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

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 4at.% 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 degrees C. Rietveld analysis revealed single-phase anatase up to 875 degrees C, while at 900 degrees C the anatase-to-rutile phase transformation occurred and at higher temperatures additional reflections of Sc-rich phases (Sc2TiO5 from 975 degrees C and Ti3Sc4O12 or Sc2O3 at 1200 degrees 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 similar to 4.7 nm/axial (001) similar to 6.9 nm at 25 degrees C to equatorial similar to 27.9 nm/axial (001) similar to 39.6 nm at 900 degrees C refined by Rietveld analysis, versus a cylinder shape with D-a,D-b = 4.3 nm and size dispersion sigma(ab) = 1.5 nm, L-c = 4.9 nm and sigma(c) = 2.3 nm at 25 degrees C to D-a,D-b = 21.4 nm, sigma(ab) = 8.3 nm, L-c = 23.9 and sigma(c) = 10.9 nm at 900 degrees 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 degrees C to unity at 900 degrees C for anatase, and from similar to 0.7 at 900 degrees C to unity at 1200 degrees C for rutile, via Rietveld analysis and DFA.