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Spectroscopic Evidence of Platinum Negative Oxidation States at Electrochemically Reduced Surfaces

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Sciences Chimiques de Rennes, Université de Rennes 1, UMR CNRS n°6226, Campus de Beaulieu, 35042 Rennes, France, and Itodys, Université de Paris 7-Denis Diderot, UMR CNRS n°7086, 1 rue Guy de la Brosse, 75005 Paris, France
Cite this: J. Phys. Chem. C 2007, 111, 15, 5701–5707
Publication Date (Web):March 28, 2007
https://doi.org/10.1021/jp068879d
Copyright © 2007 American Chemical Society

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    Abstract

    Electrochemical “reduction” of Pt was investigated using electrochemical and X-ray photoelectron spectroscopy (XPS) techniques. This transformation of a platinum metal, which is possible with a large variety of organic and inorganic cations, was investigated in DMF containing CsI salts chosen as a test system. Experiments show that considerable modifications of the chemical nature of the starting material accompany the morphological changes that were previously reported. With rather mild reduction conditions, cesium-platinides-like structures were detected. XPS investigations bring a direct spectroscopic evidence for the formation of a reduced platinum state from a metallic electrode held at a negative potential. XPS spectra clearly showed a significant and continuous shift of the Pt formal oxidation degree with the injected charge of −1.6. This behavior is analogous to a charging process. Additionally, proofs of the full reversibility of the phenomenon was provided by the XPS analyses showing that the “reduced Pt” returns to its metallic state after reaction with a diazonium salt. It is noticeable that the formation of negative oxidation state of Pt exists even when a large competitive electrochemical process occurs, as in our case with the reduction of protons from residual water.

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     Sciences Chimiques de Rennes − University of Rennes 1.

     Itodys -University of Paris 7.

    *

     To whom correspondence should be addressed.

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