Fabrication of Ionic Covalent Triazine Framework-Linked Membranes via a Facile Sol-Gel Approach

Covalent triazine framework (CTF)-based membranes have shown unique properties and wide applications in energy-related fields, but there is still no efficient strategy capable of affording CTF membranes functionalized with ionic moieties, which will bring extra merits and application possibilities. In this work, a robust CTF membrane with ionic functionalities was fabricated via a sol-gel approach promoted by a superacid (FSO3H). The CTF skeleton was constructed via the trimerization of cyano groups in the monomer, and piperazine moieties were introduced as reactive sites for the formation of ammonium cations coupled with FSO3- anions within the backbone. The obtained transparent and red protonated polymeric CTF-based membrane (PP-CTF) exhibited significant absorption at 646 nm in the solid-state ultraviolet-visible diffuse reflectance spectrum. Comparatively, the neutralized deprotonated counterparts turned to yellow color with a significant blueshift absorption to 492 nm. The theoretical calculation demonstrated that PP-CTF and deprotonated polymeric CTF membrane (DP-CTF) were stable with AB-stacking mode, and PP-CTF had a smaller band gap (0.90 eV) than that of DP-CTF (2.17 eV). The significant optical absorption and emission behavior change of PP-CTF and its robust chemical stability endowed it with the capability to act as pH indicators. The synthetic pathway developed in this work and the performance of the resultant ionic membrane opens new opportunities in the aspects of membrane design, fabrication, and application.