Previously unknown in the literature, complexes of hexamethylenetetramine (HMTA) with tungsten silicates of the composition Rb5[SiW11O39Fe(HMTA)]?20H2O, Cs5[SiW11O39Fe(HMTA)]?6H2O, Rb6[SiW11O39Zn(HMTA)]?12H2O, Cs6[SiW11O39Zn(HMTA)]?10H2O with the Keggin anion structure were synthesized and studied by electron and IR spectroscopy, nuclear magnetic resonance, thermal and X-ray phase analysis. The electronic absorption spectra of the HMTA complexes with tungsten silicatoferrates in the region of 270…600 nm indicate an octahedral environment of iron (III) atoms, and the shift of the absorption maximum of 290 nm for Rb5[SiW11O39Fe(H2O)]?10H2O to 310 nm for Rb5[SiW11O39Fe(HMTA)] indicates a change in the ligands in the immediate environment of iron atoms and the formation of HMTA complexes with tungsten silicate. This is also evidenced by the results of nuclear magnetic resonance of solutions of the synthesized zinc-containing compounds in D2O: the chemical shift of the 1H protons of the CH2 methylene groups in HMTA is 4.56 ppm, in the Rb6[SiW11O39Zn(HMTA)]?12H2O complex – 4.64 ppm; for the 13C carbon atoms in HMTA, the chemical shift is 71.1 ppm, and in the Rb6[SiW11O39Zn(HMTA)]?12H2O complex – 71.2 ppm. According to thermal analysis (TA), differential scanning calorimetry (DSC) and X-ray phase analysis, the products of thermolysis of the synthesized compounds at 650? are phases with the structure of pyrochlore and hexagonal tungsten bronzes. The catalytic properties of Rb5[SiW11O39Fe(HMTA)]?20H2O were studied in the production of carbon nanomaterials. A hybrid carbon-mineral material, nanocarbon (WOX), was obtained. It was characterized by X-ray diffraction analysis and electron microscopy. It exhibits high electrical conductivity and chemical resistance to concentrated acid solutions. The results of this study may be useful for the low-temperature synthesis of compounds with a pyrochlore structure, hexagonal tungsten bronze, and hybrid carbon-mineral nanostructures.
Yaroslav A. Moroz – Candidate of Chemical Sciences, senior research, L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, Donetsk, Russia
Nikolai S. Lozinskii – Candidate of Chemical Sciences, senior research, L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, Donetsk, Russia
Anatoliy P. Prudchenko – Candidate of Chemical Sciences, senior research, L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, Donetsk, Russia
Alexander N. Lopanov – Doctor of Technical Sciences, Professor, V. G. Shukhov Belgorod State Technological University, Belgorod, Russia
Konstantin A. Chebyshev – Candidate of Chemical Sciences, Associate Professor, Department of Physical and Inorganic Chemistry, North Caucasus Federal University, Stavropol, Russia
1. Roy S., Crans D. C., Parac-Vogt T. N., et al. Polyoxometalates in catalysis, biology, energy and materials science. Lausanne: Frontiers Media SA, 2019. 224 p. DOI: 10.3389/978-2-88963-233-6
2. Camarillo-Cisneros J., Arzola-Alvarez C., Cabral-Lares R. M., et al. Optical properties of W1-xXMoXO30,33H2O semiconductor oxides synthesized by hydrothermal and microwave techniques // Inorganic Chemistry Communication 2020. V. 119. Art. ID 107984. 9 p. DOI: 10.3390/polym11111740
3. Лозинский Н. С., Лопанов А. Н., Мороз Я. А. и др. Синтез и термические превращения комплексов вольфрамофосфатометаллатов с гексаметилентетрамином // Журнал неорганической химии. 2024. Т. 69, № 7. С. 1029 – 1038.
4. Помогайло А. Д., Джардималиева Г. И. Металлополимерные гибридные нанокомпозиты. М.: Наука, 2015. С. 136 – 149.
5. da Silva M. J., Rodrigues A. A., Lopes N. P. G. Keggin heteropolyacid salt catalysts in oxidation reactions: a review // Inorganics. 2023. V. 11. Art. ID 162. 23 p. DOI: 10.3390/inorganics11040162
6. Farsani M. R., Yadollahi B. Synthesis, characterization and catalytic performance of a Fe polyoxometalate/silica composite in the oxidation of alcohols with hydrogen peroxide // Journal of Molecular Catalysis A: Chemical. 2014. V. 392. P. 8 – 15. DOI: 10.1016/j.molcata.2014.05.001
7. Ivanova S. Hybrid organic-inorganic materials based on polyoxometalates and ionic liquids and their application in catalysis // Chemical Engineering. 2014. V. 2014. Art. ID 963792. 13 p. DOI: 10.1155/2014/963792
8. Chen W.-L., Chen B.-W., Tan H.-Q., et al. Ionothermal syntheses of three transition-metal-containing polyoxotungstate hybrids exhibiting the photocatalytic and electrocatalytic properties // Journal of Solid State Chemistry. 2010. V. 183, No. 2. P. 310 – 321. DOI: 10.1016/j.jssc.2009.11.016
9. Nunes M., Garcia-Orduna P., Atrian-Blasco E., et al. Polyoxometalate-ionic liquids for mitigating the effects of iron gall ink corrosion on cellulosic supports // ACS Omega. 2024. V. 9. P. 36609 - 36621. DOI: 10.1021/acsomega.4c04925
10. Martinetto Y., Pegot B., Roch-Marchal C., et al. Designing functional polyoxometalate-based ionic liquid crystals and ionic liquids // European Journal of Inorganic Chemistry. 2019. V. 2020, No. 3. P. 228 – 247. DOI: 10.1002/ejic.201900990
11. Herrmann S., Kostrzewa M., Wierschem A., et al. Polyoxometalate ionic liquids as self-repairing acid-resistant corrosion protection // Angewandte Chemie International Edition. 2014. V. 53, Nо. 49. P. 13596 – 13599. DOI: 10.1002/anie.201408171
12. Tajima Y., Takagi R., Nakajima T., et al. 11-Tungstophosphate with iron(II) and hydrogen peroxide efficiently detached bacterial biofilm // Biological and Pharmaceutical Bulletin. 2009. V. 32, No. 10. P. 1783 – 1789. DOI: 10.1248/bpb.32.1783
13. Lobiak E. V., Shlyakhova E. V., Bulusheva L. G., et al. Ni–Mo and Co–Mo alloy nanoparticles for catalytic chemical vapor deposition synthesis of carbon nanotubes // Journal of Alloys and Compounds. 2015. V. 621. P. 351 – 356. DOI: 10.1016/j.jallcom.2014.09.220
14. Lobiak E. V., Shlyakhova E. V., Gusel’nikov A. V., et al. Сarbon nanotube synthesis using Fe-Mo/MgO catalyst with different ratios of CH4 and H2 gases // Physica Status Solidi (B). 2017. V. 255, Art. No. 1700274. 6 p. DOI: 10.1002/pssb.201700274
15. Прудченко А. П., Мороз Я. А., Лозинский Н. С. и др. Полиоксовольфрамометаллаты 3d-металлов в синтезе гибридных углерод-минеральных наноматериалов CVD-методом // Физико-химические аспекты изучения кластеров, наноструктур и наноматериалов. Тверь: Изд-во Тверского государственного университета, 2025. Вып. 17. С. 733 – 741. DOI: 10.26456/pcascnn/2025.17.733
16. Буракова Е. А., Бесперстова Г. С., Неверова М. А. и др. Особенности получения катализатора синтеза углеродных нанотрубок // Вестник Воронежского государственного университета инженерных технологий. 2019. Т. 81, № 2. С. 261 – 267. DOI: 10.20914/2310-1202-2019-2-261-267
17. Nunes M., Garcia-Orduna P., Atrian-Blasco E., et. al. Polyoxometalate-ionic liquids for mitigating the effects of iron gall ink corrosion on cellulosic supports // ACS Omega Journal. 2024. V. 9, No. 4. P. 36609 – 36621. DOI: 10.1021/acsomega.4c04925
18. Silaen L., Elfita E., Mohadi R., et al. Soft ion divalent metals toward adsorption on Zn/Al-POM layered double hydroxide // Journal of Ecological Engineering. 2021. V. 22, No. 10. P. 109 – 120. DOI: 10.12911/22998993/142122
19. da Silva M. J., da Silva Andrade P. H., Sampaio С. F., et. al. Transition metal-substituted potassium silicotungstate salts as catalysts for oxidation of terpene alcohols with hydrogen peroxide // Catalysis Letter. 2021. V. 151, No. 18. P. 2094 – 2106. DOI: 10.1007/s10562-020-03449-9
20. Fernandes D. M., Simoes S. M. N., Carapuca H. M., et. al. Novel poly(hexylmethacrylate) composite carbon electrodes modified with Keggin-type tungstophosphate tetra-butylammonium salts // Journal of Electroanalytical Chemistry. 2010. V. 639, Nо. 1–2. P. 83 – 87. DOI: 10.1016/j.jelechem.2009.11.020
21. Vinogradoff V., Rimola A., Duvernay F., et al. The mechanism of hexamethylenetetramine (HMT) formation in the solid state at low temperature // Physical Chemistry Chemical Physics. 2012. V. 14. Р. 12309 – 12320. DOI: 10.1039/c2cp41963g
22. Жапиева Б. Н., Туленбаева М. А., Алтыбаева Д. Т. Строение комплексного соединения иодида магния с гексаметилентетрамином // Вестник науки и образования. 2017. Т. 1, № 3. C. 26 – 29.
23. Geng Ya., Dong T., Fang P., et al. Fast and effective glycolysis of poly (ethylene terephthalate) catalyzed by polyoxometalate // Polymer Degradation and Stability. 2015. V. 117. P. 30 – 36. DOI: 10.1016/j.polymdegradstab.2015.03.019
24. Chen F., Ma J., Dong Zh., et al. Characterization and catalytic performance of heteropoly acid H4SiW12O40 supported on nanoporous materials // Journal of Nanoscience and Nanotechnology. 2014. V. 14. P. 7293 – 7299. DOI: 10.1166/jnn.2014.8964
25. Chatterjee R., Mandal A. Synthesis and structural elucidation of POM based hybrid with a common cobalt centre: It’s antibacterial activity and future perspectives // International Journal for Multidisciplinary Research. 2023. V. 5, Nо. 2. P. 1 – 14. DOI: 10.36948/ijfmr.2023.v05i02.2650
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