High Uptake of ReO4− and CO2 Conversion by a Radiation‐Resistant Thorium–Nickle [Th48Ni6] Nanocage‐Based Metal–Organic Framework. Issue 18 (28th March 2019)

• Record Type: Journal Article
• Authors: Xu, Hang; Cao, Chun‐Shuai; Hu, Han‐Shi; Wang, Shi‐Bin; Liu, Jin‐Cheng; Cheng, Peng; Kaltsoyannis, Nikolas; Li, Jun; Zhao, Bin
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 18(2019)
• Page Start: 6022
• Page End: 6027
• Publication Date: 2019-03-28
• Subjects: CO2 conversion -- metal–organic frameworks -- radiation resistance -- rhenium -- thorium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201901786
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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 in1 have a unique stable electronic structure with (d–p)π aromaticity, partially rationalising1 ′s stability. Abstract : Resistance is useful : The stable [Th48 Ni6 ] nanocage‐based metal–organic framework (MOF) is radiation resistant, effectively and selectively captures ReO4 − and catalytically converts CO2 into epoxides. The aromatic character of the Th6 O8 clusters accounts for the stability of the MOF.