Sol-gel synthesis of CaBPO5: phase composition and thermal properties

Ye. Zholdas; Zh. Amanbayeva; K. Saliyeva; A. Bakhadur; A. Kuznetsov; A. Mukanov; K. Kokh

doi:10.15328/cb2026_174

Authors

Ye. Zholdas Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan https://orcid.org/0000-0002-5405-2389 (unauthenticated)
Zh. Amanbayeva Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan https://orcid.org/0009-0006-3160-0983 (unauthenticated)
K. Saliyeva Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan https://orcid.org/0009-0001-5626-3534 (unauthenticated)
A. Bakhadur Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan https://orcid.org/0000-0002-3315-7835 (unauthenticated)
A. Kuznetsov Sobolev Institute of Geology and Mineralogy SB RAS, Novosibirsk, Russia https://orcid.org/0000-0003-3808-8098 (unauthenticated)
A. Mukanov Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan https://orcid.org/0009-0002-2823-7176 (unauthenticated)
K. Kokh Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan
Sobolev Institute of Geology and Mineralogy SB RAS, Novosibirsk, Russia https://orcid.org/0000-0003-1967-9642 (unauthenticated)

DOI:

https://doi.org/10.15328/cb2026_174

Keywords:

CaBPO5, calcium borophosphate, citrate-assisted sol–gel synthesis, phase formation, powder X-ray diffraction, thermal analysis

Abstract

A citrate-assisted sol–gel route was investigated for the preparation of crystalline calcium borophosphate (CaBPO5). To the best of our knowledge, this is the first report of crystalline CaBPO5 obtained by this route. The phase compositions of products prepared with different H3BO3 excesses and precursor-concentration procedures were compared. Concentration under heating produced multiphase products containing CaBPO5 and calcium phosphate secondary phases; increasing the H3BO3 content did not eliminate these impurities. Under optimized conditions, involving 20 mol.% excess H3BO3, a reduced precursor-solution volume, and gel formation at room temperature, crystalline CaBPO5 without secondary phases detectable by powder X-ray diffraction was obtained after thermal treatment. Rietveld refinement confirmed the formation of trigonal stillwellite-type CaBPO5 in the P3121 space group, with unit-cell parameters close to reported values. The Crystallographic Information File (CIF) for the synthesized CaBPO5 sample is available in the Cambridge Structural Database under the registration number CSD 2596463. Differential thermal analysis revealed a high-temperature endothermic event with an onset temperature of 1037.1°C, assigned to the onset of incongruent melting. The study demonstrates the feasibility of citrate-assisted sol–gel synthesis of crystalline CaBPO5 and identifies a combination of precursor-preparation conditions yielding a product without PXRD-detectable secondary crystalline phases.

Author Biographies

Ye. Zholdas, Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan

PhD, al-Farabi Kazakh National University, Almaty, Kazakhstan; e-mail: yerassylzholdas1996@gmail.com
Zh. Amanbayeva, Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan

бакалавр дәрежесінің иегері, әл-Фараби атындағы Қазақ ұлттық университетінің түлегі, Алматы, Қазақстан; e-mail: zhansaiaamanbaeva05@gmail.com
K. Saliyeva, Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan

bachelor’s degree holder, graduate of al-Farabi Kazakh National University, Almaty, Kazakhstan; e-mail: bermaganbetova1705@mail.ru
A. Bakhadur, Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan

PhD, al-Farabi Kazakh National University, Almaty, Kazakhstan; e-mail: askar.bakhadur@gmail.com
A. Kuznetsov, Sobolev Institute of Geology and Mineralogy SB RAS, Novosibirsk, Russia

Doctor of Chemical Sciences, IGM SB RAS; e-mail: ky.artemy@ya.ru
A. Mukanov, Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan

PhD-student, City University of Hong Kong; e-mail: askarmukanov85@gmail.com
K. Kokh, Al-Farabi Kazakh National University, Center of Physical-Chemical Methods of Research and Analysis, Almaty, Kazakhstan, Sobolev Institute of Geology and Mineralogy SB RAS, Novosibirsk, Russia

Doctor of Geological and Mineralogical Sciences, IGM SB RAS; e-mail: k.a.kokh@gmail.com

References

1 Kniep R, Engelhardt H, Hauf C (1998) Chem Mater 10:2930-2934. https://doi.org/10.1021/cm980263g

2 Baykal A, Gözel G, Kizilyalli M, Toprak M, Kniep R (2000) Turk J Chem 24:381-388.

3 Ben Ali A, Taibi M, Aride J, Boukhari A, Antic-Fidancev E, Viana B, Aschehoug P (2001) J Alloy Compd 323-324:673-677. https://doi.org/10.1016/S0925-8388(01)01085-4

4 ul GÇ, Kurtulus F (2016) Optik 127:11674-11680. https://doi.org/10.1016/j.ijleo.2016.09.097

5 Liang H, Su Q, Tao Y, Hu T, Liu T (2002) J Alloy Compd 334:293-298. https://doi.org/10.1016/S0925-8388(01)01787-X

6 Liang H, Zeng Q, Tao Y, Wang S, Su Q (2003) Mat Sci Eng B-Solid 98:213-219. https://doi.org/10.1016/S0921-5107(03)00034-5

7 Liang H, Shi J, Su Q, Zhang S, Tao Y (2005) Mater Chem Phys 92:180-184. https://doi.org/10.1016/j.matchemphys.2005.01.012

8 Kharabe VR, Oza AH, Dhoble SJ (2015) Optik 126:4544-4547. https://doi.org/10.1016/j.ijleo.2015.08.090

9 Wei Z, Lu Y, Li X, Dong Y, Jiao D, Guan L, Dong G, Teng F (2016) J Appl Biomater Func 14:S83-S88. https://doi.org/10.5301/jabfm.5000320

10 Kumar A, Dutta S, Kim S, Kwon T, Patil SS, Kumari N, Jeevanandham S, Lee IS (2022) Chem Rev 122:12748-12863. https://doi.org/10.1021/acs.chemrev.1c00637

11 Liu XT, Xie DM, Shi CS (2004) Chem J Chinese U 25:208-211. (In Chinese)

12 Danks AE, Hall SR, Schnepp Z (2016) Mater Horiz 3:91-112. https://doi.org/10.1039/c5mh00260e

13 Carta D, Knowles JC, Guerry P, Smith ME, Newport RJ (2009) J Mater Chem 19:150-158. https://doi.org/10.1039/b813288g

14 Ali AF, Mustarelli P, Quartarone E, Tomasi C, Baldini P, Magistris A (1999) J Mater Res 14:1510-1515. https://doi.org/10.1557/JMR.1999.0202

15 Kuznetsov AB (2026) XRD Analysis Toolkit (XRD Phase Finder) [Computer software]. GitHub. https://github.com/ABKuznetsov/XRD_Analysis_Toolkit

16 Toby BH, Von Dreele RB (2013) J Appl Crystallogr 46:544-549. https://doi.org/10.1107/S0021889813003531

17 Kniep R, Gözel G, Eisenmann B, Röhr C, Asbrand M, Kizilyalli M (1994) Angew Chem Int Edit 33:749-751. https://doi.org/10.1002/anie.199407491

18 Kuznetsov AB (2026) CRAFT [Computer software]. GitHub. https://github.com/ABKuznetsov/CRAFT

19 Boudin S, Grandin A, Borel MM, Leclaire A, Raveau B (1993) Acta Crystallogr C 49:2062-2064. https://doi.org/10.1107/S0108270193005608

20 Martinez-Triana A, Mutelet F, Neveux T, Castel C, Favre E (2023) Fluid Phase Equilibr 567:113706. https://doi.org/10.1016/j.fluid.2022.113706

21 Alpatova A, Alsaadi A, Ghaffour N (2018) J Hazard Mater 351:224-231. https://doi.org/10.1016/j.jhazmat.2018.02.056

22 McFarland B, Opila EJ (2016) J Non-Cryst Solids 449:59-69. https://doi.org/10.1016/j.jnoncrysol.2016.06.041

23 Ternane R, Cohen-Adad MT, Boulon G, Florian P, Massiot D, Trabelsi-Ayedi M, Kbir-Ariguib N (2003) Solid State Ionics 160:183-195. https://doi.org/10.1016/S0167-2738(03)00161-9