Supramolecular Photocatalysts for the Reduction of CO2
Supramolecular Photocatalysts for the Reduction of CO2
复制标题
DOI：
10.1021/acscatal.7b00440
复制
发表时间：
2017-05-01
期刊：
影响因子：
12.9
通讯作者：
Ishitani, Osamu
中科院分区：
文献类型：
--
作者：
Tamaki, Yusuke;Ishitani, Osamu
利用太阳光作为能源将CO2光催化还原为富含能量的化合物，有望为化石资源短缺和全球变暖的严重问题提供解决方案。在此基础上，综述了超分子光催化剂在CO2还原反应中的研究进展，其中光敏剂和催化剂单元通过桥联配体连接。2005年报道的第一个成功的Ru（II）-Re（I）超分子光催化剂表明了开发高效的超分子光催化剂的分子结构，用于以高选择性和耐久性将CO2还原为CO。在此基础上，对桥连配体和Re（I）催化单元进行了优化，以提高催化剂的光催化活性。此外，对超分子光催化体系的组成单元进行了修饰：（1）Ir（III）和Os（II）配合物、游离卟啉和金属卟啉以及叶绿素与Ru（II）配合物相比可作为替代或更好的光敏剂单元，（2）Ru（II）羰基配合物选择性地还原CO2产生HCOOH，二氢苯并咪唑衍生物是评价超分子光催化体系潜力的合适牺牲电子给体。这些研究工作提供了高效的光催化体系，在可见光照射下具有高选择性、耐久性和反应速率。
Photocatalytic reduction of CO2 into energy-rich compounds utilizing solar light as an energy source is expected to provide a solution to serious problems of the shortage of fossil resources and global warming. In this perspective, we summarize advances in supramolecular photocatalysts for the reduction of CO2, of which photosensitizer and catalyst units are connected via a bridging ligand. The first successful Ru(II)-Re(I) supramolecular photocatalysts reported in 2005 indicated molecular architecture for developing efficient supramolecular photocatalysts for CO2 reduction to CO with high selectivity and durability. On the basis of this architecture, both the bridging ligands and Re(I) catalyst unit were optimized to increase the photocatalytic activity. In addition, the compositional units of supramolecular photocatalytic systems were modified: (1) Ir(III) and Os(II) complexes, free- and metallo-porphyrins, and chlorophyll functioned as alternative or better photosensitizer units in comparison to the Ru(II) complexes, (2) Ru(II) carbonyl complexes reduced CO2 giving HCOOH selectively, and (3) dihydrobenzoimidazole derivatives were suitable sacrificial electron donors for evaluating the potential of supramolecular photocatalytic systems. These research studies have provided efficient photocatalytic systems for CO2 reduction with high selectivity, durability, and reaction rate under visible-light irradiation.