Electroreduction of oxygen on glassy carbon electrodes modified with in situ generated anthraquinone diazonium cations |
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Authors: | Marko Kullapere Uno Mäeorg David J Schiffrin |
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Affiliation: | a Institute of Chemistry, University of Tartu, Jakobi 2, 51014 Tartu, Estonia b Department of Chemistry, UFMS, CP 549, Campo Grande, MS 79070-900, Brazil c Department of Chemistry, University of Liverpool, L69 7ZD Liverpool, United Kingdom |
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Abstract: | The electrochemical reduction of oxygen on glassy carbon (GC) electrodes modified with in situ generated diazonium cations of anthraquinone (AQ) has been studied using the rotating disk electrode (RDE) technique. The electrografting of the GC electrodes was carried out in two different media: in acetonitrile and in an aqueous acidic solution (0.5 M HCl). 1- and 2-Aminoanthraquinone were used as starting compounds for the formation of the corresponding diazonium derivatives. The anthraquinone diazonium cations were generated by reaction of the aminoanthraquinones with tert-butyl nitrite and sodium nitrite in acetonitrile and in 0.5 M HCl, respectively. For comparison purposes, the previously synthesised and crystallised diazonium tetrafluoroborates of anthraquinone were used for the GC surface modification. Cyclic voltammetry was employed to determine the surface concentration of AQ in O2 free 0.1 M KOH. The electrocatalytic behaviour towards O2 reduction was similar for all the AQ-modified electrodes studied. The kinetic parameters of oxygen reduction were determined using a surface redox catalytic cycle model. The rate constant of the reaction between the semiquinone radical anion of AQ and molecular oxygen was virtually independent of the point of attachment of the quinone to the electrode surface. |
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Keywords: | Oxygen reduction Electrocatalysis Anthraquinone In situ generation Diazonium |
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