Structure of hydrated and sulfated stannous acid. Quantum chemical modeling

Cover Page

Cite item

Full Text

Open Access Open Access
Restricted Access Access granted
Restricted Access Subscription Access

Abstract

Different complexes of H2SnO3 and its hydrated and sulfated derivatives were studied by the quantum chemical method within the framework of the cluster approximation with the ωB97XD functional and LanL2DZ(Sn), 6-31G**(O,S,H) basis sets, and with periodic boundary conditions approach with the PBE functional and the basis of the projector-augmented plane waves. It was found that among the hydrated forms, the smallest clusters with features of a SnO2 crystal (twofold and threefold coordinated oxygen atoms and fivefold and sixfold coordinated tin atoms) are (H2SnO3)6 clusters with a diameter of the described sphere d ~ 10 Å.Their combination (in the form of globules (d ~ 20 Å), chains, films) due to hydrogen bonds with each other and water molecules is energetically favorable. It is also possible their consolidation due to covalent Sn–O–Sn and Sn–OH–Sn bonds with the formation of various larger nanoparticles, for example (H2SnO3)12.The interesting thing is that some of them are hollow structures.Sulfuric acid molecules adsorbed on the surface of (SnO2)n(H2O)m clusters are bound to the surface Sn atoms by SO4 2– anions, and the protons split off in this case complete the conduction channels, forming H3O+ and H5O2 + cations in them in addition to OH-anions and water.

Full Text

Restricted Access

About the authors

Т. S. Zyubina

Federal Research Center of Problems of Chemical Physics RAS

Author for correspondence.
Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432

А. S. Zyubin

Federal Research Center of Problems of Chemical Physics RAS

Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432

R. V. Pisarev

Federal Research Center of Problems of Chemical Physics RAS

Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432

А. V. Pisareva

Federal Research Center of Problems of Chemical Physics RAS

Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432

Yu. А. Dobrovolsky

Federal Research Center of Problems of Chemical Physics RAS; Center of Hydrogen Energy (PJSFC “Sistema”)

Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432; Chernogolovka, 142432

References

  1. Hattori T., Athoh S., Tagawa T. et al. // Preparation of Catalysts IV. Amsterdam: Elsevier, 1987. p. 113. https://shop.elsevier.com/books/preparation-of-catalysts-iv/poncelet/978-0-444-42796-0
  2. Печенюк С.И. // Изв. АН. Сер. Хим. 1999. Т. 48. С. 228.
  3. Kesava М., Dinakaran K. // J. Phys. Chem. C. 2021. V. 125. Р. 130. https://dx.doi.org/10.1021/acs.jpcc.0c08739
  4. Scipioni R., Gazzoli D., Teocoli F. et al. // Membranes. 2014. V. 4. P. 123. https://www.mdpi.com/2077-0375/4/1/123
  5. Chen F., Mecheri B., D’Epifanio A. et al. // Fuel Cells. 2010. V. 10. № 5. P. 790. https://onlinelibrary.wiley.com/doi/abs/10.1002/fuce.200900179
  6. Brutti S., Scipioni R., Navarra M.A. et al. // Int. J. Nanotechnol. 2014. V. 11. P. 882. https://www.inderscienceonline.com/doi/abs/10.1504/IJNT.2014.063796
  7. Фабричный П.Б., Бабешкин А.М., Портяной В.А. и др. // Журн. структур. химии. 1970. № 4. С. 772.
  8. Fabrichnyi P.B., Babeshkin A.M., Portyanoi V.A. et al. // J. Struct. Chem. 1971. V. 11. P. 715. https://link.springer.com/article/10.1007/BF00743453
  9. Fabrichnyi P.B., Babeshkin A.M., Nesmeyanov A.N. // J. Phys. Chem. Solids. 1970. V. 31. P. 1399. https://www.sciencedirect.com/science/article/abs/pii/0022369770901447
  10. Willstuter R., Krant H., Fremery R. // Ber. 1924. Bd. 57. S. 1491.
  11. Денисова Е.Ф., Плетнев Р.Н., Федотов М.А. и др. Радиоспектроскопия твердого тела. Свердловск: УНЦ АН СССР, 1984. С. 54.
  12. FabritchnyiP., AfanassovM., DemazeauG. // C.R. Acad. Sc. Paris. 1986. V. 303. Ser. II. P. 1197.
  13. Кострыкин А.В., Спиридонов Ф.М., Линько И.В. и др. // Журн. структур. химии. 2007. Т. 52. С. 1176.
  14. Giesekke E.W., Gutowsky H.S., Kirkov P. et al. // Inorg. Chem. 1967. V. 6. P. 1294. https://pubs.acs.org/doi/10.1021/ic50053a005
  15. Паршуткин В.В., Ярославцев А.Б., Прозоровская З.Н. и др. // Журн. неорган. химии. 1985. Т. 30. № 1. C. 56.
  16. Brauer G. Handbook der Preparativen Anorganischen Chemie in drei Banden. Stuttgart: Ferdinand Enke Verlag, 1975.
  17. Karelin A.I., Leonova L.S., Tkacheva N.S. et al. // Heliyon. 2022. V. 8. P. e11450. https://doi.org/10.1016/j.heliyon.2022.e11450
  18. Liu L., Pu Y., Lu Y. et al. // J. Membr. Sci. 2021. V. 621. P. 118972. https://doi.org/10.1016/j.memsci.2020.118972
  19. Navarra M.A., Abbati C., Scrosati B. // J. Power Sources. 2008. V. 183. P. 109. https://doi.org/10.1016/j.jpowsour.2008.04.033
  20. Arata K. // Green Chem. 2009. V. 11. P. 1719. https://doi.org/10.1039/B822795K
  21. Varala R., Narayana V., Kulakarni S.R. et al. // Arab. J. Chem. 2016. V. 9. P. 550. https://www.sciencedirect.com/science/article/pii/S1878535216300028
  22. Chai J.-D., Head-Gordon M. // J. Chem. Phys. 2008. V. 128. P. 084106. https://doi.org/10.1063/1.2834918
  23. Krishnan R., Binkley J.S., Seeger R. et al. // J. Chem. Phys. 1980. V. 72. P. 650. https://doi.org/10.1063/1.438955
  24. Johnson B.J., Gill P.M.W., Pople J.A. // J. Chem. Phys. 1993. V.98. P. 5612. https://doi.org/10.1063/1.464906
  25. Wadt W.R., Hay P.J. // J. Chem. Phys. 1985. V. 82. P. 284. https://doi.org/10.1063/1.448800
  26. Frisch M.J., Trucks G.W., Schlegel H.B. et al. Gaussian 09, Revision B.01, Gaussian, Inc., Wallingford CT, 2010.
  27. Perdew J.P., Burke K., Ernzerhof M. // Phys. Rev. Lett. 1996. V. 77. P. 3865. https://doi.org/10.1103/PhysRevLett.77.3865
  28. Hafner J. // J. Comput. Chem. 2008. V.29. P. 2044. https://doi.org/10.1002/jcc.21057
  29. Kresse G., Hafner J. // Phys. Rev. B. 1993. V. 47. P. 558. https://doi.org/10.1103/PhysRevB.47.558
  30. Kresse G., Hafner J. // Phys. Rev. B. 1994. V. 49. P. 14251.
  31. Kresse G., Furthmuller J. // Phys. Rev. B. 1996. V. 54. P. 11169. https://doi.org/10.1103/physrevb.54.11169
  32. Kresse G., Joubert D. // Phys. Rev. B. 1999. V. 59. P. 1758. https://doi.org/10.1103/physrevb.59.1758
  33. Хьюи Дж. Неорганическая химия. М.: Химия, 1987. 695 с.
  34. Страумал Е.А., Юркова Л.Л., Баранчиков А.Е. и др. // Журн. неорган. химии. 2021. Т. 66. С. 298.
  35. Лермонтов С.А., Юркова Л.Л., Страумал Е.А. и др. // Журн. неорган. химии. 2018. Т. 63. С. 283.
  36. Карелин А.И., Ткачева Н.С., Надхина С.Е. и др. // Журн. неорган. химии. 2016. Т. 61. С. 1201.
  37. Карелин А.И., Леонова Л.С., Арсатов А.В. и др. // Журн. неорган. химии. 2013. Т. 58. С. 804.

Supplementary files

Supplementary Files
Action
1. JATS XML
Download
2. Fig. 1. Structures of (SnO2)n(H2O)m. Relative energies of isomers are given after the decimal point (in eV).

Download (969KB)
Indexing metadata
3. Fig. 2. Structures of (SnO2)n(H2SO4)k(H2O)m (in some cases, shown in two views). Relative energies are given after the decimal point (in eV). In some cases, hydrogen bonds are shown as dotted lines.

Download (755KB)
Indexing metadata
4. Fig. 3. Structures of a filament and a film [(H2SnO3)12(H2SO4)12(H2O)4]. Hydrogen bonds are shown as dotted lines.

Download (941KB)
Indexing metadata

Copyright (c) 2025 Russian Academy of Sciences