Reconstructed covalent organic frameworks

Weiwei Zhang, Linjiang Chen, Sheng Dai, Chengxi Zhao, Cheng Ma, Lei Wei, Minghui Zhu, Samantha Y. Chong, Haofan Yang, Lunjie Liu, Yang Bai, Miaojie Yu, Yongjie Xu, Xiao Wei Zhu, Qiang Zhu, Shuhao An, Reiner Sebastian Sprick, Marc A. Little, Xiaofeng Wu, Shan JiangYongzhen Wu, Yue Biao Zhang, He Tian, Wei Hong Zhu*, Andrew I. Cooper*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

107 Citations (Scopus)
92 Downloads (Pure)

Abstract

Covalent organic frameworks (COFs) are distinguished from other organic polymers by their crystallinity1–3, but it remains challenging to obtain robust, highly crystalline COFs because the framework-forming reactions are poorly reversible4,5. More reversible chemistry can improve crystallinity6–9, but this typically yields COFs with poor physicochemical stability and limited application scope5. 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.

Original languageEnglish
Pages (from-to)72-79
Number of pages8
JournalNature
Volume604
Issue number7904
Early online date6 Apr 2022
DOIs
Publication statusPublished - 7 Apr 2022

Bibliographical note

Funding Information:
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.

Publisher Copyright:
© 2022, The Author(s).

ASJC Scopus subject areas

  • General

Fingerprint

Dive into the research topics of 'Reconstructed covalent organic frameworks'. Together they form a unique fingerprint.

Cite this