Facile fabrication of anatase TiO2 microspheres on solid substrates and surface crystal facet transformation from {001} to {101}

Anatase TiO(2) microspheres with controlled surface morphologies and exposed crystal facets were directly synthesized on metal titanium foil substrates by means of a facile, one-pot hydrothermal method without use of any templating reagent. The obtained products were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelecron spectroscopy (XPS), and the focused ion beam (FIB) technique. The sizes of the resultant microspheres ranged from 1.1 to 2.1 μm. The transformation of anatase TiO(2) microspheres with exposed {001} facets surface to nanosheets surface with {101} facets was achieved by simply controlling the hydrothermal reaction time. The anatase TiO(2) microspheres with exposed square-shaped plane {001} facets were obtained by controlling the reaction time at 1 h. The prolonged reaction time transforms the anatase TiO(2) microspheres with exposed square-shaped plane {001} facets to eroded {001} facets then to a nanosheet surface with exposed {101} facets. With hydrothermal synthesis, the surface morphological structure and crystal facets formation are highly dependent on dissolution/deposition processes, which can be strongly influenced by attributes, such as pH of the reaction media, the total concentration of dissolved and suspended titanium species, and the concentration of fluoride in the reaction solution. The changes of these attributes during the hydrothermal process were therefore measured and used to illustrate the morphology and crystal-facet transformation processes of anatase TiO(2) microspheres. The surface morphologies and crystal-facet transformations during hydrothermal processes were found to be governed by the compositional changes of the reaction media, driven by dynamically shifted dissolution/deposition equilibria. The photocatalytic activities of the photoanodes made of anatase TiO(2) microspheres were evaluated. The experimental results demonstrated that the photocatalytic activity of anatase TiO(2) microspheres with exposed {001} facets was found to be 1.5 times higher than that of the anatase TiO(2) microspheres with exposed {101} facets.