Electrochemical reduction of nitrate ions on copper coatings of various roughness under conditions of mixed transport and kinetic control

Authors

  • Frol A. Vdovenkov Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation
  • Oleg A. Kozaderov Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation
  • Pavel P. Tarakanov Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation
  • Pavel V. Fomin Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation

DOI:

https://doi.org/10.17308/kcmf.2026.28/13556

Keywords:

Surface roughness, Copper coating, Nitrate ion, Electrochemical reduction, Mixed kinetics, Atomic force microscopy, Voltammetry

Abstract

Objectives: In this work, the influence of electrode surface roughness on the kinetics of the non-stationary electrochemical process of cathodic reduction of nitrate ion under conditions of mixed transport-kinetic control under potentiostatic polarization conditions is established.

Experimental: The research was carried out on two copper coatings obtained by galvanostatic deposition from a copper sulfate electrolyte, which was supplemented with various organic additives to vary the roughness of the synthesized copper coatings. The kinetics of the electrochemical reduction of nitrate ions on the obtained copper coatings were studied by transient electrochemical methods of voltammetry and chronoammetry in an aqueous deaerated solution of 10 mM KNO3 + 100 mM H2SO4. Potentiostatic measurements were performed at a cathodic potential of -470 mV, corresponding to a mixed transport-kinetic control. The surface roughness of the synthesized copper coatings was evaluated using atomic force microscopy and underpotential deposition of lead monolayer.

Conclusion: Based on the previously developed theoretical model of the electrochemical process occurring in a mixed transport-kinetic mode on a rough electrode, an approach is proposed for estimating the main parameters of the kinetic stage, taking into account normalization to the real surface area, using the example of the electrichemical reduction of nitrate ions on copper coatings of various roughness. Within the framework of this approach, it was found that a rougher copper coating is characterized by higher values of the heterogeneous constant of the rate and density of the exchange current, which indicates an increase in the electrocatalytic activity of copper in the reaction under study during the transition to electrodes with increased roughness

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Author Biographies

  • Frol A. Vdovenkov, Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation

    postgraduate student, Department of Physical Chemistry, Faculty of Chemistry, Voronezh State University (Voronezh, Russian Federation)

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

    Dr. Sci. (Chem.), Leading Researcher at the Laboratory of organic additives for the processes of chemical and electrochemical deposition of metals and alloys used in the electronics industry, Voronezh State University (Voronezh, Russian Federation)

  • Pavel P. Tarakanov, Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation

    student, Department of Physical Chemistry, Faculty of Chemistry, Voronezh State University (Voronezh, Russian Federation)

  • Pavel V. Fomin, Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation

    student, Department of Physical Chemistry, Faculty of Chemistry, Voronezh State University (Voronezh, Russian Federation)

References

1. Trasatti S., Parsons R. Interphases in systems of conducting phases (Recommendations 1985). Pure and Applied Chemistry. 1986;58(3): 437–454. https://doi.org/10.1351/pac198658030437

2. Bard A. J., Inzelt G., Scholz F. (Eds.). Electrochemical dictionary. Berlin, Heidelberg: Springer Berlin Heidelberg; 2012. https://doi.org/10.1007/978-3-642-29551-5

3. Jiang K., Huang Y., Zeng G., Toma F.M., Goddard III W. A., Bell A. T. Effects of surface roughness on the electrochemical reduction of CO2 over Cu. ACS Energy Letters. 2020;5(4): 1206–1214. https://doi.org/10.1021/acsenergylett.0c00482

4. Popov K. I., Živković P. M., Nikolić N. D., Branković G. The effect of the electrode surface roughness at low level of coarseness on the polarization characteristics of electrochemical processes. Electrochimica Acta. 2010;55(6): 1919–1925. https://doi.org/10.1016/j.electacta.2009.10.085

5. Xie X., Holze R. Electrode kinetic data: geometric vs. real surface area. Batteries. 2022;8(10):146. https://doi.org/10.3390/batteries8100146

6. Dobri G., Banu A., Donath C., … Marcu M. Effect of surface roughness on the electrochemical behavior and corrosion resistance of TiTaNbZrAg alloy with different amounts of tantalum in bulk composition. Materials. 2024;17(21): 5217. https://doi.org/10.3390/ma17215217

7. Xu R., Jin X., Bi H., Zhang Zh., Li M. Effect of surface roughness on contact resistance and electrochemical corrosion behavior of 446 stainless steel in simulated anode environments for proton exchange membrane fuel cell. Journal of Solid State Electrochemistry. 2024;28: 3087–3098. https://doi.org/10.1007/s10008-024-05864-z

8. Kim Y., Yoo M., Moon M. Effects of surface roughness on the electrochemical properties and galvanic corrosion behavior of CFRP and SPCC alloy. Materials. 2020;13(18): 4211. https://doi.org/10.3390/ma13184211

9. Douglass Jr. E. F., Driscoll P. F., Liu D., Burnham N. A., Lambert C. R., McGimpsey W. G. Effect of electrode roughness on the capacitive behavior of self-assembled monolayers. Analytical Chemistry. 2008:80(20): 7670–7677. https://doi.org/10.1021/ac800521z

10. Trasatti S., Petrii O. A. Real surface area measurements in electrochemistry. Journal of Electroanalytical Chemistry. 1992;327(1-2): 353–376. https://doi.org/10.1016/0022-0728(92)80162-W

11. Bard A. J., Faulkner L. R. Electrochemical methods: fundamentals and applications. 2nd Edition. New York: John Wiley & Sons; 2001.

12. Kozaderov O. А. Surface roughness effect in the kinetics of heterogeneous processes. Condensed Matter and Interphases. 2017;19(1): 6–21. (in Russ.) https://doi.org/10.17308/kcmf.2017.19/171

13. Vdovenkov F. A., Kolosov A. N., Kuzmenko G. A., Kozaderov O. A. Simulation of a non-stationary electrochemical process on rough electrodes under mixed kinetic-diffusion control. Condensed Matter and Interphases. 2025; 27(1): 592–605 https://doi.org/10.17308/kcmf.2025.27/13297

14. Lebedeva O., Kuznetsova I., Kultin D., … Kustov L. Efficiency of the electrocatalytic nitrate reduction to ammonia: do the surface nanostructures play an essential role? Catalysts. 2025;15(7): 666. https://doi.org/10.3390/catal15070666

15. Pérez-Gallent E., Figueiredo M. C., Katsounaros I., Koper M. T. M. Electrocatalytic reduction of nitrate on copper single crystals in acidic and alkaline solutions. Electrochimica Acta. 2017;227: 77–84. https://doi.org/10.1016/j.electacta.2016.12.147

16. Farina R., D’Arrigo G., Alberti A., … Libertino S. Copper micro-flowers for electrocatalytic sensing of sitrate ions in water. Sensors. 2024;24(14): 4501. https://doi.org/10.3390/s24144501

17. Hou T., Shan T., Rong H., Zhang J. Nitrate electroreduction to ammonia over copper-based catalysts. ChemSusChem. 2025;18(9): e202402331. https://doi.org/10.1002/cssc.202402331

18. Farina R., D’Arrigo G., Alberti A., … Libertino S. Electrochemical growth of copper crystals on SPCE for electrocatalysis nitrate reduction. Nanomaterials. 2024;14(21): 1704. https://doi.org/10.3390/nano14211704

19. Shih Y.-J., Wu Z.-L., Lin C.-Y., Huang Y.-H., Huang C.‑P. Manipulating the crystalline morphology and facet orientation of copper and copper-palladium nanocatalysts supported on stainless steel mesh with the aid of cationic surfactant to improve the electrochemical reduction of nitrate and N2 selectivity. Applied Catalysis B: Environmental. 2020;273: 119053. https://doi.org/10.1016/j.apcatb.2020.119053

20. Dima G. E., De Vooys A. C. A., Koper M. T. M. Electrocatalytic reduction of nitrate at low concentration on coinage and transition-metal electrodes in acid solutions. Journal of Electroanalytical Chemistry. 2003;554–555: 15–23. https://doi.org/10.1016/S0022-0728(02)01443-2

21. Rosca V., Duca M., De Groot M. T., Koper M. T. M. Nitrogen cycle electrocatalysis. Chemical Reviews. 2009;109(6): 2209–2244 https://doi.org/10.1021/cr8003696

22. Kozaderov O., Sotskaya N., Yudenkova L., Buylov N., Ilina E. Electrocrystallization and morphology of copper coatings in the presence of organic additives. Coatings. 2023;13(11): 1896. https://doi.org/10.3390/coatings13111896

23. Giri S. D., Sarkar A. Estimating surface area of copper powder: A comparison between electrochemical, microscopy and laser diffraction methods. Advanced Powder Technology. 2018;29(12): 3520–3526. https://doi.org/10.1016/j.apt.2018.09.034

24. Galus Z. Fundamentals of electrochemical analysis. Chichester: Ellis Horwood: New York: Halsted Press, a division of Wiley; 1974. 520 p.

25. Kozaderov O. A., Lozovskii V. V., Vvedenskii A. V. Chronovoltammetry of the anodic dissolution of Ag-Au alloys in nitrate environments. Protection of Metals. 2008; 44(4): 333–342. https://doi.org/10.1134/S0033173208040036

26. Bedova E. V., Kolganova D. I., Kozaderov O. A. Voltamperometry of a kinetically irreversible electrochemical process on a rough electrode. Condensed Matter and Interphases. 2020;22(2): 211–218. https://doi.org/10.17308/kcmf.2020.22/2833

27. Abir A. Y., Nizam Uddin S. M., Hasan M., … Hasnat M. A. Cu-electrodeposited gold electrode for the sensitive electrokinetic investigations of nitrate reduction and detection of the nitrate ion in acidic medium. Results in Chemistry. 2023;5: 100702. https://doi.org/10.1016/j.rechem.2022.100702

28. Butcher D. P., Gewirth D. P. Nitrate reduction pathways on Cu single crystal surfaces: effect of oxide and Cl–. Nano Energy. 2016;29: 457–465. https://doi.org/10.1016/j.nanoen.2016.06.024

29. Bae S.-E., Stewart K. L., Gewirth A. A. Nitrate adsorption and reduction on Cu(100) in acidic solution. Journal of the American Chemical Society. 2007;129(33): 10171–10180. https://doi.org/10.1021/ja071330n

30. Bae S. E., Gewirth A. A. Differential reactivity of Cu(111) and Cu(100) during nitrate reduction in acid electrolyte. Faraday Discuss. 2008;140: 113-23; https://doi.org/10.1039/b803088j

31. Pletcher D., Poorabedi Z. The reduction of nitrate at a copper cathode in aqueous acid Electrochimica Acta. 1979;24: 1253–1256. https://doi.org/10.1016/0013-4686(79)87081-4

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Published

2026-04-01

Issue

Vol. 28 No. 1 (2026)

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Original articles

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How to Cite

Electrochemical reduction of nitrate ions on copper coatings of various roughness under conditions of mixed transport and kinetic control. (2026). Kondensirovannye Sredy I Mezhfaznye Granitsy = Condensed Matter and Interphases, 28(1), 28-39. https://doi.org/10.17308/kcmf.2026.28/13556

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