全共轭二维 sp2 杂化碳共价有机框架作为高效人工光合作用系统 I。

Fully Conjugated Two-Dimensional sp -Carbon Covalent Organic Frameworks as Artificial Photosystem I with High Efficiency.

机构信息

Key Laboratory of Biobased Polymer Materials, Shandong Provincial Education Department, College of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China.

State Key Laboratory of Biobased Material and Green Papermaking, Shandong Provincial Key Laboratory of Microbial Engineering, Department of Bioengineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250353, China.

出版信息

Angew Chem Int Ed Engl. 2019 Apr 8;58(16):5376-5381. doi: 10.1002/anie.201901194. Epub 2019 Mar 13.

DOI:10.1002/anie.201901194

PMID:30761713

Abstract

The synthesis of fully conjugated sp -carbon covalent organic frameworks (COF) is extremely challenging given the difficulty of the formation of very stable carbon-carbon double bonds (-C=C-). Here, we report the successful preparation of a 2D COF (TP-COF) based on triazine as central planar units bridged by sp -carbon linkers through the -C=C- condensation reaction. High-resolution-transmission electron microscopy (HRTEM) clearly confirmed the tessellated hexagonal pore structure with a pore center-to-center distance of 2 nm. Powder X-ray diffraction (PXRD) together with structural simulations revealed an AA stacking mode of the obtained layered structure. TP-COF turned out to be an excellent semiconductor material with a LUMO energy of -3.23 eV and a band gap of 2.36 eV. Excitingly, this novel sp -carbon conjugated TP-COF exhibited unprecedented coenzyme regeneration efficiency and can significantly boost the coenzyme-assisted synthesis of l-glutamate to a record-breaking 97 % yield within 12 minutes.

摘要

完全共轭 sp 碳共价有机骨架（COF）的合成极具挑战性，因为很难形成非常稳定的碳碳双键（-C=C-）。在这里，我们报告了一种基于三嗪作为中心平面单元的二维 COF（TP-COF）的成功制备，该 COF 通过 sp 碳键合通过 -C=C- 缩合反应桥接。高分辨率透射电子显微镜（HRTEM）清楚地证实了具有 2nm 孔心到孔心距离的镶嵌六方孔结构。粉末 X 射线衍射（PXRD）和结构模拟表明，所得到的层状结构采用 AA 堆叠方式。TP-COF 是一种出色的半导体材料，具有 -3.23eV 的 LUMO 能量和 2.36eV 的能带隙。令人兴奋的是，这种新型 sp 碳共轭 TP-COF 表现出前所未有的辅酶再生效率，可在 12 分钟内将辅酶辅助合成 l-谷氨酸的产率提高到创纪录的 97%。