Blue copper model complexes with distorted tetragonal geometry acting as effective electron-transfer mediators in dye-sensitized solar cells
Blue copper model complexes with distorted tetragonal geometry acting as effective electron-transfer mediators in dye-sensitized solar cells
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DOI：
10.1021/ja0506814
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发表时间：
2005-07-06
影响因子：
15
通讯作者：
Fukuzumi, S
中科院分区：
文献类型：
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作者：
Hattori, S;Wada, Y;Fukuzumi, S
蓝铜模型配合物[（-）-金雀花碱-N，N ']的电子自交换速率常数（maleonitriledithiolato-S，S'）copper（[Cu（SP）（mmt）]）（0/-），bis（2，9-二甲基-1，10-菲咯啉）铜（[Cu（dMP）（2）]（2+/+））和双（一、本文报道了一系列二茂铁衍生物与铜（Ⅱ）的电子转移速率常数，并测定了[Cu（dmp）（2）]（2+/+）配合物的电子转移的马库斯理论。所得的电子自交换速率常数按以下顺序增加：[Cu（phen）（2）]（2+/+）< [Cu（Sp）（mmt）]（0/-）< [Cu（dMP）（2）]（2+/+），这与铜（II）和铜（I）配合物之间由于扭曲的四元环几何结构而引起的较小结构变化的顺序一致。以铜配合物为氧化还原电对构建了染料敏化太阳能电池（DSSC），并与传统的I-3（-）/I-电对进行了光电化学响应比较。使用[Cu（phen）（2）]（2+/+）、[Cu（dMP）（2）]（2+/+）和[Cu（SP）（mmt）]（0/-）的DSSC在模拟太阳光照射（100 mW/cm（2））的照明下的光能转换效率（eta）值分别记录为0.1%、1.4%和1.3%。采用[Cu（dMP）（2）]（2+/+）氧化还原电对的DSSC在20 mW/cm（2）强度的光照射下获得最大的η值（2.2%），其中与常规I-3（-）/I-电对相比，电池获得更高的开路电压。
The electron self-exchange rate constants of blue copper model complexes, [(-)-sparteine-N,N'](maleonitriledithiolato-S,S')copper ([Cu(SP)(mmt)])(0/-), bis(2,9-dimethy-1,10-phenanthroline)copper ([Cu(dMP)(2)](2+/+)), and bis(1,10-phenanthroline)copper ([Cu(dmp)(2)](2+/+)) have been determined from the rate constants of electron transfer from a homologous series of ferrocene derivatives to the copper(II) complexes in light of the Marcus theory of electron transfer. The resulting electron self-exchange rate constant increases in the order: [Cu(phen)(2)](2+/+) < [Cu(Sp)(mmt)](0/-) < [Cu(dMP)(2)](2+/+), in agreement with the order of the smaller structural change between the copper(II) and copper(I) complexes due to the distorted tetragonal geometry. The dye-sensitized solar cells (DSSC) were constructed using the copper complexes as redox couples to compare the photoelectrochemical responses with those using the conventional I-3(-)/I- couple. The light energy conversion efficiency (eta) values under illumination of simulated solar light irradiation (100 mW/cm(2)) of DSSCs using [Cu(phen)(2)](2+/+), [Cu(dMP)(2)](2+/+), and [Cu(SP)(mmt)](0/-) were recorded as 0.1%, 1.4%, and 1.3%, respectively. The maximum eta value (2.2%) was obtained for a DSSC using the [Cu(dMP)(2)](2+/+) redox couple under the light irradiation of 20 mW/cm(2) intensity, where a higher open-circuit voltage of the cell was attained as compared to that of the conventional I-3(-)/I- couple.