Electrocatalytic enhancement of formic acid oxidation reaction by acetonitrile on well-defined platinum surfaces

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Title: Electrocatalytic enhancement of formic acid oxidation reaction by acetonitrile on well-defined platinum surfaces
Authors: Briega-Martos, Valentín | Solla-Gullón, José | Koper, Marc T.M. | Herrero, Enrique | Feliu, Juan M.
Research Group/s: Electroquímica de Superficies | Electroquímica Aplicada y Electrocatálisis
Center, Department or Service: Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Electroquímica
Keywords: Formic acid oxidation | Platinum single crystal electrodes | Acetonitrile | Electrocatalysis
Knowledge Area: Química Física
Issue Date: 1-Feb-2019
Publisher: Elsevier
Citation: Electrochimica Acta. 2019, 295: 835-845. doi:10.1016/j.electacta.2018.11.016
Abstract: The formic acid oxidation reaction has been studied on Pt(111), Pt(100) and Pt nanoparticles with preferential (111) surface structure in 0.1 M HClO4 in the presence of different concentrations of acetonitrile. An electrocatalytic enhancement towards the formic acid oxidation has been observed under these conditions, and it is proposed that this enhancement is due to two different effects of the adsorbed acetonitrile species: a third-body effect which hinders the formation of CO and a promoting effect of the direct oxidation of formic acid. This promoting effect is structure sensitive. The different enhancement between Pt(111) and Pt(100) indicates that the ratio of free Pt sites and sites occupied by adsorbed acetonitrile is important in order to have the better electrocatalytic activity. On-line mass spectrometry (OLEMS) measurements confirmed the preference for the direct oxidation of formic acid to CO2, which is almost complete below 0.3 V vs. RHE for Pt(111). Finally, chronoamperometric studies confirmed the lower poisoning rate in the presence of acetonitrile but they also pointed out a competition of formed CO for the Pt sites occupied by acetonitrile species. This work constitutes an example of electrocatalytic enhancement by using an organic molecule for surface modification, which is not as common as using metallic adlayers.
Sponsor: This work has been financially supported by the MINECO-FEDER (Spain) through project CTQ2016-76221-P. V. B-M thankfully acknowledges to MINECO the award of a predoctoral grant (BES-2014-068176, project CTQ2013-44803-P) and a student stay grant (EEBB-I-16-11656). S-G. acknowledges financial support from Vicerrectorado de Investigación y Transferencia de Conocimiento of the University of Alicante (UATALENTO16-02).
URI: http://hdl.handle.net/10045/83609
ISSN: 0013-4686 (Print) | 1873-3859 (Online)
DOI: 10.1016/j.electacta.2018.11.016
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2018 Elsevier Ltd.
Peer Review: si
Publisher version: https://doi.org/10.1016/j.electacta.2018.11.016
Appears in Collections:INV - LEQA - Artículos de Revistas
INV - EQSUP - Artículos de Revistas

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