Electrochemical activity of electroless Ni-P coatings in the hydrogen evolution reaction

Keywords: Electroless Ni-P coating, Electrochemical activity, Hydrogen evolution reaction, Roughness factor, Electrode capacitance


The purpose of this study was investigation of the electrochemical activity of Ni-P coatings, differing in phosphorus content and structure, in the hydrogen evolution reaction (HER) and the identification of the reasons for their high activity in the reaction being studied.

The coatings were deposited from an electroless nickel plating solution, the phosphorus content in the coatings (from 4.8 to 8.0 wt. %) varied by changing the pH of the solution. It was found that during cathodic polarization in 0.5 M H2SO4 additional surface activation occurs as a result of dissolution of the surface layer of the coating, removal of phosphorus from the surface layer, and development of the electrode surface. Of all the coatings studied coatings containing 4.8% phosphorus were most susceptible to cathodic activation. Coatings with a phosphorus content of 8.0% were least susceptible to cathodic activation.

The similar electrochemical activity of the studied coatings (taking into account the roughness factor) in HER indicates that, as a result of cathodic polarization, the composition of the thin surface layer on which the cathodic reaction occurs is approximately the same, regardless of the initial phosphorus content


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Author Biographies

Igor V. Petukhov, Perm State University, 15 ul. Bukireva, Perm 614990, Russian Federation

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

Vladimir I. Kichigin, Perm State University, 15 ul. Bukireva, Perm 614990, Russian Federation

Cand. Sci. (Chem.), Research
Fellow, Research Fellow at the Department of Physical
Chemistry, Perm State University (Perm, Russian


Podesta J. J., Piatti R. C. V., Arvia A. J., Ekdunge P., Jüttner K., Kreysa G. The behaviour of Ni-Co-P base amorphous alloys for water electrolysis in strongly alkaline solutions prepared through electroless deposition. International Journal of Hydrogen Energy. 1992;17: 9–22. https://doi.org/10.1016/0360-3199(92)90216-J

Shervedani R. K., Lasia A. Studies of the hydrogen evolution reaction on Ni-P electrodes. Journal of The electrochemical Society. 1997;144(2): 511–518. https://doi.org/10.1149/1.1837441

Burchardt T., Hansen V., Valand T. Microstructure and catalytic activity towards the hydrogen evolution reaction of electrodeposited NiPx alloys. Electrochimica Acta. 2001;46(18): 2761–2766. https://doi.org/10.1016/S0013-4686(01)00456-X

Krolikowski A., Wiecko A. Impedance studies of hydrogen evolution on Ni-P alloys. Electrochimica Acta. 2002;47(13-14): 2065–2069. https://doi.org/10.1016/S0013-4686(02)00074-9

Paseka I. Sorption of hydrogen and kinetics of hydrogen evolution on amorphous Ni-P and Ni-Sx electrodes. Electrochimica Acta. 1993;38(16): 2449. https://doi.org/10.1016/0013-4686(93)85115-F

Paseka I. Hydrogen evolution reaction on Ni-P. The internal stress and the activities of electrodes. Electrochimica Acta. 2008;53(13): 4537–4543. https://doi.org/10.1016/j.electacta.2008.01.045

Abrantes L. M., Fundo A. M. The electrocatalitic behaviour of electroless Ni-P plating. Journal of Electroanalytical Chemistry. 2007;600: 63–79. https://doi.org/10.1016/j.jelechem.2006.03.023

Petukhov I. V., Medvedeva N. A., Subakova I. R., Kichigin V. I. Corrosion electrochemical behavior of Ni–P coatings in deaerated acidic sulfate solutions. Protection of Metals and Physical Chemistry of Surfaces. 2014;50(7): 876–883. https://doi.org/10.1134/S2070205114070144

Dolgikh O. V., Kravtsova Yu. G., Sotskaya N. V. The effect of composition of electrodeposited Ni-P alloys on the hydrogen evolution. Russian Journal of Electrochemistry. 2010;46(8): 918–924. https://doi.org/10.1134/S1023193510080094

Sotskaya N. V. Dolgikh O. V., Sapronova L. V., Kravtsova Yu. G. Kinetics of cathodic evolution of hydrogen on Ni-P systems electrodeposited alloys. Protection of Metals and Physical Chemistry of Surfaces. 2015;51 (3): 360–365. https://doi.org/10.1134/S2070205115030247

Zhao X., Chen X., Wang Y., Song P., Zhang Y. High-efficiency Ni–P catalysts in amorphous and crystalline states for the hydrogen evolution reaction. Sustainable Energy & Fuels. 2020;4: 4733–4742. https://doi.org/10.1039/d0se00201a

Hu C., Lv C., Liu S., …Watanabe A. Nickel phosphide electrocatalysts for hydrogen evolution reaction. Catalysts. 2020;10(188): 1–32. https://doi.org/10.3390/catal10020188

Huo L., Jin C., Jiang K., Bao Q., Hu Z., Chu J. Applications of nickel-based electrocatalysts for hydrogen evolution reaction. Advanced Energy and Sustainability Research. 2022;3: 2100189. https://doi.org/10.1002/aesr.202100189

Jo W. , Jeong D. , Jeong J. , … Jung H. Electrocatalytic properties of pulse-reverse electrodeposited nickel phosphide for hydrogen evolution reaction. Frontiers in Chemistry. 2021;9: 781838. https://doi.org/10.3389/fchem.2021.781838

Alexander C. L., Tribollet B., Orazem M. E. Contribution of surface distributions to constantphase- element (CPE) behavior: 1. Influence of roughness. Electrochimica Acta. 2015;173: 416–424. https://doi.org/10.1016/j.electacta.2015.05.010

Pajkossy T. Impedance of rough capacitive electrodes. Journal of Electroanalytical Chemistry. 1994;364: 111–125. https://doi.org/10.1016/0022-0728(93)02949-I

Gunning J. The exact impedance of the de Levie grooved electrode. Journal of Electroanalytical Chemistry. 1995; 392: 1–11. https://doi.org/10.1016/0022-0728(95)03951-C

Jović V. D., Jović B. M. EIS and differential capacitance measurements onto single crystal faces in different solutions. Part I: Ag(111) in 0.01 M NaCl. Journal of Electroanalytical Chemistry. 2003;541: 1–11. https://doi.org/10.1016/S0022-0728(02)01309-8

Schalenbach M., Durmus Y. E., Tempel H., Kungl H., Eichel R.-A. Double layer capacitances analysed with impedance spectroscopy and cyclic voltammetry: validity and limits of the constant phase element parameterization. Physical Chemistry Chemical Physics. 2021;23: 21097–21105. https://doi.org/10.1039/D1CP03381F

How to Cite
Petukhov, I. V., & Kichigin, V. I. (2024). Electrochemical activity of electroless Ni-P coatings in the hydrogen evolution reaction. Condensed Matter and Interphases, 26(1), 117-126. https://doi.org/10.17308/kcmf.2024.26/11815
Original articles