ORCID Profile
0000-0003-4768-3606
Current Organisation
KU Leuven
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Publisher: Elsevier BV
Date: 07-2019
Publisher: Elsevier BV
Date: 07-2004
Publisher: Wiley
Date: 28-01-2010
Abstract: A series of nitrile-functionalized ionic liquids were found to exhibit temperature-dependent miscibility (thermomorphism) with the lower alcohols. Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trifluoromethylsulfonyl)imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C(1)C(1CN)Pyr)(2)(Tf(2)N)(4)] and [Co(C(1)C(2CN)Pyr)(6)][Tf(2)N](8), which were isolated from ionic-liquid solutions, gave an insight into the coordination chemistry of functionalized ionic liquids. Smooth layers of cobalt metal could be obtained by electrodeposition of the cobalt-containing ionic liquids.
Publisher: Elsevier BV
Date: 11-2021
Publisher: Wiley
Date: 09-02-2021
DOI: 10.1002/AIC.17219
Abstract: The synergic solvent extraction system of tri‐ n ‐butyl phosphate (TBP) and FeCl 3 (or ionic liquids, ILs) has been extensively studied for selective extraction of Li from Mg‐containing brines. However, Cyanex 923 (C923), which extracts many metals stronger than TBP, has not yet been examined for Li/Mg separation. Here, we report on the unexpected observation that the C923/FeCl 3 system has opposite Li/Mg selectivity compared to the TBP/FeCl 3 system. Detailed investigations show that the opposite selectivity of the C923/FeCl 3 (or IL) system is due to three factors: (1) the strong extraction of Fe by C923 leads to a low concentration of [FeCl 4 ] − in the system, which is essential for Li extraction (2) C923 in combination with an IL extracts Mg strongly by an ion‐pair mechanism (3) most importantly, C923 extracts Mg by solvation, resulting in an insufficient concentration of C923 for Li extraction. The unexpected poor Li/Mg selectivity of C923 highlights the irreplaceable role of TBP in the selective recovery of Li.
Publisher: American Chemical Society (ACS)
Date: 20-04-2022
Publisher: American Chemical Society (ACS)
Date: 03-06-2021
Publisher: American Chemical Society (ACS)
Date: 10-06-2011
DOI: 10.1021/JP2027675
Abstract: Two series of 1-alkylpyridinium and N-alkyl-N-methylpiperidinium ionic liquids functionalized with a nitrile group at the end of the alkyl chain have been synthesized. Structural modifications include a change of the alkyl spacer length between the nitrile group and the heterocycle of the cationic core, as well as adding methyl or ethyl substituents on different positions of the pyridinium ring. The anions are the bromide and the bis(trifluoromethylsulfonyl)imide ion. All the bis(trifluoromethylsulfonyl)imide salts as well as the bromide salts with a long alkyl spacer were obtained as viscous liquids at room temperature, but some turned out to be supercooled liquids. In addition, pyrrolidinium and piperidinium ionic liquids with two nitrile functions attached to the heterocyclic core have been prepared. The crystal structures of seven pyridinium bis(trifluoromethylsulfonyl)imide salts are reported. Quantum chemical calculations have been performed on model cations and ion pairs with the bis(trifluoromethylsulfonyl)imide anion. A continuum model has been used to take solvation effects into account. These calculations show that the natural partial charge on the nitrogen atom of the nitrile group becomes more negative when the length of the alkyl spacer between the nitrile functional group and the heterocyclic core of the cation is increased. Methyl or methoxy substituents on the pyridinium ring slightly increase the negative charge on the nitrile nitrogen atom due to their electron-donating abilities. The position of the substituent (ortho, meta, or para) has only a very minor effect on the charge of the nitrogen atom. The (15)N NMR spectra of the bis(trifluoromethylsulfonyl)imide ionic liquids were recorded with the nitrogen-15 nucleus at its natural abundance. The chemical shift of the (15)N nucleus of the nitrile nitrogen atom could be correlated with the calculated negative partial charge on the nitrogen atom.
Publisher: American Chemical Society (ACS)
Date: 05-08-2019
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7RA09150H
Abstract: A solvometallurgical process based on acetic acid was developed for the recovery of lead from iron-rich residues (matte and slag).
Publisher: Elsevier BV
Date: 08-2018
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9GC02983D
Abstract: Copper is extracted from sulfidic ores by a leaching-electrodeposition system, thereby producing metallic copper and regenerating the oxidizing agent FeCl 3 .
Publisher: Elsevier BV
Date: 2021
Publisher: AIP Publishing
Date: 15-06-2020
DOI: 10.1063/5.0011756
Abstract: The protic ionic liquid diethylmethylammonium methanesulfonate ([DEMA][OMs]) was analyzed in depth by differential scanning calorimetry (DSC), nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, and broadband dielectric spectroscopy (BDS) under anhydrous conditions. Karl Fischer titration, NMR, and FT-IR spectra confirmed the high purity of [DEMA][OMs]. The melting point (37.7 °C) and the freezing point (14.0 °C) obtained by DSC agree well with the values determined by BDS (40.0 °C and 14.0 °C). The dc conductivity (σdc) above the melting/freezing point obeys the Vogel–Fulcher–Tammann (VFT) equation well, and thus, the proton conduction in [DEMA][OMs] is assumed to be dominated by the vehicle mechanism. In contrast, the σdc below the melting/freezing point can be fitted by the Arrhenius equation separately, and therefore, the proton conduction is most likely governed by the proton hopping mechanism. The non-negligible influence of previously reported low water content on the physicochemical properties of [DEMA][OMs] is found, indicating the importance of reducing water content as much as possible for the study of “intrinsic” properties of protic ionic liquids.
Publisher: American Chemical Society (ACS)
Date: 19-11-2021
Publisher: American Chemical Society (ACS)
Date: 12-02-2015
DOI: 10.1021/CG501792M
Publisher: Wiley
Date: 20-01-2009
Abstract: The dissolution process of metal complexes in ionic liquids was investigated by a multiple-technique approach to reveal the solvate species of the metal in solution. The task-specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf(2)N]) is able to dissolve stoichiometric amounts of the oxides of the rare-earth elements. The crystal structures of the compounds [Eu(2)(bet)(8)(H(2)O)(4)][Tf(2)N](6), [Eu(2)(bet)(8)(H(2)O)(2)][Tf(2)N](6) x 2 H(2)O, and [Y(2)(bet)(6)(H(2)O)(4)][Tf(2)N](6) were found to consist of dimers. These rare-earth complexes are well soluble in the ionic liquids [Hbet][Tf(2)N] and [C(4)mim][Tf(2)N] (C(4)mim = 1-butyl-3-methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, (1)H, (13)C, and (89)Y NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X-ray absorption fine structure) and HEXS (high-energy X-ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry.
Publisher: Elsevier BV
Date: 06-2022
Publisher: Wiley
Date: 24-06-2019
Publisher: American Chemical Society (ACS)
Date: 31-10-2019
Publisher: Wiley
Date: 07-07-2020
DOI: 10.1002/AIC.16545
Publisher: Wiley
Date: 04-02-2021
DOI: 10.1002/AIC.17213
Abstract: Several molecular polar solvents have been used as solvents of the more polar phase in the solvent extraction (SX) of metals. However, the use of hydrophilic ionic liquids (ILs) as solvents has seldomly been explored for this application. Here, the hydrophilic IL ethylammonium nitrate (EAN), has been utilized as a polar solvent in SX of transition metal nitrates by tri‐ n ‐butyl phosphate (TBP). It was found that the extraction from EAN is considerably stronger than that from a range of molecular polar solvents. The main species of Co(II) and Fe(III) in EAN are likely [Co(NO 3 ) 4 ] 2− and [Fe(NO 3 ) 4 ] − , respectively. The extracted species are likely Fe(TBP) 3 (NO 3 ) 3 and a mixture of Co(TBP) 2 (NO 3 ) 2 and Co(TBP) 3 (NO 3 ) 2 . The addition of H 2 O or LiCl to EAN reduces the extraction because the metal cations coordinate to water molecules and chloride ions stronger than to nitrate ions. This study highlights the potential of using hydrophilic ILs to enhance SX of metals.
Publisher: American Chemical Society (ACS)
Date: 24-12-2019
Publisher: Wiley
Date: 21-04-2020
DOI: 10.1002/AIC.16246
Publisher: Elsevier BV
Date: 05-2017
Publisher: American Chemical Society (ACS)
Date: 21-06-2019
No related grants have been discovered for Koen Binnemans.