Electrocatalytic enhancement of formic acid oxidation reaction by acetonitrile on well-defined platinum surfaces
Empreu sempre aquest identificador per citar o enllaçar aquest ítem
http://hdl.handle.net/10045/83609
Títol: | Electrocatalytic enhancement of formic acid oxidation reaction by acetonitrile on well-defined platinum surfaces |
---|---|
Autors: | Briega-Martos, Valentín | Solla-Gullón, José | Koper, Marc T.M. | Herrero, Enrique | Feliu, Juan M. |
Grups d'investigació o GITE: | Electroquímica de Superficies | Electroquímica Aplicada y Electrocatálisis |
Centre, Departament o Servei: | Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Electroquímica |
Paraules clau: | Formic acid oxidation | Platinum single crystal electrodes | Acetonitrile | Electrocatalysis |
Àrees de coneixement: | Química Física |
Data de publicació: | 1-de febrer-2019 |
Editor: | Elsevier |
Citació bibliogràfica: | Electrochimica Acta. 2019, 295: 835-845. doi:10.1016/j.electacta.2018.11.016 |
Resum: | 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. |
Patrocinadors: | 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 |
Idioma: | eng |
Tipus: | info:eu-repo/semantics/article |
Drets: | © 2018 Elsevier Ltd. |
Revisió científica: | si |
Versió de l'editor: | https://doi.org/10.1016/j.electacta.2018.11.016 |
Apareix a la col·lecció: | INV - LEQA - Artículos de Revistas INV - EQSUP - Artículos de Revistas |
Arxius per aquest ítem:
Arxiu | Descripció | Tamany | Format | |
---|---|---|---|---|
2019_Briega-Martos_etal_ElectActa_final.pdf | Versión final (acceso restringido) | 1,14 MB | Adobe PDF | Obrir Sol·licitar una còpia |
2019_Briega-Martos_etal_ElectActa_accepted.pdf | Accepted Manuscript (acceso abierto) | 818,52 kB | Adobe PDF | Obrir Vista prèvia |
Tots els documents dipositats a RUA estan protegits per drets d'autors. Alguns drets reservats.