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Formic Acid Oxidation at Ru@Pt Core-Shell Nanoparticles

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Abstract

Formic acid oxidation has been investigated at Ru@Pt core-shell nanoparticles for Pt coverages ranging from 0.4 to 1.9 monolayers (ML), in order to determine how the bi-functional and electronic effect of the Ru core and compression of the Pt lattice influence activity. By comparing voltammetric results with those for CO stripping and bulk oxidation, it has been shown that the electronic effect of the Ru core on CO oxidation is the dominant factor influencing formic acid oxidation. Thus, the indirect pathway through adsorbed CO begins at the lowest potential for sub-monolayer Pt coverages, and the formic acid oxidation rate increases as the Pt coverage is increased towards one monolayer. However, the electronic effect of the Ru becomes muted as a second Pt layer is added, CO oxidation is shifted to higher potentials and formic acid oxidation activity drops. The optimum coverage of Pt depends on a balance between the electronic effects of the Ru core on the promotion of CO oxidation and inhibition of formic acid oxidation through the direct pathway that does not produce adsorbed CO. Thus, a coverage of 0.85 ML Pt provided the best activity for 0.5 M formic acid, while 1.3 ML gave a particularly high activity for 2 M formic acid at low potentials.

One monolayer of Pt on a Ru core provides high activity for formic acid oxidation due to a strong electronic effect, while this becomes muted when a second layer of Pt is added

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Acknowledgments

This work was supported by the Natural Sciences and Engineering Research Council of Canada and Memorial University.

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Authors and Affiliations

  1. Department of Chemistry, Memorial University of Newfoundland, St. John’s, Newfoundland, A1B 3X7, Canada

    Ehab N. El Sawy & Peter G. Pickup

  2. Physical Chemistry Department, National Research Centre, El Buhouth St., Dokki, Cairo, 12311, Egypt

    Ehab N. El Sawy

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  1. Ehab N. El Sawy
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Correspondence to Peter G. Pickup.

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Supporting Information

Characterization data (EDS, TGA, STEM) and additional activity vs. coverage plots and chronoamperometry results are provided. (DOCX 1447 kb)

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El Sawy, E.N., Pickup, P.G. Formic Acid Oxidation at Ru@Pt Core-Shell Nanoparticles. Electrocatalysis 7, 477–485 (2016). https://doi.org/10.1007/s12678-016-0328-8

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