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Enhanced Visible Light Sensitization of N-doped TiO2 Nanotubes Containing Ti-Oxynitride Species Fabricated via Electrochemical Anodization of Titanium Nitride

DOI:10.1021/acs.jpcc.8b09762 期刊:The Journal of Physical Chemistry C 出版年份:2018 更新时间:2025-09-04 15:30:14
摘要: The concentration and chemical state of nitrogen represent critical factors to control the band-gap narrowing and the enhancement of visible light harvesting in nitrogen-doped titanium dioxide. In this study, photocatalytic TiO2-N nanoporous structures were fabricated by the electrochemical anodization of titanium nitride sputtered films. Doping was straightforwardly obtained by oxidizing as-sputtered titanium nitride films containing N-metal bonds varying from 7.3 to 18.5 % in the Ti matrix. Severe morphological variations into the as-anodized substrates were registered at different nitrogen concentration and studied by Small-Angle X-ray Scattering. Titanium nitride films with minimum N content of 6.2 at% N led to a quasi-nanotubular geometry, whilst an increase in N concentration up to 23.8 at% determined an inhomogeneous, polydispersed distribution of nanotube apertures. The chemical state of nitrogen in the TiO2 matrix was investigated by X-ray Photoelectron Spectroscopy depth profile analysis and correlated to the photocatalytic performance. The presence of Ti-N and β-Ti substitutional bonds, as well as Ti-oxynitride species was revealed by the analysis of N 1s X-ray Photoelectron Spectroscopy High Resolution spectra. The minimum N content of 4.1 at% in the TiO2-N corresponded to the lowest Ti-oxynitride ratio of 13.5 %. The relative variation of N-metal bonds was correlated to the visible light sensitization and the highest Ti-N/Ti oxynitride ratio of 3.3 was attributed to the lowest band-gap of 2.7 eV and associated to a threefold increase in the degradation of organic dye. Further increase of N doping led to a dramatic drop of Ti-N/Ti oxynitride ratio, from 3.3 to 0.4, which resulted in a loss photocatalytic activity. The impact of the chemical state of nitrogen towards efficient doping of TiO2 nanotubes is demonstrated with a direct correlation to the N loading and a strategy to optimise these factors based on a simple, rapid synthesis from titanium nitride.
作者: Andrea Merenda,Akshita Rana,Albert Kamal Guirguis,De Ming Zhu,Lingxue Kong,Ludovic F Dumée
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The study demonstrated the successful fabrication of TiO2-N nanoporous substrates with controlled morphology and nitrogen doping concentration, leading to enhanced visible light sensitization and photocatalytic performance. The optimal N doping concentration was found to be 4.1 at%, which resulted in the lowest band-gap and highest photocatalytic activity.

The study is limited by the technical constraints of controlling the oxidation level during the synthesis of N-doped TiO2 and the formation of Ti-NxOy intermediates. Potential areas for optimization include the precise control of N doping concentration and the minimization of charge recombination centers.

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