Visible photocatalysts based on nitrogen and carbon doped nanocrystalline titanium dioxide

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Abstract

Photocatalysts functioning in the visible spectrum range based on nanocrystalline titanium dioxide doped with nitrogen and carbon in the form of microspheres were obtained. Their structural, optoelectronic and photocatalytic properties were studied. The electron paramagnetic resonance method was used to identify spin centers (defects) and determine their concentrations in all the samples under study. Nitrogen atoms with an unpaired electron and Ti3+/oxygen vacancy centers were found in the microspheres doped with nitrogen. Dangling carbon bonds were recorded in the microspheres with carbon impurities. Photocatalysts doped simultaneously with nitrogen and carbon are characterized by both nitrogen and carbon spin centers. It was found that the concentration of defects increases during illumination, which is explained by their recharging. A correlation was established between the concentration of spin centers and the rate of photocatalysis in the obtained structures. It was shown that samples doped with two impurities are characterized by a high photocatalysis rate and prolonged catalysis for more than five hours after the illumination is turned off, as well as stable photocatalytic properties for several years, which determines the novelty of the studies and high prospects for use in ecology and biomedicine.

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About the authors

E. V. Kytina

Lomonosov Moscow State University

Email: zaytsevvb@my.msu.ru

Физический факультет

Russian Federation, Moscow, 119991

V. B. Zaitsev

Lomonosov Moscow State University; Sνenzhen MSU-BIT University

Author for correspondence.
Email: zaytsevvb@my.msu.ru

Физический факультет

Russian Federation, Moscow, 119991; China, Shenzhen, 518172

Е. А. Konstantinova

Lomonosov Moscow State University

Email: liza35@mail.ru

Физический факультет

Russian Federation, Moscow, 119991

V. А. Kulbachinskii

Lomonosov Moscow State University

Email: zaytsevvb@my.msu.ru

Физический факультет

Russian Federation, Moscow, 119991

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Supplementary files

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2. Fig. 1. Microphotographs of N-C-TiO2 microspheres. Scale bars are 100 nm (a), 1 μm (b).

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3. Fig. 2. Diffractogram of N-C-TiO2 samples.

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4. Fig. 3. Determination of the forbidden band width of doped N-C-TiO2 microspheres and TiO2 samples without impurities.

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5. Fig. 4. Kinetics of photocatalysis for TiO2 (1), N-TiO2 (2), C-TiO2 (3), N-C-TiO2 (4), N-C-TiO2_old (5) microspheres under photoexcitation in the visible range of the spectrum. The arrows show the moments of illumination on (τ = 0) and illumination off (τ = 20 min). C0 is the dye concentration at time τ = 0, C is the dye concentration at time τ.

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6. Fig. 5. EPR spectra of a series of microspheres under dark conditions and illumination: N-C-TiO2 (1 and 2), N-TiO2 (3 and 4), C-TiO2 (5 and 6), TiO2 (7).

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7. Fig. 6. Relaxation kinetics of the EPR signal amplitude relaxation from broken carbon bonds in N-C-TiO2. The inset shows the kinetics for carbon-doped TiO2.

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