Artificial photosynthesis dendrimers integrating light-harvesting, electron delivery and hydrogen production
Artificial photosynthesis dendrimers integrating light-harvesting, electron delivery and hydrogen production
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集光捕获、电子传递和产氢于一体的人工光合作用树枝状聚合物
DOI：
10.1039/c5ta02565f
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发表时间：
2015
影响因子：
11.9
通讯作者：
Li Yi
中科院分区：
文献类型：
--
作者：
Xun Zhiqing;Yu Tianjun;Zeng Yi;Chen Jinping;Zhang Xiaohui;Yang Guoqiang;Li Yi
通过在不同世代的聚芳醚树枝状大分子的外围和核心处分别连接Ir络合物和模拟的[Fe-Fe]-氢酶，构建了一系列人工光合作用络合物Gn-Ir-Hy(n=1-4)。Ir络合物作为捕光天线，氢酶模拟核是催化中心。在以三乙胺为牺牲电子供体的树枝状光合作用模拟体系中，光捕获、光诱导电子转移和氢光化学产生被层次化实现。随着树枝状催化剂生成量的增加，其催化活性增强，第四代的周转次数是第一代的近4倍。外围天线不仅收集光子，而且作为光化学产物的电子能量储存库，促进了催化过程，同时增加了树枝状骨架的捕光和保护作用。因此，有了这样的合理设计，就可以推进具有完整捕光和催化功能的高效人工光合作用系统。
A series of artificial photosynthesis complexes, Gn–Ir–Hy (n = 1–4), were constructed by attaching iridium complexes and [Fe–Fe]-hydrogenase mimic to the periphery and core, respectively, of poly(aryl ether) dendrimers of different generations. The iridium complexes act as the light-harvesting antennae and the hydrogenase mimic core is the catalytic center. Light-harvesting, photoinduced electron-transfer, and hydrogen photochemical production were hierarchically realized within the dendritic photosynthesis mimics using triethylamine as the sacrificial electron donor. The catalytic activity is enhanced as the generation of dendritic catalysts increases, and the turnover number for generation 4 is nearly 4 times more than that of generation 1. The peripheral antennae not only harvest photons but also act as electronic energy reservoirs for the photochemical production, which facilitates the catalytic process together with the increased light-harvesting and protection effects of dendritic frameworks. Therefore, efficient artificial photosynthesis systems with complete light-harvesting and catalytic functions can be advanced with such rational design.