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Mechanistic aspects of the comparative oscillatory electrochemical oxidation of formic acid and methanol on platinum electrode

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Abstract

The characteristics of the electrochemical oscillations that emerge along the catalytic oxidation of small organic molecules critically depend on the coverage and nature of adsorbates. Herein we report experimental results on the electro-oxidation of formic acid and methanol on platinum and platinum-modified electrodes, and under conventional, i.e., cyclic voltammetry, and oscillatory conditions. The investigation was focused on the role played by surface-free sites and the presence of a step with a short-lived specie adsorbed on electrode surface. In order to reduce the coverage of adsorbed species, and thus to increase the main reaction pathway, chronoamperometry in platinum oxide region followed by potential sweeps or the adsorption of ad atoms, like tin, to mitigate the surface poisoning was adopted. Overall, those strategies considerably improved the electrochemical oxidation of formic acid, but had no effect for methanol. Our results show that the efficiency of formic acid electro-oxidation is preferred powered, compared with methanol, on a less poisoned electrode surface, which is obtained through a self-cleaning process driven by the oscillatory electro-oxidation of organic molecules. These results are rationalized in terms of peculiarities of the reaction mechanisms of both systems.

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Funding

NP and CR are indebted to Prof. Robert Schlögl and to the Max Planck Institute for Chemical Energy Conversion. MVLD (Grant No. 160511/2011-9) and HV (Grant No. 306060/2017-5) acknowledges Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) for financial support. NP (Grant No. 2015/18274-5) and HV (Grants Nos. 2012/24152-1 and 2013/16930-7) acknowledge São Paulo Research Foundation (FAPESP) for financial support. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Finance Code 001.

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Authors and Affiliations

  1. Federal University of São Carlos, São Carlos, SP, 13565-905, Brazil

    Nickson Perini

  2. Institute of Chemistry of São Carlos, University of São Paulo, POBox 780, São Carlos, SP, 13560-970, Brazil

    Marcelo V. F. Delmonde & Hamilton Varela

  3. Federal Institute for Education, Science and Technology of Parana, Umuarama, PR, Brazil

    Marcelo V. F. Delmonde

  4. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Banagalore, 560012, India

    Chinmoy Ranjan

  5. Max-Planck Institute for the Physics of Complex Systems, Nöthnitzer Str. 38, D-01187, Dresden, Germany

    Hamilton Varela

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  1. Nickson Perini
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  2. Marcelo V. F. Delmonde
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Correspondence to Nickson Perini.

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Perini, N., Delmonde, M.V.F., Ranjan, C. et al. Mechanistic aspects of the comparative oscillatory electrochemical oxidation of formic acid and methanol on platinum electrode. J Solid State Electrochem 24, 1811–1818 (2020). https://doi.org/10.1007/s10008-020-04609-y

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