Electrocatalytic influence of underpotential Tl, Pb and Bi monolayers on the electrochemical behaviour of rhodizonic acid and tetrahydroxy-1,4-benzoquinone on Pt in acid solutions

Add time:08/28/2019    Source:sciencedirect.com

The electrochemical behaviour of rhodizonic acid and tetrahydroxy-1,4-benzoquinone on bare Pt and Pt surfaces covered by heavy metal monolayers deposited at underpotentials was studied in aqueous 0.5 M HClO4 solutions. It was found that Tl, Pb and Bi monolayers catalyse markedly the oxidation of rhodizonic acid and tetrahydroxy-1,4-benzoquinone. The same underpotential layers improve the reversibility of the redox system tetrahydroxy-1,4-benzoquinone/hexahydroxybenzene. The enhancement of the overall oxidation and reduction processes has been interpreted in terms of the change of the reaction mechanism from an “inner sphere” mechanism on bare platinum to an “outer sphere” one of the Pt surfaces covered by underpotential layers. The two-electron oxidation of tetrahydroxy-1,4-benzoquinone to rhodizonic acid is followed by a rapid pseudo-first-order hydration reaction, the kinetics of which were studied by ring-disc experiments.

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