Document Detail


CO electroxidation on gold in alkaline media: a combined electrochemical, spectroscopic, and DFT study.
MedLine Citation:
PMID:  20560579     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
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 other hand, 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) the apparent transfer coefficient of this unusual state is close to unity, suggesting that it is due to a presumed structural transformation coupled to OH adsorption. Finally, the effect of the adsorption potential on the bulk CO electrooxidation is also studied. It is found that, on Au(111), an increased occupation of CO on 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.
Authors:
Paramaconi Rodriguez; Nuria Garcia-Araez; Andrey Koverga; Stefan Frank; Marc T M Koper
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  Langmuir : the ACS journal of surfaces and colloids     Volume:  26     ISSN:  1520-5827     ISO Abbreviation:  Langmuir     Publication Date:  2010 Jul 
Date Detail:
Created Date:  2010-07-29     Completed Date:  2010-12-01     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9882736     Medline TA:  Langmuir     Country:  United States    
Other Details:
Languages:  eng     Pagination:  12425-32     Citation Subset:  -    
Affiliation:
Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands. rodriguezperezpb@chem.leidenuniv.nl
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