High Uptake of ReO4 - and CO2 Conversion by a Radiation-Resistant Thorium-Nickle [Th48 Ni6 ] Nanocage-Based Metal-Organic Framework.
Hang XuChun-Shuai CaoHan-Shi HuShi-Bin WangJin-Cheng LiuPeng ChengNikolas KaltsoyannisJun LiBin ZhaoPublished in: Angewandte Chemie (International ed. in English) (2019)
Assembled from [Th48 Ni6 ] nanocages, the first transition-metal (TM)-thorium metal-organic framework (MOF, 1) has been synthesized and structurally characterized. 1 exhibits high solvent and acid/base stability, and resistance to 400 kGy β irradiation. Notably, 1 captures ReO4 - (an analogue of radioactive 99 TcO4 - , a key species in nuclear wastes) with a maximum capacity of 807 mg g-1 , falling among the largest values known to date. Furthermore, 1 can enrich methylene blue (MB) and can also serve as an effective and recyclable catalyst for CO2 fixation with epoxides; there is no significant loss of catalytic activity after 10 cycles. Theoretical studies with nucleus-independent chemical shifts and natural bond orbital analysis reveal that the [Th6 O8 ] clusters in 1 have a unique stable electronic structure with (d-p)π aromaticity, partially rationalising 1's stability.