基于二氧化钛和梅氏胺聚亚胺染料的新型光敏材料

I. Kobasa, M. M. Vorobet’s, O. Sema, Yu. V. Kropelnytska
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摘要

本文研究了不同乙烯基上聚乙烯链长度的若干merocyanine染料(D)的结构对其光谱、电化学和能量特性的影响。循环伏安法测定它们的氧化和还原电位。根据光谱和电化学数据计算了所研究染料的HOMO和LUMO能级。结果表明,两种染料的能级势值相差不大(能量差范围为0.22 ~ 0.53 eV)。探讨了用merocyanins作为氧化钛(IV)的增感剂和制备光敏异质结构的可能性。为了探讨将所研究的merocyanin染料用作TiO2敏化剂的可能性,考虑了“半导体-染料-试剂”体系的能量。为此,我们将merocyanine染料的氧化还原特性与氧化钛(IV)的电物理参数以及反应参与者的氧化还原特性进行了比较。在这种系统中,电子从染料到半导体的光子转移过程是敏化所必需的,并且在热力学上允许还原剂对形成的阳离子自由基的作用使敏化剂的原始形态再生。不同辐照条件和不同染料浓度下D/TiO2异质结构在亚甲基蓝甲醛回收反应中的光催化活性的研究结果证实了所研究的merocyanines作为有效敏化剂的可能性。对所发现的规律进行了解释。科学的方法来生产新的光敏系统与扩大范围的光敏性和给定水平的光催化活性已经发展。
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New light-sensitive materials based on TiO2 and merocianin polymetine dye
The influence of the structure of a number of merocyanine dyes (D), which differ in the length of the polyethylene chain on one vinyl group, on their spectral, electrochemical and energy characteristics is established. Cyclic voltammetry determines their oxidation and reduction potentials. The values ​​of the HOMO and LUMO energy levels of the studied dyes from spectral and electrochemical data were calculated. It is shown that the obtained values ​​of the potentials of the energy levels of the dyes differ little (the energy difference ranges from 0,22–0,53 eV). The possibility of using merocyanins as sensitizers of titanium(IV) oxide and the creation of photosensitive heterostructures has been made. In order to investigate the possibility of using the merocyanin dyes under study as TiO2 sensitizers, the energy of the «semiconductor – dye – reagents» systems was considered. For this purpose, we compared the redox characteristics of merocyanine dyes with the electrophysical parameters of titanium(IV) oxide, as well as the redox characteristics of the reaction participants. It is established that in such systems the processes of photon transfer of the electron from the dye to the semiconductor are necessary for sensitization, and the regeneration of the original form of the sensitizers by the action of the reducing agent on the cation radicals formed is thermodynamically allowed. The conclusion about the possibility of using the studied merocyanines as effective sensitizers was confirmed by the results of the study of the photocatalytic activity of D/TiO2 heterostructures in the reaction of methylene blue formaldehyde recovery under different irradiation conditions and at different dye concentrations. The explanation for the found laws is offered. Scientific approaches to the production of new photosensitive systems with an expanded range of photosensitivity and a given level of photocatalytic activity have been developed.
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