Initial stages of Pt(111) electrooxidation: dynamic and structural studies by surface X-ray diffraction

In-situ surface X-ray diffraction is used to characterize the surface oxides on a Pt(111) surface in 0.1 M HClO4. Detailed analysis at two potentials confirms that the surface restructuring in the initial oxidation stages is consistent with a place exchange process between Pt and O atoms, and the ex...

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Bibliographic Details
Published in:Electrochimica acta 2017-01, Vol.224, p.220-227
Main Authors: Drnec, Jakub, Ruge, Martin, Reikowski, Finn, Rahn, Björn, Carlà, Francesco, Felici, Roberto, Stettner, Jochim, Magnussen, Olaf M., Harrington, David A.
Format: Article
Language:English
Subjects:
Anodizing
Diffraction
Electrolytes
Exchanging
Oxidation
Oxide
Oxides
Place exchange
Polycrystals
Pt oxidation
Surface X-ray diffraction
X-ray diffraction
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Summary:In-situ surface X-ray diffraction is used to characterize the surface oxides on a Pt(111) surface in 0.1 M HClO4. Detailed analysis at two potentials confirms that the surface restructuring in the initial oxidation stages is consistent with a place exchange process between Pt and O atoms, and the exchanged Pt atoms are located above their original positions in the Pt(111) lattice. The (1,1,1.5) reflection is used to dynamically study the surface during cyclic voltammetry. The restructuring associated with the place exchange initiates with the CV peak at 1.05V, even though multiple cycles to 1.17V lead to no changes in the CV. The restructuring is reversible below a critical coverage of place exchanged Pt atoms, which we estimate to be between 0.07 and 0.15 ML. Extensive cycling to potentials higher or equal to 1.17V leads to progressive disordering of the surface.
ISSN:0013-4686
1873-3859
DOI:10.1016/j.electacta.2016.12.028