期刊
ACS APPLIED MATERIALS & INTERFACES
卷 11, 期 29, 页码 25817-25823出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsami.9b04768
关键词
iodine capture; chemisorption; metal-organic frameworks; aryl C-H bond activation; single crystal-single crystal transformation
资金
- National Research Foundation of Korea (NRF) - Korean government [NRF-2016R1C1B2009987, NRF-2016M2B2A9912217]
- Faculty Start-up Fund of the Daegu Gyeongbuk Institute of Science and Technology (DGIST) [2018010058]
- National Research Foundation of Korea [2016M2B2A9912217] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
The ability to chemisorb iodine is important for the safe long-term storage of fission products from nuclear reactors. Herein, we successfully used single-crystal X-ray diffraction analysis to crystallographically visualize I-2 binding sites in two isostructural metal-organic frameworks, viz. Co-2(m-DOBDC) (m-DOBDC4- = 4,6-dioxo-1,3-benzenedicarboxylate) and Co-2(p-DOBDC) (p-DOBDC4- = 2,5-dioxo-1,4-benzenedicarboxylate), with increasing I-2 loading. Interestingly, the C-H bond at the electron-rich carbon (C5) of m-DOBDC4- is activated toward electrophilic aromatic substitution, forming an aryl C-I bond and I- or I-3(-) that coordinates to unsaturated open Co sites. Cooperation between the ligand and the open Co sites leads to rapid chemisorption of I-2 even under mild adsorption conditions, such as room temperature. In contrast, molecular I-2 coordinates to the open Co sites of Co-2(p-DOBDC). Owing to the chemisorption of I-2, I-2@Co-2(m-DOBDC) decomposes at a much higher temperature than I(2)pCo(2)(p-DOBDC), as revealed by thermogravimetric analysis.
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