基于TiO2和方碱染料敏化剂的光敏异质结构

I. Kobasa, O. Sema, O. I. Panimarchyk
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摘要

在纳米分散氧化钛(IV)和方碱染料敏化剂(D)的基础上,制备了具有一定光催化活性和扩大光敏性范围的新型异质结构(HS)。通过对光谱、电化学和能量特性测量结果的分析,认为可以将所测方碱作为有效的TiO2敏化剂。首次采用循环伏安法测定了方碱染料的氧化还原电位,并考察了氧化还原过程的可逆性。结果表明,峰值电流与速度扫描速率平方根的关系曲线是线性函数。研究发现,该电化学过程是可逆的,且受扩散控制。建立了氧化还原电位的值可以用来计算标准电位和自由能的值。根据测得的多甲基氧化还原电位,计算了HOMO和LUMO的能量值,并构建了方宁能级与氧化钛(IV)电物理特性的关系图。分析了所研究的方碱染料敏化性能的特点,提出了光催化作用机理,并在亚甲蓝回收反应研究中得到了证实。研究了HS D/TiO2的光催化活性与染料浓度和辐照条件的关系。结果表明,当异质结构光被染料吸收后,在低浓度(0.02÷0.2 mg/g)下,光敏剂的光催化活性增加,在1.0÷2.0 mg/g含量下,光敏剂的光催化活性降低。氧化钛(IV)吸收的光照射HS时,其光催化活性随方碱含量的增加而降低。
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Light-sensitive heterostructures based on TiO2 and squaraine dye-sensitizer
On the basis of nanodispersed titanium(IV) oxide and squaraine dye-sensitizer (D), new heterostructures (HS) have been created with a given level of photocatalytic activity and an expanded range of photosensitivity. On the basis of the analysis of the results of the measurement of spectral, electrochemical and energy characteristics, it is concluded that it is possible to use the tested squaraine as an effective TiO2 sensitizer. For the first time, using the method of cyclic voltammetry, the redox potentials of squaraine dye were determined and the redox processes were checked for reversibility. It is shown that the plot of the peak current versus the square root of the velocity sweep rate is described by a linear function. It has been found that the electrochemical processes are reversible and diffusion controlled. It is established that the values ​​of redox potentials can be used to calculate the values ​​of standard potentials and free energy. Based on the measured oxidation and reduction potentials of polymethine, the values ​​of the HOMO and LUMO energies were calculated and diagrams of the energy levels of squaraine relative to the electrophysical characteristics of titanium (IV) oxide were constructed. The peculiarities of the sensitizing ability of the studied squaraine dye were analyzed, the mechanism of photocatalytic action was proposed and its confirmation was obtained during the study of the methylene blue recovery reaction. The dependences of the photocatalytic activity of HS D/TiO2 on the dye concentration and irradiation conditions were revealed. It is shown that, when irradiated with heterostructures by light absorbed by the dye, at low concentrations of the latter (0.02÷0.2 mg/g), the photocatalytic activity increases, and at the content of the sensitizer 1.0÷2.0 mg/g, it decreases. When irradiated with HS by light absorbed by titanium(IV) oxide, photocatalytic activity decreases with increasing squaraine content.
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