In situ high-temperature X-ray diffraction study of Sc-doped titanium oxide nanocrystallites

0535911 - ÚACH 2021 RIV GB eng J - Článek v odborném periodiku
Zenou, V. Y. - Bertolotti, F. - Guagliardi, A. - Toby, B. H. - von Dreele, R. B. - Bakardjieva, Snejana
In situ high-temperature X-ray diffraction study of Sc-doped titanium oxide nanocrystallites.
Journal of Applied Crystallography. Roč. 53, č. 6 (2020), s. 1452-1461. ISSN 0021-8898. E-ISSN 1600-5767
Grant CEP: GA ČR(CZ) GA18-15613S
Institucionální podpora: RVO:61388980
Klíčová slova: Rietveld analysis * Debye function analysis * Ti site-occupancy factor * Sc doping defects * high-resolution transmission electron microscopy * HRTEM image analysis
Obor OECD: Inorganic and nuclear chemistry
Impakt faktor: 3.304, rok: 2020
Způsob publikování: Omezený přístup
https://doi.org/10.1107/S1600576720012017

Titanium dioxide is an inexpensive wide-gap highly ionic semiconductor with striking photocatalytic capabilities in several heterogeneous photoredox reactions. A small crystal size is desirable to maximize the surface area, since photocatalytic reactions occur at the surface of a photocatalyst. Presented here are the synthesis and microstructural characterization of 4 at.% Sc-doped TiO2 (4SDT) prepared by water-based co-precipitation. The crystal structure of 4SDT was examined via in situ high-temperature powder X-ray diffraction experiments from 25 to 1200°C. Rietveld analysis revealed single-phase anatase up to 875°C, while at 900°C the anatase-to-rutile phase transformation occurred and at higher temperatures additional reflections of Sc-rich phases (Sc2TiO5 from 975°C and Ti3Sc4O12 or Sc2O3 at 1200°C) were observed. Debye function analysis (DFA) was applied to model the total scattering pattern directly in reciprocal space, allowing the reconstruction of Ti vacancies. Both Rietveld and DFA methods were applied to estimate the nanocrystallite size and shape with consistent growth in crystallite size with temperature: an ellipsoid shape with equatorial ∼4.7 nm / axial (001) ∼6.9 nm at 25°C to equatorial ∼27.9 nm / axial (001) ∼39.6 nm at 900°C refined by Rietveld analysis, versus a cylinder shape with Da,b = 4.3 nm and size dispersion σab = 1.5 nm, Lc = 4.9 nm and σc = 2.3 nm at 25°C to Da,b = 21.4 nm, σab = 8.3 nm, Lc = 23.9 and σc = 10.9 nm at 900°C estimated by DFA. The microstructural changes obtained by Rietveld and DFA methods were supported by high-resolution transmission electron microscopy image analysis, as well as by the less direct nitrogen sorption techniques that provide information on the size of non-agglomerated and dense particles. The Ti site-occupancy factor showed a linear increase from 0.6–0.8 at 25°C to unity at 900°C for anatase, and from ∼0.7 at 900°C to unity at 1200°C for rutile, via Rietveld analysis and DFA.
Trvalý link: http://hdl.handle.net/11104/0314162


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