Tian Peng-Ju, Han Xiang-Hao, Qi Qiao-Yan, Zhao Xin
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
Chem Sci. 2024 May 13;15(25):9669-9675. doi: 10.1039/d4sc01780c. eCollection 2024 Jun 26.
Covalent organic frameworks have attracted considerable attention in recent years as a distinct class of crystalline porous organic materials. Their functional properties are inherently linked to their structural characteristics. Although hundreds of COFs have been reported so far, the types of their topologic structure are still limited. In this article, we report the identification of topology for three porphyrin-based two-dimensional COFs, which are constructed from [4 + 4] imine condensation reactions. The net is generated by pentagonal tiling, which has not been identified for COFs before. The structure of the COFs is elucidated by a variety of experimental characterization and structural simulations, by which their reticular frameworks exclusively composed of pentagonal pores have been confirmed. Moreover, the COFs exhibit high performance in photocatalytic hydrogen evolution from water, with the best one up to 10.0 mmol g h after depositing 0.76 wt% Pt as a co-catalyst. This study identifies topology for COFs for the first time and highlights the potential of these COFs as promising photocatalysts for sustainable hydrogen production from water.
近年来，共价有机框架作为一类独特的晶体多孔有机材料受到了广泛关注。它们的功能特性与结构特征有着内在联系。尽管到目前为止已经报道了数百种共价有机框架，但它们的拓扑结构类型仍然有限。在本文中，我们报告了三种基于卟啉的二维共价有机框架的拓扑结构鉴定，这些框架是通过[4 + 4]亚胺缩合反应构建的。该网络由五边形平铺生成，这在之前的共价有机框架中尚未被发现。通过各种实验表征和结构模拟阐明了共价有机框架的结构，证实了它们的网状框架完全由五边形孔组成。此外，这些共价有机框架在光催化水分解制氢方面表现出高性能，在负载0.76 wt%的铂作为助催化剂后，性能最佳的可达10.0 mmol g⁻¹ h⁻¹。本研究首次鉴定了共价有机框架的拓扑结构，并突出了这些共价有机框架作为从水中可持续制氢的有前景的光催化剂的潜力。
