The distribution constants of 4-benzoyl-3-phenyl-5-isoxazolone (HPBI) and deprotonated one (PBI-) between hydrophobic ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C1C4im][Tf2N]) and aqueous phases were determined, together with the acid-dissociation constant of HPBI. The solvent extraction of three selected lanthanoid ions (La3+, Eu3+, and Lu3+) with HPBI from aqueous nitrate phase into [C1C4im][Tf2N] has been investigated. Application of the ionic liquid as the extracting phase greatly enhanced the extraction performance of HPBI for lanthanoid ions compared with that in the chloroform system. A slope analysis was conducted in order to compare the results of the solution 4f-ion coordination chemistry in ionic and molecular media. The composition of the extracted species was established to be anionic tetrakis entities, Ln(PBI)4-, for light, middle, and heavy lanthanoid ions in an ionic environment (Ln denotes lanthanoid ion). Nevertheless, the typical neutral chelate lanthanoid complexes of the type Ln(PBI)3 have been detected when the conventional molecular diluent chloroform was applied as an organic phase.

The recycling of rare metals such as platinum (Pt) from secondary resources, such as waste electronic and electrical equipment and automotive catalysts, is an urgent global issue. In this study, simple secondary amides and urea, N-(2-ethylhexyl)acetamide, N-(2-ethylhexyl)octanamide, and 1-butyl-3-(2-ethylhexyl)urea, which selectively extract Pt(IV) from a simulated effluent containing numerous metal ions, such as in an actual hydrometallurgical process, were synthesized and achieved efficient Pt(IV) stripping using only water. Comparison of Pt(IV) extraction behavior with a tertiary amide without N–H moieties suggests that the secondary amides and urea extractants effectively use hydrogen bonding to the hexachloroplatinate anion by N–H moieties. Examining the conditions for the third phase formation revealed that the secondary amide extractant with the longest alkyl chain can be used in the extraction process for a long time without forming any third phase, despite its lower Pt(IV) extraction capacity. The practical trial with simple compounds developed in this study should contribute to the development of Pt separation and purification processes.

We compare the extraction performance of new extractant, fluorous phosphate tris(4,4,5,5,6,6,7,7,7-nonafluoroheptyl) phosphate (TFP) in the fluorinated diluent perfluorohexane, for Zr(IV) with a conventional organic extractant, tri-n-butyl phosphate (TBP) in n-octane. It is surprising that fluorinating TBP to TFP improved the extraction performance, as normally fluorinating the hydrocarbon substituents on neutral extractants tends to decrease the extraction strength. We examined the origin of the superior extraction performance of TFP by analyzing the equilibrium of the chemical reaction during the extraction. The equilibrium reaction of Zr(IV) with TFP is , whereas that with TBP is . Phosphorus-31 nuclear magnetic resonance and infrared spectroscopy measurements of TFP and TBP showed similar electron densities at the phosphorus atom and vibration modes of the P=O group, implying similar coordination to Zr(IV). In addition, the concentrations of all components (Zr(IV), HNO₃, and water) in the fluorous and organic phases after solvent extraction were evaluated by inductively coupled plasma-mass spectrometry, ion chromatography, and Karl-Fischer titration. The concentrations of water and HNO₃ molecules in the fluorous phase become low during the Zr(NO₃)₄(TFP)₃ extraction, indicating that water and HNO₃ molecules do not preferentially interact with Zr(NO₃)₄(TFP)₃ in contrast to Zr(NO₃)₄(TBP)₂ in n-octane We speculate that the excellent performance originated from the stability of Zr(NO₃)₄(TFP)₃ in the fluorous phase. Hence, TFP is expected to be used as an alternative extractant to TBP.