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Formic Acid Electrooxidation on Palladium Nano-Layers Deposited onto Pt(111): Investigation of the Substrate Effect

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Abstract

The influence of Pd nano-layers electro-deposited onto Pt(111) single crystal has been systematically studied toward the formic acid electrochemical oxidation reaction in H2SO4 and HClO4. The studied PdxML/Pt(111) surfaces (x = 1, 2, 5, and 16 monolayers (ML)) are all more active than Pt(111) toward formic acid oxidation, even if the activity is very sensitive to the Pd film thickness and morphology. In sulfate solution, the competitive adsorption of long-range ordered (bi)sulfate on the pseudomorphic Pd terraces effectively hinders the formic acid oxidation only on the thinnest films. We could observe the different roles of the (bi)sulfate adsorption on the first and on the following deposited Pd layers. The sulfate adsorption competitive role rapidly fades away beyond about 5 ML of equivalent thickness, due to the surface roughness increasing and terraces width diminishing. In perchlorate media, anions do not adsorb competitively with formic acid intermediates, allowing a larger activity of the formic acid oxidation up to about 5 ML. At higher thicknesses, the difference in activity between the two electrolytic media is reduced, and it drops in both electrolytes close to 0.5 V vs. RHE, where Pd surface oxides are formed. Coupling the electrochemical results with the Pd layer structural description previously obtained from in situ SXRD experiments, the outstanding activity of Pd1ML/Pt(111) observed in perchloric solution can be explained by the ligand effect of the underlying platinum atoms on the first pseudomorphic Pd layer. This advantageous effect is lost for Pd deposits thicker than 1 ML.

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The datasets generated during the current study are available from the corresponding author on request.

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Funding

This work has been financially supported by the CAPES (project 728714–3).

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Authors and Affiliations

  1. Univ. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP*, LEPMI, 38000 Grenoble, France, *Institute of Engineering and Management Univ. Grenoble Alpes, 38000, Grenoble, France

    Vanessa L. Oliveira, Yvonne Soldo-Olivier, Marian Chatenet & Eric Sibert

  2. Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trab. São-carlense 400, CP 780, CEP 13560-970, São Carlos, SP, Brazil

    Vanessa L. Oliveira & Edson A. Ticianelli

  3. CNRS, Univ. Grenoble Alpes, Institut Néel, 38042, Grenoble, France

    Yvonne Soldo-Olivier

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  1. Vanessa L. Oliveira
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Oliveira, V.L., Soldo-Olivier, Y., Ticianelli, E.A. et al. Formic Acid Electrooxidation on Palladium Nano-Layers Deposited onto Pt(111): Investigation of the Substrate Effect. Electrocatalysis 14, 561–569 (2023). https://doi.org/10.1007/s12678-023-00816-z

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