Double borate NaScB2O5: synthesis, thermal stability, ionic conductivity, IR spectroscopy, and electronic structure

Andrey N. Sobolev; Evgeniy V. Kovtunets; Tatyana S. Spiridonova; Alexander I. Bogdanov; Alexey K. Subanakov

doi:10.17308/kcmf.2025.27/13022

Andrey N. Sobolev Baikal Institute of Nature Management, Siberian branch of the Russian Academy of Sciences 6 Sakhyanovoy st., Ulan-Ude 670047, Russian federation; Banzarov Buryat State University, 24a Smolina st., Ulan-Ude 670000, Russian Federation https://orcid.org/0009-0006-2286-1380
Evgeniy V. Kovtunets Baikal Institute of Nature Management, Siberian branch of the Russian Academy of Sciences 6 Sakhyanovoy st., Ulan-Ude 670047, Russian federation; Banzarov Buryat State University, 24a Smolina st., Ulan-Ude 670000, Russian Federation https://orcid.org/0000-0003-1301-1983
Tatyana S. Spiridonova Baikal Institute of Nature Management, Siberian branch of the Russian Academy of Sciences 6 Sakhyanovoy st., Ulan-Ude 670047, Russian federation; Banzarov Buryat State University, 24a Smolina st., Ulan-Ude 670000, Russian Federation https://orcid.org/0000-0001-7498-5103
Alexander I. Bogdanov Vinogradov Institute of Geochemistry, Siberian branch of the Russian Academy of Sciences 1a building, Favorskogo st., Irkutsk 664033, Russian Federation https://orcid.org/0000-0001-8639-4730
Alexey K. Subanakov Baikal Institute of Nature Management, Siberian branch of the Russian Academy of Sciences 6 Sakhyanovoy st., Ulan-Ude 670047, Russian federation; Banzarov Buryat State University, 24a Smolina st., Ulan-Ude 670000, Russian Federation https://orcid.org/0000-0002-1674-283X

DOI: https://doi.org/10.17308/kcmf.2025.27/13022

Keywords: Sodium scandium borate, Solid-phase synthesis, Thermal analysis, IR spectroscopy, Electrical conductivity

Abstract

Purpose: The double sodium scandium borate, NaScB₂O₅, whose crystal structure was solved by Backer and Held in 2001, remains a poorly explored object. The crystal structure has wide channels that may suggest ionic conduction of sodium ions. Based on this, the aim of the study was to investigate the ionic conductivity of this object, as well as to study its thermal behavior, measure the IR spectrum and calculate the electronic structure by quantum chemical method.

Experimental: The synthesis of sodium scandium double borate, NaScB₂O₅, was achieved using a solid-state reaction method. NaScB₂O₅ was explored by using thermal analysis, IR spectroscopy, ionic conductivity, theoretical estimates of activation energy, ion transport pathways, and Ab initio calculations of electronic structure.

Conclusions: Rietveld method was engaged: monoclinic symmetry (sp. gr. P21/c), a = 7.2460(2) Å, b = 9.7887(3) Å, c = 5.9289(2) Å, β = 71.318(1)°, Z = 4, V = 398.37(2) Å3, Rwp = 2.81, GOF = 1.64. NaScB₂O₅ borate is characterized by incongruent melting at 1090 °C. Ab initio calculated IR spectrum of NaScB₂O₅, exhibited a high degree of consistency with the experimentally obtained IR spectrum. The calculated energy barrier
for oxygen ion migration, determined to be 0.998 eV, exhibits a reasonable degree of agreement with the experimentally determined activation energy of 0.9 eV. The title compound exhibits an ionic conductivity of 0.6·10^–3 S/cm at 1023 K. The band gap was about 6.83 eV

Downloads

Download data is not yet available.

Author Biographies

Andrey N. Sobolev, Baikal Institute of Nature Management, Siberian branch of the Russian Academy of Sciences 6 Sakhyanovoy st., Ulan-Ude 670047, Russian federation; Banzarov Buryat State University, 24a Smolina st., Ulan-Ude 670000, Russian Federation

Laborant at the Institute of Natural Sciences, Banzarov Buryat State University (Ulan-Ude,
Russian Federation)

Evgeniy V. Kovtunets, Baikal Institute of Nature Management, Siberian branch of the Russian Academy of Sciences 6 Sakhyanovoy st., Ulan-Ude 670047, Russian federation; Banzarov Buryat State University, 24a Smolina st., Ulan-Ude 670000, Russian Federation

Research Scientist of the Baikal Institute of Nature Management SB RAS, (Ulan-Ude, Russian Federation)

Tatyana S. Spiridonova, Baikal Institute of Nature Management, Siberian branch of the Russian Academy of Sciences 6 Sakhyanovoy st., Ulan-Ude 670047, Russian federation; Banzarov Buryat State University, 24a Smolina st., Ulan-Ude 670000, Russian Federation

Cand. Sci. (Chem.), Senior Research Scientist of the Baikal Institute of Nature Management SB RAS, (Ulan-Ude, Russian Federation)

Alexander I. Bogdanov, Vinogradov Institute of Geochemistry, Siberian branch of the Russian Academy of Sciences 1a building, Favorskogo st., Irkutsk 664033, Russian Federation

Cand. Sci. (Phys.–Math.), Senior Research Scientist of the Vinogradov Institute of Geochemistry SB RAS, (Irkutsk, Russian Federation)

Alexey K. Subanakov, Baikal Institute of Nature Management, Siberian branch of the Russian Academy of Sciences 6 Sakhyanovoy st., Ulan-Ude 670047, Russian federation; Banzarov Buryat State University, 24a Smolina st., Ulan-Ude 670000, Russian Federation

Cand. Sci. (Chem.), Head of the Oxide Systems Laboratory of the Baikal Institute of Nature
Management SB RAS, (Ulan-Ude, Russian Federation)

References

Huang C., Mutailipu M., Zhang F., … Pan S. Expanding the chemistry of borates with functional [BO2]− anions. Nature Communications. 2021;12: 1–8. https://doi.org/10.1038/s41467-021-22835-4

Li S., Li W., Li X., … Li C. A bifunctional primitive strategy induces enhancements of large second harmonic generation and wide UV transmittance in rare-earth borates containing [B5O10] groups. Chemical Science. 2024;15: 8959–8965. https://doi.org/10.1039/d4sc01853b

Wu H., Wei Z., Hu Z., Wang J., Wu Y., Yu H. Assembly of π-conjugated [B3O6] units by mer-isomer [YO3F3] octahedra to design a UV nonlinear optical material, Cs2Yb3O6F2. Angewandte Chemie. 2024;136. https://doi.org/10.1002/ange.202406318

Zhang W., Hou X., Han S., Pan S. Toward the ultraviolet (UV) or deep-UV nonlinear optical crystals: the combination of π-conjugated planar [XY3] and tetrahedral [XY4]. Coordination Chemistry Reviews. 2024;505: 215664. https://doi.org/10.1016/j.ccr.2024.215664

Li Q.-F., Chen W.-F., Lan Y.-Z., Cheng J.-W. Recent progress in ultraviolet and deep-ultraviolet nonlinear optical aluminoborates. Chinese Journal of Structural Chemistry. 2023; 42(3): 100036. https://doi.org/10.1016/j.cjsc.2023.100036

Kang L., Lin Z. Deep-ultraviolet nonlinear optical crystals: concept development and materials discovery. Light: cience & Applications. 2022;11: 1–12. https://doi.org/10.1038/s41377-022-00899-1

Halasyamani P. S Zhang W. Viewpoint: inorganic materials for UV and deep-UV nonlinear-optical applications. Inorganic Chemistry. 2017;56: 12077–12085. https://doi.org/10.1021/acs.inorgchem.7b02184

Chen C., Li R. The anionic group theory of the nonlinear optical effect and its applications in the development of new high-quality nlo crystals in the borate series. International Reviews in Physical Chemistry. 1988;8: 65–91. https://doi.org/10.1080/01442358909353223

Chen C., Wu Y., Jiang A., …. Lin S. New nonlinearoptical crystal: LiB3O5. Journal of the Optical Society of America B. 1989;6(4): 616. https://doi.org/10.1364/josab.6.000616

Mori Y., Kuroda I., Nakajima S., Sasaki T., Nakai S. New nonlinear optical crystal: cesium lithium borate. Applided Physics Letters. 1995;67: 1818–1820. https://doi.org/10.1063/1.115413

Chen C. T., Wang G. L., Wang X. Y., Xu Z. Y. Deep-UV nonlinear optical crystal KBe2BO3F2-discovery, growth, optical properties and applications. Applied Physics B. 2009;97: 9–25. https://doi.org/10.1007/s00340-009-3554-4

Chen C., Wang Y., Wu B., Wu K., Zeng W., Yu L. Design and synthesis of an ultraviolet-transparent nonlinear optical crystal Sr2Be2B2O7. Nature. 1995;373: 322–324. https://doi.org/10.1038/373322a0

Fröhlich R., Bohatý L., Liebertz J. Acta Crystallographica Section C: Structural Chemistry. Die Kristallstruktur von Wismutborat, BiB3O6. 1984;40: 343–344. https://doi.org/10.1107/S0108270184004078

Guoqing Z., Jun X., Xingda C., …. Fuxi G. Growth and spectrum of a novel birefringent α-BaB2O4 crystal. Journal of Crystal Growth. 1998;191(3): 517–519. https://doi.org/10.1016/S0022-0248(98)00162-6

Zhang S., Wu X., Song Y., Ni D., Hu B., Zhou T. Growth of birefringent Ca3(BO3)2 crystals by the Czochralski method. Journal of Crystal Growth. 2003;252: 246–250. https://doi.org/10.1016/S0022-0248(03)00867-4

Ming H., Xiaolong C., Yuping S., Jun L., Jingtai Z., Chengjun D. YBa3B9O18: a promising scintillation crystal. Crystal Growth and Design. 2007;7(2): 199–201. https://doi.org/10.1021/cg0606141

Chen X., Zhang B., Zhang F., …. Pan S. Designing an excellent deep-ultraviolet birefringent material for light polarization. Journal of the American Chemical Society. 2018;140: 16311–16319. https://doi.org/10.1021/JACS.8B10009

Berger S. V., Hassel O., Webb M., Rottenberg M. The crystal structure of cobaltpyroborate. Acta Chemica Scandinavica. 1950;4: 1054–1065. https://doi.org/10.3891/ACTA.CHEM.SCAND.04-1054

Cheng W. D., Zhang H., Zheng F. K., Chen J. T., Zhang Q. E., Pandey R. Electronic structures and linear optics of C2B2O5 (A = Mg, Ca, Sr) pyroborates. Chemistry of Materials. 2000;12: 3591–3594. https://doi.org/10.1021/cm000188l

Zhou C., Cheng J., Li H., Beysen S. Li3.366Mg0.317B2O5: the first pyroborate in the Li2O-MgO-B2O3 system. Inorganic Chemistry Communications. 2018;93: 92–96. https://doi.org/10.1016/j.inoche.2018.05.018

Maschmeyer E. M., Sanjeewa L. D., Ranmohotti G. S. Crystal structure of BaMnB2O5 containing structurally isolated manganese oxide sheets. Acta Crystallogr Sect E Crystallogr Commun. 2016;72: 1315–11320. https://doi.org/10.1107/S2056989016013074

Platunov M. S., Ivanova N. B., Kazak N. V., Ovchinnikov S. G. Crystal structure and magnetism of Co2−xNixB2O5 pyroborate. Journal of Siberian Federal University. Mathematics & Physics. 2011;4: 298–307. Режим доступа: https://elib.sfu-kras.ru/bitstream/handle/2311/2425/platunov.pdf?sequence=1

Busche S., Bluhm K. Synthese und Kristallstruktur der ersten zinkhaltigen Pyroborate Ni1.5Zn0.5(B2O5) und Co1.5Zn0.5(B2O5). Zeitschrift für Naturforschung B. 1995;50(10): 1445–1449. https://doi.org/10.1515/znb-1995-1003

Yan J., Chu D., Chen Z., Han J. Li2PbB2O5: a pyroborate with large birefringence induced by the synergistic effect of stereochemical active lone pair cations and π-conjugated [B2O5] groups. Inorganic Chemistry. 2022;61(46): 18795–801. https://doi.org/10.1021/acs.inorgchem.2c03469

Held P., Becker P. Dipraseodymium(III) pyroborate molybdate(VI), Pr2(B2O5)(MoO4). Crystallographic Communications. 2008;64(6). https://doi.org/10.1107/S1600536808010386

Zhang M., An D., Hu C., Chen X., Yang Z., Pan S. Rational design via synergistic combination leads to an outstanding deep-ultraviolet birefringent Li2Na2B2O5 material with an unvalued B2O5 functional gene. Journal of the American Chemical Society. 2019;141: 3258–3264. https://doi.org/10.1021/jacs.8b13402

Becker P., Held P. Crystal structure of sodium scandium borate, NaScB2O5. Zeitschrift für Kristallographie –New Crystal Structures. 2001;216(1-4): 35. https://doi.org/10.1524/NCRS.2001.216.14.35

Rietveld H. M. A profile refinement method for nuclear and magnetic structures. Journal of Applied Crystallography. 1969;2: 65–71. https://doi.org/10.1107/s0021889869006558

Coelho A. A. Topas: general profile and structure analysis software for powder diffraction data. Bruker AXS, 2005.

Dinnebier R. E., Leineweber A., Evans J. Rietveld refinement practical powder diffraction pattern analysis using TOPAS. 2019. https://doi.org/10.1515/9783110461381-201

Chen H., Wong L. L., Adams S. SoftBV – a software tool for screening the materials genome of inorganic fast ion conductors. Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials. 2019;75: 18–33. https://doi.org/10.1107/S2052520618015718

Kresse G. Ab initio molecular dynamics for liquid metals. Journal of Non-Crystalline Solids. 1995;192–193: 222–229. https://doi.org/10.1016/0022-3093(95)00355-X

Perdew J. P., Ruzsinszky A., Csonka G. I., … Burke K. Restoring the density-gradient expansion for exchange in solids and surfaces. Physical Review Letter.s 2008;100: 1–4. https://doi.org/10.1103/PhysRevLett.100.136406

Togo A., Tanaka I. First principles phonon calculations in materials science. Scripta Materialia. 2015;108: 1–5. https://doi.org/10.1016/j.scriptamat.2015.07.021

Krukau A. V., Vydrov O. A., Izmaylov A. F., Scuseria G. E. Influence of the exchange screening parameter on the performance of screened hybrid functionals. The Journal of Chemical Physics. 2006; 125(22). https://doi.org/10.1063/1.2404663

Shendrik R. Yu., Plechov P. Yu., Smirnov S. Z. ArDI –the system of mineral vibrational spectroscopy data processing and analysis. New Data on Minerals. 2024;58(2): 26–35. (In Russ.). https://doi.org/10.25993/fm.2024.58.2024.008