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Monitoring the Structure Evolution of Titanium Oxide Photocatalysts: From the Molecular Form via the Amorphous State to the Crystalline Phase

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Onur Şahin,  Ezgi
Research Group Weidenthaler, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Dai,  Yitao
Research Group Tüysüz, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Chan,  Candace K.
Research Group Tüysüz, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Materials Science and Engineering, School for Engineering of Matter, Transport and Energy (SEMTE), Arizona State University;

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Tüysüz,  Harun
Research Group Tüysüz, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Schmidt,  Wolfgang
Research Group Schmidt, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Lim,  Joohyun
Nanoanalytics and Interfaces, Independent Max Planck Research Groups, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society;
Department of Chemistry Kangwon National University 24341 Chuncheon, Republic of Korea;

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Zhang,  Siyuan
Nanoanalytics and Interfaces, Independent Max Planck Research Groups, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society;

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Scheu,  Christina
Nanoanalytics and Interfaces, Independent Max Planck Research Groups, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society;

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Weidenthaler,  Claudia
Research Group Weidenthaler, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Onur Şahin, E., Dai, Y., Chan, C. K., Tüysüz, H., Schmidt, W., Lim, J., et al. (2021). Monitoring the Structure Evolution of Titanium Oxide Photocatalysts: From the Molecular Form via the Amorphous State to the Crystalline Phase. Chemistry – A European Journal, 27, 1-10. doi:10.1002/chem.202101117.


Cite as: http://hdl.handle.net/21.11116/0000-0008-F434-A
Abstract
Amorphous TixOy with high surface area has attracted significant interest as photocatalyst with higher activity in ultraviolet (UV) light-induced water splitting applications compared to commercial nanocrystalline TiO2. Under photocatalytic operation conditions, the structure of the molecular titanium alkoxide precursor rearranges upon hydrolysis and leads to higher connectivity of the structure-building units. Structurally ordered domains with sizes smaller than 7 Å form larger aggregates. The experimental scattering data can be explained best with a structure model consisting of an anatase-like core and a distorted shell. Upon exposure to UV light, the white TixOy suspension turns dark corresponding to the reduction of Ti4+ to Ti3+ as confirmed by electron energy loss spectroscopy (EELS). Heat-induced crystallisation was followed by in situ temperature-dependent total scattering experiments. First, ordering in the Ti−O environment takes place upon to 350 °C. Above this temperature, the distorted anatase core starts to grow but the structure obtained at 400 °C is still not fully ordered.