A novel and simple method for preparing highly photoactive nanocrystalline F--doped
TiO2 photocatalyst with anatase and brookite phase was developed by hydrolysis of titanium
tetraisopropoxide in a mixed NH4F−H2O solution. The prepared F--doped TiO2 powders
were characterized by differential thermal analysis-thermogravimetry (DTA-TG), X-ray
diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV−vis absorption spectroscopy,
photoluminescence spectra (PL), transmission electron microscopy (TEM), and BET surface
areas. The photocatalytic activity was evaluated by the photocatalytic oxidation of acetone
in air. The results showed that the crystallinity of anatase was improved upon F- doping.
Moreover, fluoride ions not only suppressed the formation of brookite phase but also
prevented phase transition of anatase to rutile. The F--doped TiO2 samples exhibited stronger
absorption in the UV−visible range with a red shift in the band gap transition. The
photocatalytic activity of F--doped TiO2 powders prepared by this method exceeded that of
Degussa P25 when the molar ratio of NH4F to H2O was kept in the range of 0.5−3.
TiO2 thin films were prepared on fused quartz by the liquid-phase deposition (LPD) method from a (NH4)2TiF6
aqueous solution upon addition of boric acid (H3BO3) and calcined at various temperatures. The as-prepared
films were characterized with thermogravimetry (TG), Fourier transform infrared spectra (FTIR), X-ray
diffraction (XRD), UV−Visible spectrophotometry (UV−Vis), scanning electron microscopy (SEM),
photoluminescence spectra (PL), and X-ray photoelectron spectroscopy (XPS), respectively. The photocatalytic
activity of the samples was evaluated by photocatalytic decolorization of methyl orange aqueous solution. It
was found that the as-prepared TiO2 thin films contained not only Ti and O elements, but also a small amount
of F, N, and Si elements. The F and N came from the precursor solution, and the amount of F decreased with
increasing calcination temperature. Two sources of Si were identified. One was from the SiF6
2- ions, which
were formed by a reaction between the treatment solution and quartz substrate. The other was attributed to
the diffusion of Si from the surface of quartz substrate into TiO2 thin film at 700 °C or higher calcination
temperatures. With increasing calcination temperature, the photocatalytic activity of the TiO2 thin films gradually
increased due to the improvement of crystallization of the anatase TiO2 thin films. At 700 °C, the TiO2 thin
film showed the highest photocatalytic activity due to the increasing amount of SiO2 as an adsorbent center
and better crystallization of TiO2 in the composite thin film. Moreover, the SiO2/TiO2 composite thin film
showed the lowest PL intensity due to a decrease in the recombination rate of photogenerated electrons and
holes under UV light irradiation, which further confirms the film with the highest photocatalytic activity at
700 °C. When the calcination temperature is higher than 700 °C, the decrease in photocatalytic activity is
due to the formation of rutile and the sintering and growth of TiO2 crystallites resulting in the decrease of
surface area.
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