The effective capture of radioiodine exhausted from nuclear power plants, is of paramount importance for the radioactivity control and remediation tasks. Herein, a robust metal–organic framework Ag-Tipe integrating with open Ag+ metal sites and imidazole groups is designed for efficient capture of I2 and CH3I. The dense imidazolium groups are expected to interact with the I2 through charge transfer, enhancing the binding affinity and trapping CH3I as a reactant in the methylation reaction. In addition, the fully open silver metal center in Ag-Tipe can coordinate with iodine species to form AgI. Therefore, the Ag-Tipe exhibits high I2 and CH3I uptake capacities of 3.31 and 0.55 g/g at 75 °C, respectively. The density functional theory (DFT) calculations reveal that the I2 and CH3I binding energy at different sites in Ag-Tipe follows the order Ag > imidazole > benzene ring. This work demonstrates the important role of the binding site of the adsorbent in achieving high I2/CH3I trapping performance.
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