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.
고분해능 전자에너지손실 및 자외선광전자 분광법을 사용하여 단결정 NbC(111)면의 산소횹착을 연구하였다. NbC(111) 표면에는 산소가 원자 및 분자상태로 흡착되었다. 산소원자는 3-fold hollow site에 흡착되며 진동수는 548cm-1이었다. 산소분자의 신축진동수는 968cm-1로서 기체상태인 산소분자의 진동수보다 크게 낮았으며, 산소분자의 흡착으로 일함수가 증가하였다. 이는 NbC(111) 기판으로부터 산소분자의 2ppig 궤도로 전자가 이동하였음을 보여주는 증거이다.
고분해능 전자에너지손실과 자외선광전자분광법을 사용하여 단결정 ZrC(111)면의 산소흡착을 연구하였다. 산소는 낮은 산소노출량에서 (√3×√3)R30˚ 구조로 흡착된다. 노출량이 승가하면 1×1 구조로 바뀌는데 이때 흡착하는 산소원자는 (√3×√3)R30˚ 구조에서보다 흡착높이가 낮으며 3-fold hollow site의 중심에 놓이지 않고 bridge site에 가까와진다. 서로 다른 산소흡착 거동은 개끗한 ZrC(111) 표면에서 두개의 표면전자상태에 기인한다.