Structure of the electrochemical interface of mechanically renewable graphite electrode with aqueous solutions of surface inactive electrolyte

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Abstract

Using the method of electrochemical measurements on electrodes with mechanically renewable surface, we studied the behavior of graphite electrode in aqueous solutions of surface inactive electrolytes. The potential region in which this electrode can be considered as ideally polarizable was found. Capacitance curves measured in this potential range have some characteristic properties. Namely, the values of double layer capacitance on graphite electrode at potentials corresponding to positive surface charges (σ > 0) are ca. 1.5–2 times lower than those values at typical mercury-like metals. At the same time, we can observe that these double layer capacitances draw together (up to practical confluence) at potentials corresponding to negative surface charges (σ < 0). Analysis of experimental data have shown that peculiarities of capacitance curves on graphite electrode are resulted from the semi-conductive properties of material of this electrode. We have proposed and substantiated new approach to the model description of experimental data that allowed us to quantitatively estimate the values of such important semi-conductive parameters as a flat-band potential and a concentration of charges in the conduction zone of the graphite material under consideration. Taking into account the active use of graphite and other carbon materials in science and practice, we believe that results of this investigation will promote to more deep understanding the mechanism of electrochemical processes realizing on like materials in different systems.

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V. А. Safonov

M.V. Lomonosov Moscow State University

Author for correspondence.
Email: safon@elch.chem.msu.ru

Faculty of Chemistry

Russian Federation, Moscow

М. A. Choba

M.V. Lomonosov Moscow State University

Email: safon@elch.chem.msu.ru

Faculty of Chemistry

Russian Federation, Moscow

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2. Fig. 1. CVA dependences measured in narrow (from –0.8 to 0.2 V) and wider (from –1.2 to 0.4 V) potential regions on a graphite electrode in an aqueous solution of 0.05 M KPF6 at a potential scanning rate of 50 mV/s (explanations in the text).

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3. Fig. 2. Nyquist diagrams on a renewable graphite electrode in a 0.05 M KPF6 solution, measured at three potential values ​​(shown in the figure) in the region of ideal polarizability. The dots are experimental data, the solid lines are the results of calculations within the equivalent circuit shown in the inset (explanations in the text).

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4. Fig. 3. (a) Calculated from impedance diagrams the dependence of the capacitance of the double electric layer of the graphite electrode (per unit of visible surface) on the potential in aqueous solutions of KPF6 of different concentrations, M: (1) 0.2, (2) 0.1, (3) 0.05, (4) 0.025, (5) 0.0125; (b) the Parsons-Zobel dependence constructed from data at the minimum potential (i.e., at Eσ = 0).

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5. Fig. 4. Calculated from impedance diagrams of the dependence of the capacity of the DEL of a graphite electrode (related to the unit of true surface) on the potential in aqueous solutions of KPF6 of different concentrations, M: (1) 0.2, (2) 0.1, (3) 0.05, (4) 0.025, (5) 0.0125.

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6. Fig. 5. Comparison of the C, E-dependencies calculated taking into account the roughness coefficient on a graphite electrode in KPF6 solutions of the following concentrations, M: (1) 0.1, (2) 0.025 with the C, E-dependencies given in [23] on a mercury electrode (3, 4) in similar solutions. The inset shows an equivalent circuit simulating the structure of the interface between a semiconductor electrode and a solution of a surface-inactive electrolyte, where C1 is the capacitance characterizing the surface layer of the electrode (space charge region), and C2 is the capacitance of the double layer at the interface between the electrode and the electrolyte, which can be represented as series-connected capacitances of the dense and diffuse layers.

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7. Fig. 6. Dependences of the capacity (1, 2) and charge (1 ʹ, 2 ʹ) of the DES on the potential φ in 0.1 M KPF6 on a renewable graphite electrode (1 and 1 ʹ) and a mercury electrode (2 and 2 ʹ), simulating the boundary of the graphite electrode with the electrolyte solution.

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8. Fig. 7. Dependences of potentials φ1 (1) and φ2(2) on the total potential jump φ.

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9. Fig. 8. Calculated dependencies (a) C1 – φ1 on a renewable graphite electrode in KPF6 solutions of different concentrations (shown in the figure); (b) the same dependencies in Mott–Schottky coordinates.

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Note

The article was presented by a participant in the All-Russian Conference “Electrochemistry-2023”, held from October 23 to October 26, 2023 in Moscow at the Institute of Physical Chemistry and Electrochemistry named after A.N. Frumkin RAS.


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