Determination of the formation mechanism of zinc and nickel layered double hydroxides

Authors

DOI:

https://doi.org/10.15587/1729-4061.2026.358469

Keywords:

potentiometric titration, formation mechanism, Zn-Al LDH, Ni-Al LDH, Ni(II)-Ni(III) LDH

Abstract

The object of the study – the formation mechanism of Zn-Al nitrate, Zn-Al tripolyphosphate, Ni-Al carbonate and Ni(II)-Ni(III) carbonate layered-double hydroxides (LDHs).

To calculate the composition of the precipitate at the LDH formation stage, the following hypotheses were proposed:

1) basic salt hypothesis (BSH): all cations completely precipitate, then OH- ions replace the anions;

2) variable cation composition hypothesis (VCCH): the precipitate is formed by a saturated "guest" cation, and subsequently the amount of the "host" cation increases.

Potentiometric titration with a glass electrode was used to determine the LDH formation mechanism.

A two-stage formation mechanism was observed for Zn-Al-NO3 LDH. At the first stage, aluminum hydroxide forms (pH = 6.47) via the formation of the hydroxo salt Al(OH)0,667(NO3)2,333 (pH = 4.98). At the second stage, LDH formation proceeds through intermediate stages: at pH = 7.36, the is composition Zn0,8Al0,2(OH)1,20(NO3)1,00 (BSH) or Zn0,667Al0,333(OH)2(NO3)1,667 (VCCH), at pH = 9.35, the composition is Zn0,8Al0,2(OH)1,93(NO3)0,27 (BSH) or Zn0,793Al0,207(OH)2(NO3)0,204 (VCCH).

A two-stage mechanism is characteristic of Zn-Al-P3O10 LDH. At pH = 6.25, the hydroxo salt Al(OH)2,66(P3O10)0,067 is formed, whereas at pH = 9.25, LDH with the composition Zn0,8Al0,2(OH)2,00(P3O10)0,040 is obtained. For Zn-Al LDH, a pH range of 7–10 is recommended.

It was found that during the formation of Ni-Al-CO3 LDH, the stage of Al hydroxocompound formation is absent due to the complete irreversible hydrolysis of Al3+ in the presence of  At pH = 6.5, the precipitate Ni0,8Al0,2(OH)1,066(CO3)0,567 (BSH) or Ni0,624Al0,376(OH)2(CO3)0,376 (VCCH) is formed, which is transformed into LDH upon further alkalization. The synthesis of Ni-Al-CO3 LDH should be carried out at pH = 8–11.

A single-stage formation mechanism is determined for Ni(II)-Ni(III)-CO3 LDH, with a recommended synthesis pH range of 10–11.

Comparative analysis shows that the VCCH better describes the change in the precipitate composition during LDH formation

Author Biographies

Vadym Kovalenko, Ukrainian State University of Science and Technologies

PhD, Associate Professor

Department of Analytical Chemistry and Chemical Technologies of Food Additives and Cosmetics

Anastasiia Borysenko, Dnipro State Medical University

Doctor of Philosophy (PhD), Junior Researcher

Department of Biochemistry and Medical Chemistry

Dmytro Andreiev, Ukrainian State University of Science and Technologies

PhD Student

Department of Analytical Chemistry and Chemical Technologies of Food Additives and Cosmetics

Anton Dopira, Ukrainian State University of Science and Technologies

PhD Student

Department of Analytical Chemistry and Chemical Technologies of Food Additives and Cosmetics

Oleksii Demchenko, Dnipro University of Technology

PhD Student

Department of Mining Engineering and Education

Valerii Kotok, Ukrainian State University of Science and Technologies

PhD, Associate Professor

Department of Processes, Apparatus and General Chemical Technology

Volodymyr Medianyk, Dnipro University of Technology

PhD, Associate Professor

Department of Mining Engineering and Education

Dmytro Sukhomlyn, Dnipro University of Technology

PhD, Associate Professor

Department of Chemistry and Chemical Engineering

German Shuklin, National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”

PhD, Associate Professor

Department of Software Engineering in Energy

Volodymyr Verbitskiy, Dragomanov Ukrainian State University; National Ecology and Nature Center

Doctor of Pedagogical Sciences, Professor

Director

Department of Medical, Biological and Valeological Basics of Life and Health Protection

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Determination of the formation mechanism of zinc and nickel layered double hydroxides

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Published

2026-04-30

How to Cite

Kovalenko, V., Borysenko, A., Andreiev, D., Dopira, A., Demchenko, O., Kotok, V., Medianyk, V., Sukhomlyn, D., Shuklin, G., & Verbitskiy, V. (2026). Determination of the formation mechanism of zinc and nickel layered double hydroxides. Eastern-European Journal of Enterprise Technologies, 2(6 (140), 62–71. https://doi.org/10.15587/1729-4061.2026.358469

Issue

Vol. 2 No. 6 (140) (2026): Technology organic and inorganic substances

Section

Technology organic and inorganic substances

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Copyright (c) 2026 Vadym Kovalenko, Anastasiia Borysenko, Dmytro Andreiev, Anton Dopira, Oleksii Demchenko, Valerii Kotok, Volodymyr Medianyk, Dmytro Sukhomlyn, German Shuklin, Volodymyr Verbitskiy

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