Structural Modulation of Nitrogen-Rich Covalent Organic Frameworks for Iodine Capture.

Developing efficient adsorbent materials for iodine scavenging is essential to mitigate the threat of radioactive iodine causing adverse effects on human health and the environment. In this context, we explored N-rich two-dimensional covalent organic frameworks (COFs) with diverse functionalities for iodine capture. The pyridyl-hydroxyl-functionalized triazine-based novel 5,5',5″-(1,3,5-triazine-2,4,6-triyl)tris(pyridine-2-amine) (TTPA)-COF possesses high crystallinity (crystalline domain size: 24.4 ± 0.6 nm) and high porosity (specific BET surface area: 1000 ± 90 m g). TTPA-COF exhibits superior vapor-phase iodine adsorption (4.43 ± 0.01 g g) compared to analogous COF devoid of pyridinic moieties, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT)-COF. The high iodine capture by TTPA-COF is due to the enhanced binding affinity conferred by the extra pyridinic active sites. Furthermore, the crucial role of long-range order in porous adsorbents has been experimentally evidenced by comparing the performance of iodine vapor capture of TTPA-COF with an amorphous network polymer having identical functionalities. We have also demonstrated the high iodine scavenging ability of TTPA-COF from the organic and aqueous phases. The mechanism of iodine adsorption by the heteroatom-rich framework is elucidated through FTIR, XPS, and Raman spectral analyses. The present study highlights the need for structural tweaking of the building blocks toward the rational construction of advanced functional porous materials for a task-specific application.