A first principles analysis of the electro-oxidation of CO over Pt(1 1 1)

Michael J. Janik, Matthew Neurock

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Abstract

First principle density functional theoretical calculations carried out within a constant potential half-cell formalism were used to model the electro-oxidation of CO over Pt(1 1 1). The method involves tuning the potential by the addition or removal of electrons from the system. The free energy for different adsorbed species within the double-layer is analyzed over a range of different potentials to establish the lowest energy states and the reaction energies that connect these states. The potentials are calculated based on a novel double-reference approach [J.S. Filhol, M. Neurock, Angew. Chem. Int. Ed. 45 (2006) 402] discussed earlier. The potential-dependent reaction energies are reported for the elementary steps of water activation in the presence of co-adsorbed CO and CO oxidation over the model Pt(1 1 1) surface. The potential-dependent activation barriers are computed for the key elementary steps in CO oxidation to develop a detailed reaction energy profile as a function of electrode potential. The results suggest that the coupling of co-adsorbed CO and OH controls the rate. Water activation, however, is necessary to supply a critical coverage of the surface OH oxidant.

Original languageEnglish (US)
Pages (from-to)5517-5528
Number of pages12
JournalElectrochimica Acta
Volume52
Issue number18
DOIs
StatePublished - May 10 2007

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Electrochemistry

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