STUDY OF THE MECHANISMS OF THE INITIAL STAGES OF MnO2 FORMATION IN SULPHATE AND ACETATE ELECTROLYTES USING THE RRDE METHOD IN COMPARISON WITH THE RESULTS OF QUANTUM-CHEMICAL CALCULATIONS
DOI:
https://doi.org/10.15421/jchemtech.v33i2.329025Keywords:
Mangan dioxide; RRDE; quantum chemical calculations.Abstract
The formation of selective electrodes with high sensitivity for electrochemical biosensors is one of the most important tasks in the development of such devices. Therefore, understanding the mechanisms of electrochemical formation of MnO2 as an electrode material is an important factor in the strategy of coating synthesis for the determination of hydrogen peroxide in microquantities. In this article, for the first time, such a mechanism is analysed by comparing RRDE (rotating disk electrode with a ring) measurements with the results of quantum chemical calculations. The investigation was carried out in sulphate solutions with pH 1, pH 2 and pH 3.5. In sulfate electrolytes with pH 1 and pH 2, the mechanism of direct electron transfer has been fixed at the potentials for the initiation of the oxidation reaction of Mn2+ particles. The proposed mechanism of oxidation of divalent manganese by active oxygen-containing particles was not recorded. But we do not exclude their influence at more positive potentials. We note the important influence of hydrolysis on the process, which is seen in the difference in RRDE dependences at different pH of solutions. We assume that with an increase in pH to 3.5, Mn3+ hydrolyzed complexes attach to the surface and further transformations are associated with oxidation in a dense surface coating. The process occurring in the acetate electrolyte was also investigated. The RRDE method confirmed the assumption of the possibility of disproportionation of Mn3+ particles to Mn2+ and Mn4+ in the composition of acetate complexes. SEM photographs of MnO2 coatings obtained in the studied electrolytes illustrate that the nature of the electrolyte and the pH of the solution affect the structure and morphology of the resulting precipitate.
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