Coupling of anode reactions in the process of electrooxidation of glycine anion on gold

Ilya D. Zartsyn; Alexander V. Vvedenskii; Elena V. Bobrinskaya; Oleg A. Kozaderov

doi:10.17308/kcmf.2024.26/11938

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 https://orcid.org/0000-0003-2210-5543
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

DOI: https://doi.org/10.17308/kcmf.2024.26/11938

Keywords: Graph-kinetic analysis, Coupled processes, Electrooxidation, Glycine, Voltammetry

Abstract

Electrochemical processes involving organic substances are complex multi-stage reactions. In our opinion, it is incorrect to describe their kinetics using the principle of independent partial processes (or their individual stages) since electrode reactions can be coupled due to competition for active surface sites, due to common intermediate stages, or through an electron. In this case, the theory of coupled reactions or the graph-kinetic method should be used to provide the kinetic description of the process. In general, graph theory makes it possible to identify the relationship between the “structure” and the kinetic behavior of complex systems by means of graphical analysis. In the case of electrochemical reactions, structural elements are substances adsorbed on the metal surface and (or) a set of substances interacting in the reactions. The relationship between their concentrations can be characterized quantitatively by a transformation law, for example,
the law of effective masses. Thus, a graph is a set of reacting substances and a sequence of reactions represented graphically. Graphs allow setting a system of kinetic equations and analyzing them by associating a certain behavior of the system with the structure of the corresponding graph. Under the assumption that one intermediate particle is involved in each elementary stage, the kinetic expressions will be linear, which corresponds to the first-order reaction model.

Graph-kinetic analysis of the processes within the Au|Gly^–,OH^–,H₂O system confirmed that the partial multi-stage reactions of anode oxidation of glycine and hydroxyl anions are kinetically coupled. We obtained expressions for partial currents of electrooxidation of hydroxide ions and glycine anions during the anodic process occurring on gold in an alkaline glycinecontaining solution. It was shown that with an increase in the anode potential, the nature of the limiting stage of the anodicprocess changes.

Formal constants of rates and equilibria of electrochemical reactions involving particles of background electrolyte and glycinate ion were calculated. It was found that the rates of partial oxidation reactions of adsorbed OH particles and O H are significantly higher than those of organic anions (Gly^- and HCOO^–). This indicates that the kinetics of the electrooxidation processes of Glyis in the Au|Gly^-,OH^–,H₂O system are determined by the kinetic features of the electrooxidation reactions of hydroxide ions

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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

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., 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.)

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.)

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

Zhen Ch.-H. 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., Uczak T., Holze R. Electrocatalytic oxidation of mono- and polyhydric alcohols on gold and platinum. Journal of Applied Electrochemistry. 1997;27: 999–1011. https://doi.org/10.1023/a:1018422206817

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

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

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 potentiodynamic electroformation 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 oxygen 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

Burke L. D., Nugent P. F. The electrochemistry of gold: II the electrocatalytic behaviour of the metal in aqueous media. Gold Bull. 1998;31: 39–49. https://doi.org/10.1007/bf03214760

Brown D. H., Smith W. E., Fox P., Sturrock R. D. The reactions of gold (0) with amino acids and the significance of these reactions in the biochemistry of gold. Inorganica Chimica Acta. 1982:(67): 27–30. https://doi.org/10.1016/s0020-1693(00)85035-5

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