Scalable Fabrication of Crystalline COF Membranes from Amorphous Polymeric Membranes

Chunyang Fan; Hong Wu; Jingyuan Guan; Xinda You; Chao Yang; Xiaoyao Wang; Li Cao; Benbing Shi; Quan Peng; Yan Kong; Yingzhen Wu; Niaz Ali Khan; Zhongyi Jiang

doi:10.1002/anie.202102965

Scalable Fabrication of Crystalline COF Membranes from Amorphous Polymeric Membranes

Angew Chem Int Ed Engl. 2021 Aug 9;60(33):18051-18058. doi: 10.1002/anie.202102965. Epub 2021 Jul 9.

Authors

Chunyang Fan^{1

2}, Hong Wu^{1

2

3}, Jingyuan Guan^{1

2}, Xinda You^{1

2}, Chao Yang^{1

2}, Xiaoyao Wang^{1

2}, Li Cao^{1

2}, Benbing Shi^{1

2}, Quan Peng^{1

2}, Yan Kong^{1

2}, Yingzhen Wu^{1

2}, Niaz Ali Khan^{1

2}, Zhongyi Jiang^{1

2

4}

Affiliations

¹ Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, China.
² Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, China.
³ Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin, 300072, China.
⁴ Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, 350207, China.

PMID: 34062042
DOI: 10.1002/anie.202102965

Abstract

Covalent organic framework (COF) membranes hold potential for widespread applicability, but scalable fabrication is challenging. Here, we demonstrate the disorder-to-order transformation from amorphous polymeric membrane to crystalline COF membrane via monomer exchange. Solution processing is used to prepare amorphous membrane and the replacing monomer is selected based on the chemical and thermodynamical stability of the final framework. Reversible imine bonds allow the extraneous monomers to replace the pristine monomers within amorphous membrane, driving the transformation from disordered network to ordered framework. Incorporation of intramolecular hydrogen bonds enables the crystalline COF to imprint the amorphous membrane morphology. The COF membranes harvest proton conductivity up to 0.53 S cm^-1 at 80 °C. Our strategy bridges amorphous polymeric and crystalline COF membranes for large-scale fabrication of COF membranes and affords guidance on materials processing.

Keywords: covalent organic frameworks; disorder-to-order; membranes; proton transport; solution processability.

Abstract

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