Sr掺杂对CaO(100)表面吸附甲醇影响的分子模拟

厉志鹏; 牛胜利; 赵改菊; 韩奎华; 李英杰; 路春美; 程屾

Sr掺杂对CaO(100)表面吸附甲醇影响的分子模拟

1.
山东大学能源与动力工程学院, 山东济南 250061
2.
齐鲁工业大学(山东省科学院)能源研究所, 山东济南 250014
3.
齐鲁工业大学能源与动力工程学院, 山东济南 250353

基金项目:

国家自然科学基金 51876106

山东省重点研发计划 2018GGX104027

山东大学青年学者未来计划资助项目 2015WLJH33

齐鲁工业大学（山东省科学院）青年博士合作基金项目 2018BSHZ0017

详细信息

中图分类号: TK6
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- 被引次数: 0
出版历程
- 收稿日期: 2019-09-30
- 修回日期: 2019-12-19
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-02-10

Molecular simulation study of strontium doping on the adsorption of methanol on CaO(100) surface

1.
School of Energy and Power Engineering, Shandong University, Jinan 250061, China
2.
Energy Research Institute, Qilu University of Technology(Shandong Academy of Science), Jinan 250014
3.
School of Energy and Power Engineering, Qilu University of Technology, Jinan 250353

Funds:

The project was supported by the National Natural Science Foundation of China 51876106

Primary Research & Development Plan of Shandong Province 2018GGX104027

Young Scholars Program of Shandong University 2015WLJH33

Qilu University of Technology(Shandong Academy of Sciences) Youth PhD Cooperation Fund Project 2018BSHZ0017

More Information

Corresponding author: NIU Sheng-li, E-mail: nsl@sdu.edu.cn

摘要

摘要: 借助分子模拟手段，研究了锶掺杂对氧化钙表面甲醇吸附行为的影响。构建了甲醇在CaO（100）和CaO（100）-Sr表面吸附的模型，计算了甲醇在氧化钙表面的吸附能和解离活化能，分析了甲醇在氧化钙表面成键的态密度以及锶掺杂前后甲醇在氧化钙表面电荷布局和差分电荷密度，评估了锶掺杂量对氧化钙表面甲醇吸附性能的影响。结果表明，锶掺杂能够显著强化氧化钙对甲醇的吸附性能，降低甲醇的解离活化能，且吸附性能随锶掺杂量的增加而增强；甲醇在氧化钙表面吸附时活化，锶掺杂后活化程度增加。
- 生物柴油 /
- 氧化钙 /
- 锶掺杂 /
- 甲醇吸附 /
- 分子模拟
Abstract: The influence of strontium doping on the adsorption of methanol on calcium oxide surface was investigated by molecular simulation. The model for methanol adsorption onto the CaO(100) and CaO(100)-Sr surfaces was constructed; the adsorption energy and activation energy were then calculated and the density of states was portrayed for the methanol bond on the calcium oxide surface. The methanol activation degrees on the calcium oxide surface before and after strontium doping were then compared by analyzing the Mulliken atomic charge population and deformation density. The results illustrate that the adsorption of methanol onto the calcium oxide surface can be significantly enhanced through the strontium doping; moreover, the enhancement increases with an increase in the doping content of strontium. After doping calcium oxide with strontium, the energy required for methanol activation is reduced; as a result, the strontium doping can also enhance the activation degree of methanol, as methanol is activated upon adsorption onto the calcium oxide surface.
- biodiesel /
- calcium oxide /
- strontium doping /
- methanol adsorption /
- molecular simulation

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图 1 CaO(100)和CaO(100)-Sr模型

Figure 1 Surface structure of CaO(100) (a) and CaO(100)-Sr (b)

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图 2 甲醇构型

Figure 2 Structure of methanol molecule in gas phase

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图 3 甲醇在催化剂表面的吸附位置

Figure 3 Adsorption position of methanol on the catalyst surfaces

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图 4 甲醇分子在CaO(100)和CaO(100)-Sr表面吸附后的俯视图和侧视图

Figure 4 Adsorption of methanol molecule on the CaO(100) and CaO(100)-Sr surfaces

(a): side view of CaO(100); (b): side view of CaO(100)-Sr; (c): top view of CaO(100); (d): top view of CaO(100)-Sr

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图 5 CaO(100)-2Sr模型构型以及甲醇在CaO(100)-2Sr表面吸附后的视图

Figure 5 Structure of the CaO(100)-2Sr surface (a) and the adsorption of methanol molecule on the CaO(100)-2Sr surface of side view (b) and top view (c)

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图 6 不同O原子在CaO(100)和CaO(100)-Sr表面吸附前后局部态密度图

Figure 6 Partial densities of states of the O atom before and after adsorption on the CaO(100) and CaO(100)-Sr surfaces

(a): O atom on methanol; (b): O atom on catalyst surface

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图 7 甲醇在催化剂表面吸附后的差分电荷密度

Figure 7 Deformation density for the methanol adsorption on the CaO(100) (a) and CaO(100)-Sr surfaces (b)

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表 1 CaO(100)、CaO(100)-Sr表面化学键分布统计

Table 1 Statistical distribution of chemical bonds on the CaO(100) and CaO(100)-Sr surfaces

Catalyst surface	Bond types	Bond length /nm	Bond numbers	Relative bond length D^a
CaO(100) surface	Ca-O	0.2405	36	0.835
CaO(100)-Sr surface	Ca-O	0.2425	8	0.829
		0.2337	4
		0.2390	4
		0.2409	8
		0.2383	8
	Sr-O	0.2496	4
note: ^a: relative bond length D^[22]was calculated by formula (1)

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表 2 甲醇在催化剂表面的吸附能(E_{ads, adsorbate}、E_{ads, adsorbate^*})和解离活化能(E_{a, diss})

Table 2 Adsorption energies and activation energies of methanol on the catalyst surfaces

Catalyst surface	E_{ads, adsorbate} /(kJ·mol^-1)	E_{ads, adsorbate^*} /(kJ·mol^-1)	E_{a, diss} /(kJ·mol^-1)
CaO(100)	-127.887	-64.0870	4.186
CaO(100)-Sr	-144.170	-79.0580	-

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表 3 甲醇在CaO(100)和CaO(100)-Sr表面吸附的Mulliken电荷布局分析

Table 3 Mulliken atomic charge populations for methanol adsorption on the CaO(100) and CaO(100)-Sr surfaces

Atom	Charge/e
Atom	free methanol	methanol/CaO(100)	methanol/CaO(100)-Sr
H₁	0.254	0.383	0.378
O₂	-0.503	-0.807	-0.837
C₃	0.111	-0.002	0.004
H₄	0.039	0.007	0.044
H₅	0.042	0.056	0.047
H₆	0.057	0.061	0.061

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