Protonated Carboxyl Anchor for Stable Adsorption of Ru N749 Dye (Black Dye) on a TiO2 Anatase (101) Surface.
Protonated Carboxyl Anchor for Stable Adsorption of Ru N749 Dye (Black Dye) on a TiO2 Anatase (101) Surface.
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DOI：
10.1021/jz201583n
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发表时间：
2012-01
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影响因子：
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通讯作者：
Keitaro Sodeyama;M. Sumita;C. O’Rourke;U. Terranova;A. Islam;Liyuan Han;D. Bowler;Y. Tateyama
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文献类型：
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作者：
Keitaro Sodeyama;M. Sumita;C. O’Rourke;U. Terranova;A. Islam;Liyuan Han;D. Bowler;Y. Tateyama
用第一性原理方法研究了染料敏化太阳能电池(DSCs)的高效染料Ru N749染料[黑染料(BD)]通过质子化和去质子化的羧基锚定在锐钛矿型二氧化钛(101)表面的吸附稳定性。对含超晶胞的表面体系进行了几何优化，并对优化后的染料结构进行了紫外-可见光谱计算。在具有一个和两个锚基的构型中，与大多数以前的报道相反，以一个质子化羧基锚定的BD吸附被发现是最稳定的。BD中保留的质子与表面氧之间的氢键是质子化锚稳定的原因。我们证实了计算得到的最稳定染料结构的紫外-可见光谱与实验数据的一致性最好。结果还表明，态的电子态密度很大程度上取决于质子的位置。这种通过质子化的羧基锚吸附的新方面为DSCs的界面电子过程提供了一个新的视角。
We have investigated the adsorption stability of ruthenium N749 dye [black dye (BD)], a highly efficient dye for dye-sensitized solar cells (DSCs), through protonated and deprotonated carboxyl group anchors on a TiO2 anatase (101) surface by using first-principles calculations. Geometry optimizations of the surface system with a supercell and the UV-visible spectrum calculation of the optimized dye structure were carried out. Among the configurations with one and two anchors, the BD adsorption anchored with one protonated carboxyl group was found to be the most stable, in contrast to most previous reports. Hydrogen bonding between the proton retained in BD and the surface oxygen is responsible for the stability of the protonated anchor. We confirmed that the calculated UV-visible spectrum of the most stable dye structure shows the best consistency with the experimental data. It is also demonstrated that the electronic density of states largely depends on the proton position. This novel aspect of adsorption via a protonated carboxyl anchor gives a new perspective for interfacial electronic processes of DSCs.