Effect of different valence metals doping on methane activation over La<sub>2</sub>O<sub>3</sub>(001) surface

ZHANG Jia-yu; SUN Na; LING Li-xia; ZHANG Ri-guang; JIA Li-tao; LI De-bao; WANG Bao-jun

doi:10.1016/S1872-5813(23)60343-3

Volume 51 Issue 5

May 2023

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Article Navigation > Journal of Fuel Chemistry and Technology > 2023 > 51(5): 673-683

ZHANG Jia-yu, SUN Na, LING Li-xia, ZHANG Ri-guang, JIA Li-tao, LI De-bao, WANG Bao-jun. Effect of different valence metals doping on methane activation over La2O3(001) surface[J]. Journal of Fuel Chemistry and Technology, 2023, 51(5): 673-683. doi: 10.1016/S1872-5813(23)60343-3

Citation:

ZHANG Jia-yu, SUN Na, LING Li-xia, ZHANG Ri-guang, JIA Li-tao, LI De-bao, WANG Bao-jun. Effect of different valence metals doping on methane activation over La₂O₃(001) surface[J]. Journal of Fuel Chemistry and Technology, 2023, 51(5): 673-683. doi: 10.1016/S1872-5813(23)60343-3

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Effect of different valence metals doping on methane activation over La₂O₃(001) surface

doi: 10.1016/S1872-5813(23)60343-3

ZHANG Jia-yu^{1, 2
,},
SUN Na^{1, 2
,},
LING Li-xia^{1, 3
,
,},
ZHANG Ri-guang^2
,,
JIA Li-tao^4
,,
LI De-bao^4
,,
WANG Bao-jun^{1, 2, 3
,
,}

1.
College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China
2.
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China
3.
Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan 030024, China
4.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

Funds: The project was supported by the National Key R&D Program of China (2021YFA1502804), Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering (2022SX-FR001), the Key Projects of National Natural Science Foundation of China (21736007), and the Natural Science Foundation of Shanxi Province (20210302123094)

More Information

Corresponding author: E-mail: linglixia@tyut.edu.cn; wangbaojun@tyut.edu.cn
Received Date: 2022-10-23
Accepted Date: 2022-12-15
Rev Recd Date: 2022-12-08

Available Online: 2023-02-27

Publish Date: 2023-05-15

Abstract

Abstract

La₂O₃ as a catalyst is used for oxidative coupling of methane (OCM) reactions due to its excellent stability and high C₂ selectivity, but poor activity on methane dissociation limits its wide application. Different valence metals are doped on the La₂O₃(001) surface to improve the methane conversion activity, and the activation of methane on metal-doped La₂O₃(001) surfaces has been investigated via the density functional theory (DFT) calculations. The relationship between the valence states of doped metals and the methane conversion activities shows that doping low valence metals (Li, Na, K, Mg, Ca, Sr and Ba) and equivalent metals (Al, Ga, In) can significantly improve the conversion activity of methane. Among them, the activation energy of methane on the Li-La₂O₃(001) surface is the lowest, which is only 13.0 kJ/mol. However, doping of high valence metals (Zr, Nb, Re and W) cannot improve the CH₄ dissociation activity. Furthermore, the relationships between surface oxygen vacancy formation energies, acid-base properties and the activation energies of CH₄ have also been investigated. The results show that with the increase of metal valence state, the oxygen vacancy formation energy increases, while the dissociation activity of CH₄ decreases. The introduction of alkali and alkaline earth metals increases the alkalinity of La₂O₃(001) surface, and the alkalinity of La₂O₃(001) doped with the alkali metal is stronger than that with the alkaline earth metal, exhibiting higher dissociation activity of CH₄. Our research may provide a guide for improving methane conversion activity on La₂O₃ catalysts.
- methane,
- La₂O₃ catalyst,
- metal doping,
- activity,
- density functional theory

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References(40)

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