Abstract
The adsorption of species coming from the disodium salt of croconic acid (4,5-dihydroxy-4-cyclopentene-1,2,3-trione, H2C5O5) at chemically deposited silver electrodes was studied in aqueous sodium fluoride solutions by combining in situ ATR-SEIRAS (Surface-Enhanced Infrared Reflection Absorption Spectroscopy experiments under Attenuated Total Reflection conditions) and Density Functional Theory (DFT) calculations. Voltammetric experiments suggest the existence of reversible adsorption processes in the potential range between −0.55 and −0.20 V vs Ag/AgCl (KCl 1 M), whereas irreversible reduction is observed for potentials below-0.55 V. ATR-SEIRA spectra show potential-dependent adsorbate bands in the potential range for reversible adsorption, that were assigned according to DFT calculations. Calculated optimized geometry of adsorbed croconate and bicroconate correspond to bonding to the silver surface in a bidentate configuration through two oxygen atoms with the molecular plane perpendicular to the metal surface. The broadening and splitting at high electrode potentials of the CO stretching bands for adsorbates coming from croconic acid can be explained by invoking the existence of collective vibrational modes appearing at high coverage. In overall, the ATR-SEIRA spectra obtained with Ag thin layer electrodes resembles that reported for Au thin layers. As a difference, higher adsorbate coverage seems to be obtained in the case of silver. Moreover, a strong feature at ca. 1580 cm−1 is experimentally observed, that was much weaker on gold samples. The calculated frequencies for adsorbed croconate and bicroconate do not change significantly with the adsorption bonding sites for the optimized geometries. Taking into account the calculated frequencies of both types of species, a better agreement with the experimental behavior (including the splitting/shifting caused by dipole–dipole coupling in high-coverage collective modes) is obtained in the case of bicroconate. The coexistence with some adsorbed croconate species cannot be ruled out.
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