Bismuth (III) trifluoromethanesulfonate, also known as bismuth triflate, is an economical, efficient, and environmentally friendly catalyst for the synthesis of organic products. Currently, bismuth triflate is not produced in Russia, so developing a technology for producing bismuth triflate is an important task. Bismuth triflate can be obtained using two methods: by reacting bismuth hydroxide with triflic acid, and by reacting bismuth oxide with triflic acid. The production of bismuth triflate from bismuth hydroxide is a long process that does not proceed to the end and has a yield of no more than 40%. The bismuth oxide obtained by thermal decomposition of bismuth hydroxide has several polymorphic modifications. Heating was carried out to 750 °C and cooled for 8 hours. The γ-bismuth oxide obtained in this way is dissolved in triflic acid for 2 hours and forms high-concentration solutions. The solubility values of bismuth triflate were determined at different acidity levels. X-ray analysis showed that bismuth nonahydrate triflate formed needle-like crystals. The α-phase of bismuth oxide obtained by decomposition of bismuth hydroxide at 450 °C did not dissolve completely in the acid. The process was carried out for 4 hours, and the yield was 92%. The resulting crystals of a bipyramidal shape were studied by differential thermal analysis, which showed that the crystals are pentahydrate of bismuth triflate, which loses crystallization water in the temperature range of 64-130 °C. Up to 320 °C, the substance is thermally stable. At a temperature of 327 °C, it melts with decomposition, which is accompanied by the formation of bismuth oxo-sulfates. According to X-ray diffraction data, the composition of the resulting phases is Bi28O32(SO4)10 and Bi34.7O100S16. Further heating to 380 °C leads to the decomposition of bismuth oxo-sulfates, resulting in the formation of the stable monoclinic modification of bismuth oxide, α-Bi2O3.

1. Siddig L.A., Alzard R.H., Nguyen H.L. et al. Cyclic carbonate formation from cycloaddition of CO2 to epoxides over bismuth subgallate photocatalyst. Inorganic Chemistry Communications. 2022. vol. 142. p. 109672. doi: 10.1016/j.inoche.2022.109672

2. Kumar M., Singh R., Sharma P. et al. Bismuth-catalyzed stereoselective 2-deoxyglycosylation of disarmed/armed glycal donors. Organic Letters. 2022. vol. 24. no. 2. pp. 575–580. doi: 10.1021/acs.orglett.1c04008

3. Nakate A.K. Lewis acid-catalysed α and π activation triggered cascade annulation reactions of alkynyl alcohols to construct heterocyclic compounds. Tetrahedron Letters. 2023. vol. 114. p. 154282.

4. Zenebe F.C., Taddesse A.M., Sivasubramanian M. et al. Highly efficient CdS/CeO2/Ag3PO4 nanocomposite as novel heterogenous catalyst for Knoevenagel condensation and acetylation reactions. Heliyon. 2024. vol. 10. no. 11. p. e31798. doi: 10.1016/j.heliyon.2024.e31798

5. Steber H.B., Singh Y., Demchenko A.V. Bismuth(III) triflate as a novel and efficient activator for glycosyl halides. Organic & Biomolecular Chemistry. 2021. vol. 19. no. 14. pp. 3220–3233. doi: 10.1039/d1ob00093d

6. Tereschenko D.S., Glazunova T.Yu., Buzoverov M.E. et al. Synthesis and crystal structure of new trinuclear fluorocarboxylate complexes of cobalt(II) and nickel(II). Coordination Chemistry. 2022. vol. 48. no. 9. pp. 534–542. doi: 10.31857/s0132344x22090079 (in Russian)

7. Yukhin Yu.M., Mishchenko K.V., Daminov A.S. Production of bismuth salt solutions with its preliminary oxidation. Theoretical Foundations of Chemical Engineering. 2017. vol. 51. no. 4. pp. 470–477. doi: 10.7868/s0040357117040157 (in Russian)

8. Yukhin Yu.M., Naydenko E.S., Daminov A.S. et al. Production of bismuth compounds for technology and medicine. Chemistry for Sustainable Development. 2018. vol. 26. no. 3. pp. 345–351. doi: 10.15372/khur20180309 (in Russian)

9. Weber M., Schmidt J., Wagner M. et al. Polymorphism and visible-light-driven photocatalysis of doped Bi2O3: M (M= S, Se, and Re). Inorganic Chemistry. 2022. vol. 61. no. 3. pp. 1571–1589. doi: 10.1021/acs.inorgchem.1c03330

10. Plotnikova S.E., Peregudov Yu.S., Gorbunova E.M. et al. Prospects for the use of liquid waste from the production of soda ash as a refrigerant based on the CaCl2-K2Cr2O7-H2O ternary system. Bulletin of VSUET. 2020. vol. 82. no. 3. pp. 233–238. doi: 10.20914/2310-1202-2020-233-238 (in Russian)

11. Plotnikova S.E., Gorbunova E.M., Niftaliev S.I. et al. Study of phase equilibria in water-salt systems containing components of whey. Bulletin of VSUET. 2023. vol. 85. no. 4. pp. 139–144. doi: 10.20914/2310-1202-2023-4-139-144 (in Russian)

12. Leng D., Wang T., Du C. et al. Synthesis of β-Bi2O3 nanoparticles via the oxidation of Bi nanoparticles: Size, shape and polymorph control, anisotropic thermal expansion, and visible-light photocatalytic activity. Ceramics International. 2022. vol. 48. no. 13. pp. 18270–18277. doi: 10.1016/j.ceramint.2022.03.085

13. Gandhi A.C., Lai C.Y., Wu K. et al. Phase transformation and room temperature stabilization of various Bi2O3 nano-polymorphs: effect of oxygen-vacancy defects and reduced surface energy due to adsorbed carbon species. Nanoscale. 2020. vol. 12. no. 47. pp. 24119–24137. doi: 10.1039/d0nr06552h

14. Zhao X.G., Malyi O.I., Zunger A. Polymorphous nature of the local structure of δ-Bi2O3. Physical Review Materials. 2024. vol. 8. no. 12. p. 125403. doi: 10.1103/physrevmaterials.8.125403

15. Sharutin V.V., Mosunova T.V. Synthesis, structure and application of aryl bismuth compounds. Bulletin of South Ural State University. Series: Chemistry. 2020. vol. 12. no. 3. pp. 7–66. (in Russian)

16. Ikramova Z., Kadirov M., Dadakhodzhaeva M. et al. Bismuth: element characteristics and its impact on the human body. Modern aspects of the development of fundamental sciences and issues of their teaching. 2023. vol. 1. no. 1. pp. 81–86. (in Russian)

17. Chetverikova D.K., Yudin A.A. Production of metallic bismuth and its structural analysis. Physical Materials Science. Actual problems of strength: collection of materials of the X International School and LXIII International Conference. Tolyatti: 2021.

18. Yukhin Yu.M., Koledova E.S., Timakova E.V. Complex processing of metallic bismuth to obtain oxide. Metallurgy of Non-Ferrous, Rare and Noble Metals. 2022. pp. 231–236. (in Russian)

19. Levitskaia T.G., Chatterjee S., Pourmand A. et al. A review of bismuth(III)-Based materials for remediation of contaminated sites. ACS Earth and Space Chemistry. 2022. vol. 6. no. 4. pp. 883–908. doi: 10.1021/acsearthspacechem.1c00114

20. Yan H., Hu J., Deng Y.X. et al. Long-life high-voltage all-solid-state batteries enabled by bismuth(III) triflate mediated polymer electrolytes. Chemical Engineering Journal. 2024. vol. 484. p. 149516. doi: 10.1016/j.cej.2024.149516

21. Tian Y., Sakaki S. Theoretical study on bismuth(III) catalysts for synthesis of phenylsulfonyl fluoride: reasons of their catalysis. ACS Catalysis. 2024. vol. 14. no. 4. pp. 2758–2774. doi: 10.1021/acscatal.3c04874

22. Planas O., Peciukenas V., Cornella J. Bismuth-catalyzed oxidative coupling of arylboronic acids with triflate and nonaflate salts. Journal of the American Chemical Society. 2020. vol. 142. no. 26. pp. 11382–11387. doi: 10.1021/jacs.0c05343