Half-wave potential as affected by supporting electrolyte nature: Interplay of adsorption and ionic association for electroreduction of V(V)-mixed addenda Keggin tungstophosphate

V(V)-mixed addenda Keggin tungstophosphate demonstrates the pronounced dependence of polarographic half-wave potential E1/2 at positively charged mercury surface on the nature of supporting alkali metal cation. This effect (typical for polyoxometalates) complicates the straightforward application of...

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Bibliographic Details
Published in:Electrochimica acta 2013-11, Vol.111, p.292-298
Main Authors: Pugolovkin, Leonid V., Naumova, Maria A., Fedorova, Anna A., Borzenko, Marina I., Tsirlina, Galina A.
Format: Article
Language:English
Subjects:
Adsorption
Cations
Electrolytes
Electroreduction
Ionic association
Isopolytungstate
Mercury (metal)
Reduction
Stabilization
Surface chemistry
Surface tension
V(V)-mixed addenda Keggin tungstophosphate
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Summary:V(V)-mixed addenda Keggin tungstophosphate demonstrates the pronounced dependence of polarographic half-wave potential E1/2 at positively charged mercury surface on the nature of supporting alkali metal cation. This effect (typical for polyoxometalates) complicates the straightforward application of E1/2 values to analysis of various thermodynamic trends and correlations. Cation-induced E1/2 shifts are explained under assumption of Keggin anions reduction from compact adlayers containing the cations. Strong adsorption of the reactant is confirmed by a decrease of interfacial surface tension and by pronounced inhibitory effect on the outer-sphere electron transfer reactions. Stabilization of adlayers by co-adsorbing supporting cations increases in a series Li+
ISSN:0013-4686
1873-3859
DOI:10.1016/j.electacta.2013.08.067