Owing to the rapid rise of global energy demands, the operation of nuclear power plants is still indispensable. However, following the nuclear accident at Fukushima-Daiichi in 2011, the secure sequestration of radioactive waste has become critical for ensuring safe operations. Among various forms of nuclear wastes, capturing radioactive organic iodide (ROIs, e.g., methyl iodide, ethyl iodide, and propyl iodide) as one of the important species in gas phase waste has been challenged owing to the insufficient sorbent materials. The environmental release of ROIs with high volatility can give rise to adverse effects, including the accumulation of these substances in the thyroid and the development of conditions such as hypothyroidism and thyroid cancer. Compared to an iodine molecule, ROIs exhibit low affinity for conventional sorbents such as Ag@mordenite zeolite and triethylenediamine-impregnated activated carbon (TED@AC), resulting in lower sorption rates and capacities. Furthermore, in conditions resembling practical adsorption environments with high humidity, the presence of H2O significantly impedes the adsorption process, leading to a nearly complete cessation of adsorption. To address these issues, metal-organic frameworks (MOFs) can be effective alternative sorbents owing to their high surface area and designable and tailorable pore properties. In addition, the wellfined crystalline structures of MOFs render in-depth study on the structure-properties relationship. However, there has been limited research on the adsorption of ROIs using MOFs, with the majority of adsorption processes relying on highly reversible physisorption. This type of ROIs adsorption not only exists in a precarious state that is susceptible to volatilization but also exhibits significantly reduced adsorption capabilities in humid environments. Thus, for the secure adsorption of the volatile ROIs, the development of sorbents capable of chemisorption is highly desirable. In this study, we focused on ROIs adsorption by electrophilic aromatic substitution with the electron-rich m-DOBDC4− (m-DOBDC4− = 4,6-dioxo-1,3-benzenedicarboxylate) present in Co2(m -DOBDC). The chemisorption of ROIs via electrophilic aromatic substitution not only leads to the formation of C-C bonds, ensuring stability but also triggers color changes in the crystal by interacting with open-metal sites and iodide ions. Leveraging these advantages, we developed an infrared radiation-based sensing method that demonstrates superior performance, exhibiting high adsorption capacities and rates, even under the challenging conditions of high-humidity practical environments.

• Byeongchan Lee(Daegu Gyeongbuk Institute of Science and Technology (DGIST))
• Bogyeong Go(Daegu Gyeongbuk Institute of Science and Technology (DGIST))
• Jinhee Park(Daegu Gyeongbuk Institute of Science and Technology (DGIST)) Corresponding author