Spectroelectrochemical and DFT approaches to the study of croconic acid adsorption at gold electrodes in acidic solutions
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Título: | Spectroelectrochemical and DFT approaches to the study of croconic acid adsorption at gold electrodes in acidic solutions |
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Autor/es: | Cheuquepán, William | Rodes, Antonio | Orts, José M. |
Grupo/s de investigación o GITE: | Grupo de Espectroelectroquímica y Modelización (GEM) |
Centro, Departamento o Servicio: | Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Electroquímica |
Palabras clave: | Croconic acid | Croconate anions | Gold | Thin film electrodes | ATR-SEIRAS | DFT |
Área/s de conocimiento: | Química Física |
Fecha de publicación: | 1-sep-2021 |
Editor: | Elsevier |
Cita bibliográfica: | Journal of Electroanalytical Chemistry. 2021, 896: 115396. https://doi.org/10.1016/j.jelechem.2021.115396 |
Resumen: | The adsorption of species coming from croconic acid (4,5-dihydroxy-4-cyclopentene-1,2,3-trione, H2C5O5, CA) at gold electrodes was studied spectroelectrochemically in aqueous perchloric acid solutions. Voltammetric experiments suggest the existence of reversible adsorption processes in the potential range between 0.30 and 0.80 V vs RHE. Surface-Enhanced Infrared Reflection Absorption Spectroscopy experiments under Attenuated Total Reflection conditions (ATR-SEIRA) show potential-dependent adsorbate bands in the latter potential range that, according to Density Functional Theory calculations, can be assigned to adsorbed croconate. Calculated optimized geometry corresponds to bonding of croconate species to the gold surfaces involving two oxygen atoms in a bidentate configuration, with the molecular plane perpendicular to the metal surface for low and high crocoanate coverage. For intermediate coverage, lateral repulsions between neighbor croconate adsorbates give rise to the tilting of the molecular plane. The broadening and splitting at high electrode potentials of the Csingle bondO stretching bands for adsorbed croconate can be explained by invoking the existence of collective vibrational modes appearing at high coverage. The cyclic voltammograms recorded in the CA-containing solutions also show the existence of reversible redox processes at potentials below 0.30 V involving adsorbed species, which are detected in the collected ATR-SEIRA spectra. |
Patrocinador/es: | The funding by Ministerio de Ciencia e Innovación through project PID2019-105653GB-100, by Conselleria d’Innovació, Universitats, Ciència i Societat Digital (Generalitat Valenciana, project PROMETEO/2020/063) and by the University of Alicante (VIGROB-263) is acknowledged. |
URI: | http://hdl.handle.net/10045/117618 |
ISSN: | 1572-6657 (Print) | 1873-2569 (Online) |
DOI: | 10.1016/j.jelechem.2021.115396 |
Idioma: | eng |
Tipo: | info:eu-repo/semantics/article |
Derechos: | © 2021 Elsevier B.V. |
Revisión científica: | si |
Versión del editor: | https://doi.org/10.1016/j.jelechem.2021.115396 |
Aparece en las colecciones: | INV - GEM - Artículos de Revistas |
Archivos en este ítem:
Archivo | Descripción | Tamaño | Formato | |
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Cheuquepan_etal_2021_JElectroanalChem_final.pdf | Versión final (acceso restringido) | 1,63 MB | Adobe PDF | Abrir Solicitar una copia |
Cheuquepan_etal_2021_JElectroanalChem_revised.pdf | Versión revisada (acceso abierto) | 2,64 MB | Adobe PDF | Abrir Vista previa |
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