High Uptake of ReO4- and CO2 Conversion by a Radiation-Resistant Thorium-Nickle [Th48Ni6] Nanocage-Based Metal-Organic Framework

摘要

Assembled from [Th48Ni6] 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 400kGy irradiation. Notably, 1 captures ReO4- (an analogue of radioactive (TcO4-)-Tc-99, a key species in nuclear wastes) with a maximum capacity of 807 mgg(-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 [Th6O8] clusters in 1 have a unique stable electronic structure with (d-p)pi aromaticity, partially rationalising 1's stability.