Topics in Catalysis

, Volume 56, Issue 11, pp 874–884 | Cite as

Decomposition of Ethanol Over Ru(0001): A DFT Study

Original Paper

Abstract

We studied decomposition pathways of ethanol on Ru(0001) with periodic slab-model calculations using a DFT-GGA approach. We calculated the adsorption modes of ethanol and several of its dehydrogenation products and we evaluated reaction energies as well as activation barriers of pertinent dehydrogenation, C–C, and C–O cleavage steps. The calculated barrier heights of C–C and C–O scission steps can be related to the number of hydrogen atoms bound to the C1–C2 and C1–O moieties of the intermediates, respectively. Two counteracting effects are at work, increasing with each dehydrogenation: (i) higher order of the pertinent bond of the adsorbate, and (ii) stronger substrate-surface interaction and thus better stabilization of the transition state. For most intermediates we determined C–O cleavage to be both kinetically and thermodynamically favored over C–C scission, except for the highly dehydrogenated species CH k CO (k = 1, 2). Based on the calculated energetics, the most likely decomposition pathway, with a rate-determining barrier at 77 kJ·mol−1, leads to the formation of ketene CH2CO and subsequent C–C cleavage yielding methylene and CO.

Keywords

Ethanol Ru(0001) DFT Biomass Catalysis 

Notes

Acknowledgments

C.C.C. is grateful for a fellowship by the International Graduate School of Science and Engineering at Technische Universität München. The work of N.R. was supported by Fonds der Chemischen Industrie. We acknowledge generous computing resources at Leibniz Rechenzentrum München.

Supplementary material

11244_2013_51_MOESM1_ESM.pdf (1.1 mb)
Supplementary material 1 (PDF 1171 kb)

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Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  • Cheng-chau Chiu
    • 1
  • Alexander Genest
    • 1
    • 2
  • Notker Rösch
    • 1
    • 2
  1. 1.Department Chemie and Catalysis Research CenterTechnische Universität MünchenGarchingGermany
  2. 2.Institute of High Performance ComputingAgency for Science, Technology and ResearchSingaporeSingapore

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