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

DOI:10.1016/j.apcatb.2019.01.074 期刊:Applied Catalysis B: Environmental 出版年份:2019 更新时间:2025-09-19 17:15:36
摘要: 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°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°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 rather to these modifier-induced structural and electronic changes of the photocatalysts than to any other function of dopants, including photosensitization, enhanced charge separation, catalytic activity, at which most of studies are focused.
作者: Marcin Surówka,Marcin Kobielusz,Mateusz Trochowski,Marta Buchalska,Krzysztof Krucza?a,Pawe? Bro?,Wojciech Macyk
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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.

Iron species and other metal modifiers act as phase-composition controllers (PCC) during TiO2 synthesis, influencing morphology and phase composition (anatase to rutile ratio), which predominantly enhances photocatalytic activity. Doping with iron is detrimental, but composites with low iron content show improved activity. The effect is general for various metal species, with anatase to rutile ratio being a key factor. Modifiers indirectly affect activity through structural changes rather than direct catalytic roles.

The study is limited to specific modifiers and synthesis conditions (sol-gel method, calcination temperatures up to 900°C). The small amounts of modifiers may not be sufficient for certain catalytic effects, and the findings may not generalize to other synthesis methods or modifiers. Potential optimizations include exploring a wider range of modifiers and conditions.

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