Effect of zirconium doping on the properties of defect titanium dioxide films: quantum chemical calculations

  • O. V. Smirnova Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
  • A. G. Grebenyuk Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
  • V. V. Lobanov Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
Keywords: anatase, IR-, UV-, XPS spectra, zirconium dioxide, electron density functional theory method (DFT)

Abstract

The spatial and electronic structures of cluster (Ti13ZrH22O39, Ti13ZrN2H22O37, Ti13ZrN2H22O36 ) which model pure titanium dioxide (anatase modification) and that with zirconium impurities as well as pure zirconium composition (ZrO2 content), are considered. The theoretically calculated infrared, electron and X-ray spectra of these clusters are analyzed. The spectra of small particles of zirconium are shown to be highly characteristic of the spectral transition energies and uniquely correspond to their spatial structures. It is shown that in the photoelectron spectra the energy level of Zr 3p is characteristic and its intensity in the RF spectra and position on the energy scale is slightly dependent on the chemical environment of the zirconium atom. The calculated oscillation frequency in the IR spectra of the considered clusters was determined to be “breathing” vibrations of Zr – O bonds (538 cm– 1) and stretching vibrations of Zr = O bonds (955 cm– 1). It is determined that the search for an approximate solution by imposing symmetry on a real object is appropriate, because the symmetry of the cluster corresponds to the real symmetry of the crystal. The results of the studies are compared with the properties of molecular models for the bulk and surface phases of titanium dioxide, calculated by the method of electron density functional theory (DFT). It is found that the results of spectral studies of the properties of samples of titanium dioxide can clearly indicate the presence of zirconium impurities in them, or their absence.

References

Smirnova O., Grebenyuk A., Lobanov V. Titanium dioxide defect structures as catalytic sites. Surface. - 2017. 9(24): 44. https://doi.org/10.15407/Surface.2017.09.044

Tsunekawa S., Ito S., Kawazoe Y. Critical Size of the Phase Transition from Cubic to Tetragonal in Pure Zirconia Nanoparticles. Nano Lett. 2003. 3 (7): 871. https://doi.org/10.1021/nl034129t

Smirnova O., Grebenyuk A., Linnik O., Lobanov V. Quantum Chemical Study of Water Molecule Adsorption on the Nitrogen-Doped Titania Thin Films. Nanophysics, Nanomaterials, Interface Studies, and Applications: Selected Proc. 4th Int. Conf. Nanotechnology and Nanomaterials (NANO2016, Aug. 24-27, 2016, Lviv, Ukraine). - Springer. 2017: 603. https://doi.org/10.1007/978-3-319-56422-7_45

Cohen A.J., Mori-Sanchez P., Yang W. Challenges for density functional theory. Chem. Rev. 2012. 112: P. 289. https://doi.org/10.1021/cr200107z

Becke A. et al. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. V. 98 (7). 1993: P. 5648. https://doi.org/10.1063/1.464913

Runge E., Gross E. K. U. Density-Functional Theory for Time-Dependent Systems. Phys. Rev. Lett. 1984. 52(12): 997. https://doi.org/10.1103/PhysRevLett.52.997

Tardio S., Cumpson P.J. Practical estimation of XPS binding energies using widely available quantum chemistry software. Surface and iInterface Analysis. 2018. 50(1): 5. https://doi.org/10.1002/sia.6319

Schmidt M., Baldridge K., Boatz J., Elbert S., Gordon M., Jensen J., Koseki S., Matsunaga N., Nguyen K., Su S., Windus T., Dupuis M., Montgomery J. General Atomic and Molecular Electronic Structure System. J. Comput. Chem. 1993. 14: 1347. https://doi.org/10.1002/jcc.540141112

Sauer J. Molecular models in ab initio studies of solids and surfaces: from ionic crystals and semiconductors to catalysts. Chem. Rev. 1989. 89(1): 199. https://doi.org/10.1021/cr00091a006

Zhidomirov G.M., Mikheikin I.D. Cluster approximation in quantum-chemical studies of chemisorption and surface structures. Molecular structure and chemical bond (Results of science and technology VINITI AN USSR). 1984. 9: 3.

Smirnova O., Grebenyuk A., Lobanov V. A quantum chemical study on the chemical environment of water molecules adsorbed on the anatase surface. Applied Nanoscience. 2019. 9: 1251. https://doi.org/10.1007/s13204-019-01100-7

Published
2019-10-30
How to Cite
Smirnova, O. V., Grebenyuk, A. G., & Lobanov, V. V. (2019). Effect of zirconium doping on the properties of defect titanium dioxide films: quantum chemical calculations. Surface, (11(26), 372-381. https://doi.org/10.15407/Surface.2019.11.372
Section
Theory of surface chemical structure and reactivity.