Polyoxotungstometalates of 3d metals in the synthesis of hybrid carbon-mineral nanomaterials by the CVD method
A.P. Prudchenko1, Y.A. Moroz1, N.S. Lozinsky1, O.Yu.. Poliakova1, J.S. Protasevich1, V.A. Glazunova2,1, G.K. Volkova2,1, V.V. Burkhovetsky2,1
1 L.M. Litvinenko Institute of Physical Organic and Coal Chemistry
2 Galkin Donetsk Institute for Physics and Engineering
DOI: 10.26456/pcascnn/2025.17.733
Original article
Abstract: This paper presents the results of an assessment of the possibility of obtaining hybrid carbon-mineral nanomaterials by the method of catalytic chemical deposition of carbon from the gas phase using complexes of polyoxotungstometalates with 3d-metals of the general formula (NH4)X[PW11O39Me(L)]×nH2O, where Ме – Fe, Co, Ni, Cu; L – H2O, C6H12N4 (hexamethylenetetramine), as components of metal oxide catalysts for the growth of carbon nanotubes, which are a source of reduced metal particles active in the catalytic process. The synthesis products were studied by transmission electron microscopy and X-ray phase analysis. It has been established that even at a very low molar metal-carrier ratio (0,03÷1), a catalytic process is realized with the formation of carbon nanotubes. It is shown that, regardless of the qualitative composition of the catalyst, there is also an accumulation of the product of the non–catalytic flow, nanocarbon, which forms a hybrid supramolecular carbon-carbon complex in the form of lateral deposits of graphene-like carbon on the outer surface of carbon nanotubes. According to X-ray phase analysis of isolated and purified synthesis products using structurally different polyoxotungstometalates, X-ray diffractograms show reflexes at the same angular positions, which makes it possible to assume the formation of two types of hybrid carbon-mineral nanomaterials: carbon nanotubes-nanocarbon-tungsten oxides and nanocarbon-tungsten oxides.
Keywords: carbon nanotubes, metal oxide catalysts, polyoxotungstometalates, hybrid carbon-mineral nanomaterials
- Anatoliy P. Prudchenko – Ph. D., Senior Researcher, Department of Supramolecular Chemistry, L.M. Litvinenko Institute of Physical Organic and Coal Chemistry
- Yaroslav A. Moroz – Ph. D., Senior Researcher, Department of Supramolecular Chemistry, L.M. Litvinenko Institute of Physical Organic and Coal Chemistry
- Nikolai S. Lozinsky – Ph. D., Senior Researcher, Department of Supramolecular Chemistry, L.M. Litvinenko Institute of Physical Organic and Coal Chemistry
- Oksana Yu.. Poliakova – Junior Researcher, Department of Supramolecular Chemistry, L.M. Litvinenko Institute of Physical Organic and Coal Chemistry
- Julia S. Protasevich – Leading Engineer, Department of Supramolecular Chemistry, L.M. Litvinenko Institute of Physical Organic and Coal Chemistry
- Valentina A. Glazunova – Researcher, Department of Physics and Engineering of High Pressure and Advanced Technologies, Galkin Donetsk Institute for Physics and Engineering, Engineer, Department of Supramolecular Chemistry L.M. Litvinenko Institute of Physical Organic and Coal Chemistry
- Galina K. Volkova – Researcher, Department of Physics and Engineering of High Pressure and Advanced Technologies, Galkin Donetsk Institute for Physics and Engineering, Engineer, Department of Supramolecular Chemistry L.M. Litvinenko Institute of Physical Organic and Coal Chemistry
- Valery V. Burkhovetsky – Research, Department of Physics and Diagnostics of Advanced Materials, Galkin Donetsk Institute for Physics and Engineering, Engineer, Department of Supramolecular Chemistry L.M. Litvinenko Institute of Physical Organic and Coal Chemistry
For citation:
Prudchenko A.P., Moroz Y.A., Lozinsky N.S., Poliakova O.Yu.., Protasevich J.S., Glazunova V.A., Volkova G.K., Burkhovetsky V.V. Polioksovolframometallaty 3d-metallov v sinteze gibridnykh uglerod-mineralnykh nanomaterialov CVD-metodom [Polyoxotungstometalates of 3d metals in the synthesis of hybrid carbon-mineral nanomaterials by the CVD method], Fiziko-khimicheskie aspekty izucheniya klasterov, nanostruktur i nanomaterialov [Physical and chemical aspects of the study of clusters, nanostructures and nanomaterials], 2025, issue 17, pp. 733-741. DOI: 10.26456/pcascnn/2025.17.733. ⎘
Full article (in Russian): download PDF file
References:
1. Lim X.X., Low S.C., Oh W.D. A critical review of heterogeneous catalyst design for carbon nanotubes synthesis: functionalities, performances, and prospects, Fuel Processing Technology, 2023, vol. 241, art. no. 107624, 28 p. DOI: 10.1016/j.fuproc.2022.107624.
2. Basova Т., Polyakov M. Hybrid materials based on carbon nanotubes and polyaromatic molecules: methods of
functionalization and sensor properties, Macroheterocycles, 2020, vol. 13, issue 2, pp. 91-112. DOI: 10.6060/mhc200710b.
3. Esawi A.M.K., Morsi K., Sayed A. et al. The influence of carbon nanotube (CNT) morphology and diameter on the processing and properties of CNT-reinforced aluminium composites, Composites Part A: Applied Science and Manufacturing, 2011, vol. 42, no. 3, pp. 234-243. DOI: 10.1016/j.compositesa.2010.11.008.
4. Zare Y, Rhee K.Y. The effective conductivity of polymer carbon nanotubes (CNT) nanocomposites, Journal of Physics and Chemistry of Solids, 2019, vol. 131, pp. 15-21. DOI: 10.1016/j.jpcs.2019.03.006.
5. Navrotskaya А., Aleksandrova D., Krivoshapkina E. et al. Hybrid materials based on carbon nanotubes and nanofibers for environmental applications, Frontiers in Chemistry, 2020, vol. 8, issue 546, pp. 1-9. DOI: 10.3389/fchem.2020.00546.
6. Wu Z., Gao S., Chen L. et al. Electrically insulated epoxy nanocomposites reinforced with synergistic core-shell SiO2 @MWCNTs and montmorillonite bifillers, Macromolecular Chemistry and Physics, 2017, vol. 218, issue 23, art. no. 1700357, 9 p. DOI: 10.1002/macp.201700357.
7. Poliakova O.Yu., Prudchenko A.P., Protasevich Yu.S. Influence of the nature of chelating agents on the activity and structural pre-organization of metal oxide catalysts for the growth of carbon nanotubes synthesized by the method of polymerized complex precursors, Physics of Particles and Nuclei Letters, 2024, vol. 21, issue 4, pp. 761-763. DOI: 10.1134/S1547477124701280.
8. Roy S., Crans D.C., Parac-Vogt T.N. Editorial: Polyoxometalates in catalysis, biology, energy and materials science, Frontiers in Chemistry, 2019, vol. 7, art. no. 646, 2 p. DOI: 10.3389/fchem.2019.00646.
9. Murmu G., Samajdar S., Ghosh S. et al. Tungsten-based Lindqvist and Keggin type polyoxometalates as efficient photocatalysts for degradation of toxic chemical dyes, Chemosphere, 2024, vol. 346, art. no. 140576, 8 p. DOI: 10.1016/j.chemosphere.2023.140576.
10. Moroz Ya.A., Lozinskii N.S., Lopanov A.N., Chebyshev K.A. Low-temperature synthesis of compounds with the pyrochlore and hexagonal tungsten bonze structure, Inorganic Materials, 2021, vol. 57, issue 8, pp. 835-842. DOI: 10.1134/S0020168521080069.
11. Lozinsky N.S., Lopanov A.N., Moroz Ya.A. Preparation of powdered materials by thermolysis of heteropolytungstosilicates, Russian Journal of Applied Chemistry, 2025, vol. 98, issue 2, pp. 3-13. DOI: 10.31857/S00444618250201e3.
12. Moroz Ya.A., Lozinskii M.S., Zaritovskii A.N. et al. Iron-containing polyoxotungstophosphates and products of their thermolysis, Russian Journal of General Chemistry, 2023, vol. 93, issue 7, pp. 1139-1148. DOI: 10.1134/S1070363223070198.
13. Prudchenko A.P., Polyakova O.Yu., Protasevich Yu.S. Metal oxide catalysts for low-temperature template CCVD synthesis of carbon nanotubes, Journal of Advanced Materials and Technologies, 2024, vol. 9, issue 1, pp. 12-22. DOI: 10.17277/jamt 01.pp.012-022.
14. GOST 27578-87. Gazy uglevodorodnye szhizhennye dlya avtomobil'nogo transporta. Tekhnicheskie usloviya [Liquefied hydrocarbon gases for motor transport. Specifications]. Moscow, USSR National Committee on Standards, 1987, 10 p. (In Russian).
15. Awadallah, A.E. Promoting effect of group VI metals on Ni/MgO for catalytic growth of carbon nanotubes by ethylene chemical vapour deposition, Chemical Papers, 2015, vol. 69, issue 2, pp. 316-324. 2. DOI: 10.1515/chempap-2015–0029.