Photochromic radical states in 3D covalent organic frameworks with zyg topology for enhanced photocatalysis  

作　　者：Tian-Tian Ma Guo-Zhang Huang Xiao-Han Wang Yan Liang Run-Han Li Bin Wang Su-Juan Yao Jia-Peng Liao Shun-Li Li Yong Yan Ya-Qian Lan 

机构地区：[1]School of Chemistry,South China Normal University,Guangzhou 510006,China [2]Department of Chemistry,Guangdong Provincial Key Laboratory of Catalytic Chemistry,Southern University of Science and Technology,Shenzhen 518055,China

出　　处：《National Science Review》2024年第7期171-182,共12页国家科学评论（英文版）

基　　金：supported by the National Key R&D Program of China(2023YFA1507204);the National Natural Science Foundation of China(22225109,22071109 and 22271103).

摘　　要：Covalent-organic frameworks(COFs)with photoinduced donor-acceptor(D-A)radical pairs show enhanced photocatalytic activity in principle.However,achieving long-lived charge separation in COFs proves challenging due to the rapid charge recombination.Here,we develop a novel strategy by combining[6+4]nodes to construct zyg-type 3D COFs,first reported in COF chemistry.This structure type exhibits a fused Olympic-rings-like shape,which provides a platform for stabilizing the photoinduced D-A radical pairs.The zyg-type COFs containing catalytically active moieties such as triphenylamine and phenothiazine(PTZ)show superior photocatalytic production rates of hydrogen peroxide(H_(2)O_(2)).Significantly,the photochromic radical states of these COFs show up to 400%enhancement in photocatalytic activity compared to the parent states,achieving a remarkable H_(2)O_(2) synthesis rate of 3324μmol g^(−1) h^(−1),which makes the PTZ-COF one of the best crystalline porous photocatalysts in H_(2)O_(2) production.This work will shed light on the synthesis of efficient 3D COF photocatalysts built on topologies that can facilitate photogenerating D-A radical pairs for enhanced photocatalysis.

关 键 词：3D covalent-organic frameworks photochromic radical states donor and acceptor hydrogen peroxide PHOTOCATALYSIS 

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]