Facile fabrication of hollow tubular covalent organic frameworks using decomposable monomer as building block

Abstract

In this study, a commercial and low-toxicity hydrazide-containing building block has been used to construct azine-linked covalent organic frameworks (COFs). New style COFs were constructed between flexible formic hydrazide (FH) and 1,3,5-triformylphloroglucinal (Tp) or 1,3,5-triformylbenzene (TFB). The two resulting COFs (TpFH and TFBFH) exhibited uniform hollow tubular morphology (20–50 nm for TpFH, 50–100 nm for TFBFH). Compared to hydrazine, FH has low-toxicity and is a flexible monomer, consisting of amine and aldehyde groups. The decomposition of FH slows down the reaction rate and the as-synthesized FH-series COFs (708 m² g⁻¹ for TpFH and 888 m² g⁻¹ for TFBFH) had higher specific surface area than hydrazine-series COFs (617 m² g⁻¹ for TpAzine and 472 m² g⁻¹ for TFBAzine). A detailed time-dependent investigation was carried out to interpret the mechanism of hollow structure formation, and Ostwald ripening possibly happens during the formation of hollow COF microstructures. Considering the porous and high density N, O elements of these materials, preliminary applications of the metal ions removal from aqueous solution and gas storage were implemented.