SYNTHESIS AND INVESTIGATION OF APATITE-RELATED PHOSPHATO-VANADATES
DOI: https://doi.org/10.17721/1728-2209.2025.1(60).5
Keywords:
phosphate-vanadates, nanoparticles, hydroxyapatite, the band gap, FTIR spectroscopyAbstract
Background. Apatite-related modified calcium phosphates have increasing interest for use in orthopedics as bone substitutes. In addition, partial substitution of phosphate by vanadate-group in the anionic sublattice opens up wide opportunities in the development of catalysts for organic synthesis, as well as materials with special optical properties. The aim of the work are the synthesis of apatite-related calcium phosphate-vanadates and the study of the effect of partial substitution of phosphate by the vanadate-anion in the structure and the sorption of zinc cations from an aqueous solution on the band gap of materials.
Methods. The samples were synthesized from aqueous solutions of the system NH4+-Сa2+-PO43--NO3--VO43- with molar ratios Сa2+:PO43-:-VO43- = 10: (6-х): х, heated to 500°С and used for sorption of Zn2+ cations from the aqueous solution with subsequent heating to 500°С for 2 hours. The methods of powder X-ray diffraction, FTIR and electron spectroscopy were used for their characterization.
Results. According to the X-ray diffraction data, the synthesized samples are monophasic and belong to the hexagonal system, space group P63/m (apatite-type structure), and the calculated parameters of the lattice increase as the vanadate content in their composition increases. FTIR spectroscopy data confirm the presence of two types of anions (РО4 and VO4) in the composition of the synthesized phases. A decrease in the band gap width was established as the degree of substitution of phosphate anion by vanadate increased to 50%, as well as upon sorption of Zn2+ cations onto the surface of synthesized nanoparticles of vanadate-containing hydroxyapatites and their heating to 500°С.
Сonclusions. The obtained results can be used in the future in the development of materials with special optical properties or catalysts for organic transformations based on apatite-related calcium phosphate-vanadates.
References
Abdi, F.F.; Berglund, S.P. (2017) Recent Developments in Complex Metal Oxide Photoelectrodes. J. Phys. D: Appl. Phys. 50, 193002, https://doi.org/10.1088/1361-6463/aa6738.
Boechat, C. B..Terra, J., Eon, J.-G., Ellis, D.E., Rossi, A. M. (2003). Reduction by hydrogen of vanadium in vanadate apatite solid solutions Phys. Chem. Chem. Phys., 5, 4290-4298.https://doi.org/10.1039/B306176K
Dasireddy, V.D.B.C.; Singh, S.; Friedrich, H.B. (2012) Oxidative Dehydrogenation of N-Octane Using Vanadium Pentoxide-Supported Hydroxyapatite Catalysts. Applied Catalysis A: General 421–422, 58–69. https://doi.org/10.1016/j.apcata.2012.01.034.
Dasireddy, V.D.B.C.; Singh, S.; Friedrich, H.B. (2013) Activation of N-Octane Using Vanadium Oxide Supported on Alkaline Earth Hydroxyapatites. Applied Catalysis A: General 456, 105–117, https://doi.org/10.1016/j.apcata.2013.02.006.
Dasireddy, V.D.B.C.; Singh, S.; Friedrich, H.B. (2014) Vanadium Oxide Supported on Non-Stoichiometric Strontium Hydroxyapatite Catalysts for the Oxidative Dehydrogenation of n-Octane. J. Molec. Cat. A: Chemical, 395,398–408, https://doi.org/10.1016/j.molcata.2014.08.044.
Gonçalves, J.M.; da Silva, I., Angnes, M., Araki, L. K. (2020) Vanadium-Containing Electro and Photocatalysts for the Oxygen Evolution Reaction: A Review. J. Mater. Chem. A, 8, 2171–2206, https://doi.org/10.1039/C9TA10857B
Hara T., Satoko, K., Mori, K., Mizugaki, T., Ebitani, K., Jitsukawa, K., Kaneda K. (2006) Highly Efficient C−C Bond-Forming Reactions in Aqueous Media Catalyzed by Monomeric Vanadate Species in an Apatite Framework. J. Org. Chem. 71, 19, 7455–7462. https://doi.org/10.1021/jo0614745
Hayashi, K., Zhang, C., Nazir, A., Alashkar, T., Ishikawa, K. (2024) Carbonate Apatite Honeycomb Scaffold-Based Drug Delivery System for Repairing Osteoporotic Bone Defects. ACS Appl. Mater. Interfaces, 16, 35, 45956–45968. https://doi.org/10.1021/acsami.4c08047
Kalanur, S.S., Lee, Y.J., Seo, H. (2021) Exploring the Synthesis, Band Edge Insights, and Photoelectrochemical Water Splitting Properties of Lead Vanadates. ACS Appl. Mater. Interfaces, 13, 25906–25917. https://doi.org/10.1021/acsami.1c03109.
Maeda, Y., Washitake, Y., Nishimura, T., Iwai, K., Yamauchi, T., Uemura, S. (2004) Calcium PhosphateVanadate Apatite (CPVAP)-Catalyzed Aerobic Oxidation of Propargylic Alcohols with Molecular Oxygen. Tetrahedron 60, 9031–9036. https://doi.org/10.1016/j.tet.2004.08.004.
Midorikawa, K., Hiromoto, S., Yamamoto, T. (2024) Carbonate content control in carbonate apatite coatings of biodegradable magnesium Ceramics International, 50, 4, 6784-6792. https://doi.org/10.1016/j.ceramint.2023.12.021
Munir, M. U., Salman, S., Javed, I., Nasir, S., Bukhari, A., Ahmad, N., Shad, N. A., Aziz. F. (2021) Nano-hydroxyapatite as a delivery system: overview and advancements, Artificial Cells, Nanomedicine, and Biotechnology, 49,1, 717-727, https://doi.org/10.1080/21691401.2021.2016785
Nakajima, T., Isobe, M., Tsuchiya, T., Ueda, Y.; Manabe, T. (2010) Correlation between Luminescence Quantum Efficiency and Structural Properties of Vanadate Phosphors with Chained, Dimerized, and Isolated VO4 Tetrahedra. J. Phys. Chem. C 114, 5160–5167. https://doi.org/10.1021/jp910884c
Ogo, S.; Onda, A.; Yanagisawa, K. Hydrothermal Synthesis of Vanadate-Substituted Hydroxyapatites, and Catalytic Properties for Conversion of 2-Propanol. Applied Catalysis A: General 2008, 348, 129–134, https://doi.org/10.1016/j.apcata.2008.06.035.
Onda, A., Ogo, S., Kajiyoshi, K., Yanagisawa, K. (2008) Hydrothermal Synthesis of Vanadate/Phosphate Hydroxyapatite Solid Solutions. Mater. Lett. 62, 1406-1409. https://doi.org/10.1016/j.matlet.2007.08.087
Singh, R.K., Kim, T.-H., Patel, K. D., Kim, J.-J., Kim, H.-W. (2014) Development of biocompatible apatite nanorod-based drug-delivery system with in situ fluorescence imaging capacity. J. Mater. Chem. B, 2, 2039-2050. https://doi.org/10.1039/c3tb21156h
Srivastav, A., Chandanshive, B., Dandekar, P., Khushalani, D., Jain, R. (2019) Biomimetic Hydroxyapatite a Potential Universal Nanocarrier for Cellular Internalization & Drug Delivery. Pharm. Res. 36, 60. https://doi.org/10.1007/s11095-019-2594-7
Sugiyama, S.,Osaka, T., Hirata, Y., Sotowa, K. (2006) Enhancement of the Activity for Oxidative Dehydrogenation of Propane on Calcium Hydroxyapatite Substituted with Vanadate. Applied Catalysis A: General, 312, 52–58, https://doi.org/10.1016/j.apcata.2006.06.018.
Venkatesan, J., Kim, S.K. (2014) Nano-Hydroxyapatite Composite Biomaterials for Bone Tissue Engineering—A Review. J. Biomed. Nanotechnol. 10, 3124–3140. https://doi.org/10.1166/jbn.2014.1893
Zakaria, S.M., Sharif Zein, S.H., Othman, M.R., Yang, F., Jansen, J.A. (2013) Nanophase Hydroxyapatite as a Biomaterial in Advanced Hard Tissue Engineering: A Review. Tissue Eng. Part B Rev. 19, 431–441. https://doi.org/10.1089/ten.TEB.2012.0624
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