Recent studies on tungsten oxide preparation are mainly motivated by its applications in smart windows, energy harvesting and, recently, in cancer therapy. Peroxotungstic acid (PTA) is an important precursor to obtain tungsten oxide in an environmentally-friendly way, through the colloidal synthesis in aqueous media. Despite giving chemically pure products, PTA originates oxides with various morphologies depending on the experimental conditions, a subject open to discussion. PTA, in the presence of sodium dodecyl sulfate (SDS) as architecture-directing agent, was investigated in ethanol/water medium by small angle X-ray scattering (SAXS), fluorescence, surface tension and conductivity measurements; the morphology of tungsten oxide obtained from the precursor systems was also characterized by scanning electron microscopy (SEM). PTA/SDS/ethanol/water systems show a two-level organization in which small micelles are aggregated as fractal structures. There is an inverse correlation between gyration radius of the fractal structures of the PTA/SDS systems and particle size of the tungsten oxide films. The interaction of PTA with SDS is observed by reducing the Gibbs energy of micellization; also, it is evidenced that the supressive effect of PTA on pyrene emission is overrided in presence of SDS.
Tungsten oxides show different stoichiometries, crystal lattices and morphologies. These characteristics are important mainly when they are used as photocatalysts. In this work tungsten oxide thin films were obtained by thermal evaporation on (100) silicon substrates covered with gold and heated at 350 and 600 ºC, with different deposition times. The stoichiometry of the films, morphology, crystal structure and resistance to leaching were characterized through X-ray photoelectron spectroscopy, micro-Raman spectroscopy, scanning and transmission electron microscopy, X-ray diffractometry, Rutherford backscattering spectrometry and O16(α,α')O16 resonant nuclear reaction. Films obtained at higher temperatures show well-defined spherical nanometric structure; they are composed of WO3.1 and the presence of hydrated tungsten oxide was also observed. The major crystal structure observed is the hexagonal. Thin films obtained through thermal evaporation present resistance to leaching in aqueous media and excellent performance as photocatalysts, evaluated through the degradation of the methyl orange dye.
Óxidos de tungstênio apresentam diferentes estequiometrias, estruturas cristalinas e morfologias. Estas características são importantes principalmente quando se deseja utilizá-los como fotocatalisadores. Neste trabalho foram obtidos filmes finos de óxido de tungstênio por evaporação térmica sobre substratos de silício (100) recobertos com ouro, aquecidos a 350 e 600 ºC. A estequiometria dos filmes formados, morfologia, estrutura cristalina e resistência à lixiviação foram caracterizadas por espectroscopia de fotoelétrons de raios X, espectroscopia micro-Raman, microscopias eletrônicas de varredura e transmissão, difratometria de raios X, espectrometria de retroespalhamento Rutherford e reação nuclear ressonante O16(α,α')O16. Os filmes apresentam estrutura nanométrica, cuja forma torna-se bem definida com o aumento da temperatura. O sistema apresenta-se na forma de WO3.1 e cristaliza principalmente na fase hexagonal, sendo obtidas também estruturas de óxido de tungstênio hidratadas. Os filmes obtidos através de evaporação térmica apresentam resistência à lixiviação em ambiente aquoso e excelente atividade fotocatalítica, que foi testada na degradação do corante alaranjado de metila.