Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy

Title

Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy

 Author

Huang, Yi Fan (Universiteit Leiden)
Kooyman, P.J. (TU Delft ChemE/Catalysis Engineering; University of Cape Town)
Koper, M.T.M. (Universiteit Leiden)

Date

2016-08-12

 Abstract

Understanding the atomistic details of how platinum surfaces are oxidized under electrochemical conditions is of importance for many electrochemical devices such as fuel cells and electrolysers. Here we use in situ shell-isolated nanoparticle-enhanced Raman spectroscopy to identify the intermediate stages of the electrochemical oxidation of Pt(111) and Pt(100) single crystals in perchloric acid. Density functional theory calculations were carried out to assist in assigning the experimental Raman bands by simulating the vibrational frequencies of possible intermediates and products. The perchlorate anion is suggested to interact with hydroxyl phase formed on the surface. Peroxo-like and superoxo-like two-dimensional (2D) surface oxides and amorphous 3D α-PtO2 are sequentially formed during the anodic polarization. Our measurements elucidate the process of the electrochemical oxidation of platinum single crystals by providing evidence for the structure-sensitive formation of a 2D platinum-(su)peroxide phase. These results may contribute towards a fundamental understanding of the mechanism of degradation of platinum electrocatalysts.


 To reference this document use:

http://resolver.tudelft.nl/uuid:bf0fec03-2b70-43f0-b859-aa55cd0454be

 DOI

https://doi.org/10.1038/ncomms12440

 ISSN

2041-1723

 Source

Nature Communications, 7

 Part of collection

Institutional Repository

 Document type

journal article

 Rights

© 2016 Yi Fan Huang, P.J. Kooyman, M.T.M. Koper
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