Abstract
UV light sensitive undoped and moderate (4 at.%) Sc-doped anatase nanocrystallites were prepared by an efficient and environmentally benign method based on homogeneous hydrolysis of TiOSO4 and Sc2(C2O4)3.5H2O aqueous solutions using urea as a precipitation agent, without post-synthesis calcination or annealing.X-ray diffraction study of the obtained powders revealed single phase anatase in both samples. Two different methods were applied to estimate the anatase crystallite size and shape from the X-ray diffraction data. The first one is based on the more conventional Scherrer equation (as implanted in GSAS-II program) while the second one is based on Debye function analysis (as implanted in DUBUSSY suite version 2.2), which is considered to be more adequate for nanocrystallites. Although each program has its own shape models, both methods indicated similar results of elongated nanocrystallite geometry for Sc-doped TiO2: (i) GSAS-II confirmed ellipsoid shape with equatorial size of 5.1(0) nm and axial size of 6.8(0), (ii) DEBUSSY suite 2.2 showed cylinder shape with diameter of equivalent circle in the ab-plane, Dab = 4.9(1.0) nm and crystallite length along the c-axis, Lc = 5.4(3.2) nm. For the undoped TiO2 sample, equatorial size of 5.5(0) nm and axial size of 7.3(0) nm for the ellipsoid shape was determined according to GSAS-II, while Dab = 5.5(1.3) nm and Lc = 6.0(2.2) nm for the cylinder shape was determined by DEBUSSY suite 2.2. These outcomes were found to corroborate with HRTEM analysis.Doping with 4 at.% Sc caused ~0.3% growth of lattice parameters from a = 3.7979 [4] Å, c = 9.4995 [9] Å for the undoped sample to a = 3.8110 [7] Å, c = 9.5274 [16] Å for the moderately Sc doped sample, while reduction in the Ti vacancies by half was confirmed by both methods.The introducing of Sc as electronically active secondary species into the crystal lattice of TiO2 can greatly alter its optical absorption. The incorporation of Sc into the crystal lattice of TiO2 favors the substitution of Ti, as both have approximately the same ionic size, and generates surface oxygen vacancies which can act as trapping center for the photogenerated electrons and reduce the recombination of electron–hole pairs. We can expect Sc doped TiO2 nanomaterials to have applications as effective photocatalysts for selective photocatalytic oxidation of various environmental organic pollutants.
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