Easily Accessible Rare-Earth-Containing Phosphonium Room-Temperature Ionic Liquids: EXAFS, Luminescence, and Magnetic Properties

Alvarez-Vicente, Jorge; Dandıl, Sahra; Banerjee, Dipanjan; Gunaratne, H. Q. Nimal; Gray, Suzanne L.; Felton, Solveig; Сринивасан, Г.; Kaczmarek, Anna; Deun, Rik Van; Nockemann, Peter

doi:10.1021/acs.jpcb.6b03870

Cited by 28 publications

(17 citation statements)

References 41 publications

(80 reference statements)

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“…No significant differences were observed in the position and intensities of the peaks in the spectra of the different samples, except for the presence of strong water peaks in water-saturated [A336][Cl] around cm -1 and in the region between 3000 and 3500 cm -1 . 3-complexes in quaternary phosphonium or imidazolium salts has already been reported in the literature [36][37][38]. The excitation spectra of the dry [A336][Cl] samples containing the Eu(III) ion have a broad excitation band arising from the singlet ground state of the [A336] cation and sharp peaks which can be attributed to the 7 F0 electronic level of the Eu(III) ion (Figure 3).…”

Section: Speciationmentioning

confidence: 62%

Mechanism for Solvent Extraction of Lanthanides from Chloride Media by Basic Extractants

et al. 2018

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The solvent extraction of lanthanides from chloride media to an organic phase containing an anion exchanger in the chloride form is known to show low extraction percentages and small separation factors. The coordination chemistry of the lanthanides in combination with this kind of extractants is poorly understood. Previous work has mainly used solvent extraction based techniques (slope analysis, fittings of the extraction curves) to derive the extraction mechanism of lanthanides from chloride media. In this paper, EXAFS spectra, luminescence lifetimes, excitation and emission spectra and organic phase loadings of lanthanides in dry, water-saturated and diluted Aliquat 336 chloride or Cyphos IL 101 have been measured. The data show the formation of the hydrated lanthanide ion [Ln(H2O)8-9] 3+ in undiluted and diluted Aliquat 336 and the complex [LnCl6] 3in dry Aliquat 336. The presence of the same species [Ln(H2O)8-9] 3+ in the aqueous and in the organic phase explains the small separation factors and the poor selectivities for the separation of mixtures of lanthanides. Changes in separation factors with increasing chloride concentrations can be explained by changes in stability of the lanthanide chloro complexes in the aqueous phase, in combination with the extraction of the hydrated lanthanide ion to the organic phase. Finally, it is shown that the organic phase can be loaded with 107 g•L -1 of Nd(III) under the optimal conditions.

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Section: Speciationmentioning

confidence: 62%

Mechanism for Solvent Extraction of Lanthanides from Chloride Media by Basic Extractants

et al. 2018

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“…Based on a literature survey, it seems that the fitted Ln–Cl distances for Nd and Eu correlate quite well with CN’s of six and five, respectively (Table S13). − This is much lower than the fitted CN of 10 for both lanthanides. Homoleptic Nd 3+ - and Eu 3+ -chloro complexes tend to be six-coordinate octahedra, with average Ln–Cl distances of 2.73 and 2.69 Å, respectively.…”

Section: Results and Discussionmentioning

confidence: 81%

Spectroscopic Study into Lanthanide Speciation in Deep Eutectic Solvents

et al. 2021

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Deep eutectic solvents are a new class of green solvents that are being explored as an alternative for used nuclear fuel and critical material recycling. However, there is a paucity of knowledge regarding metal behavior in them. This paper explores the underlying chemistry of rare-earth elements in choline chloride-based deep eutectic solvents by using a multi-technique spectroscopic methodology. Results show that speciation is highly dependent on the choice of the hydrogen-bond donor. Collected EXAFS data showed Ln 3+ coordination with ethylene glycol and urea in their respective solvents and coordination with chloride in the lactic acid system. Generalized coordination environments were determined to be [LnL 4–5 ], [LnL 7–10 ], and [LnL 5–6 ] in the ethylene glycol, urea, and lactic acid systems, respectively. Collected UV/vis spectra for Nd 3+ and Er 3+ showed variations with changing solvents, showing that Ln–Cl interactions do not dominate in these systems. Luminescence studies were consistent, showing varying emission spectra with varying solvent systems. The shortest luminescent lifetimes were observed in the choline chloride–ethylene glycol deep eutectic solvent, suggesting coordination through O–H groups. Combining all collected data allowed Eu 3+ coordination geometries to be assigned.

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“…are particularly common and span across most metals in the periodic table. 24 The functionality of halometallate IL is typically defined by the properties of its anionic species, and catalytic, 25 magnetic, 26 and luminescent 27 ILs have been reported. For the present study, we have chosen tetraalkylphosphonium cations, namely, tetrabutylphosphonium (TBP) and trihexyltetradecylphosphonium (THTDP) to pair with lead(II) halide, yielding luminescent ILs.…”

Section: Resultsmentioning

confidence: 99%

Luminescent Lead Halide Ionic Liquids for High-Spatial-Resolution Fast Neutron Imaging

et al. 2021

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The fast neutron imaging technique with recoil proton detection harbors significant potential for imaging of thick, large-scale objects containing high-Z elements. However, the challenge to find efficient fast neutron scintillators with high spatial resolution is ongoing. The list of requirements for such scintillators is long and demanding: a proton-rich, scattering-free material combining high light yield with the absence of light reabsorption. To meet these challenges, we look for a suitable material among a rising class of 0D organic–inorganic Pb(II) halide hybrids. The use of large organic cations, e . g., trihexyltetradecylphosphonium, results in room-temperature ionic liquids that combine highly Stokes-shifted (up to 1.7 eV), reabsorption-free, and efficient emission (photoluminescence quantum yield up to 60%) from molecularly small and dense (PbX 2 molar fraction up to 0.33) emitting centers. We investigate the optical properties of the resulting ionic liquids and showcase their utility as fast neutron imaging scintillators. Concomitantly with good light yield, such fast-neutron scintillators exhibit both higher spatial resolution and lower γ-ray sensitivity compared with commercial ZnS:Cu-based screens.

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Easily Accessible Rare-Earth-Containing Phosphonium Room-Temperature Ionic Liquids: EXAFS, Luminescence, and Magnetic Properties

Cited by 28 publications

References 41 publications

Mechanism for Solvent Extraction of Lanthanides from Chloride Media by Basic Extractants

Mechanism for Solvent Extraction of Lanthanides from Chloride Media by Basic Extractants

Spectroscopic Study into Lanthanide Speciation in Deep Eutectic Solvents

Luminescent Lead Halide Ionic Liquids for High-Spatial-Resolution Fast Neutron Imaging

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