Combined experimental and DFT-TDDFT computational study of photoelectrochemical cell ruthenium sensitizers
Combined experimental and DFT-TDDFT computational study of photoelectrochemical cell ruthenium sensitizers
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DOI：
10.1021/ja052467l
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发表时间：
2005-12-07
影响因子：
15
通讯作者：
Grätzel, M
中科院分区：
文献类型：
--
作者：
Nazeeruddin, MK;De Angelis, F;Grätzel, M
我们报道了来自[Ru（dcbpyH（2））（2）（NCS）（2）]，N-3和[Ru（dcbpyH（2））（tdbpy）（NCS）（2）]，N621（dcbpyH（2）= 4，4 '-二羧基-2，2'-联吡啶，tdbpy = 4，4 '-十三烷基-2，2'-联吡啶）配合物的几种钌（II）敏化剂的实验和计算研究。开发了纯化程序以获得两种类型的敏化剂的纯N-键合异构体。吸附在TiO 2薄膜上的纯N3和N621敏化剂在其单质子化和双质子化状态下的光伏数据，表现出显着的功率转换效率在1太阳，11.18和9.57%，分别。一个广泛的密度泛函理论（DFT）-时间依赖的DFT研究这些敏化剂在溶液中进行，调查质子化的末端羧基和抗衡离子的电子结构和光学性质的染料的效果。计算的吸收光谱与实验结果吻合较好，从而可以详细地归属这两种染料的紫外-可见光谱特征。计算的不同配合物的分子轨道与模型TiO 2纳米粒子的带边的对齐提供了额外的见解的电子因素，染料敏化太阳能电池器件的效率。
We report a combined experimental and computational study of several ruthenium(II) sensitizers originated from the [Ru(dcbpyH(2))(2)(NCS)(2)], N-3, and [Ru(dcbpyH(2))(tdbpy)(NCS)(2)], N621, (dcbpyH(2) = 4,4'-dicarboxy-2,2'-bipyridine, tdbpy = 4,4'-tridecyl-2,2'-bipyridine) complexes. A purification procedure was developed to obtain pure N-bonded isomers of both types of sensitizers. The photovoltaic data of the purified N3 and N621 sensitizers adsorbed on TiO2 films in their monoprotonated and diprotonated state, exhibited remarkable power conversion efficiency at 1 sun, 11.18 and 9.57%, respectively. An extensive Density Functional Theory (DFT)-Time Dependent DFT study of these sensitizers in solution was performed, investigating the effect of protonation of the terminal carboxylic groups and of the counterions on the electronic structure and optical properties of the dyes. The calculated absorption spectra are in good agreement with the experiment, thus allowing a detailed assignment of the UV-vis spectral features of the two types of dyes. The computed alignments of the molecular orbitals of the different complexes with the band edges of a model TiO2 nanoparticle provide additional insights into the electronic factors governing the efficiency of dye-sensitized solar cell devices.