Spectroscopic Evidence of Platinum Negative Oxidation States at Electrochemically Reduced Surfaces

Jalal Ghilane 1 Maryline Guilloux-Viry 1 Philippe Hapiot 1 Jacques Simonet 1 Corinne Lagrost 1 Michel Delamar 2 Claire Mangeney 2
1 ISCR - Institut des Sciences Chimiques de Rennes
2 ITODYS UMR7086 - Interfaces, Traitements, Organisation et Dynamique des Systèmes
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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Submitted on : Tuesday, November 20, 2007 - 11:08:24 AM
Last modification on : Friday, January 4, 2019 - 5:32:55 PM

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UNIV-RENNES1 | INSA-RENNES | UNIV-PARIS7 | SCR_MACSE | ISCR | ISCR-CSM | INC-CNRS | UR1-UFR-SPM | USPC | UNIV-RENNES | INSA-GROUPE

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Jalal Ghilane, Maryline Guilloux-Viry, Philippe Hapiot, Jacques Simonet, Corinne Lagrost, et al.. Spectroscopic Evidence of Platinum Negative Oxidation States at Electrochemically Reduced Surfaces. Journal of Physical Chemistry C, American Chemical Society, 2007, 111, pp.5701-5707. ⟨10.1021/jp068879d⟩. ⟨hal-00189100⟩

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