najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2025-16-5-700-705najo-1541Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХEffect of labyrinth-like arrays formation of nickel nanorods on nickel surface as a result of galvanic substitution reaction in aqueous solutions of CuCl2 and NaCl mixtureЭффект формирования лабиринтообразных массивов никелевых наностержней на поверхности никеля в результате реакции гальванического замещения в водных растворах смеси CuCl2 и NaClhttps://orcid.org/0000-0003-3857-7238ТолстойВ. П.TolstoyV. P.

Валерий П. Толстой 

Valeri P. Tolstoy

26, Peterhof, Saint Petersburg, 198504

v.tolstoy@spbu.ruhttps://orcid.org/0009-0007-1409-5214НикитинК. Д.NikitinK. D.

Кирилл Д. Никитин 

Kirill D. Nikitin

26, Peterhof, Saint Petersburg, 198504

st069423@student.spbu.ruhttps://orcid.org/0000-0001-8264-2135БатищеваЕ. В.BatischevaE. V.

Елизавета В. Батищева 

Elisaveta V. Batischeva

26, Peterhof, Saint Petersburg, 198504

batischevaelisaveta@gmail.comInstitute of Chemistry, St. Petersburg State UniversityRussian Federation202505112025165700705Copyright © Tolstoy V.P., Nikitin K.D., Batischeva E.V., 20252025Толстой В.П., Никитин К.Д., Батищева Е.В.Tolstoy V.P., Nikitin K.D., Batischeva E.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/1541

The article describes the nickel surface treatment conditions in aqueous solutions of a mixture of CuCl2 and NaCl salts. This investigation reveals the occurrence of selective etching on the nickel surface, facilitated by a galvanic replacement reaction (GRR). The etching process gives rise to the formation of arrays of labyrinths with walls of nickel nanorods with a diameter ranging from 10 to 50 nanometers and a length of up to 0.5 micrometers are formed, located primarily in the direction perpendicular to the surface. The experimental results obtained have enabled the formulation of hypotheses concerning the sequence of chemical reactions occurring on the surface and the role of the A. Turing diffusion-chemical model in the formation of the observed labyrinths. It has been demonstrated that the presence of such labyrinths on the surface of nickel leads to a decrease in the angles of its wetting with water.

В статье излагаются условия обработки поверхности никеля в водных растворах смеси солей CuCl2 и NaCl. В результате исследования впервые установлено наличие селективного травления поверхности никеля, обусловленного реакцией гальванического замещения (ГРЗ). В процессе травления формируются массивы лабиринтов со стенками из никелевых наностержней диаметром от 10 до 50 нанометров и длиной до 0,5 мкм, расположенных преимущественно в направлении, перпендикулярном поверхности. Полученные экспериментальные результаты позволили сформулировать гипотезы о последовательности химических реакций, протекающих на поверхности, и роли диффузионно-химической модели А. Тьюринга в формировании наблюдаемых лабиринтов. Показано, что наличие таких лабиринтов на поверхности никеля приводит к уменьшению углов его смачивания водой.

никельCuCl2гальваническое замещениенаностержнимассивыnickelCuCl2galvanic replacementnanorodsarraysThis work was partly supported by the Russian Science Foundation (Grant No. 23-19-00566).ReferencesReboul J., Li Z.-Y., Yuan J., Nakatsuka K., Saito M., Mori K., Yamashita H., Xia Y., Louis C. Synthesis of small Ni-core–Au-shell catalytic nanoparticles on TiO2 by galvanic replacement reaction. Nanoscale Advances, 2021, 3 (3), P. 823–835.Reboul J., Li Z.-Y., Yuan J., Nakatsuka K., Saito M., Mori K., Yamashita H., Xia Y., Louis C. Synthesis of small Ni-core–Au-shell catalytic nanoparticles on TiO2 by galvanic replacement reaction. Nanoscale Advances, 2021, 3 (3), P. 823–835.Lei H., Li X., Sun C., Zeng J., Singh S.S., Zhang Q. Galvanic Replacement–Mediated Synthesis of Ni-Supported Pd Nanoparticles with Strong Metal-Support Interaction for Methanol Electro-oxidation. Small, 2019, 15 (11), 1804722.Lei H., Li X., Sun C., Zeng J., Singh S.S., Zhang Q. Galvanic Replacement–Mediated Synthesis of Ni-Supported Pd Nanoparticles with Strong Metal-Support Interaction for Methanol Electro-oxidation. Small, 2019, 15 (11), 1804722.Kaneva M.V., Borisov E.V., Tolstoy V.P. Pt(0) microscrolls obtained on nickel surface by galvanic replacement reaction in H2PtCl6 solution as the basis for creating new SERS substrates. Nanosystems: Physics, Chemistry, Mathematics, 2022, 13 (5), P. 509–513.Kaneva M.V., Borisov E.V., Tolstoy V.P. Pt(0) microscrolls obtained on nickel surface by galvanic replacement reaction in H2PtCl6 solution as the basis for creating new SERS substrates. Nanosystems: Physics, Chemistry, Mathematics, 2022, 13 (5), P. 509–513.Tolstoy V., Nikitin K., Kuzin A., Zhu F., Li X., Goltsman G., Gorin D., Huang G., Solovev A. and Mei Y. Rapid synthesis of Pt (0) motorsmicroscrolls on a nickel surface via H2PtCl6-induced galvanic replacement reaction. Chemical Communications, 2024, 60 (23), P. 3182–3185.Tolstoy V., Nikitin K., Kuzin A., Zhu F., Li X., Goltsman G., Gorin D., Huang G., Solovev A. and Mei Y. Rapid synthesis of Pt (0) motorsmicroscrolls on a nickel surface via H2PtCl6-induced galvanic replacement reaction. Chemical Communications, 2024, 60 (23), P. 3182–3185.Kaneva M.V., Tolstoy V.P. The ”rolling up” effect of platinum layer obtained on nickel surface by interaction with solution of H2PtCl6 and its electrocatalytic properties in hydrogen evolution reaction during water electrolysis in alkaline medium. Nanosystems: Physics, Chemistry, Mathematics, 2021, 12 (5), P. 630–633.Kaneva M.V., Tolstoy V.P. The ”rolling up” effect of platinum layer obtained on nickel surface by interaction with solution of H2PtCl6 and its electrocatalytic properties in hydrogen evolution reaction during water electrolysis in alkaline medium. Nanosystems: Physics, Chemistry, Mathematics, 2021, 12 (5), P. 630–633.Shviro M., Polani S., Zitoun D. Hollow octahedral and cuboctahedral nanocrystals of ternary Pt–Ni–Au alloys. Nanoscale, 2015, 7 (32), P. 13521– 13529.Shviro M., Polani S., Zitoun D. Hollow octahedral and cuboctahedral nanocrystals of ternary Pt–Ni–Au alloys. Nanoscale, 2015, 7 (32), P. 13521– 13529.Batishcheva E.V., Tolstoy V.P. Formation of Arrays of 1D Copper (II) Oxide Nanocrystals on the Nickel Surface upon Its Galvanic Replacement in a CuCl2 Solution and Their Electrocatalytic Properties in the Hydrogen Evolution Reaction during Water Splitting in an Alkaline Medium. Russian J. of Inorganic Chemistry, 2022, 67 (6), P. 898–903.Batishcheva E.V., Tolstoy V.P. Formation of Arrays of 1D Copper (II) Oxide Nanocrystals on the Nickel Surface upon Its Galvanic Replacement in a CuCl2 Solution and Their Electrocatalytic Properties in the Hydrogen Evolution Reaction during Water Splitting in an Alkaline Medium. Russian J. of Inorganic Chemistry, 2022, 67 (6), P. 898–903.Muscetta M., Andreozzi R., Clarizia L., Marotta R., Palmisano G., Policastro G., Race M., Yusuf A., Di Somma I., Recovery of nickel from spent multilayer ceramic capacitors: A novel and sustainable route based on sequential hydrometallurgical and photocatalytic stages. Separation and Purification Technology, 2023, 326, 124780.Muscetta M., Andreozzi R., Clarizia L., Marotta R., Palmisano G., Policastro G., Race M., Yusuf A., Di Somma I., Recovery of nickel from spent multilayer ceramic capacitors: A novel and sustainable route based on sequential hydrometallurgical and photocatalytic stages. Separation and Purification Technology, 2023, 326, 124780.Muscetta M., Minichino N., Marotta R., Andreozzi R., Di Somma I. Zero-valent palladium dissolution using NaCl/CuCl2 solutions. J. of Hazardous Materials, 2021, 404, 124184.Muscetta M., Minichino N., Marotta R., Andreozzi R., Di Somma I. Zero-valent palladium dissolution using NaCl/CuCl2 solutions. J. of Hazardous Materials, 2021, 404, 124184.Yazici E.Y., Deveci H.A.C.I. Cupric chloride leaching (HCl–CuCl2–NaCl) of metals from waste printed circuit boards (WPCBs). Int. J. of Mineral Processing, 2015, 134, P. 89–96.Yazici E.Y., Deveci H.A.C.I. Cupric chloride leaching (HCl–CuCl2–NaCl) of metals from waste printed circuit boards (WPCBs). Int. J. of Mineral Processing, 2015, 134, P. 89–96.Gulina L.B., Gurenko V.E., Tolstoy V.P., Mikhailovski V.Y., Koroleva A.V. Interface-Assisted Synthesis of the Mn3−xFexO4 Gradient Film with Multifunctional Properties. Langmuir, 2019, 35 (47), P. 14983–14989.Gulina L.B., Gurenko V.E., Tolstoy V.P., Mikhailovski V.Y., Koroleva A.V. Interface-Assisted Synthesis of the Mn3−xFexO4 Gradient Film with Multifunctional Properties. Langmuir, 2019, 35 (47), P. 14983–14989.Grzybowski B.A., Bishop K.J., Campbell C.J., Fialkowski M., Smoukov S.K. Micro- and nanotechnology via reaction–diffusion. Soft Matter, 2005, 1 (2), P. 114–128.Grzybowski B.A., Bishop K.J., Campbell C.J., Fialkowski M., Smoukov S.K. Micro- and nanotechnology via reaction–diffusion. Soft Matter, 2005, 1 (2), P. 114–128.Gu J., Li L., Xie Y., Chen B., Tian F., Wang Y., Zhong J., Shen J., Lu J. Turing structuring with multiple nanotwins to engineer efficient and stable catalysts for hydrogen evolution reaction. Nature Communications, 2023, 14 (1), 5389.Gu J., Li L., Xie Y., Chen B., Tian F., Wang Y., Zhong J., Shen J., Lu J. Turing structuring with multiple nanotwins to engineer efficient and stable catalysts for hydrogen evolution reaction. Nature Communications, 2023, 14 (1), 5389.Fromenteze T., Yurduseven O., Uche C, Arnaud E., Smith D.R., Decroze C. Morphogenetic metasurfaces: unlocking the potential of turing patterns. Nature Communications, 2023, 14 (1), 6249.Fromenteze T., Yurduseven O., Uche C, Arnaud E., Smith D.R., Decroze C. Morphogenetic metasurfaces: unlocking the potential of turing patterns. Nature Communications, 2023, 14 (1), 6249.Kondo S., Iwashita M., Yamaguchi M. How animals get their skin patterns: fish pigment pattern as a live Turing wave. Proceeding of “Systems Biology”, Springer, Tokyo, 2009, P. 37–46.Kondo S., Iwashita M., Yamaguchi M. How animals get their skin patterns: fish pigment pattern as a live Turing wave. Proceeding of “Systems Biology”, Springer, Tokyo, 2009, P. 37–46.Ishida T. Emergence of Diverse Epidermal Patterns via the Integration of the Turing Pattern Model with the Majority Voting Model. Biophysica, 2024, 4, P. 283–297.Ishida T. Emergence of Diverse Epidermal Patterns via the Integration of the Turing Pattern Model with the Majority Voting Model. Biophysica, 2024, 4, P. 283–297.Staddon M.F. How the zebra got its stripes: Curvature-dependent diffusion orients Turing patterns on three-dimensional surfaces. Physical Review E, 2024, 110, 034402. [18] Kondo S., Watanabe M., Miyazawa S. Studies of Turing pattern formation in zebrafish skin. Phil. Trans. R. Soc. A, 2021, 379, 20200274.Staddon M.F. How the zebra got its stripes: Curvature-dependent diffusion orients Turing patterns on three-dimensional surfaces. Physical Review E, 2024, 110, 034402. [18] Kondo S., Watanabe M., Miyazawa S. Studies of Turing pattern formation in zebrafish skin. Phil. Trans. R. Soc. A, 2021, 379, 20200274.Hunter P. Of Turing and zebras. EMBO reports, 2023, 24, e57405.Hunter P. Of Turing and zebras. EMBO reports, 2023, 24, e57405.Almjasheva O.V., Popkov V.I., Proskurina O.V., Gusarov V.V. Phase formation under conditions of self-organization of particle growth restrictions in the reaction system. Nanosystems: Physics, Chemistry, Mathematics, 2022, 13 (2), P. 164–180.Almjasheva O.V., Popkov V.I., Proskurina O.V., Gusarov V.V. Phase formation under conditions of self-organization of particle growth restrictions in the reaction system. Nanosystems: Physics, Chemistry, Mathematics, 2022, 13 (2), P. 164–180.

The authors declare that there are no conflicts of interest present.