Isabelle Billard's research while affiliated with Université Savoie Mont Blanc and other places

Publications (170)

Article
Full-text available
The factors influencing metal partition in acidic aqueous biphasic systems (AcABS) containing phosphonium-based ILs are still poorly explored. To assess their influence the effect of the IL counter anion, acid and its concentration, and temperature, were systematically evaluated on the extraction of four transition metals (Cu(II), Co(II), Ni(II), a...
Preprint
Ionic-liquid based acidic aqueous biphasic solutions (AcABS) recently offered a breakthrough in the field of metal recycling. Indeed, the mixture of tributyltetradecylphosphonium chloride (P$_{44414}$Cl) and acid with water content larger than 60 \% presents a phase separation with very good extraction efficiency for metallic ions. Moreover, this t...
Article
Starting from a real Proton Exchange Membrane Fuel Cell (PEMFC) leachate, separation of the strategic metals platinum(IV) and cobalt(II) was carried out using two distinct strategies applying ionic liquids (ILs), either via solvent extraction (SX) or acidic aqueous biphasic system (AcABS). The versatility of ILs and their ability to provide origina...
Article
Full-text available
In this work, the important role played by metal ions such as Fe(II/III), Cr(III) and Ni(II) in the formation and binodal behaviour of aqueous biphasic systems (ABS) composed of HCl and the ionic liquid, [P 44414 ]Cl, or the polymer, PEG-600, is investigated. The concentration of metal ions used in this work exceeds several g L À1 for an industrial...
Article
Full-text available
Cet article présente une revue actualisée et critique de l'état des connaissances sur les liquides ioniques (LI). Après avoir décrit brièvement l'évolution des méthodes de synthèse, une large part est dédiée aux propriétés des LI, incluant densité, viscosité, plage accessible de température, propriétés électrochimiques, structure des phases liquide...
Article
Full-text available
The metal extraction mechanism of basic extractants is typically described as an anion exchange process, but this mechanism does not correctly explain all observations. This paper introduces a novel model for the extraction of metals by basic extractants from chloride media supported by experimental data on methyltrioctylammonium chloride and Aliqu...
Article
Full-text available
In this work, the aqueous speciation of Rh(III) in chloride medium was investigated by UV-vis spectroscopy for ligand to metal ratios R = (Cl ⁻ )/(Rh) ranging from 300 to 5000, at fixed Rh concentration (2.4 × 10 ⁻³ M). Under the chemical conditions of this work, no time evolution was observed, which allows for the fitting of the UV-vis data by Pri...
Article
An acidic aqueous biphasic system (AcABS), in which the inorganic salt component of a traditional aqueous biphasic system (ABS) is replaced by the inorganic acid inherently present in typical hydrometallurgical leachate solution, is shown to selectively separate cobalt from nickel, a separation relevant to the recycling of nickel metal hydride (NiM...
Article
General considerations about urban mining and green solvents are first briefly discussed. Then, the use of green solvents in the recycling processes of technological objects present in urban mines is reviewed, focusing on metal recovery.
Patent
The application concerns a method for separating lanthanide from a metal alloy comprising at least one transition metal and at least one lanthanide, said method comprising the steps of: a) providing a metal alloy comprising at least one transition metal and at least one lanthanide, b) bringing the metal alloy into contact with an aqueous solution o...
Article
Full-text available
Waste electrical and electronic equipment (WEEE) is the fastest growing type of waste globally and is an important challenge due to its heterogeneity, intrinsic toxicity and potential environmental impact. However, WEEE also represents an important secondary source of critical and valuable elements and must be viewed as a resource within the contex...
Article
The complexation of cobalt cations (Co(II)) by dicyanamide (DCA–) in water and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([C1C4Pyrr][NTf2]) has been investigated by recording UV–vis spectra at 20 °C for solutions containing different ratios for the concentrations of DCA–vs. Co(II) (R = [DCA–]/[Co(II)]). The variation of the a...
Article
Full-text available
Extraction of U(VI), Eu(III) and Am(III) has been performed from acidic aqueous solutions (HNO3, HClO4) into the ionic liquid [C4mim][Tf2N] in which a new extracting task-specific ionic liquid, based on the CMPO unit {namely 1-[3-[2-(octylphenylphosphoryl)acetamido]propyl]-3-methyl-1H-imidazol-3-ium bis(trifluoromethane)sulfonamide, hereafter noted...
Article
Ionic-liquid-based aqueous biphasic systems (IL-based ABS) have demonstrated exceptional performance in bioseparation processes. However, IL-based ABS are of limited interest for metal extraction as most metals are not stable in their neutral or alkaline pH conditions. In the quest for better extraction systems for metals, the development of IL-bas...
Patent
La demande concerne un procédé d'extraction ou de séparation d'ions métalliques en utilisant une composition comprenant : - un liquide ionique de formule C +,-X, dans laquelle : - C + est un cation onium comprenant au moins une chaîne hydrocarbonée R 1 comprenant de 6 à 20 atomes de carbone - X P - est un anion de charge p, ledit liquide ionique ay...
Article
Ionic liquid-based acidic aqueous biphasic systems (AcABS) represent a promising alternative to solvent extraction process for the recovery of critical metals in which the substitution of the inorganic salt by an acid allows for the ‘one pot’ approach to the leaching and separation of metals. However, a more fundamental understanding of AcABS forma...
Article
The first instance of an acidic aqueous biphasic system (AcABS) based on tributyltetradecylphosphonium chloride ([P44414][Cl]) and an acid is here reported. This AcABS exhibits pronounced thermomorphic behavior and is shown to be applicable to the extraction of metal ions from concentrated acidic solutions. Metal ions such as cobalt(II), iron(III),...
Article
The first instance of an acidic aqueous biphasic system (AcABS) based on tributyltetradecylphosphonium chloride ([P44414][Cl]) and an acid is here reported. This AcABS exhibits pronounced thermomorphic behavior and is shown to be applicable to the extraction of metal ions from concentrated acidic solutions. Metal ions such as cobalt(II), iron(III),...
Article
Several mixtures of butyl acetate (BA) and an ionic liquid (1-methyl-3-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C1C8Pyrro][NTf2], 1-octyl-pyridinium bis(trifluoromethylsulfonyl)imide, [C8Pyr][NTf2]), 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide, [C1C4Im][NTf2] or 1-octyl-3-methyl-imidazolium bis(trifluoromethylsulfon...
Article
Liquid-liquid extraction studies of uranium(VI) were carried out from nitric acid medium using di-n-hexyloctanamide (DHOA) in several room-temperature ionic liquids (RTIL). The extraction of the metal ion as a function of nitric acid concen tration showed different trends based on the alkyl substituents of the RTIL. While the DU values decreased wi...
Article
Extraction of polyphenols, polysaccharides and organic acids present in a liquor issued from a pulping factory, so-called black liquor, was studied using two ionic liquids trihexyltetradecylphosphonium chloride ([P66614]Cl) and trihexyltetradecylphosphonium bromide ([P66614]Br). The extraction of each of the three compounds mentioned above was repo...
Article
A process for the separation of cerium from a lanthanide powder using ionic liquids is reported. In a first step, starting from a mixture of cerium(III) sulphate, neodymium(III) sulphate, lanthanum(III) chloride and praseodymium(III) chloride, cerium(III) was successfully oxidised into cerium(IV) under alkaline conditions, whereas all other lanthan...
Chapter
The extraction of metallic ions by the use of mixtures of water and ILs, possibly completed by mineral acids, salts, and/or extracting agents, leading to ionic-liquid-aqueous biphasic systems (IL-ABS), is critically reviewed. In this chapter, the extraction performance induced by temperature or concentration stimulus is considered. First, the IL-AB...
Article
The extraction of Pd(ii) and Rh(iii) from acidic solutions containing between 1 and 8 M HCl towards three ionic liquids, namely [P66614][Cl], [P66614][Br] and [P66614][DCA], based on the trihexyltetradecylphosphonium cation ([P66614]) and chloride, bromide or dicyanamide (DCA) anions, respectively, is reported. Extraction of Pd(ii) is quantitative...
Article
The extraction mechanism of Pt(IV) from aqueous HCl solutions towards the ionic liquid 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C1C8IM][NTf2]) is deciphered. To that end, aqueous speciation of Pt(IV) as a function of HCl was studied by 195Pt NMR. Influence of the concentration of HCl (ranging from 1 to 12 M) and of the initi...
Article
The C1C4im+ and Tf2N- solubilities in nitric aqueous phases have been measured for several ligand types and concentrations (0.04 M tributylphosphine oxide -TBPO, 0.05 M N,N'-dimethyl-N,N'-dibutylmalonamide -DMDBMA, 0.10 M 1-methyl-3-[4-(dibutylphosphinoyl)butyl]-3H-imidazol-1-ium bis-trifluoromethylsulphonylimidate -[C1imC4P(O)Bu2][Tf2N] and 1.1 M...
Article
The complex formation of nitrate ions with nickel(II) in dry [C4mim][Tf2N] ionic liquid (IL) was investigated by means of UV-visible spectrophotometry, isothermal titration calorimetry (ITC), extended X-ray absorption fine structure spectroscopy (EXAFS), and molecular dynamics (MD) simulations. EXAFS spectroscopy and MD simulations show that the so...
Article
A thorough investigation of the reference electrodes for electrochemical measurements is presented in three ionic liquids (ILs), namely 1-butyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide [BMIM][Tf2N], 1-octyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide [OMIM][Tf2N] and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)...
Article
We present new insights into the extraction of uranium(vi) from a nitric acid aqueous phase into 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquid ([C4mim][Tf2N]) using a malonamide extractant, namely N,N′-dimethyl-N,N′-dibutylmalonamide (DMDBMA). UV-vis absorption spectrophotometry and extended X-ray absorption fine struc...
Article
Full-text available
Solvent extraction of lanthanoids (La-Gd) with mixtures of a chelating extractants (HL), either 4-(4-fluorobenzoyl)-3-methyl-1-phenyl-pyrazol-5-one(HPMFBP) or 3-methyl-4-(4-methylbenzoyl)-1-phenyl-pyrazol-5-one (HPMMBP) and 1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedione (thenoyltrifluoroacetone, HTTA) has been studied in benzene. The composition of...
Article
Full-text available
A detailed NMR study on the possible interactions between a series of imidazolium based ionic liquids (1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide, RmimTf2N, n = 4, 6, 8, 10), and compounds commonly applied in the solvent extraction and separation of 4f and 5f-ions as acidic chelating agents and neutral extractants is presented....
Article
An investigation on a process designed for separating Pt(iv) and Pd(ii) dissolved in acidic aqueous solution containing HCl using two ionic liquids, 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([OMIM][NTf2]) and trihexyltetradecylphosphonium bromide (Cyphos 102), is presented. To this end, the single extraction of platinum in [OMI...
Data
Two Eu(III) complexes were synthesized using 4-acylpyrazolone ligands: 3-methyl-4-(4-methylbenzoyl)-1-phenylpyrazol-5-one (HPMMBP) and 3-methyl-1-phenyl-4-(4-phenylbenzoyl)-pyrazol-5-one (HPPMBP). The composition of the obtained solid complexes was determined as Eu(PMMBP)3.C2H5OH and Eu(PPMBP)3.3H2O based on elemental analysis and was further studi...
Article
Full-text available
Two Eu(III) complexes were synthesized using 4-acylpyrazolone ligands: 3-methyl-4-(4-methylbenzoyl)-1-phenyl-pyrazol-5-one (HPMMBP) and 3-methyl-1-phenyl-4-(4-phenylbenzoyl)-pyrazol-5-one (HPPMBP). The composition of the obtained solid complexes was determined as Eu(PMMBP)3·C2H5OH and Eu(PPMBP)3·3H2O based on elemental analysis and was further stud...
Article
Full-text available
The study of trivalent lanthanoid (La, Nd, Eu, Ho and Lu) extraction by two individual ligands, one acidic such as a pyrazolone derivative, 3-methyl-1-phenyl-4-(4-phenylbenzoyl)-pyrazol-5-one (HL), and one neutral such as 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis-(dimethylphosphinoylmethoxy)calix[4]arene (SIV), was performed in CHCl3 and in...
Article
We present new results on the liquid-liquid extraction of uranium (VI) from a nitric acid aqueous phase into a tri-n-butyl phosphate/1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (TBP/[C4 mim][Tf2 N]) phase. The individual solubilities of the ionic-liquid ions in the upper part of the biphasic system are measured over the whole acid...
Poster
Full-text available
Aqueous/ionic liquid (A-IL) biphasic systems have been examined in terms of water and acid solubilities in the IL-rich phase at ambient temperature. First, the biphasic mixtures were composed of acids of various concentrations (H+; Сl-;H+; NO3-, H+; ClO4- from lx10-2 to lxl0-4 mol dm-3 mainly) and four ionic liquids of the imidazolium family [C1Cni...
Article
Extraction of U(VI) and Pu(IV) using several tri-alkylamines such as tri-n-butylamine (TBA), tri-n-hexylamine (THA), tri-n-octylamine (TOA), and tri-iso-octylamine (TiOA) in room temperature ionic liquids, [Cnmim][Tf2N] (where n = 4, 6 or 8), was investigated from nitric acid as well as hydrochloric acid medium. In the absence of the amines, the ex...
Article
Aqueous–ionic liquid biphasic systems have been examined in terms of water and acid solubilities in the IL-rich phase at ambient temperature. The biphasic mixtures were comprised of acids of various concentrations (H+; Cl−, H+; \( {\text{NO}}_{3}^{ - } \), H+; \( {\text{ClO}}_{4}^{ - } \), mainly from 1 × 10−2 to 1 × 10−4 mol·dm−3) and four ionic l...
Article
Aqueous-ionic liquid (A-IL) biphasic systems have been examined in terms of deuterated water, acid, and IL cation and anion mutual solubilities in the upper (water-rich, in mole fraction) and lower phase of aqueous/IL biphasic systems at ambient temperature. The biphasic mixtures were composed of deuterated acids of various concentrations (mainly D...
Article
The electrochemistry of AuBr4− complexes extracted into ionic liquids [C8PYR][NTf2] or [C8MIM][NTf2] saturated with water and gas has been studied by cyclic voltammetry on a glassy carbon macro electrode and by linear voltammetry on a platinum microelectrode. Unlike AuCl4−, the reduction of AuBr4− to Au(0) is achieved following a one reduction step...
Article
Full-text available
Anionic complexes of iridium(IV) were extracted from acidic solutions of HCl using ionic liquids (IL). Influence of the cation structure of IL and of the aqueous phase pH on the distribution coefficients of IrCl62- was investigated. Liquid-liquid extraction and precipitation of iridium(IV) were studied. Iridium(IV) was precipitated out from aqueous...
Article
Full-text available
The complexation properties of a pyrazolone derivative, 3-methyl-1-phenyl-4-(4-trifluoromethylbenzoyl)-pyrazol-5-one (HL), in chloroform were examined and it was found that it possesses improved complexation ability in comparison with 4-benzoyl, 4-(4-methylbenzoyl) and 4-(4-fluorobenzoyl) derivatives. Mixed ligand chelate extractions of trivalent l...
Article
Full-text available
Aqueous-ionic liquid (A-IL) biphasic systems containing deuterated water, deuterated nitric acid (10−2 M to 7 M) and either [C1C4im+][Tf2N−], [C1C10im+][Tf2N−] or [Me3BuN+][Tf2N−] have been examined in terms of water and acid solubilities in the IL-rich phase and in terms of IL cation and anion solubilities in the water-rich phase. Other experiment...
Article
Ionic Liquids are of great interest in all fields of chemistry and material science. Apart from their "green" properties, their radioresistance and fantastic chemical versatility offer a new playground to nuclear chemists and others in view of liquid/liquid extraction of RE and actinides. Following a brief summary of RE and An liquid/liquid extract...
Article
The kinetics of metal transfer in the system Eu3+/HNO3//TODGA/[C1C4im][Tf2N], where TODGA is N,N,N′,N′-tetraoctyl diglycolamide, is shown to depend on the chemical conditions (nitric acid and TODGA concentrations) and the time needed to reach equilibrium which may vary from less than 10 min to more than 4 h. At [HNO3] = 4 M, a detailed kinetic stud...
Article
Full-text available
A general chemical model describing the extraction mechanism of cations from an acidified aqueous phase toward an ionic liquid phase in which an extracting agent is dissolved is proposed. On this basis, fits are made which recover very satisfactorily the variation of the distribution ratio as a function of [HNO(3)] for several experimental data set...
Article
The photophysics of 3,3′-diethylthiacarbocyanine iodide (DTCI), as a fluorescence probe, in liquid mixtures of dimethyl sulfoxide (DMSO) with either trimethyl(butyl)ammonium bis((trifluoromethyl)sulfonyl)imide ([N(4)111] [Tf2N]) or 1-butyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide ([bmim] [Tf2N]) was studied by means of steady-state a...
Article
Full-text available
Extraction of tetrachloroaurate or tetrabromoaurate anions has been carried out at acidic pHs (1 and 4) with several ionic liquids bearing halide or bis(trifluoromethanesulfonyl)imide NTf2− anions and cations 1-octyl-3-methylimidazolium, 1-octylpyridinium or 1-methyl-1-octylpyrrolidinium. The removal of gold anionic moieties from water was first st...
Article
Full-text available
The extraction of uranyl from acidic (HNO(3)) aqueous solutions toward an ionic liquid phase, C(1)-C(4)-imTf(2)N (1-methyl,3-butylimidazolium Tf(2)N), has been investigated as a function of initial acid concentration and ligand concentration for two different extracting moieties: a classical malonamide, N,N'-dimethyl-N,N'-dibutylmalonamide (DMDBMA)...
Article
The complexation between uranium(vi) and nitrate ions in a hydrophobic ionic liquid (IL), namely [BMI][NO(3)] (BMI = 1-butyl-3-methylimidazolium(+)), is investigated by EXAFS spectroscopy. It was performed by dissolution of uranyl nitrate UO(2)(NO(3))(2)·6H(2)O or UO(2)(Tf(2)N)(2) (Tf(2)N = bis(trifluoromethylsulfonyl)imide (CF(3)SO(2))(2)N(-)). Th...
Article
Full-text available
We have studied the extraction of four HA acids (HNO(3), HReO(4), HClO(4), HCl) to a hydrophobic ionic liquid (IL) 1-butyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)amide (BMI(+) Tf(2)N(-)) at room temperature, in a wide range of acidic concentrations in water. The effect of tributylphosphate (TBP) as co-solvent is investigated. According to...
Article
The complexation of perrhenate (ReO(4)(-)) anions by the uranyl (UO(2)(2+)) cation has been investigated by joint molecular dynamics simulations and spectroscopic (UV-vis, TRLFS, and EXAFS) studies in aqueous solution, acetonitrile, and three ionic liquids (ILs), namely, [Bmi][Tf(2)N], [Me(3)BuN][Tf(2)N], and [Bu(3)MeN][Tf(2)N] that are based on th...