用于多相光催化的基于二维卟啉的sp碳共轭共价有机框架的设计合成

Designed Synthesis of a 2D Porphyrin-Based sp Carbon-Conjugated Covalent Organic Framework for Heterogeneous Photocatalysis.

作者信息

Chen Rufan, Shi Ji-Long, Ma Yuan, Lin Guiqing, Lang Xianjun, Wang Cheng

机构信息

Key Laboratory of Biomedical Polymers (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China.

Corrosion and Protection Center, University of Science and Technology Beijing, Beijing, 100083, China.

出版信息

Angew Chem Int Ed Engl. 2019 May 6;58(19):6430-6434. doi: 10.1002/anie.201902543. Epub 2019 Apr 4.

Abstract

The construction of stable covalent organic frameworks (COFs) for various applications is highly desirable. Herein, we report the synthesis of a novel two-dimensional (2D) porphyrin-based sp carbon-conjugated COF (Por-sp c-COF), which adopts an eclipsed AA stacking structure with a Brunauer-Emmett-Teller surface area of 689 m  g . Owing to the C=C linkages, Por-sp c-COF shows a high chemical stability under various conditions, even under harsh conditions such as 9 m HCl and 9 m NaOH solutions. Interestingly, Por-sp c-COF can be used as a metal-free heterogeneous photocatalyst for the visible-light-induced aerobic oxidation of amines to imines. More importantly, in comparison to imine-linked Por-COF, the inherent structure of Por-sp c-COF equips it with several advantages as a photocatalyst, including reusability and high photocatalytic performance. This clearly demonstrates that sp carbon-linked 2D COFs can provide an interesting platform for heterogeneous photocatalysis.

摘要

构建适用于各种应用的稳定共价有机框架(COF)是非常有必要的。在此,我们报道了一种新型二维(2D)基于卟啉的sp碳共轭COF(Por-sp c-COF)的合成,它采用重叠AA堆积结构,比表面积为689 m² g⁻¹。由于C=C键,Por-sp c-COF在各种条件下都表现出高化学稳定性,即使在诸如9 m HCl和9 m NaOH溶液等苛刻条件下也是如此。有趣的是,Por-sp c-COF可以用作无金属多相光催化剂,用于可见光诱导的胺有氧氧化为亚胺。更重要的是,与亚胺连接的Por-COF相比,Por-sp c-COF的固有结构使其作为光催化剂具有几个优点,包括可重复使用性和高光催化性能。这清楚地表明,sp碳连接的二维COF可以为多相光催化提供一个有趣的平台。

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