First-Principles Microkinetic Modeling of Methane Oxidation over Pd(100) and Pd(111)
Journal article, 2016

The intrinsic activity of Pd(100) and Pd(111) for methane oxidation is investigated by Density Functional Theory (DFT)-based mean-field microkinetic modeling. The model includes 32 reaction steps, and the calculated turnover frequencies together with reaction orders compare favorably with experimental data. On both surfaces, the reaction proceeds via complete dehydrogenation of methane to elemental carbon followed by different mechanisms for carbon oxidization. Pd(100) is found to be more active than Pd(111) at temperatures from 400 to 1000 K. For both surfaces, the reaction order in methane approaches unity with increasing temperature. The reaction order in water is positive at low temperatures owing to water-promoted carbon oxidation. Methane dissociation is the main rate-controlling step for Pd(111), whereas formation of COH and CO is also controlling the rate over Pd(100). The present work uncovers the detailed reaction mechanisms for complete methane oxidation over palladium, which can be used in catalyst design to target the rate-controlling steps.

methane oxidation

heterogeneous catalysis




microkinetic modeling



Mikkel Jørgensen

Competence Centre for Catalysis (KCK)

Chalmers, Physics, Chemical Physics

Henrik Grönbeck

Competence Centre for Catalysis (KCK)

Chalmers, Physics, Chemical Physics

ACS Catalysis

2155-5435 (eISSN)

Vol. 6 10 6730-6738

Areas of Advance

Nanoscience and Nanotechnology (2010-2017)

Subject Categories

Physical Chemistry

Other Physics Topics

Theoretical Chemistry

Condensed Matter Physics


C3SE (Chalmers Centre for Computational Science and Engineering)



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