文献类型：期刊文献

英文题名：Reconstructed covalent organic frameworks

作者：Zhang, Weiwei[1,2];Chen, Linjiang[1,2,3,4];Dai, Sheng[1,2];Zhao, Chengxi[1,2,3,4];Ma, Cheng[5];Wei, Lei[6];Zhu, Minghui[5];Chong, Samantha Y.[3,4];Yang, Haofan[3,4];Liu, Lunjie[3,4];Bai, Yang[3,4];Yu, Miaojie[1,2];Xu, Yongjie[3,4];Zhu, Xiao-Wei[3,4];Zhu, Qiang[3,4];An, Shuhao[1,2];Sprick, Reiner Sebastian[3,4];Little, Marc A.[3,4];Wu, Xiaofeng[1,2,3,4];Jiang, Shan[6];Wu, Yongzhen[1,2];Zhang, Yue-Biao[6];Tian, He[1,2];Zhu, Wei-Hong[1,2];Cooper, Andrew, I[1,2,3,4]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Frontiers Sci Ctr Materiobiol & Dynam Chem,Key La, Feringa Nobel Prize Scientist Joint Res Ctr,Joint, Shanghai, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem & Mol Engn, Frontiers Sci Ctr Materiobiol & Dynam Chem,Inst F, Feringa Nobel Prize Scientist Joint Res Ctr,Joint, Shanghai, Peoples R China;[3]Univ Liverpool, LeverhuLme Ctr Funct Mat Design, Mat Innovat Factory, Liverpool, Merseyside, England;[4]Univ Liverpool, Dept Chem, Liverpool, Merseyside, England;[5]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai, Peoples R China;[6]ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai, Peoples R China

年份：2022

卷号：604

期号：7904

起止页码：72

外文期刊名：NATURE

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000779100400018)】；

基金：We gratefully acknowledge funding from the National Natural Science Foundation of China (NSFC) Science Center Program (21788102); the NSFC (21905091, 21636002); Shanghai Municipal Science and Technology Major Project (2018SHZDZX03, 21JC1401700); Shanghai Municipal Science and Technology (20120710200); the Engineering and Physical Sciences Research Council (EPSRC) (EP/N004884/1, EP/P034497/1, EP/S017623/1); the Leverhulme Trust through the Leverhulme Research Centre for Functional Materials Design; and China Postdoctoral Science Foundation (no. 2019M651418). S.D. acknowledges support from the Shanghai Rising Star Program (20QA1402400) and the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning. W.Z. thanks the Research Center of Analysis and Testing of East China University of Science and Technology for the characterization of elemental microanalyses.

语种：英文

摘要：Covalent organic frameworks (COFs) are distinguished from other organic polymers by their crystallinity(1-3), but it remains challenging to obtain robust, highly crystalline COFs because the framework-forming reactions are poorly reversible(4,5). More reversible chemistry can improve crystallinity(6-9), but this typically yields COFs with poor physicochemical stability and limited application scope(5). Here we report a general and scalable protocol to prepare robust, highly crystalline imine COFs, based on an unexpected framework reconstruction. In contrast to standard approaches in which monomers are initially randomly aligned, our method involves the pre-organization of monomers using a reversible and removable covalent tether, followed by confined polymerization. This reconstruction route produces reconstructed COFs with greatly enhanced crystallinity and much higher porosity by means of a simple vacuum-free synthetic procedure. The increased crystallinity in the reconstructed COFs improves charge carrier transport, leading to sacrificial photocatalytic hydrogen evolution rates of up to 27.98 mmol h(-1) g(-1). This nanoconfinement-assisted reconstruction strategy is a step towards programming function in organic materials through atomistic structural control.