光催化还原杂环化共价有机框架构筑富电子吸附剂实现碘的理想吸附  

Constructing quinazolinone-anchored electron-rich covalent organic frameworks by photocatalytic reductive cyclization for idealizing iodine capture

作　　者：黄易伟 喻志武 张晴云 罗峰 Yiwei Huang;Zhiwu Yu;Qingyun Zhang;Feng Luo(School of Chemistry,Biology and Materials Science,East China University of Technology,Nanchang 330013,China;High Magnetic Field Laboratory,Chinese Academy of Sciences,Hefei 230031,China)

机构地区：[1]School of Chemistry,Biology and Materials Science,East China University of Technology,Nanchang 330013,China [2]High Magnetic Field Laboratory,Chinese Academy of Sciences,Hefei 230031,China

出　　处：《Science China Materials》2023年第6期2339-2345,共7页中国科学（材料科学（英文版）

基　　金：financially supported by the Training Program for Academic and Technical Leaders of Major Disciplines in Jiangxi Province(20194BCJ22010);the National Natural Science Foundation of China(21966002,21871047,42177444,and U1932218);the Youth Leading Talent Project of Fuzhou(2020ED64);Jiangxi Project(DHSQT22021007)。

摘　　要：碘的理想吸附剂通常需要具有两个特征,即高的吸附容量和快的吸附速率,但是这项课题仍然富有挑战性.本文通过构筑杂环化共价有机框架,阐述了一种有效构筑理想碘吸附剂的方法.这种杂环化基于一种后修饰的方式,采用了一种原位光催化双键与邻氨基苯甲酰胺成环的技术.基于该方法得到的材料ECUT-COF-13具有高的碘吸附容量(10.81 g g^(-1),高于所有报道的碘吸附材料)和吸附速率(1.4 g h^(-1),高于所有报导的二维共价有机框架材料).该材料优异的碘吸附性能是基于一种富电子机理,这种富电子状态主要来源于光催化还原杂环化共价有机框架(同时提高了网格的共轭性和氮含量).该研究成果不仅提供了一种构筑功能共价有机框架的新路径,同时提供了一种构筑富电子共价有机框架结构的通用策略.Constructing ideal adsorbent for the capture of radioactive iodine often requires both high adsorption capacity and fast adsorption kinetics.However,this remains a challenging issue.Herein,we present an effective method to idealize iodine capture with both ultrahigh adsorption capacity and fast adsorption rate through the construction of quinazolinone-anchored covalent organic frameworks(COFs).Post-synthesis modification was employed to functionalize two vinyl free-standing COFs with quinazolinone units through in-situ photocatalytic reductive cyclization between vinyl and 2-aminobenzamide units.The developed material,ECUT-COF-13,exhibits not only I_(2)uptake capacity as high as 10.81 g g^(-1),exceeding all established adsorbents for such use,but also very fast adsorption rate of 1.4 gh^(-1),surpassing all previously reported two-dimensional COFs.The outstanding I_(2)capture performance mainly results from an electron-rich mechanism,since anchoring quinazolinone units in COFs will lead to enhancedπ-conjugated net and ultrahigh nitrogen content.The results demonstrate not only a new avenue for functionalizing COFs,but also a general electron-rich strategy for COFs.

关 键 词：邻氨基苯甲酰胺 共轭性 光催化还原 电子状态 吸附速率 共价有机框架材料 碘吸附 吸附容量 

分 类 号：TQ424[化学工程] X771[环境科学与工程—环境工程]