Selective separation of Am(iii) from lanthanides(iii) by solvent extraction with hydrophobic field of “superweak” anion

Naganawa, Hirochika; Suzuki, H.; Noro, Junji; Kimura, Takaumi

doi:10.1039/b502763m

Cited by 15 publications

(12 citation statements)

References 7 publications

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“…values were found to be in the range of several thousands using Me-BTP even with 0.1 M HNO 3 and as shown from Table 1, such a high S.F. 31 In a previous study, we reported an enhancement in the selectivity (S.F. Carbamoylmethylenephosphine oxide (CMPO), an extensively studied ligand for the actinide partitioning, does not show any selectivity between trivalent actinides and lanthanides.…”

Section: Distribution Studies In [C N Mim]·[ntf 2 ]mentioning

confidence: 76%

A remarkable enhancement in Am³⁺/Eu³⁺selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results

et al. 2015

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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 Am(3+) over Eu(3+) 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 Am(3+) and Eu(3+) 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-à-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 Am(3+) over Eu(3+) with Me-BTP was attributed to the formation of a 1 : 4 complex for Am(3+), 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 Am(3+) complexes as compared to that in the case of Eu(3+) 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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Section: Distribution Studies In [C N Mim]·[ntf 2 ]mentioning

confidence: 76%

A remarkable enhancement in Am³⁺/Eu³⁺selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results

et al. 2015

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“…For this reason, B 12 F 12 2─ has been called a "weakly coordinating" or "superweak" anion. 25,[27][28][29][30] While a good deal is known about the structures and properties of polyboron chlorides, bromides, and iodides, 18 the literature concerning experimental investigation of polyboron fluoride clusters is relatively sparse. 16,[18][19][20][21][22] For the most part, structural characterization of small boron halide clusters has been achieved by gas-phase electron diffraction or X-ray crystallography of low-temperature B n F m crystals.…”

Section: Introductionmentioning

confidence: 99%

Infrared-Driven Charge Transfer in Transition Metal B₁₂F₁₂ Clusters

et al. 2015

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A combination of infrared multiple photon dissociation (IRMPD) spectroscopy and density functional theory calculations is used to investigate the structures and charge-transfer properties of clusters containing transition metals (TM = Co(II), Ni(II), Cu(I), Zn(II), Rh(III), Pd(II), Ag(I), Cd(II)) and the dodecafluorododecaboron dianion, B12F12(2-). In all cases, IRMPD resulted in transfer of electron density to the metal center and production of B12F12(-). Metals that exhibit the highest degree of charge transfer are found to induce reaction among the B12F12 cages, leading to production of BnFm (up to n = m = 24).

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“…As reported in Table (1), the extraction efficiency of the metals is higher, due to the occurrence of these concomitant mechanisms. Another effect of the highly hydrophobic anion TFPB has been detailed by Naganawa et al [46]. The non-coordinating anion favors the transfer of dehydrated metallic ion pairs.…”

Section: Effect Of Sacrificial Cationmentioning

confidence: 95%

Separation of lithium, cobalt and nickel from spent lithium-ion batteries using TBP and imidazolium-based ionic liquids

Zante

Masmoudi

Barillon

et al. 2020

Journal of Industrial and Engineering Chemistry

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Solvent extraction of lithium ions from sulfuric acid solutions was investigated using imidazolium-based ionic liquids as diluents and tri-n-butyl phosphate as specific ligand. Aqueous phases used were simulating leach liquors of spent lithium-ion batteries, with lithium, cobalt and nickel ions in acidic solutions. A low acidity and a large amount of extractant can ensure high extraction efficiency. But the better selectivity for the lithium ions over the transition metals is obtained using a low amount of extractant and a low pH (pH<3). The extraction of the lithium ions occurs by cation exchange with the ionic liquid cations. A sacrificial cation was introduced in the organic phase to prevent the losses, but the cation exchange is only reduced by 20 %. The increase of the ionic liquid cation alkyl chain length can presumably suppress the cation exchange mechanism, reducing substantially the losses. But the addition of a lipophilic counter-anion in the organic phase is needed to ensure a mechanism of ion pairing with the lithium ion in the organic phase. Using the 1-decyl 3methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid associated to tri-butyl phosphate, a satisfying extraction efficiency is obtained for the lithium ion, together with a sufficient selectivity among the transition metal ions.

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Selective separation of Am(iii) from lanthanides(iii) by solvent extraction with hydrophobic field of “superweak” anion

Cited by 15 publications

References 7 publications

A remarkable enhancement in Am³⁺/Eu³⁺selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results

A remarkable enhancement in Am³⁺/Eu³⁺selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results

Infrared-Driven Charge Transfer in Transition Metal B₁₂F₁₂ Clusters

Separation of lithium, cobalt and nickel from spent lithium-ion batteries using TBP and imidazolium-based ionic liquids

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Selective separation of Am(iii) from lanthanides(iii) by solvent extraction with hydrophobic field of “superweak” anion

Cited by 15 publications

References 7 publications

A remarkable enhancement in Am3+/Eu3+selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results

A remarkable enhancement in Am3+/Eu3+selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results

Infrared-Driven Charge Transfer in Transition Metal B12F12 Clusters

Separation of lithium, cobalt and nickel from spent lithium-ion batteries using TBP and imidazolium-based ionic liquids

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A remarkable enhancement in Am³⁺/Eu³⁺selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results

A remarkable enhancement in Am³⁺/Eu³⁺selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results

Infrared-Driven Charge Transfer in Transition Metal B₁₂F₁₂ Clusters