期刊
DALTON TRANSACTIONS
卷 44, 期 13, 页码 6193-6201出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5dt00149h
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Mutual separation of trivalent actinide (An(3+)) and lanthanide (Ln(3+)) using several soft (N) donor ligands (bis(5,6-dialkyl-1,2,4-triazinyl) pyridine (R-BTP)) is attempted for the first time in room temperature ionic liquid (RTIL) medium. The results indicate a spectacular enhancement in the selectivity as compared to that in molecular diluents with a separation factor (S.F.) of >3000 for Am3+ over Eu3+ using the methyl derivative (Me-BTP) in RTIL medium using [C(n)mim].[NTf2] as the diluents (where n = 2, 3, 4, 6 or 8). Such a high S.F. value has never been reported before with any of the R-BTP derivatives in molecular diluents. An opposite trend in the distribution ratio values of both Am3+ and Eu3+ with the increasing size of the alkyl (R) group is observed in RTIL medium when compared with that in molecular diluents. The differences in the extraction behaviour of R-BTPs in RTILs vis-a-vis molecular diluents are explained on the basis of the difference in the nature of complexes extracted in these two distinctly different media as supported by the time resolved fluorescence (TRFS) study. An unusually high extractability and selectivity for Am3+ over Eu3+ with Me-BTP was attributed to the formation of a 1 : 4 complex for Am3+, which was never reported earlier with any of the R-BTP derivatives in molecular diluents. DFT studies indicated higher metal 'd' and 'f' orbital participation (covalence) in the bonding with R-BTP in the case of Am3+ complexes as compared to that in the case of Eu3+ complexes, which resulted in the selectivity of these classes of ligands. The observed results may have a great significance in the radioactive waste management involving the partitioning and transmutation strategy.
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