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Electro-oxidation of Ethanol on Rh/Pt and Ru/Rh/Pt Sub-monolayers Deposited on Au/C Nanoparticles

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Abstract

Electrocatalysts composed of Pt, and combined RhPt and RuRhPt sub-monolayers deposited on Au/C nanoparticles, were investigated for the electro-oxidation of ethanol. The Au/C substrates were characterized by transmission electron microscopy (TEM) and X-ray absorption near edge structure (XANES) in situ. The electrochemical activity and the products of the ethanol electro-oxidation were investigated by online differential electrochemical mass spectrometry (DEMS). TEM analysis of the Au/C substrate indicated a homogeneous dispersion of the Au atoms onto the carbon support, with particle sizes varying from 5 to 10 nm. The XANES results have evidenced lower increase of the Pt white line magnitude for the mixed layers as the electrode potential was increased. This was associated to a lower oxide formation at the Pt surface due to the presence of neighboring Rh and Ru atoms. Electrochemical stripping of adsorbed CO showed higher activities for the mixed layers as compared to the pure Pt layer and to Pt/C. The electrochemical results for the ethanol electro-oxidation evidenced very similar onset potential for the mixed sub-monolayers and Pt/C. DEMS measurements pointed out a negligible signal of CO2 for the pure Pt layer but an efficiency improvement for the CO2 formation when Rh was present on the electrocatalyst surface. The deposition of a second Pt layer induced a slight increase in the electrocatalyst activity and CO2 formation, which approached to that of Pt/C. It was demonstrated that the electrocatalyst efficiency can be hampered by optimizing the particle shell composition.

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Acknowledgments

The authors thank the Fundação de Amparo à Pesquisa do Estado de São Paulo for financial support, the Brazilian Synchrotron Light Laboratory (LNLS) for the XAS experiments, and the MINATEC, Grenoble, for the TEM measurements.

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Authors and Affiliations

  1. Instituto de Química de São Carlos, Universidade de São Paulo, CEP 13560-970, CP 780, São Carlos, SP, Brazil

    Fabio H. B. Lima, D. Profeti, D. Riello, E. A. Ticianelli & E. R. Gonzalez

  2. Laboratoire d’Electrochimie et de Physico-chimie des Matériaux et des Interfaces, LEPMI, UMR 5631 CNRS/Grenoble, BP 75, 38402, Saint Martin d’Hères Cedex, France

    M. Chatenet

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  1. Fabio H. B. Lima
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  2. D. Profeti
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  3. M. Chatenet
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  4. D. Riello
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  5. E. A. Ticianelli
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  6. E. R. Gonzalez
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Correspondence to Fabio H. B. Lima.

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Lima, F.H.B., Profeti, D., Chatenet, M. et al. Electro-oxidation of Ethanol on Rh/Pt and Ru/Rh/Pt Sub-monolayers Deposited on Au/C Nanoparticles. Electrocatal 1, 72–82 (2010). https://doi.org/10.1007/s12678-010-0014-1

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