Journal of Physical Chemistry C
Journal of Physical Chemistry C
5 years ago

Electrochemical and Computational Study of Ion Association in the Electroreduction of PW12O403–

Electrochemical and Computational Study of Ion Association in the Electroreduction of PW12O403–
J. M. Gómez-Gil, A. Molina, E. Laborda, R. G. Compton, J. Gonzalez
Insights into ion pairing effects on the redox properties of the Keggin-type polyoxotungstate PW12O403– are gained by combining electrochemical experiments and density functional theory (DFT) calculations. Such effects have been reported to affect the performance of these species as molecular electrocatalysts. Experimental square wave voltammetry (SWV) of the two-electron reduction of PW12O403– in acetonitrile evidences that the reduced forms PW12O404– and PW12O405– can be significantly stabilized by ion association. The strength and stoichiometry of the corresponding aggregates are estimated as a function of the nature of the cation (lithium, sodium, and tetramethylammonium) and the oxidation state of the polyoxometalate. The results obtained in combination with DFT enable us to examine the roles of the cation solvation and the charge number and distribution of the polyanions.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b07073

DOI: 10.1021/acs.jpcc.7b07073

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