CO electroxidation on gold in alkaline media: A combined electrochemical, spectroscopic, and DFT study

Research output: Contribution to journalArticlepeer-review

Authors

  • Paramaconi Rodriguez
  • Nuria Garcia-Araez
  • Andrey Koverga
  • Stefan Frank
  • Marc T M Koper

Colleges, School and Institutes

External organisations

  • FOM Institute for Atomic and Molecular Physics (AMOLF)
  • Leiden University
  • Leiden Institute of Chemistry
  • FOM Institute for Atomic and Molecular Physics - AMOLF

Abstract

The aim of the present work is to provide a deeper understanding of gold catalysis for CO electrooxidation in alkaline media, through a combined electrochemical, spectroscopic, and DFT study. Voltammetric and spectroscopic measurements evidence that the amount of CO irreversibly adsorbed on gold increases as the adsorption potential becomes more negative (vs SHE). This explains why higher CO coverages can be achieved in more alkaline solutions, since the value of adsorption potential vs RHE becomes more negative vs SHE with increasing pH. On the otherhand, the combination of FTIRRAS experiments and DFT calculations shows that the adsorption site of irreversibly adsorbed CO on Au(111) depends on the value of the adsorption potential. It is concluded that CO adsorption on top sites takes place at all studied potentials, and hollow and bridge sites also become occupied for adsorption potentials lower and higher than 0 V vs RHE, respectively. However, it should be noted that our DFT calculations give values of the CO binding energies that are not strong enough to explain CO irreversible adsorption. This may be partly attributed to the fact that OH coadsorption is not included in the calculations. Indeed, this work presents two experimental facts that suggest that CO adsorption on gold promotes the coadsorption of OH species: (i) CO irreversibly adsorbed on Au(111) and Au(100) leads to an unusual voltammetric feature, whose charge indicates the stabilization of one OH species per adsorbed CO species; (ii) theapparent transfer coefficient of this unusual state is close to unity, suggestingthat it is due to a presumed structural transformation coupled to OH adsorption. Finally, the effect of the adsorption potential on the bulkCO electrooxidation isalso studied. It is found that, on Au(111), an increased occupation ofCOon multifold (hollow) sites seems to result in a less efficient catalysis. However, on Au(110), an increased coverage of CO on top sites does not produce any significant change in catalysis.

Details

Original languageEnglish
Pages (from-to)12425-12432
Number of pages8
JournalLangmuir
Volume26
Issue number14
Publication statusPublished - 20 Jul 2010