Heterostructures based on nanodispersed TiO2 and binary systems TiO2-CdTe, TiO2-Cu(In,Ga)Se2 sensitized by polymethyn dye, as photocatalysts of redox processes

Abstract

New light-sensitive heterostructures of semiconductors (TiO2, TiO2-CdTe, TiO2-Cu(In,Ga)Se2) sensitized with an anionic polymethine dye with three conjugated chromophores have been developed. Based on the analysis of the results of spectral, electrochemical and energy characteristics of the studied dye, the possibility of its use as an effective sensitizer of these semiconductor materials is shown. It was found that the deposition of the dye on TiO2 leads to both batochromic and hypsochromic shifts of long wavelength absorption bands, the values ​​of which depend on the dye content in the heterostructure. This leads to a redistribution of the intensities of the absorption bands, they expand and cover almost the entire part of the visible and near-IR regions of the spectrum. This feature of the created heterostructure allows to increase the efficiency of their photocatalytic action through the use of light quanta of a wide energy range. The results of the analysis of the absorption spectra of heterostructures testify to the significant influence of semiconductors on the electronic system of dye molecules. As a result, the angle between the directions of the chromophores changes. The antibate dependence of the degree of conformational changes on the amount of dye in the heterostructure is revealed. This indicates a decrease in the interaction with the semiconductor with increasing concentration and explains the decrease in the photocatalytic activity of heterostructures at a significant content of sensitizer. Using the method of cyclic voltammetry, for the first time the oxidation and reduction potentials of the investigated polymethine dye were determined. The values ​​of HOMO and LUMO energy levels are calculated, a forecast is made regarding the possibility of their use as sensitizers of the studied semiconductors and the creation of highly efficient redox systems. The photocatalytic activity of heterostructures in the reactions of reduction of methylene blue and oxidation of iodide ions under irradiation with light absorbed by a semiconductor and a sensitizer has been revealed. Based on the analysis of energy parameters of electronic processes, the scheme of this photocatalytic transformation is proposed and substantiated.