Peculiarities of the formation, structural and morphological properties of zinc whitlockite (Ca18Zn2(HPO4)2(PO4)12) synthesized via a phase transformation process under hydrothermal conditions

Agne Kizalaite; Vytautas Klimavicius; Justina Versockiene; Egle Lastauskiene; Tomas Murauskas; Ramunas Skaudzius; Taishi Yokoi; Masakazu Kawashita; Tomoyo Goto; Tohru Sekino; Aleksej Zarkov

doi:10.1039/d2ce00497f

Peculiarities of the formation, structural and morphological properties of zinc whitlockite (Ca₁₈Zn₂(HPO₄)₂(PO₄)₁₂) synthesized via a phase transformation process under hydrothermal conditions

Agne Kizalaite
, Vytautas Klimavicius
, Justina Versockiene
, Egle Lastauskiene
, Tomas Murauskas
, Ramunas Skaudzius
, Taishi Yokoi
, Masakazu Kawashita
, Tomoyo Goto
, Tohru Sekino
, Aleksej Zarkov^*

^*Corresponding author for this work

Vilnius University
Institute of Science Tokyo
The University of Osaka

Research output: Contribution to journal › Article › peer-review

16 Citations (Scopus)

Abstract

Zinc whitlockite (Zn-WH, Ca₁₈Zn₂(HPO₄)₂(PO₄)₁₂) is a new synthetic analog of the second most abundant biomineral - magnesium whitlockite (Mg-WH, Ca₁₈Mg₂(HPO₄)₂(PO₄)₁₂), which is considered as a potential material for bone regeneration. In the present work, the formation of Zn-WH via a dissolution-precipitation process under hydrothermal conditions was investigated in detail. The influence of medium pH, reaction time, temperature and concentration of precursors on the formation of the single-phase material was studied. It was demonstrated that the phase-pure material can be obtained in the pH range from 5.6 to 6.2 in a very short period of time - 1 h. Variation of chemical composition in terms of the Ca-to-Zn ratio was determined to be possible in a narrow range. The structural properties of the synthesized Zn-WH were investigated by powder X-ray diffraction analysis along with ¹H and ³¹P solid-state NMR spectroscopy, FTIR spectroscopy, Raman spectroscopy and XPS. Rietveld refinement confirmed that the synthesized material has a rhombohedral structure with the R3c space group. The NMR study confirmed the presence of three inequivalent phosphorus atoms in the crystal structure, whereas only one PO₄³⁻ tetrahedron was determined to be protonated. The size and shape of the particles can be controlled by the concentration of the precursors as well as by the initial Ca-to-Zn ratio in the reaction mixture.

Original language	English
Pages (from-to)	5068-5079
Number of pages	12
Journal	CrystEngComm
Volume	24
Issue number	28
DOIs	https://doi.org/10.1039/d2ce00497f
Publication status	Published - 2 Jun 2022
Externally published	Yes

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Kizalaite, A., Klimavicius, V., Versockiene, J., Lastauskiene, E., Murauskas, T., Skaudzius, R., Yokoi, T., Kawashita, M., Goto, T., Sekino, T., & Zarkov, A. (2022). Peculiarities of the formation, structural and morphological properties of zinc whitlockite (Ca₁₈Zn₂(HPO₄)₂(PO₄)₁₂) synthesized via a phase transformation process under hydrothermal conditions. CrystEngComm, 24(28), 5068-5079. https://doi.org/10.1039/d2ce00497f

@article{db84531d43e047bb9e84beb613b81807,

title = "Peculiarities of the formation, structural and morphological properties of zinc whitlockite (Ca18Zn2(HPO4)2(PO4)12) synthesized via a phase transformation process under hydrothermal conditions",

abstract = "Zinc whitlockite (Zn-WH, Ca18Zn2(HPO4)2(PO4)12) is a new synthetic analog of the second most abundant biomineral - magnesium whitlockite (Mg-WH, Ca18Mg2(HPO4)2(PO4)12), which is considered as a potential material for bone regeneration. In the present work, the formation of Zn-WH via a dissolution-precipitation process under hydrothermal conditions was investigated in detail. The influence of medium pH, reaction time, temperature and concentration of precursors on the formation of the single-phase material was studied. It was demonstrated that the phase-pure material can be obtained in the pH range from 5.6 to 6.2 in a very short period of time - 1 h. Variation of chemical composition in terms of the Ca-to-Zn ratio was determined to be possible in a narrow range. The structural properties of the synthesized Zn-WH were investigated by powder X-ray diffraction analysis along with 1H and 31P solid-state NMR spectroscopy, FTIR spectroscopy, Raman spectroscopy and XPS. Rietveld refinement confirmed that the synthesized material has a rhombohedral structure with the R3c space group. The NMR study confirmed the presence of three inequivalent phosphorus atoms in the crystal structure, whereas only one PO43− tetrahedron was determined to be protonated. The size and shape of the particles can be controlled by the concentration of the precursors as well as by the initial Ca-to-Zn ratio in the reaction mixture.",

author = "Agne Kizalaite and Vytautas Klimavicius and Justina Versockiene and Egle Lastauskiene and Tomas Murauskas and Ramunas Skaudzius and Taishi Yokoi and Masakazu Kawashita and Tomoyo Goto and Tohru Sekino and Aleksej Zarkov",

note = "Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

year = "2022",

month = jun,

day = "2",

doi = "10.1039/d2ce00497f",

language = "English",

volume = "24",

pages = "5068--5079",

journal = "CrystEngComm",

issn = "1466-8033",

publisher = "Royal Society of Chemistry",

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Kizalaite, A, Klimavicius, V, Versockiene, J, Lastauskiene, E, Murauskas, T, Skaudzius, R, Yokoi, T, Kawashita, M, Goto, T, Sekino, T & Zarkov, A 2022, 'Peculiarities of the formation, structural and morphological properties of zinc whitlockite (Ca₁₈Zn₂(HPO₄)₂(PO₄)₁₂) synthesized via a phase transformation process under hydrothermal conditions', CrystEngComm, vol. 24, no. 28, pp. 5068-5079. https://doi.org/10.1039/d2ce00497f

Peculiarities of the formation, structural and morphological properties of zinc whitlockite (Ca₁₈Zn₂(HPO₄)₂(PO₄)₁₂) synthesized via a phase transformation process under hydrothermal conditions. / Kizalaite, Agne; Klimavicius, Vytautas; Versockiene, Justina et al.
In: CrystEngComm, Vol. 24, No. 28, 02.06.2022, p. 5068-5079.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Peculiarities of the formation, structural and morphological properties of zinc whitlockite (Ca18Zn2(HPO4)2(PO4)12) synthesized via a phase transformation process under hydrothermal conditions

AU - Kizalaite, Agne

AU - Klimavicius, Vytautas

AU - Versockiene, Justina

AU - Lastauskiene, Egle

AU - Murauskas, Tomas

AU - Skaudzius, Ramunas

AU - Yokoi, Taishi

AU - Kawashita, Masakazu

AU - Goto, Tomoyo

AU - Sekino, Tohru

AU - Zarkov, Aleksej

PY - 2022/6/2

Y1 - 2022/6/2

N2 - Zinc whitlockite (Zn-WH, Ca18Zn2(HPO4)2(PO4)12) is a new synthetic analog of the second most abundant biomineral - magnesium whitlockite (Mg-WH, Ca18Mg2(HPO4)2(PO4)12), which is considered as a potential material for bone regeneration. In the present work, the formation of Zn-WH via a dissolution-precipitation process under hydrothermal conditions was investigated in detail. The influence of medium pH, reaction time, temperature and concentration of precursors on the formation of the single-phase material was studied. It was demonstrated that the phase-pure material can be obtained in the pH range from 5.6 to 6.2 in a very short period of time - 1 h. Variation of chemical composition in terms of the Ca-to-Zn ratio was determined to be possible in a narrow range. The structural properties of the synthesized Zn-WH were investigated by powder X-ray diffraction analysis along with 1H and 31P solid-state NMR spectroscopy, FTIR spectroscopy, Raman spectroscopy and XPS. Rietveld refinement confirmed that the synthesized material has a rhombohedral structure with the R3c space group. The NMR study confirmed the presence of three inequivalent phosphorus atoms in the crystal structure, whereas only one PO43− tetrahedron was determined to be protonated. The size and shape of the particles can be controlled by the concentration of the precursors as well as by the initial Ca-to-Zn ratio in the reaction mixture.

AB - Zinc whitlockite (Zn-WH, Ca18Zn2(HPO4)2(PO4)12) is a new synthetic analog of the second most abundant biomineral - magnesium whitlockite (Mg-WH, Ca18Mg2(HPO4)2(PO4)12), which is considered as a potential material for bone regeneration. In the present work, the formation of Zn-WH via a dissolution-precipitation process under hydrothermal conditions was investigated in detail. The influence of medium pH, reaction time, temperature and concentration of precursors on the formation of the single-phase material was studied. It was demonstrated that the phase-pure material can be obtained in the pH range from 5.6 to 6.2 in a very short period of time - 1 h. Variation of chemical composition in terms of the Ca-to-Zn ratio was determined to be possible in a narrow range. The structural properties of the synthesized Zn-WH were investigated by powder X-ray diffraction analysis along with 1H and 31P solid-state NMR spectroscopy, FTIR spectroscopy, Raman spectroscopy and XPS. Rietveld refinement confirmed that the synthesized material has a rhombohedral structure with the R3c space group. The NMR study confirmed the presence of three inequivalent phosphorus atoms in the crystal structure, whereas only one PO43− tetrahedron was determined to be protonated. The size and shape of the particles can be controlled by the concentration of the precursors as well as by the initial Ca-to-Zn ratio in the reaction mixture.

UR - https://www.scopus.com/pages/publications/85133592216

U2 - 10.1039/d2ce00497f

DO - 10.1039/d2ce00497f

M3 - Article

AN - SCOPUS:85133592216

SN - 1466-8033

VL - 24

SP - 5068

EP - 5079

JO - CrystEngComm

JF - CrystEngComm

IS - 28

ER -

Peculiarities of the formation, structural and morphological properties of zinc whitlockite (Ca₁₈Zn₂(HPO₄)₂(PO₄)₁₂) synthesized via a phase transformation process under hydrothermal conditions

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