Centrum pre nanodiagnostiku materiálov

BAKARDJIEVA, Snejana – MAREŠ, Jakub – KOCI, Eva – TOLASZ, Jakub – FAJGAR, Radek – RYUKHTIN, Vasyl – KLEMENTOVÁ, Mariana – MICHNA, Štefan – BIBOVÁ, Hana – HOLMESTAD, Randi – TITORENKOVA, Rositsa – ČAPLOVIČOVÁ, Mária.

In Nanomaterials. Vol. 12, iss. 5 (2022)

https://doi.org/10.3390/nano12050750

Abstract

Ag-decorated TiO₂ nanostructured materials are promising photocatalysts. We used non-standard cryo-lyophilization and ArF laser ablation methods to produce TiO₂ nanosheets and TiO₂ nanostructured thin films decorated with Ag nanoparticles. Both methods have a common advantage in that they provide a single multiply twinned Ag⁽⁰⁾ characterized by {111} twin boundaries. Advanced microscopy techniques and electron diffraction patterns revealed the formation of multiply twinned Ag⁽⁰⁾ structures at elevated temperatures (500 °C and 800 °C). The photocatalytic activity was demonstrated by the efficient degradation of 4-chlorophenol and Total Organic Carbon removal using Ag-TiO₂ nanosheets, because the multiply twinned Ag⁽⁰⁾ served as an immobilized photocatalytically active center. Ag-TiO₂ nanostructured thin films decorated with multiply twinned Ag⁽⁰⁾ achieved improved photoelectrochemical water splitting due to the additional induction of a plasmonic effect. The photocatalytic properties of TiO₂ nanosheets and TiO₂ nanostructured thin films were correlated with the presence of defect-twinned structures formed from Ag⁽⁰⁾ nanoparticles with a narrow size distribution, tuned to between 10 and 20 nm. This work opens up new possibilities for understanding the defects generated in Ag-TiO₂ nanostructured materials and paves the way for connecting their morphology with their photocatalytic activity.

T. Roch, M. Gregor, S. Volkov, M. Čaplovičová, L. Satrapinskyy, A. Plecenik

Applied Surface Science, Volume 551, 2021, 149333

https://doi.org/10.1016/j.apsusc.2021.149333

Abstract

Niobium nitride (NbN) has suitable mechanical properties for application as protective coatings in mechanical engineering, and also its superconductivity can be utilized in thin film devices for sensorics or in combination with ferromagnet in spintronics. Long-range superconducting proximity effect at the heterostructures with a weak ferromagnet can be used for generation of spin-polarized current. For any operational heterostructure application the high quality NbN thin films need to be prepared. In this work we have investigated impact of the substrates on the structure and preferential orientation of niobium nitride thin films fabricated by pulsed laser deposition at 600 °C on Si (0 0 1), MgO (0 0 1), C-plane and R-plane Al₂O₃ substrates. Growth parameters have been tuned in order to obtain single superconducting δ-NbN phase. Microstructure was analyzed by X-ray diffraction and transmission electron microscopy. Si substrate does not induce the film preferential orientation. Films on MgO are epitaxial (0 0 1) oriented. Films on R-Al₂O₃ show (1 3 5) orientation with twinned crystallites on the lower symmetry substrate surface. The (1 1 1) epitaxial growth with the largest crystallites and their smallest tilting was achieved on C-Al₂O₃ substrate leading to the best superconducting properties.

Thirunavukkarasu Guru Karthikeyan, Monfort Olivier, Motola Martin, Motlochová Monika, Gregor Maroš, Roch Tomáš, Čaplovicová Maria, Lavrikova Aleksandra Y., Hensel Karol, Brezová Vlasta, Jerigová Monika, Šubrt Ján, Plesch, Gustáv

New J. Chem., 2021, 45, 4174-4184

https://doi.org/10.1039/D0NJ05976E

Abstract

Titanium dioxide aerogel (TiAP) powders were prepared by lyophilization of peroxo-polytitanic gels followed by annealing at 800 °C to obtain an anatase structure. The surface modification of TiAP was performed for the first time by low amounts of Ce ions (in the range of 0.0025 to 0.025 wt%) using a wet impregnation method. The photocatalytic activity of the aerogel samples was investigated for the removal of different organic pollutants (i.e., Rhodamine B, phenol and caffeine) and the results were compared with the reference P25. Both TiAP and Ce ion surface-modified TiAP (Ce/TiAP) have exhibited better degradation efficiencies for the removal of pollutants than P25, especially for Ce/TiAP with an enhancement in the degradation efficiencies of +18% and +37% for the removal of caffeine and Rhodamine B, respectively. These results have been partly explained by the high active surface area of Ce/TiAP compared to TiAP as well as its better photoelectrochemical properties which have shown, for instance, ∼10% increased incident photon-to-electron conversion efficiency at 360 nm. Interestingly, the energetic position of the valence band maximum of Ce/TiAP is shifted from 3.2 eV to 2.8 eV (compared to TiAP), thus improving the generation of reactive oxygen species (ROS), especially hydroxyl radicals. Indeed, the presence of HO˙ is confirmed by electron paramagnetic resonance, and fluorescence spectroscopy and their photoinduced generation are enhanced in the case of Ce/TiAP. Finally, the surface modification of TiAP by cerium ions led not only to better photoinduced properties, thus limiting the electron–hole pair recombination, but also to the improvement of ROS generation via different plausible mechanisms.