Kinetics of the Regeneration by Iodide of Dye Sensitizers Adsorbed on Mesoporous Titania
Regeneration of dye sensitizer molecules by reducing species contained in the electrolyte is a key mechanism in liquid dye-sensitized solar cells because it competes kinetically with a detrimental charge recombination process. Kinetics of the reduction by iodide ions of the oxidized states (S+) of two RuII complex dyes and four organic π-conjugated bridged donor−acceptor sensitizers were examined as a function of the electrolyte concentration. Results show that two different cases can be distinguished. A sublinear behavior of the regeneration rate and a plateau value reached at high bulk iodide concentrations were found for N820 ruthenium dye and interpreted as being due to an associative interaction involving the formation of (S+, I−)···I− surface complexes prior to the reaction. On the other hand, feeble reaction rates at low electrolyte concentrations and a superlinear behavior are observed predominantly for the organic dyes, pointing to a repulsive interaction between the dyed surface and iodide anions. At higher iodide bulk concentration, a linear behavior is reached, providing an estimate of a second-order rate constant. A correlation of these two opposite behaviors with the structure of the dye is observed, emphasizing the role of sulfur atoms in the association of I− anions in the dye-sensitized layer. These findings allow for a better understanding of the dye−electrolyte interaction and of the effect of the iodide concentration on the photovoltaic performances of dye-sensitized solar cells.
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Teuscher, J., Marchioro, A., Andrès, J., Roch, L. M., Xu, M., Zakeeruddin, S. M., Wang, P., Grätzel, M., & Moser, J.-E. (2014). Kinetics of the Regeneration by Iodide of Dye Sensitizers Adsorbed on Mesoporous Titania. Journal of Physical Chemistry C, 118(30), 17108–17115. https://doi.org/10.1021/jp501481c
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