Isolation of partial coupled processes of anodic oxidation of OH– ion on gold using a combination of a graph-kinetic analysis method and linear voltammetry data

  • Ilya D. Zartsyn Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation
  • Alexander V. Vvedenskii Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation
  • Elena V. Bobrinskaya Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation https://orcid.org/0000-0001-7123-4224
  • Oleg A. Kozaderov Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation https://orcid.org/0000-0002-0249-9517
Keywords: Electrode processes, Conjugation, Graphic-kinetic analysis, Adsorption, Voltammetry

Abstract

The presence of several interconnected electrochemical processes occurring on the surface of an electrode, strictly speaking, does not allow the use of the principle of independent reactions. Often, partial reactions of a complex multi-stage electrochemical process are coupled both through common intermediates and through the competitive adsorption of electroactive species. The presence of conjugation leads either to a change in the potential at which the corresponding electrochemical process becomes possible or to a change in the rate of partial processes. The latter is called kinetic coupling. This does not allow the simple calculation of the rate of each partial reaction as the difference between the current density of the target and background processes. The method of kinetic diagrams can be used to establish the kinetic patterns of
such processes. This study shows that this method is applicable not only for the analysis of coupled electrochemical processes of various types, but can also be used in obtaining partial currents of the stages of a separate complex electrode reaction occurring in a background solution. As an example, options for the kinetic modelling of the total voltammogram of the anodic process on an Au electrode in an aqueous alkaline medium in the mode of linear potential change are considered.

The stationary degrees of covering of the gold surface with various surface-active forms of oxygen are calculated depending on the electrode potential. It was established that the change in concentration of ОН- ions mainly affects the region of their adsorption potentials. A detailed analysis of stationary partial anodic processes in the Au|OH-,H2O system was carried out and the shape of the general stationary voltammogram was determined by calculation. The latter is in qualitative agreement with the experimental polarization dependence.

It was shown that the type of calculated polarization dependence is determined by the degree of reversibility of individual stages and the rate of their occurrence. The performed analysis is necessary not only for the detailed scheme of the background anodic reaction on gold in an alkaline solution, but also for the  ubsequent kinetic description of the electrooxidation process of organic substances on a gold electrode

Downloads

Download data is not yet available.

Author Biographies

Ilya D. Zartsyn, Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation

Dr. Sci. (Chem.), Professor of the
Department of Physical Chemistry of the Voronezh
State University (Voronezh, Russian Federation)

Alexander V. Vvedenskii, Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation

Dr. Sci. (Chem.), Full
Professor of the Department of Physical Chemistry of
the Voronezh State University (Voronezh, Russian
Federation)

Elena V. Bobrinskaya, Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation

Cand Sci. (Chem.), Associate
Professor of the Department of Physical Chemistry of
the Voronezh State University (Voronezh, Russian
Federation)

Oleg A. Kozaderov, Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation

Dr. Sci. (Chem.), Docent, Head
of the Department of Physical Chemistry, Voronezh
State University (Voronezh, Russian Federation)

References

Zartcyn I. D., Shugurov A. E., Marshakov I. K. Thermodynamic coupling of anode and cathodic reactions in case of metal dissolution in the electrolytes. Tambov University Reports. Series Natural and Technical Sciences. 1997;2: 23–26. (In Russ., abstract in Eng.). Available at: https://w w w.elibrar y.ru/item.asp?id=16398081

Zartcyn I. D., Shugurov A. E., Marshakov I. K. The anomalous dissolution of iron as a result of the chemical conjugation between iron ionization and hydrogen evolution. Protection of Metals. 2001;37(2): 138–143. https://doi.org/10.1023/a:1010369904266

Zartcyn I. D., Shugurov A. E., Marshakov I. K. Kinetics of chemically conjugate reactions of metal dissolution in the presence of oxidant. Protection of Metals. 2000;36(2): 140–145. https://doi.org/10.1007/bf02758337

Zhen C.-H., Sun S.-G., Fan C.-J., Chen S.-P., Mao B.-W., Fan Y.-J. In situ FTIRS and EQCM studies of glycine adsorption and oxidation on Au (111) electrode in alkaline solutions. Electrochimica Acta. 2004;49(8): 1249–1255. https://doi.org/10.1016/j.electacta.2003.09.048

Chun-Hua Z., Chun-Jie F., Yan-Juan G., Sheng- Pei C., Shi-Gang S. Adsorption and oxidation of glycine on Au film electrodes in alkaline solutions. Acta Physico-Chimica Sinica. 2003;19: 60–64. https://doi.org/10.3866/pku.whxb20030114

Beltowska-Brzezinka M., Łuczak T., Holze R. Electrocatalytic oxidation of mono- and polyhydric alcohols on gold and platinum. Journal of Applied Electrochemistry. 1997;27(9): 999–1011. https://doi.org/10.1023/A:1018422206817

Kraschenko T. G., Bobrinskaya E. V., Vvedenskii A. V., Kuleshova N. E. Kinetics of electrochemical oxidation of anion glycine on gold. Condensed Matter and Interphases. 2014;16 (1): 42–49. (In Russ., abstract in Eng.). Available at: https://www.elibrary.ru/item.asp?id=21490889

Goldshtein B. N., Volkenshtein M. V. Investigation of nonstationary complex monomolecular reactions by the graph method*. Doklady of the USSR Academy of Sciences. 1968;78: 386–388. (In Russ.)

Goldshtein B. N., Magarshak D. B., Volkenshtein M. V. Analysis of monosubstrate enzyme reactions by graph method*. Doklady of the USSR Academy of Sciences. 1970;191: 1172–1174. (In Russ.)

Goldshtein B. N., Shevelev E. A., Volkenshtein M. V. Stability analysis of enzyme systems with feedbacks by the graph method*. Doklady of the USSR Academy of Sciences. 1983;273: 486–488. (In Russ.)

Goldshtein B. N., Volkenshtein M. V. Simple kinetic models explaining critical phenomena in enzymatic reactions with enzyme and substrate isomerization*. Doklady of the USSR Academy of Sciences. 1988;22: 1381–1392. (In Russ.)

Štrbac S., Hamelin A., Adžić R. R. Electrochemical indication of surface reconstruction of (100), (311) and (111) gold faces in alkaline solutions. Journal of Electroanalytical Chemistry. 1993;362: 47–53. https://doi.org/10.1016/0022-0728(93)80005-3

Chang S. C., Ho Y., Weaver M. J. Applications of real-time FTIR spectroscopy to the elucidation of complex electroorganic pathways: electrooxidation of ethylene glycol on gold, platinum, and nickel in alkaline solution. Journal of the American Chemical Society. 1991;113(25): 9506–9513. https://doi.org/10.1021/ja00025a014

Beltramo G. L., Shubina T. E., Koper M. T. M. Oxidation of formic acid and carbon monoxide on gold electrodes studied by surface-enhanced Raman spectroscopy and DFT. ChemPhysChem. 2005;6: 2597–2606. https://doi.org/10.1002/cphc.200500198

Martins M. E., Córdova O. R., Arvia A. J. The potentio dynamic electro for mation and electroreduction of the O-containing layer on gold in alkaline solutions. Electrochimica Acta. 1981;26: 1547–1554. https://doi.org/10.1016/0013-4686(81)85127-4

Bruckenstein S., Shay M. An in situ weighing study of the mechanism for the formation of the adsorbed exygen monolayer at gold electrode Journal of Electroanalytical Chemistry and Interfacial Electrochemistry. 1985;188: 131–136. https://doi.org/10.1016/s0022-0728(85)80057-7

Burke L. D. Cunnane V. J., Lee B. H. Unusual postmonolayer oxide behavior of gold electrodes in base. Journal of The Electrochemical Society. 1992;139: 399–406. https://doi.org/10.1149/1.2069230

Vitus C. M., Davenport A. J. In situ scanning tunneling microscopy studies of the formation and reduction of a gold oxide monolayer on Au(111). Journal of The Electrochemical Society. 1994;1413(5): 1291–1298. https://doi.org/10.1149/1.2054912

Goldshtein B. N., Zalkind Ts. I., Veselovskii V.I. Electrochemical adsorption of oxygen on a gold electrode in solutions of chloric and sulfuric acids*. Soviet Electrochemistry. 1973;9 (5): 699–702. (In Russ.)

Chen A., Lipkowski J. Electrochemical and spectroscopic studies of hydroxide adsorption at the Au(111) electrode. The Journal of Physical Chemistry B. 1999;103: 682–691. https://doi.org/10.1021/jp9836372

Vetter K. J. Elektrochemische kinetik. Springer Berlin, Heidelberg; 1961. https://doi.org/10.1007/978-3-642-86547-3

Tremiliosi-Filho G., Gonzalez E. R., Motheo A. J., Belgsir E. M., Léger J.-M., Lamy C. Journal of Electroanalytical Chemistry. 1998;444: 31–39. https://doi.org/10.1016/S0022-0728(97)00536-6

Nechaev I. V., Vvedenskii A. V. Quantum chemical modeling of hydroxide ion adsorption on group IB metals from aqueous solutions. Protection of Metals and Physical Chemistry of Surfaces. 2009;45(4): 391–397. https://doi.org/10.1134/s2070205109040029

Patritio E. M., Olivera P. P., Sellers H. The nature of chemosorbed hydroxyl radicals. Surface Science. 1994;306: 447–458. https://doi.org/10.1016/0039-6028(94)90085-x

Alonso C., Gonzalez-Velasco J. Study of the electrooxidation of 1,3-propanediol on a gold electrode in basic medium. Journal of Applied Electrochemistry. 1988;18: 538–545. https://doi.org/10.1007/bf01022248

Safronov A. U., Kristensen P. A. IR spectroscopic characteristics of the surface of the gold electrode in solutions with different pH*. Soviet Electrochemistry. 1990;26(7): 869–873. (In Russ.)

Kirk D. W., Foulkes F. R., Graydon W. F. The electrochemical formation of Au(I) hydroxide on gold in aqueous potassium hydroxide. Journal of The Electrochemical Society. 1980;127(10): 1069–1076. https://doi.org/10.1149/1.2129819

Icenhower D. E., Urbach H. B., Harrison J. H. Use of the potential-step method to measure surface oxides. Journal of The Electrochemical Society. 1970; 117(12): 1500–1506. https://doi.org/10.1149/1.2407359

Štrbac S., Adžić R. R. The influence of OHchemisorption on the catalytic properties of gold single crystal surfaces for oxygen reduction in alkaline solutions. Journal of Electroanalytical Chemistry. 1996;403: 169–181. https://doi.org/10.1016/0022-0728(95)04389-6

Burke L. D. Scope for new applications for gold arising from the electrocatalytic behaviour of its metastable surface states. Gold Bulletin. 2004;37(1-2): 125–135. https://doi.org/10.1007/bf03215520

Dobberpuhl D. A., Johnson D. C. Pulsed electrochemical detection at ring of a ring-disk electrode applied to a study of amine adsorption at gold electrodes. Analytical Chemistry. 1995;67: 1254–1258. https://doi.org/10.1021/ac00103a017

Xiao Sun S.-G., Yao J.-L., Wu Q.-H., Tian Z.-Q. Surface-enhanced Raman spectroscopic studies of dissotiative adsorption of amino acids on platinum and gold electrodes in alkaline solutions. Langmuir. 2002;18: 6274-6279. https://doi.org/10.1021/la025817f

Hill T. L. Studies in irreversible thermodynamic IV. Diagramatic representation of steady state fluxes for unimolecular systems. Journal of Theoretical Biology. 1966; 10: 442–459. https://doi.org/10.1016/0022-5193(66)90137-8

Goldshtein B. N. Kinetic graphs in enzymology. Мoscow: Nauka Publ.; 1989. 164 p. (In Russ.)

Volkenshtein M. V., Goldshtein B. N., Stefanov V. E. Investigation of nonstationary enzyme reactions. Doklady of the USSR Academy of Sciences. 1967;1: 52–58. (In Russ.)

Suhotin A. M. Handbook of electrochemistry*. Мoscow: Khimiya Publ.; 1981. 487 p. (In Russ.)

Published
2024-01-31
How to Cite
Zartsyn, I. D., Vvedenskii, A. V., Bobrinskaya, E. V., & Kozaderov, O. A. (2024). Isolation of partial coupled processes of anodic oxidation of OH– ion on gold using a combination of a graph-kinetic analysis method and linear voltammetry data. Kondensirovannye Sredy I Mezhfaznye Granitsy = Condensed Matter and Interphases, 26(1), 55-67. https://doi.org/10.17308/kcmf.2024.26/11809
Section
Original articles

Most read articles by the same author(s)

<< < 1 2