Experimental and theoretical studies on the extraction behavior of Cf(iii) by NTAamide(C8) ligand and the separation of Cf(iii)/Cm(iii). Issue 6 (26th January 2023)

• Record Type: Journal Article
• Authors: Wang, Yi-lin; Li, Feng-feng; Xiao, Zhe; Wang, Cong-zhi; Liu, Yang; Shi, Wei-qun; He, Hui
• Is Part Of: RSC advances. Volume 13:Issue 6(2023)
• Page Start: 3781
• Page End: 3791
• Publication Date: 2023-01-26
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2ra07660h
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : We performed basic chemical studies on Cf using NTAamide extractant. The results of experiments and DFT calculations show that NTAamide has a good coordination ability to Cf/Cm and is expected to be applied to Cf/Cm separation. Abstract : In this work we studied the extraction behaviors of Cf(iii ) by NTAamide ( N, N, N ′, N ′, N ′′, N ′′-hexaocactyl-nitrilotriacetamide, C8) in nitric acid medium. Influencing factors such as contact time, concentration of NTAamide(C8), HNO3 and NO3 − as well as temperature were considered. The slope analysis showed that Cf(iii ) should be coordinated in the form of neutral molecules, and the extraction complex should be Cf(NO3 )3 ·2L (L = NTAamide(C8)), which can achieve better extraction effect under the low acidity condition. When the concentration of HNO3 was 0.1 mol L −1, the separation factor (SFCf/Cm ) was 3.34. The extractant has application prospect to differentiate the trivalent Cf(iii ) and Cm(iii ) when the concentration of nitric acid is low. On the other hand, density functional theory (DFT) calculations were conducted to explore the coordination mechanism of NTAamide(C8) ligands with Cf/Cm cations. The NTAamide(C8) complexes of Cf(iii )/Cm(iii ) have similar geometric structures, and An(iii ) is more likely to form a complex with 1 : 2 stoichiometry (metal ion/ligands). In addition, bonding property and thermodynamics analyses showed that NTAamide(C8) ligands had stronger coordination ability with Cf(iii ) over Cm(iii ). Our work provides meaningful information with regard to the in-group separation of An(iii ) in practical systems.