Charge density differences of X-Gr(A) Al-Gr; (B) Si-Gr; (C) P-Gr; (D) S-Gr.

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煤层气在含Al, Si, P和S煤结构模型上吸附的密度泛函理论研究

Coalbed Methane Adsorption on Al-, Si-, P- and S-containing Coal Models Predicted by Density Functional Theory^†

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煤层气在含Al, Si, P和S煤结构模型上吸附的密度泛函理论研究

Coalbed Methane Adsorption on Al-, Si-, P- and S-containing Coal Models Predicted by Density Functional Theory†

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Coalbed Methane Adsorption on Al-, Si-, P- and S-containing Coal Models Predicted by Density Functional Theory^†