Dirhodium-Based Supramolecular Framework Catalyst for Visible-Light-Driven Hydrogen Evolution
Dirhodium-Based Supramolecular Framework Catalyst for Visible-Light-Driven Hydrogen Evolution
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DOI：
10.1021/acs.inorgchem.1c01279
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发表时间：
2021-07-16
影响因子：
4.6
通讯作者：
Masaoka, Shigeyuki
中科院分区：
文献类型：
--
作者：
Chinapang, Pondchanok;Iwami, Hikaru;Masaoka, Shigeyuki
将太阳能直接转化为清洁燃料，作为化石燃料的替代品，是解决全球能源短缺和环境问题的重要途径。在这里，我们介绍了一种新的基于镝配合物的框架组件，作为一种基于非均相分子的光催化剂，用于可见光下的析氢。设计并合成了两种具有可见光捕获功能的二吡咯甲烷硼（BODIPY， BDP）配合物。得到的配合物自组装成框架结构（超分子框架催化剂），是稳定的分子间非共价相互作用。这些框架保留了BDP基团优异的可见光捕获特性。结果表明，在可见光照射下，含有重原子的超分子框架催化剂具有良好的成氢性能，反应速率为275.8 μ mol g(-1) h(-1)，而不含重原子的超分子框架催化剂则无活性。此外，该系统还具有高耐久性（长达96小时）、可重复使用和易于从反应混合物中去除的额外优点。我们还揭示了BDP部分的重原子对催化活性的影响，并提出了反应机理。
The direct conversion of solar energy to clean fuels as alternatives to fossil fuels is an important approach for addressing the global energy shortage and environmental problems. Here, we introduce a new dirhodium-complex-based framework assembly as a heterogeneous molecule-based photocatalyst for hydrogen evolution using visible light. Two dirhodium complexes bearing visible-light-harvesting BODIPY (boron dipyrromethene, BDP) moieties were newly designed and synthesized. The obtained complexes were self-assembled to framework structures (supramolecular framework catalysts), which are stabilized intermolecular noncovalent interactions. These frameworks retained excellent visible-light-harvesting properties of BDP moieties. Investigation of the catalytic performance of the supramolecular framework catalysts revealed that the supramolecular framework catalyst with heavy atoms at BDP moieties exhibited excellent performance in the formation of hydrogen with a reaction rate of 275.8 mu mol g(-1) h(-1) under irradiation of visible light, whereas the supramolecular framework catalyst without heavy atoms at BDP moieties was inactive. Moreover, the system has the additional benefits of high durability (up to 96 h), reusability, and facile removal from the reaction mixture. We also disclosed the effect of heavy atoms at BDP moieties on the catalytic activity and proposed a reaction mechanism.