Robust dioxin-linked metallophthalocyanine tbo topology covalent organic frameworks and their photocatalytic properties  

作　　者：Yucheng Jin Qianjun Zhi Hailong Wang Xiaoning Zhan Dongdong Qi Baoqiu Yu Xu Ding Tianying Wang Heyuan Liu Mingxue Tang Jie Liu Jianzhuang Jiang 

机构地区：[1]Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials,Department of Chemistry and Chemical Engineering,School of Chemistry and Biological Engineering,University of Science and Technology Beijing,Beijing 100083,China [2]School of Materials Science and Engineering,China University of Petroleum(East China),Qingdao 266580,China [3]Center for High Pressure Science and Technology Advanced Research,Beijing 100193,China

出　　处：《National Science Review》2025年第1期126-139,共14页国家科学评论(英文版)

基　　金：supported by the National Natural Science Foundation of China(22235001,22175020,22131005,22473115 and 22261132512);Xiaomi Young Scholar Program,the Fundamental Research Funds for the Central Universities(FRF-EYIT-23-02 and QNXM2023);Taishan Scholar program of Shandong Province(tsnq202312119);the University of Science and Technology Beijing.

摘　　要：Constructing 3D functional covalent organic frameworks(COFs)with both robust linkage and planar macrocycle building blocks sti l l remains a challenge due to the difficulty in adjusting both the crystallinity and the dominant 2D structures.In addition,it is also challenging to selectively convert inert C(sp^(3))-H bonds into value-added chemicals.Herein,robust 3D COFs,USTB-28-M(M=Co,Ni,Cu),have been polymerized from the nucleophilic aromatic substitution reaction of D_(3h)-symmetric 2,3,6,7,14,15-hexahydroxyltriptycene with D_(4h)-symmetric hexadecafluorophthalocyanine(MPcF_(16))under solvothermal conditions.These chemically stable dioxin-linked COFs show isostructural tbo topology made up of three kinds of polyhedron subunits,exhibiting high Brunauer−Emmett−Teller surface areas of≤1477 m^(2) g^(−1).In particular,the multiple polyhedron subunits in USTB-28-M could trap N-hydroxyphthalimide at their corners for easily forming stable phthalimide-N-oxyl radicals under visible-light irradiation.The generated radicals efficiently promote the aerobic oxidation of alkyl benzenes with an inert C(sp^(3))-H bond into various ketones.Among the three investigated COFs,the USTB-28-Co radical initiator exhibits the best photocatalytic oxidation activity,converting ethylbenzene into acetophenone with a turnover frequency of 63 h^(−1),which is much higher than those of the monomer CoPcF16(8 h^(−1))and 2D dioxin-linked counterparts(13 h^(−1)).This is due to the much prolonged lifetime of the excited state for USTB-28-Co based on the femtosecond transient absorption result.The present work not only presents 3D functional COFs with robust connection and permanent porosity,but also illustrates the uniqueness of porous structures of 3D COFs for high-performance photocatalysis.

关 键 词：covalent organic frameworks robust connection tbo topology PHOTOCATALYSIS trapping effect 

分 类 号：TQ116.2[化学工程—无机化工] O643.36[理学—物理化学] O644.1[理学—化学]