Physical and chemical aspects of the study of clusters, nanostructures and nanomaterials. Founded at 2009

In-situ modification of nanostructured hydroxyapatite by CdS particles

N.S. Kozhevnikova1, E.A. Bogdanova2, V.M. Skachkov1, I.V. Baklanova1, A.P. Tyutyunnik1, L.Yu. Buldakova1, M.Yu. Yanchenko1

1 Institute of Solid State Chemistry of the Ural Branch of RAS
2 JSC «Giredmet»

DOI: 10.26456/pcascnn/2025.17.851

Original article

Abstract: The article discusses the possibility of obtaining functional composite materials with pronounced photocatalytic properties. A hybrid composite material has been developed by in-situ modification of nanostructured hydroxyapatite obtained by precipitation from solution with cadmium sulfide particles. The initial components and synthesized samples were certified using modern physicochemical methods of analysis: X-ray phase analysis, energy-dispersive X-ray analysis, Raman spectroscopy, scanning electron microscopy, and the Brunauer-Emmett-Teller method. The functional characteristics of the developed composite materials based on hydroxyapatite and cadmium sulfide, in particular, photocatalytic activity under the action of ultraviolet or visible radiation, have been studied. The efficiency of using the developed composite material as a photocatalyst was estimated by the oxidation rate of n-dihydroxybenzene (hydroquinone). Based on the obtained experimental data, the values of the reaction rate constants of photocatalytic oxidation of hydroquinone and its half-life under various conditions were calculated. It was proven that the developed composite material based on nanosized cadmium sulfide and hydroxyapatite has pronounced catalytic properties and is a promising material for use as a photocatalyst. A patent application has been filed for the developed composite material.

Keywords: cadmium sulfide, chemical condensation from aqueous solutions, hydroxyapatite, composite material, hydroquinone, photocatalysis

  • Natal’ya S. Kozhevnikova – Ph. D., Senior Researcher, Laboratory of non-stoichiometric compounds, Institute of Solid State Chemistry of the Ural Branch of RAS
  • Ekaterina A. Bogdanova – Ph. D., Leading Researcher, Laboratory of electrochemical devices for hydrogen energy, JSC «Giredmet»
  • Vladimir M. Skachkov – Ph. D., Senior Researcher, Laboratory of heterogeneous processes chemistry, Institute of Solid State Chemistry of the Ural Branch of RAS
  • Inna V. Baklanova – Ph. D., Senior Researcher, Laboratory of quantum chemistry and spectroscopy named after A.L. Ivanovsky, Institute of Solid State Chemistry of the Ural Branch of RAS
  • Alexandr P. Tyutyunnik – Ph. D., Head of the Laboratory of structural and phase analysis, Institute of Solid State Chemistry of the Ural Branch of RAS
  • Larisa Yu. Buldakova – Ph. D., Senior Researcher, Laboratory of physical-chemical methods of analysis, Institute of Solid State Chemistry of the Ural Branch of RAS
  • Mikhail Yu. Yanchenko – Ph. D., Senior Researcher, Laboratory of physical-chemical methods of analysis, Institute of Solid State Chemistry of the Ural Branch of RAS

For citation:

Kozhevnikova N.S., Bogdanova E.A., Skachkov V.M., Baklanova I.V., Tyutyunnik A.P., Buldakova L.Yu., Yanchenko M.Yu. In-situ modifitsirovanie nanostrukturirovannogo gidroksiapatita nanochastitsami CdS [In-situ modification of nanostructured hydroxyapatite by CdS particles], Fiziko-khimicheskie aspekty izucheniya klasterov, nanostruktur i nanomaterialov [Physical and chemical aspects of the study of clusters, nanostructures and nanomaterials], 2025, issue 17, pp. 851-864. DOI: 10.26456/pcascnn/2025.17.851. ⎘

Full article (in Russian): download PDF file

References:

1. Parmon V.N. Photokataliz: voprosy tervinologii [Photocalysis: terminology issues], Fotokataliticheskoe preobrazovanie solnechnoj energii [Photocatalytic conversion of solar energy], ed. by K.I. Zamaraev, V.N. Parmon. Novosibirsk, Nauka Publ., 1991, pp. 7-17. (In Russian).
2. Yepseu A.P., Ngoudjou L.E.T, Tigwere G.A. et al. Hot injection synthesis of CuS decorated CdS and ZnS nanomaterials from metal thiosemicarbazone complexes as single source precursors: Application in the photocatalytic degradation of methylene blue, Inorganic Chemistry Communications, 2024, vol. 166, art. no. 112650. 10 p. DOI: 10.1016/j.inoche.2024.112650.
3. Alrababah Y.M., Sheng C.K. Wurtzite CdS ratio tunability on α-Fe2O3/CdS synergistic heterostructure for enhanced UV-induced photocatalytic decomposition of rhodamine 6G dye pollutant, Alexandria Engineering Journal, 2024, vol. 100, pp. 300-311. DOI: 10.1016/j.aej.2024.05.050.
4. Raju A.G., Rao B.D., Himabindu G., Botsa S.M. Fabrication of a heterostructure composite with CuO and FeS2 as efficient photocatalyst for decolourisation of brilliant green, Journal of Materials Research and Technology, 2022, vol. 17, pp. 2648-2656. DOI: 10.1016/j.jmrt.2022.01.166.
5. Zgura I., Preda N., Enculescu M. et al. Cytotoxicity, antioxidant, antibacterial, and photocatalytic activities of ZnO–CdS powders, Materials, 2020, vol. 13, issue 1, art. no 182, 17 p. DOI: 10.3390/ma13010182.
6. Pouretedal H.R., Basati S. Characterization and photocatalytic activity of ZnO, ZnS, ZnO/ZnS, CdO, CdS and CdO/CdS nanoparticles in mesoporous SBA-15, Iranian Journal of Chemistry and Chemical Engineering, 2015, vol. 34, issue 1, pp. 11-19. DOI: 10.30492/ijcce.2015.12617.
7. Aziz N.A.B., Sheng C.K. Impact of CuO loading for enhanced photocatalytic performance of CdS/CuO photocatalyst on rhodamine 6G dye decomposition under ultraviolet irradiation, Materials Letters, 2023, vol. 47, art. no. 134589. 4 p. DOI: 10.1016/j.matlet.2023.134589.
8. Khan M.D., Farooq M.H., Iqra F., Zulfiqar A., Rizwan M. Designing of visible light active composites of CuS and ZnO for improved photocatalytic performance under solar light irradiation, Optik, 2022, vol. 271, art. no. 170147. 9 p. DOI: 10.1016/j.ijleo.2022.170147.
9. Weldegebrieal G.K., Sibhatu A.K. Photocatalytic activity of biosynthesized α-Fe2O3 nanoparticles for the degradation of methylene blue and methyl orange dyes, Optik, 2021, vol. 241, art. no. 167226. 15 p. DOI: 10.1016/j.ijleo.2021.167226.
10. Huang W., Lu X., Jia D. et al. Characterization of structural, optical and photocatalytic properties of yttrium modified hematite (α-Fe2O3) nanocatalyst, Ceramics International, 2023, vol. 49, issue 15, pp. 25602-25611. DOI: 10.1016/j.ceramint.2023.05.101.
11. Yan T., Li N., Jiang Z., Guan W., Qiao Z., Huang B. Self-sacrificing template synthesis of CdS quantum dots/Cd-Hap composite photocatalysts for excellent H2 production under visible light, International Journal of Hydrogen Energy, 2018, vol. 43, issue 45, pp. 20616-20626. DOI: 10.1016/j.ijhydene.2018.09.093.
12. Singh H., Bokare A., Kumar A. et al. Formation of magnetite-based ceramic materials and their photocatalytic applications, Advanced ceramics for versatile interdisciplinary applications (Elsevier Series on Advanced Ceramic Materials), 2022, chapter 6, pp. 115-146. DOI: 10.1016/B978-0-323-89952-9.00016-6.
13. Liu Y., Liu Z., Huang D. et al. Metal or metal-containing nanoparticle@MOF nanocomposites as a promising type of photocatalyst, Coordination Chemistry Reviews, 2019, vol. 388, pp. 63-78. DOI: 10.1016/j.ccr.2019.02.031.
14. Zhu K., Yanagisawa K., Onda A., Kajiyoshi K. Hydrothermal synthesis and morphology variation of cadmium hydroxyapatite, Journal of Solid State Chemistry, 2004, vol. 177, issue 12, pp. 4379-4385. DOI: 10.1016/j.jssc.2004.09.025.
15. Kozhevnikova N.S., Vorokh A.S., Uritskaya A.A. Cadmium sulfide nanoparticles prepared by chemical bath deposition, Russian Chemical Reviews, 2015, vol. 84, issue 3, pp. 225-250. DOI: 10.1070/rcr4452.
16. Vorokh A.S., Kozhevnikova N.S., Baklanova I.V. et al. Mechanism of the formation of photosensitive nanostructured TiO2 with low content CdS nanoparticles, Doklady Physical Chemistry, 2016, vol. 467, issue 2, pp. 56-59. DOI: 10.1134/S0012501616040059.
17. Nishikawa H., Omamiuda K. Photocatalytic activity of hydroxyapatite for methyl mercaptane, Journal of Molecular Catalysis A: Chemical, 2002, vol. 179, issue 1-2, pp. 193-200. DOI: 10.1016/S1381-1169(01)00325-9.
18. Velisoju V.K., Aytam H.P., Akula V. Selective hydrogenation and dehydrogenation using hydroxyapatite-based catalysts, Design and Applications of Hydroxyapatite-Based Catalysts. Weinheim, Wiley-VCH, 2022, chapter 7, pp. 241-268. DOI: 10.1002/9783527830190.ch7.
19. Nasr-Esfahani M., Fekri S. Alumina/TiO2/hydroxyapatite interface nanostructure composite filters as efficient photocatalysts for the purification of air, Reaction Kinetics, Mechanisms and Catalysis, 2012, vol. 107, issue 1, pp. 89-103. DOI: 10.1007/s11144-012-0457-x.
20. Navarro-Jaén S., Bobadilla L.F., Romero-Sarria F. et al. Evaluation of the oxygen mobility in CePO4-supported catalysts: mechanistic implications on the water–gas shift reaction, Journal of Physical Chemistry C, 2020, vol. 124, issue 30, pp. 16391-16401. DOI: 10.1021/acs.jpcc.0c03649.
21. Tawfik A., Tan X., Elsamadony M. et al. Graphene/hydroxyapatite nano-composite for enhancement of hydrogen productivity from delignified duckweed, Fuel, 2022, vol. 330, art. no. 125537, 12 p. DOI: 10.1016/j.fuel.2022.125537.
22. Trung T.S., Minh N.C., Cuong H.N. et al. Valorization of fish and shrimp wastes to nano-hydroxyapatite/chitosan biocomposite for wastewater treatment, Journal of Science: Advanced Materials and Devices, 2022, vol. 7, issue 4, art. no. 100485. 9 p. DOI: 10.1016/j.jsamd.2022.100485.
23. Hossain Md.S., Sarkar S., Tarannum S. et al. Exploration of photo-catalytic activity of nano-hydroxyapatite based on the crystallographic parameters: Estimation of crystallite size using X-ray diffraction data, Journal of Saudi Chemical Society, 2023, vol. 27, issue 6, art. no. 101769. 13 p. DOI: 10.1016/j.jscs.2023.101769.
24. Piccirillo C., Castro P.M.L. Calcium hydroxyapatite-based photocatalysts for environment remediation: characteristics, performances and future perspectives, Journal of Environmental Management, 2017, vol. 193, pp. 79-91. DOI: 10.1016/j.jenvman.2017.01.071.
25. Sahoo S.K., Das A.A., Deka D., Naik B., Sahoo N.K. Organic-inorganic hybrid hydroquinone bridged V-CdS/HAP/Pd-TCPP: A novel visible light active photocatalyst for phenol degradation, Journal of Molecular Liquids, 2021, vol. 339, art. no.116721, 12 p. DOI: 10.1016/j.molliq.2021.116721.
26. Xiaofang L., Tianhong X., Weifeng Y., Qiang W., Rongjiang Z. Hollow hydroxyapatite microspheres modified by CdS nanoparticles for efficiently photocatalytic degradation of tetracycline, Journal of the Taiwan Institute of Chemical Engineers, 2020, vol. 106, pp. 148-158. DOI: 10.1016/j.jtice.2019.10.023.
27. Bogdanova E.A., Skachkov V.M. Ex-situ modifitsirovanie nanostrukturirovannogo GAP kolloidnymi chastitsami CdS [Ex-situ modification of nanostructured HAP by colloidal CdS particles], Fiziko-khimicheskie aspekty izucheniya klasterov, nanostruktur i nanomaterialov [Physical and chemical aspects of the study of clusters, nanostructures and nanomaterials], 2024, issue 16, pp. 183-197. DOI: 10.26456/pcascnn/2024.16.183. (In Russian).
28. Bogdanova E.A., Kozhevnikova N.S.,Skachkov V.M. Sposob polucheniya kompozicionnogo materiala na osnove gidroksiapatita, soderzhashhego nanochasticy sulfida kadmiya [Method of produsing hydroxyapatite-based composite material containing cadmium sulphide nanoparticles] Patent RF, no. 2838999, 2025. (In Russian).
29. Sabirzyanov N.A., Bogdanova E.A., Khonina T.G. Sposob polucheniya suspenzii gidroksiapatita [A method of obtaining a suspension of hydroxyapatite]. Patent RF, no. 2406693, 2010. (In Russian).
30. Sabirzyanov N.A., Bogdanova E.A., Skachkov V.M. Sposob polucheniya suspenzii apatita [Method of preparing apatite suspension]. Patent RF, no. 2652193, 2018. (In Russian).
31. Bogdanova E.A., Skachkov V.М., Medyankina I.S. et al. Formation of nanodimensional structures in precipitated hydroxyapatite by fluorine substitution, SN Applied Sciences, 2020, vol. 2, issue 9, art. no. 1565, 7 p. DOI: 10.1007/s42452-020-03388-5.

⇐ Prevoius journal article | Content | Next journal article ⇒