Photoexcited charge manipulation in conjugated polymers bearing a Ru(<scp>ii</scp>) complex catalyst for visible-light CO<sub>2</sub> reduction
Photoexcited charge manipulation in conjugated polymers bearing a Ru(<scp>ii</scp>) complex catalyst for visible-light CO<sub>2</sub> reduction
复制标题
带有 Ru(<scp>ii</scp>) 络合物催化剂的共轭聚合物中的光激发电荷操控用于可见光 CO<sub>2</sub> 还原
DOI：
10.1039/d2ta02183h
复制
发表时间：
2022
影响因子：
11.9
通讯作者：
Chang Ho-Chol
中科院分区：
文献类型：
--
作者：
Nakada Akinobu;Miyakawa Ryuichi;Itagaki Ren;Kato Kosaku;Takashima Chinami;Saeki Akinori;Yamakata Akira;Abe Ryu;Nakai Hiromi;Chang Ho-Chol
共轭聚合物是一种很有前途的光催化材料。最大限度地提高共轭骨架和催化剂部分之间的协同作用的设计原则是实现高效光催化的迫切需要。本文用分子工程的方法研究了以Ru(II)络合物为光催化剂的共轭聚合物中的光激发电荷操纵。基于超快光谱和理论计算的组合研究表明，在聚合物中引入一个给电子的咔唑(Cz)骨架可以增强Ru(II)络合物催化剂部分的光激电荷捕获。基于咔唑的聚合物[Cz-bpyRu]n在可见光下甚至在500 nm以上的可见光下促进二氧化碳的还原，表现出比苯基(Ph)和苯并噻二唑(Bt)高7-15倍的活性。因此，本研究结果为分子工程中实现高效光催化的光激发电荷操纵提供了新的思路。
Conjugated polymers have emerged as promising candidates for photocatalyst materials. Design principles that maximize the synergy between the conjugated skeleton and catalyst moiety are strongly desired to be established for achieving efficient photocatalysis. Herein, the photoexcited charge manipulation was demonstrated by molecular engineering in conjugated polymers bearing a Ru(II) complex as the CO2 reduction photocatalyst. Combinational studies based on ultrafast spectroscopies and theoretical calculations revealed that the introduction of an electron-donating carbazole (Cz) skeleton in the polymer enables enhanced photoexcited charge trapping on the Ru(II)-complex catalyst moiety. The carbazole-based polymer [Cz-bpyRu]n facilitates CO2 reduction under visible light even longer than 500 nm and exhibited 7- to 15-fold greater activity than those of phenyl (Ph) and benzothiadiazole (Bt) counterparts. The findings of this study thus provide insights into molecular engineering for photoexcited charge manipulation to achieve efficient photocatalysis.