Abstract
The removal of radioactive gaseous iodine is crucial for sustainable nuclear energy development, safe spent fuel management, and secure disposal of radioactive waste and radioactive medical waste. However, the efficient capture of gaseous iodine, particularly methyl iodide, under conditions of low concentration and high-flow rate that are representative of real-world scenarios remains underexplored. Herein, we adopted a "theory-first" strategy to design adsorbents with a superior affinity for methyl iodide. The rigorous theoretical calculations for both physisorption and chemisorption have guided us to rationally design a piperazine-based covalent organic framework material (Pip-COF, Pip = piperazine). The pioneering hot-testing under dynamic conditions, featuring low concentrations of 5 ppm radioactive CH(3) (131)I and a high-flow rate of 600 mL/min, demonstrated Pip-COF's exceptional capture performance. Pip-COF exhibits saturated capacities of 39 mg/g at 75 °C and 78 mg/g at 25 °C, significantly outperforming the previously reported best COF (COF-TAPT, 6 mg/g at 25 °C) in this scenario. The gradual process of methylation and the identification of specific high-affinity sites were elucidated by time-resolved FT-IR spectroscopy and density functional theory (DFT) analysis, consistent with the design philosophy. This study exemplifies rational material design in facilitating the separation of trace pollutants in challenging environments.