Methane Oxidation on the Surfaces of Manganese Oxides: a First Principles Study

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摘要 A comprehensive density functional theory calculation was employed to investigate the possible reaction pathways and mechanisms of methane complete oxidation (CH4 + 2O2 → CO2 + 2H2O) on different manganese oxides including -MnO2(100) and -MnO2(111) surfaces. According to a coupling of the Mars-van Krevelen and Langmuir-Hinshelwood mechanism, the activation energy barrier and the reaction energy of each elementary surface reaction were determined. Our calculated results show that the detailed processes for methane oxidation on two surfaces are different due to the differences in the surface structure. The breaking of the last C–H bond of CH4 molecule is the rate-determining step with an activation barrier of 0.85 eV for -MnO2(100) surface. By contrast, the overall reaction rate on -MnO2(111) surface is limited by the dissociation of the second O2 molecule adsorbed on the vacancy site, and re-oxidation of the reduced -MnO2(111) surface by the gaseous oxygen requires a much higher energy barrier of 1.44 eV. As a result, the -MnO2(100) exhibits superior activity and durability in the methane oxidation reaction than -MnO2(111) surface. The present study provides insight into understanding the structure-catalytic activity relationship of the catalysts based on manganese oxides towards the methane oxidation reaction.

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	王秉乾
	陶慧琳
	汤吉林
	李奕
	林伟
	章永凡

关键词 ： manganese oxides, methane oxidization, dehydrogenation, reaction mechanism, density functional theory

Abstract：A comprehensive density functional theory calculation was employed to investigate the possible reaction pathways and mechanisms of methane complete oxidation (CH4 + 2O2 → CO2 + 2H2O) on different manganese oxides including -MnO2(100) and -MnO2(111) surfaces. According to a coupling of the Mars-van Krevelen and Langmuir-Hinshelwood mechanism, the activation energy barrier and the reaction energy of each elementary surface reaction were determined. Our calculated results show that the detailed processes for methane oxidation on two surfaces are different due to the differences in the surface structure. The breaking of the last C–H bond of CH4 molecule is the rate-determining step with an activation barrier of 0.85 eV for -MnO2(100) surface. By contrast, the overall reaction rate on -MnO2(111) surface is limited by the dissociation of the second O2 molecule adsorbed on the vacancy site, and re-oxidation of the reduced -MnO2(111) surface by the gaseous oxygen requires a much higher energy barrier of 1.44 eV. As a result, the -MnO2(100) exhibits superior activity and durability in the methane oxidation reaction than -MnO2(111) surface. The present study provides insight into understanding the structure-catalytic activity relationship of the catalysts based on manganese oxides towards the methane oxidation reaction.

Key words： manganese oxides methane oxidization dehydrogenation reaction mechanism density functional theory

收稿日期: 2019-05-08 出版日期: 2020-08-12

基金资助:The project was supported by the National Natural Science Foundation of China (21773030) and Natural Science Foundation of Fujian Province (2017J01409)

通讯作者: zhangyf@fzu.edu.cn E-mail: zhangyf@fzu.edu.cn

引用本文:

王秉乾;陶慧琳;汤吉林;李奕;林伟;章永凡. Methane Oxidation on the Surfaces of Manganese Oxides: a First Principles Study[J]. 结构化学, 2020, 39(8): 1405-1421.
WANG Bing-Qian;TAO Hui-Lin;TANG Ji-Lin;LI Yi;LIN Wei;ZHANG Yong-Fan. Methane Oxidation on the Surfaces of Manganese Oxides: a First Principles Study. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2020, 39(8): 1405-1421.

链接本文:

http://manu30.magtech.com.cn/jghx/CN/ 或 http://manu30.magtech.com.cn/jghx/CN/Y2020/V39/I8/1405

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