DFT and spectroelectrochemical study of cyanate adsorption on gold single crystal electrodes in neutral medium

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Title: DFT and spectroelectrochemical study of cyanate adsorption on gold single crystal electrodes in neutral medium
Authors: Cheuquepán, William | Orts Mateo, José M. | Rodes García, Antonio | Feliu, Juan M.
Research Group/s: Grupo de Espectroelectroquímica y Modelización (GEM) | Electroquímica de Superficies
Center, Department or Service: Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Electroquímica
Keywords: Cyanate adsorption | DFT | IRRAS | Cyclic voltammetry | Au(111) | Au(100) | Gold single crystal electrodes
Knowledge Area: Química Física
Issue Date: 15-May-2017
Publisher: Elsevier
Citation: Journal of Electroanalytical Chemistry. 2017, 793: 147-156. doi:10.1016/j.jelechem.2016.10.011
Abstract: The adsorption of cyanate anions at Au(111) and Au(100) single crystal electrodes has been studied spectroelectrochemically in neutral solutions. Potential-dependent in situ InfraRed Reflection Absorption spectra obtained below the onset of cyanate oxidation were compared with previously published data and analyzed on the basis of periodical Density Functional Theory (DFT) calculations. The calculated adsorption energies for cyanate and related species suggest that cyanic and isocyanic acid adsorb weakly at the studied gold surfaces and, thus, seems not to be at the origin of any of the adsorbate bands in the experimental infrared spectra collected in the cyanate-containing solutions. The latter features can be clearly ascribed to the asymmetric OCN stretching of N-bonded cyanate species. The observation of absorption bands in a wide spectral region, including features above 2200 cm− 1, agrees with the coexistence of N-bonded cyanate species with different adsorption sites and tilting angles. DFT calculations have revealed that although these adspecies can have significantly different frequencies, their adsorption energies are rather close. In addition, the existence of collective in-phase vibrations at relatively high cyanate coverages also contributes to the widening of the absorption bands.
Sponsor: The authors acknowledge the funding by the Ministerio de Economía y Competitividad (project CTQ2013-44083-P) and the University of Alicante (VIGROB-263). William Cheuquepán is grateful for the award of a F.P.I. grant associated to project CTQ2009-13142.
URI: http://hdl.handle.net/10045/67737
ISSN: 1572-6657 (Print) | 1873-2569 (Online)
DOI: 10.1016/j.jelechem.2016.10.011
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2016 Elsevier B.V.
Peer Review: si
Publisher version: http://dx.doi.org/10.1016/j.jelechem.2016.10.011
Appears in Collections:INV - EQSUP - Artículos de Revistas
INV - GEM - Artículos de Revistas

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