Yang Hongjie, Lu Zhen, Yin Xiangyu, Wu Shengjin, Hou Linxi
Department of Materials-Oriented Chemical Engineering, School of Chemical Engineering, Fuzhou University Fuzhou 350116 P. R. China
Qingyuan Innovation Laboratory Quanzhou 362801 P. R. China.
Chem Sci. 2023 Jul 5;14(30):8095-8102. doi: 10.1039/d3sc01719b. eCollection 2023 Aug 2.
Boosting the dissociation of excitons is essential to enhance the photocatalytic efficiency. However, the relationship between the structure of the catalyst and the exciton effect on the photocatalytic activity is still unclear as the main problem. Here, it is proposed that as a descriptive factor, an experimentally measurable dielectric constant () is available to quantitatively describe its relationship with exciton binding energy () and photocatalytic activity. With tuning the linker of covalent organic frameworks (COFs), the "air gap" structure is oriented to shrink, leading to an increased of COFs and a lower to facilitate exciton dissociation. Meanwhile, taking "water-/oxygen-fueled" photo-induced electron transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization as a demonstration platform, it can be seen that COFs with a small "air gap" structure have relatively superior photocatalytic activity. This provides important implications for the evolution of efficient photocatalysts.
提高激子的解离对于增强光催化效率至关重要。然而，作为主要问题，催化剂结构与激子对光催化活性的影响之间的关系仍不明确。在此，有人提出，作为一个描述性因素，实验可测量的介电常数（）可用于定量描述其与激子结合能（）和光催化活性的关系。通过调整共价有机框架（COF）的连接体，“气隙”结构趋于收缩，导致COF的介电常数增加，激子结合能降低，从而促进激子解离。同时，以“水/氧驱动”的光诱导电子转移可逆加成-断裂链转移（PET-RAFT）聚合作为示范平台，可以看出具有小“气隙”结构的COF具有相对优异的光催化活性。这为高效光催化剂的发展提供了重要启示。
