Chemistry, Physics and Technology of Surface, 2021, 12 (3), 184-189.

IR spectral manifestation of tin impurity sites in titanium dioxide



DOI: https://doi.org/10.15407/hftp12.03.184

O. V. Smirnova, A. G. Grebenyuk, V. V. Lobanov, T. A. Khalyavka, N. D. Shcherban, M. V. Shapovalova, V. V. Permyakov

Abstract


It is known that titanium dioxide as photocatalyst has significant drawback - limited absorption spectrum in the ultraviolet region makes it impossible to use solar energy. To expands the absorption spectrum of TiO2, the doping of impurities (metal, non-metal, etc.) were used. They affected the electronic structure and spectral characteristics of TiO2. The aim of our work was to investigate the influence of tin impurities on spectral characteristics of titanium dioxide using experimental and theoretical methods. The TiO2 powders modified by different amount of tin (Sn/TiO2) were synthesized by sol-gel method. The samples were characterized by SEM, EDX, FT-IR and UV-VIS spectroscopy. It has been found that Sn/TiO2 consists of fragmented agglomerates in the range of 5–10 mm. EDX spectroscopy prove that powders include Ti, O and Sn elements. Modification of titanium dioxide with tin leads to band gap narrowing of samples, which explains by insertion of Sn atoms into crystal lattice of titanium dioxide, because Ti4+ and Sn4+ ions radii are close. The band gap values increased with increasing of tin content. The work also analyzes the vibrational spectra of Sn/TiO2 both experimentally and theoretically. In order to interpret the results obtained, quantum chemical calculations on the spatial and electronic structures of cluster models of titanium dioxide (anatase) with inserted tin atoms using the density functional theory B3LYP method and the basis set 6-31G (d, p) were carried out and the corresponding FT-IR spectra have been simulated. By comparing the experimental and theoretical results, the influence has been analyzed of the number and arrangement of impurity tin atoms in clusters on the observed IR spectra of the samples. This makes it possible to forgive the most probable structural motives of titanium dioxide particles doped with tin atoms, as well as to establish the fact of the presence of tin atoms in the samples. Based on the comparison of the IR spectra of samples with different numbers of tin atoms, it is possible to quantify their composition.


Keywords


infrared spectra; titanium oxide nanoparticles; tin impurities; quantum chemistry; cluster models

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DOI: https://doi.org/10.15407/hftp12.03.184

Copyright (©) 2021 O. V. Smirnova, A. G. Grebenyuk, V. V. Lobanov, T. A. Khalyavka, N. D. Shcherban, M. V. Shapovalova, V. V. Permyakov

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