How organic switches grafting on TiO(2) modifies the surface potentials: theoretical insights.
How organic switches grafting on TiO(2) modifies the surface potentials: theoretical insights.
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DOI：
10.1039/d3ra00537b
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发表时间：
2023-05-15
期刊：
影响因子：
3.9
通讯作者：
Zhang, Shaolin
中科院分区：
文献类型：
--
作者：
Huang, Haiming;Ding, Mingquan;Zhang, Yu;Zhang, Shuai;Ling, Yiyun;Wang, Weiliang;Zhang, Shaolin
混合有机开关-无机半导体系统在光响应智能表面和微流体器件中都有重要的应用。在此背景下，我们进行了第一性原理计算，以研究低指数锐钛矿板吸附的反式/顺式偶氮苯氟和原始/氧化三甲氧基硅烷的一系列有机开关。从电子结构和电位分布的角度考察了表面吸附物相互作用的趋势。因此，我们发现顺式氟化偶氮苯（氧化三甲氧基硅烷）端锐钛矿表面比反式氟化偶氮苯（原始三甲氧基硅烷）端锐钛矿表面具有更低的电离电位，这是由于其较小的诱导偶极矩（较大的本征偶极矩），其方向指向从底物向内（向外），这源于界面上的电子电荷重新分配（连接羟基的极性）。通过结合诱导极性相互作用分析和文献中的实验测量，我们证明了电离势是吸附体系表面润湿特性的重要预测因子。偶氮氟苯接枝锐钛矿和三甲氧基硅烷接枝锐钛矿的各向异性吸收光谱也分别与紫外光照射下的光异构化和氧化过程有关。我们研究了光敏有机/无机杂化体系的表面电位，将表面-吸附物相互作用与其表面性质联系起来，并提供理论指导。
Hybrid organic switch-inorganic semiconductor systems have important applications in both photo-responsive intelligent surfaces and microfluidic devices. In this context, herein, we performed first-principles calculations to investigate a series of organic switches of trans/cis-azobenzene fluoride and pristine/oxidized trimethoxysilane adsorbed on low-index anatase slabs. The trends in the surface–adsorbate interplay were examined in terms of the electronic structures and potential distributions. Consequently, it was found that the cis-azobenzene fluoride (oxidized trimethoxysilane)-terminated anatase surface attains a lower ionization potential than the trans-azobenzene fluoride (pristine trimethoxysilane)-terminated anatase surface due to its smaller induced (larger intrinsic) dipole moment, whose direction points inwards (outwards) from the substrate, which originates from the electron charge redistribution at the interface (polarity of attached hydroxyl groups). By combining the induced polar interaction analysis and the experimental measurements in the literature, we demonstrate that the ionization potential is an important predictor of the surface wetting properties of adsorbed systems. The anisotropic absorbance spectra of anatase grafted with azobenzene fluoride and trimethoxysilane are also related to the photoisomerization and oxidization process under UV irradiation, respectively. We studied the surface potentials of hybrid photosensitive organic/inorganic systems to correlate the surface–adsorbate interplay with their surface properties and provide theoretical guidance.
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