Iron and other metal species as phase-composition controllers influencing the photocatalytic activity of TiO2 materials

The goal of the work is to verify which properties of TiO2-based materials, influenced by small amounts of Fe, Co, Ga, Bi, W, Mo, V and Ni species used as modifiers, play the predominant role in changing the photoactivity of TiO2. Two groups of materials were studied: TiO2 synthesized in the presence of nanocrystalline metal oxide and dissolved metal ions (cations or oxyanions). Sols were calcined at 450, 600 or 900 degrees C. Physicochemical properties of the materials were characterized by XRD, DRS, SEM, EPR, porosimetry and photocurrent measurements. The most detailed studies were focused on modifications by iron species. TiO2 doping was achieved for both Fe3+ and Fe2O3 modifiers after calcination at temperatures equal to or higher than 450 and 900 degrees C, respectively. Morphology of the materials (phase composition, specific surface area, etc.) were influenced by iron species even if they were not introduced into the crystal lattice of TiO2. Comparison of activity of photocatalysts and elucidation of the role of various reactive oxygen species were based on photooxidation tests involving Azure B and terephthalic acid. In general, iron species improved photocatalytic activity, nevertheless, doping of the materials appeared detrimental. A particular improvement of the activity was achieved for composites with low iron contents (ca. 0.01%mol Fe:Ti). The studies revealed, that beside the widely discussed mechanisms (photo-Fenton processes, charge separation, photosensitization, etc.) iron species can indirectly influence the photocatalytic activity of TiO2 acting as phase-composition controllers (PCC) during the synthesis of this oxide, which determine morphology of the resulting photocatalyst. To support this hypothesis, several sets of other TiO2 materials were modified with Co, Ga, Bi, W, Mo, V and Ni species. We show, that the use of these modifiers in small amounts can influence indirectly the activity of photocatalysts regardless to the type of modifier. Therefore different photoactivity of the tested materials should be attributed to these modifier-induced structural and electronic changes of the photocatalysts rather than to any other function of dopants, including photosensitization, enhanced charge separation, catalytic activity, at which most of studies are focused.