Šárka Paušová

Graphitic carbon nitride (g-C₃N₄) is a conjugated polymer, which recently drew a lot of attention as a metal-free and UV and visible light responsive photocatalyst in the field of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability and earth-abundant nature. In the present work, bulk g-C₃N₄ was synthesized by thermal decomposition of melamine. This material was further exfoliated by thermal treatment. S-doped samples were prepared from thiourea or further treatment of exfoliated g-C₃N₄ by mesylchloride. Synthesized materials were applied for photocatalytic removal of air pollutants (acetaldehyde and NO_x) according to the ISO 22197 and ISO 22197-1 methodology. The efficiency of acetaldehyde removal under UV irradiation was negligible for all g-C₃N₄ samples. This can be explained by the fact that g-C₃N₄ under irradiation does not directly form hydroxyl radicals, which are the primary oxidation species in acetaldehyde oxidation. It was proved by electron paramagnetic resonance (EPR) spectroscopy that the dominant species formed on the irradiated surface of g-C₃N₄ was the superoxide radical. Its production was responsible for a very high NO_x removal efficiency not only under UV irradiation (which was comparable with that of TiO₂), but also under visible irradiation.

Transfer of semiconductor thin films on transparent and or flexible substrates is a highly desirable process to enable photonic, catalytic, and sensing technologies. A promising approach to fabricate nanostructured TiO₂ films on transparent substrates is self-ordering by anodizing of thin metal films on fluorine-doped tin oxide (FTO). Here, we report pulsed direct current (DC) magnetron sputtering for the deposition of titanium thin films on conductive glass substrates at temperatures ranging from room temperature to 450 °C. We describe in detail the influence that deposition temperature has on mechanical, adhesion and microstructural properties of titanium film, as well as on the corresponding TiO₂ nanotube array obtained after anodization and annealing. Finally, we measure the photoelectrochemical water splitting activity of different TiO₂ nanotube samples showing that the film deposited at 150 °C has much higher activity correlating well with the lower crystallite size and the higher degree of self-organization observed in comparison with the nanotubes obtained at different temperatures. Importantly, the film showing higher water splitting activity does not have the best adhesion on glass substrate, highlighting an important trade-off for future optimization.

This work describes the preparation of transparent TiO₂ nanotube (TNT) arrays on fluorine-doped tin oxide (FTO) substrates. An optimized electrolyte composition (0.2 mol dm⁻³ NH₄F and 4 mol dm⁻³ H₂O in ethylene glycol) was used for the anodization of Ti films with different thicknesses (from 100 to 1300 nm) sputtered on the FTO glass substrates. For Ti thicknesses 600 nm and higher, anodization resulted in the formation of TNT arrays with an outer nanotube diameter around 180 nm and a wall thickness around 45 nm, while for anodized Ti thicknesses of 100 nm, the produced nanotubes were not well defined. The transmittance in the visible region (λ = 500 nm) varied from 90% for the thinnest TNT array to 65% for the thickest TNT array. For the fabrication of transparent TNT arrays by anodization, the optimal Ti thickness on FTO was around 1000 nm. Such fabricated TNT arrays with a length of 2500 nm exhibit stable photocurrent densities in aqueous electrolytes (~300 µA cm⁻² at potential 0.5 V vs. Ag/AgCl). The stability of the photocurrent response and a sufficient transparency (≥65%) enables the use of transparent TNT arrays in photoelectrochemical applications when the illumination from the support/semiconductor interface is a necessary condition and the transmitted light can be used for another purpose (photocathode or photochemical reaction in the electrolyte).

BACKGROUND: The objective of this work is to prepare various TiO₂/SiO₂ composites, determine their photocatalytic activity and suggest the most promising materials for further application.RESULTS: TiO₂/SiO₂ composites were successfully prepared as a powder, obtained by the heterocoagulation of mixed TiO₂ and SiO₂ aqueous colloidal suspensions. The heterocoagulation of prepared amorphous TiO₂ in the presence of SiO₂ led to the crystallization of TiO₂ with anatase structure. Photocatalytic activity was tested in the liquid phase by dye degradation and in the gas phase by hexane degradation. In aqueous phase the presence of SiO₂ increased the rate of degradation of Methylene Blue in comparison with pure TiO₂ in acidic conditions, whereas Acid Orange 7 photodegradation was faster in basic solution in the presence of TiO₂/SiO₂ 1:1 composite. In gaseous phase, composites prepared by heterocoagulation showed improved photoactivity (conversion around 35%).CONCLUSION: Composites prepared by heterocoagulation with ratio TiO₂/SiO₂ 1:10 can be used as photocatalyst in self‐cleaning paints. SiO₂ partly covers the TiO₂ surface and acts as a barrier which separates the active surface of TiO₂ from contact with the binder or polymeric substrate. © 2014 Society of Chemical Industry