Chen Rufan, Wang Yang, Ma Yuan, Mal Arindam, Gao Xiao-Ya, Gao Lei, Qiao Lijie, Li Xu-Bing, Wu Li-Zhu, Wang Cheng
Sauvage Center for Molecular Sciences and Key Laboratory of Biomedical Polymers (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, China.
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, China.
Nat Commun. 2021 Mar 1;12(1):1354. doi: 10.1038/s41467-021-21527-3.
Covalent organic frameworks have recently gained increasing attention in photocatalytic hydrogen generation from water. However, their structure-property-activity relationship, which should be beneficial for the structural design, is still far-away explored. Herein, we report the designed synthesis of four isostructural porphyrinic two-dimensional covalent organic frameworks (MPor-DETH-COF, M = H, Co, Ni, Zn) and their photocatalytic activity in hydrogen generation. Our results clearly show that all four covalent organic frameworks adopt AA stacking structures, with high crystallinity and large surface area. Interestingly, the incorporation of different transition metals into the porphyrin rings can rationally tune the photocatalytic hydrogen evolution rate of corresponding covalent organic frameworks, with the order of CoPor-DETH-COF < HPor-DETH-COF < NiPor-DETH-COF < ZnPor-DETH-COF. Based on the detailed experiments and calculations, this tunable performance can be mainly explained by their tailored charge-carrier dynamics via molecular engineering. This study not only represents a simple and effective way for efficient tuning of the photocatalytic hydrogen evolution activities of covalent organic frameworks at molecular level, but also provides valuable insight on the structure design of covalent organic frameworks for better photocatalysis.
共价有机框架最近在光催化水制氢方面受到越来越多的关注。然而，它们的结构-性质-活性关系（这对结构设计应该是有益的）仍远未得到充分探索。在此，我们报告了四种同构卟啉二维共价有机框架（MPor-DETH-COF，M = H、Co、Ni、Zn）的设计合成及其在制氢中的光催化活性。我们的结果清楚地表明，所有四种共价有机框架都采用AA堆积结构，具有高结晶度和大表面积。有趣的是，将不同的过渡金属引入卟啉环可以合理地调节相应共价有机框架的光催化析氢速率，顺序为CoPor-DETH-COF < HPor-DETH-COF < NiPor-DETH-COF < ZnPor-DETH-COF。基于详细的实验和计算，这种可调性能主要可以通过分子工程对其定制的电荷载流子动力学来解释。这项研究不仅代表了一种在分子水平上有效调节共价有机框架光催化析氢活性的简单有效方法，而且为更好地进行光催化的共价有机框架结构设计提供了有价值的见解。
