Iron Insertion and Hematite Segregation on Fe-Doped TiO2 Nanoparticles Obtained from Sol-Gel and Hydrothermal Methods

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Iron-doped TiO2 (Fe:TiO2) nanoparticles were synthesized by the sol-gel method (with Fe/Ti molar ratio corresponding to 1, 3, and 5%), followed by hydrothermal treatment, drying, and annealing. A similar methodology was used to synthesize TiO2 and alpha-Fe2O3 nanoparticles. For comparison, a mixture hematite/titania, with Fe/Ti = 4% was also investigated. Characterization of the samples using Rietveld refinement of X-ray diffraction data revealed that TiO2 consisted of 82% anatase and 18% brookite; for Fe:TiO2, brookite increased to 30% and hematite was also identified (0.5, 1.0, and 1.2 wt % for samples prepared with 1, 3, and 5% of Fe/Ti). For hematite/titania mixture, Fe/Ti was estimated as 4.4%, indicating the Rietveld method tenability for estimation of phase composition. Because the band gap energy, estimated as 3.2 eV for TiO2, gradually ranged from 3.0 to 2.7 eV with increasing Fe content at Fe:TiO2, it can be assumed that a Fe fraction was also inserted as dopant in the TiO2 lattice. Extended X-ray absorption fine structure spectra obtained for the Ti K-edge and Fe K-edge indicated that absorbing Fe occupied a Ti site in the TiO2 lattice, but hematite features were not observed. Hematite particles also could not be identified in the images obtained by transmission electron microscopy, in spite of iron identification by elemental mapping, suggesting that hematite can be segregated at the grain boundaries of Fe:TiO2.41055555561Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)National Institute of Science, Technology and Innovation on Advanced Complex Materials (INOMAT)National Institute of Science and Technology for Bioanalytics (INCTBio).Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP