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Effect of Plasma-Assisted Electrochemical Treatment of Glassy Carbon Electrode on the Reversible and Irreversible Electrode Reactions

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Abstract

A glassy carbon electrode is modified by generating cathodic and anodic electrolytic plasma near its surface. Voltage pulses of amplitude up to 250 V, pulse-on time of 10 ms, and rise time <0.5 µs in the Na2SO4 aqueous solution are used to form plasma. It is found that, as a result of treatment by the anodic plasma, the glassy carbon surface acquires electrocatalytic properties toward the oxygen reduction reaction, whereas the cathodic plasma has no noticeable effect as compared to the pristine glassy carbon. At the same time, a pronounced effect of plasma-assisted electrochemical treatment of surface on the electron transfer rate constants is found only for the [Fe(CN)6]4–/3– redox reaction. By contrast, for the outer-sphere ([Ru(NH3)6]2+/3+) and inner-sphere (Fe2+/3+) reactions, the effect is not observed. It is supposed that the observed electrocatalytic effect toward the oxygen reduction reaction is caused by the formation of carbonyl fragments of functional groups, which are active centers of oxygen reduction, on the surface of glassy carbon electrode under the action of anodic plasma. However, they have no pronounced effect on the [Ru(NH3)6]2+/3+ and Fe2+/3+ redox systems.

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ACKNOWLEDGMENTS

We are grateful to A.A. Belmesov (Laboratory of Solid-State Electrochemical Systems) for AFM measurements, and to E.N. Kabachkov for XPS studies.

The work has been performed using the equipment of the Multi-User Analytical Center of IPCP RAS and the equipment of the Multi-User Center of Scientific Center in Chernogolovka RAS.

Funding

The work was performed on the State Assignment, State Registration number 0089-2014-0024.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432, Chernogolovka, Moscow oblast, Russia

    A. G. Krivenko & R. A. Manzhos

  2. Department of Chemistry, Moscow State University, 119992, Moscow, Russia

    V. K. Kochergin

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  1. A. G. Krivenko
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Correspondence to R. A. Manzhos.

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Krivenko, A.G., Manzhos, R.A. & Kochergin, V.K. Effect of Plasma-Assisted Electrochemical Treatment of Glassy Carbon Electrode on the Reversible and Irreversible Electrode Reactions. Russ J Electrochem 55, 663–671 (2019). https://doi.org/10.1134/S102319351907005X

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