Jin Enquan, Fu Shuai, Hanayama Hiroki, Addicoat Matthew A, Wei Wenxin, Chen Qiang, Graf Robert, Landfester Katharina, Bonn Mischa, Zhang Kai A I, Wang Hai I, Müllen Klaus, Narita Akimitsu
Max Planck Institute for Polymer Research, Ackermannweg 10, 55128, Mainz, Germany.
Organic and Carbon Nanomaterials Unit, Okinawa Institute of Science and Technology Graduate University, Kunigami-gun, Okinawa, 904-0495, Japan.
Angew Chem Int Ed Engl. 2022 Jan 26;61(5):e202114059. doi: 10.1002/anie.202114059. Epub 2021 Dec 16.
Synthesis of covalent organic frameworks (COFs) with desirable organic units furnishes advanced materials with unique functionalities. As an emerging class of two-dimensional (2D) COFs, sp -carbon-conjugated COFs provide a facile platform to build highly stable and crystalline porous polymers. Herein, a 2D olefin-linked COF was prepared by employing nanographene, namely, dibenzo[hi,st]ovalene (DBOV), as a building block. The DBOV-COF exhibits unique ABC-stacked lattices, enhanced stability, and charge-carrier mobility of ≈0.6 cm V s inferred from ultrafast terahertz photoconductivity measurements. The ABC-stacking structure was revealed by the high-resolution transmission electron microscopy and powder X-ray diffraction. DBOV-COF demonstrated remarkable photocatalytic activity in hydroxylation, which was attributed to the exposure of narrow-energy-gap DBOV cores in the COF pores, in conjunction with efficient charge transport following light absorption.
合成具有理想有机单元的共价有机框架（COF）可提供具有独特功能的先进材料。作为一类新兴的二维（2D）COF，sp-碳共轭COF为构建高度稳定且结晶的多孔聚合物提供了一个便捷的平台。在此，通过使用纳米石墨烯，即二苯并[hi,st]戊搭烯（DBOV）作为结构单元，制备了一种二维烯烃连接的COF。DBOV-COF表现出独特的ABC堆叠晶格、增强的稳定性以及通过超快太赫兹光电导率测量推断出的约0.6 cm² V⁻¹ s⁻¹的电荷载流子迁移率。通过高分辨率透射电子显微镜和粉末X射线衍射揭示了ABC堆叠结构。DBOV-COF在羟基化反应中表现出显著的光催化活性，这归因于COF孔中窄能隙DBOV核的暴露，以及光吸收后有效的电荷传输。
