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Formic acid oxidation on Pd/RuO2: does the RuO2 support enhance the electrocatalytic activity of Pd nanoparticles?

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Abstract

The aim of this work was to study the effect of a RuO2 support on the activity of Pd nanoparticles for formic acid oxidation, comparing the results with those obtained for Pd/C. In contrast with reports of enhancing effects of RuO2 for other systems, such as methanol oxidation on Pt particles, our data reveal a detrimental effect of the RuO2 support on the activity of Pd nanoparticles for the oxidation of formic acid. FTIR spectra show CO2 formation at potentials as low as 0.10 V and absence of adsorbed CO signals, suggesting that a bifunctional mechanism involving OH species on the oxide support surface does not occur nor has a significant contribution and that formic acid oxidation on Pd/RuO2 and Pd/C takes place by the direct pathway. The unfavorable effect of the RuO2 support on activity seems likely to be due to metal-support interactions that modify the Pd electronic properties.

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Acknowledgements

Thanks are also due to Prof. Edson C. Botelho, Prof. Paulo A. Suzuki, and Dr. Maurício R. Baldan for access to TGA, DRX, and SEM measurements; to Prof. Cecílio S. Fugivara for access to video recording during experiments; to the Structural Characterization Laboratory (LCE) - UFSCar for access to TEM facility; and to Cabot (Brazil) for supplying XC-72R carbon.

Funding

We gratefully acknowledge the financial support by Brazilian agencies Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) (476690/2013-7, 407143/2013-0), Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) (2015/21816-4), and PROPe/UNESP. G.M.A. and J.P. acknowledge the scholarships granted by FAPESP (18/20780-4) and PROPe/UNESP, respectively.

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Authors and Affiliations

  1. Institute of Chemistry, São Paulo State University (UNESP), Rua Prof. Francisco Degni, 55, Araraquara, São Paulo, 14800-060, Brazil

    Gabriel M. Alvarenga & Hebe M. Villullas

  2. School of Engineering and Sciences, São Paulo State University (UNESP), Av. Ariberto Pereira da Cunha, 333, Guaratinguetá, São Paulo, 12516-410, Brazil

    Julio Palombarini, Rosana A. Gonçalves, Olivia M. Berengue, Ronaldo S. Nunes & Eduardo G. Ciapina

  3. Center of Engineering, Modeling and Applied Social Sciences, Federal University of ABC-UFABC, Santo Andre, Sao Paulo, Brazil

    Sydney F. Santos

Authors
  1. Gabriel M. Alvarenga
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  2. Julio Palombarini
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  3. Rosana A. Gonçalves
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  4. Olivia M. Berengue
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  5. Ronaldo S. Nunes
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  6. Sydney F. Santos
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  7. Hebe M. Villullas
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  8. Eduardo G. Ciapina
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Corresponding authors

Correspondence to Hebe M. Villullas or Eduardo G. Ciapina.

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Supplementary Information

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10008_2023_5524_MOESM1_ESM.pdf

Supplementary file1 Supplementary material containing X-ray diffraction pattern of the RuOxHy precursor, EDS spectrum of Pd/RuO2, cyclic voltammogram recorded for Pd/RuO2 in Ar-saturated 0.1 M formic acid in 0.5 M H2SO4 solution, and in situ FTIR spectra are provided. (PDF 591 KB)

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Alvarenga, G.M., Palombarini, J., Gonçalves, R.A. et al. Formic acid oxidation on Pd/RuO2: does the RuO2 support enhance the electrocatalytic activity of Pd nanoparticles?. J Solid State Electrochem 27, 2465–2477 (2023). https://doi.org/10.1007/s10008-023-05524-8

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  • DOI: https://doi.org/10.1007/s10008-023-05524-8

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