Creating free standing covalent organic framework membranes by nanocrystal suturing in sol gel solutions

The sol-gel synthesis represents a versatile platform to fabricate ceramic inorganic membranes. However, it is still a grand challenge to push the boundary of sol-gel chemistry towards high-quality organic membrane construction. Herein, a facile and controlled nanocrystal suturing strategy in sol-gel solutions is developed to afford highly crystalline and free-standing covalent organic framework membranes. The key chemistry design lies in deploying tiny threads (1 mol% dual-NH₂-tail linear polymer) to efficiently suture the highly charged covalent organic framework nanocrystals stabilized and confined in sol-gel solutions, creating a continuous and intact membrane surface. A subsequent treatment heals the sutured covalent organic framework nanocrystals, yielding a free-standing membrane with high crystallinity and ordered pores. The structure evolution and role of the thread linker are elucidated via operando spectroscopy and microscopy. The as-afforded covalent organic framework membranes demonstrate attractive proton transport performance in high temperature and anhydrous fuel cell applications.