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The study investigates modified glassy carbon electrodes functionalized with manganese(III) complexes of various tetraazamacrocycles immobilized within a Nafion film. Spectroelectrochemical and electrochemical analyses revealed the oxidation mechanism from mononuclear to dinuclear di-μ-oxo manganese complexes and evaluated the electrode's stability, diffusion rates, and catalytic efficiency.

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Abstract

Modified electrodes were obtained by immobilizing Mn3+ complexes with the following tetraazamacrocycles (1,4,7,10-tetraazacyclododecane ([12]aneN4), 1,4,8,11-tetrazacyclotetradecane ([14]aneN4), 1,4,7,11-tetrazacyclotetradecane (iso[14]aneN4), and 1,4,8,12-tetrazacyclopentadecane ([15]aneN4) in a Nafion film on the surface of a glassy carbon electrode (GCE). Based on spectroelectrochemical, chronopotentiometric, and chronoamperometric studies, oxidation of mononuclear complexes to dinuclear di-μ-oxo complexes of Mn3+ and Mn4+ was observed, and the mechanism and influence of Nafion on this process were determined. On the basis of voltammetric and chronocoulometric studies, the electroactivity, stability, and diffusion rates of such modified electrodes were demonstrated. Based on voltammetric and chronocoulometric studies, their electrocatalytic properties were analyzed in relation to the oxidation of model compounds used in this type of research, namely, ascorbic acid, glycolaldehyde, and glycolic acid.

Key findings

  • Oxidation of mononuclear Mn(III) complexes leads to the formation of dinuclear di-μ-oxo complexes containing Mn(III) and Mn(IV) species.
  • The Nafion layer significantly influences the electrochemical process, affecting the stability and diffusion characteristics of the immobilized complexes.
  • The modified electrodes demonstrate effective electrocatalytic properties for the oxidation of model compounds including ascorbic acid, glycolaldehyde, and glycolic acid.

Keywords

NafionElectrocatalystGlassy carbonElectrodeInorganic chemistryAnode

Identifiers

DOI
10.3390/molecules31050800
Journal
Molecules
Year
2026