Citation: Bing-Qian WANG, Hui-Lin TAO, Ji-Lin TANG, Yi LI, Wei LIN, Yong-Fan ZHANG. Methane Oxidation on the Surfaces of Manganese Oxides: a First Principles Study[J]. Chinese Journal of Structural Chemistry, ;2020, 39(8): 1405-1421. doi: 10.14102/j.cnki.0254–5861.2011–2449 shu

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

College of Chemistry, Fuzhou University, Fuzhou 350116, China

Corresponding author: Yong-Fan ZHANG, zhangyf@fzu.edu.cn
Received Date: 8 May 2019
Accepted Date: 11 June 2020

Fund Project: the National Natural Science Foundation of China 21773030Natural Science Foundation of Fujian Province 2017J01409

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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 α-MnO₂(100) and β-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 α-MnO₂(100) surface. By contrast, the overall reaction rate on β-MnO₂(111) surface is limited by the dissociation of the second O₂ molecule adsorbed on the vacancy site, and re-oxidation of the reduced β-MnO₂(111) surface by the gaseous oxygen requires a much higher energy barrier of 1.44 eV. As a result, the α-MnO₂(100) exhibits superior activity and durability in the methane oxidation reaction than β-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.
- manganese oxides,
- methane oxidization,
- dehydrogenation,
- reaction mechanism,
- density functional theory
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