Into Ionic Liquids Research Articles

Stability and growth behavior of transition metal nanoparticles in ionic liquids prepared by thermal evaporation: how stable are they really?

Recently we developed an access to metal- and metal-oxide colloids based on thermal evaporation of metals into ionic liquids (ILs). Here we present systematic studies on the long-time stability of gold and copper nanoparticles (NPs) in different ILs. The influence of metal concentration and temperature on the ripening of the as-prepared gold NPs in different ILs was investigated by transmission electron microscopy (TEM) and UV-vis absorption measurements. Short alkyl chain-length-methyl-imidazolium salts with weakly coordinating perfluorinated counter anions (PF(6), BF(4) or Tf(2)N, bis(trifluoromethanesulfonyl)amide) were found to be better stabilizers compared to ILs with cations bearing long alkyl chains (trihexyltetradecylphosphonium, 1-octyl-3-methylimidazolium) and anions of higher coordination strength (DCA, dicyanamide). In the latter ILs fast particle growth and agglomeration was observed. In the well-stabilizing ILs initially very small NPs form which undergo a similar ripening process at room temperature as at higher temperatures. The final particle size depends largely on the used IL and the metal and to a minor extent on the temperature. The metal concentration seems to be an unimportant factor.

Fabrication of Transition Metal Oxide Nanoparticles Highly Dispersed in Ionic Liquids by Sputter Deposition

Abstract Sputter deposition of transition metals W, Mo, Nb, and Ti into ionic liquids (ILs) produced corresponding metal oxide nanoparticles (NPs) smaller than 6 nm. The NPs were obtained in a highly dispersed manner without any additional stabilizing agent in ILs.

Recovery of Sugars from Ionic Liquid Biomass Liquor by Solvent Extraction

The dissolution of biomass into ionic liquids (ILs) has been shown to be a promising alternative biomass pretreatment technology, facilitating faster breakdown of cellulose through the disruption of lignin and the decrystallization of cellulose. Both biological and chemical catalysis have been employed to enhance the conversion of IL-treated biomass polysaccharides into monomeric sugars. However, biomass-dissolving ILs, sugar monomers, and smaller carbohydrate oligomers are all soluble in water. This reduces the overall sugar content in the recovered solid biomass and complicates the recovery and recycle of the IL. Near-complete recovery of the IL and the holocellulose is essential for an IL-based pretreatment technology to be economically feasible. To address this, a solvent extraction technique, based on the chemical affinity of boronates such as phenylboronic acid and naphthalene-2-boronic acid for sugars, was applied to the extraction of glucose, xylose, and cellobiose from aqueous mixtures of 1-ethyl-3-methylimidazolium acetate. It was shown that boronate complexes could extract up to 90% of mono- and disaccharides from aqueous IL solutions, 100% IL systems, and hydrolysates of corn stover containing IL. The use of boronate complexes shows significant potential as a way to recover sugars at several stages in ionic liquid biomass pretreatment processes, delivering a concentrated solution of fermentable sugars, minimizing toxic byproducts, and facilitating ionic liquid cleanup and recycle.

Extraction behavior of lanthanides using a diglycolamide derivative TODGA in ionic liquids

Liquid-liquid extraction of lanthanides from aqueous solutions into ionic liquids (ILs) has been investigated using N,N,N',N'-tetra(n-octyl)diglycolamide (TODGA) as an extractant, and compared with that in the isooctane system. Application of ILs as the extracting phase provided unprecedented enhancement of the extraction performance of TODGA for lanthanides compared with that of the isooctane system. Slope analysis confirmed that TODGA in ILs formed a 1:3 complex with La3+, Eu3+, or Lu3+. On the other hand, the molar ratios of species extracted into isooctane were 1:3 for La3+ or 1:4 for Eu3+ and Lu3+, depending on the atomic number of the lanthanide. The transfer of lanthanides with TODGA into ILs proceeded via a cation-exchange mechanism, in contrast to ion pair extraction in the isooctane system. Furthermore, we clarified that TODGA provided selectivity for the middle lanthanides in the ILs systems, but heavier lanthanides in the isooctane system.

Solvent Extraction and Stripping of Lanthanides into Ionic Liquids with a Multidentate Ligand

The extraction behavior of lanthanides from aqueous solutions into ionic liquids (ILs) and the stripping test have been investigated with N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) as a ligand. TPEN in ILs shows the extremely high extraction performance for lanthanides compared to that in chloroform. The stripping of lanthanides from ILs into a receiving phase is successfully achieved under acidic conditions. Furthermore, the leaching of TPEN from ILs into the receiving phase is negligible small, although almost all TPEN molecules in chloroform readily leach.

Extractive Solubilization, Structural Change, and Functional Conversion of Cytochrome c in Ionic Liquids via Crown Ether Complexation

This article reports on the extraction behavior of heme proteins from an aqueous phase into ionic liquids (ILs) with dicyclohexano-18-crown-6 (DCH18C6), and the structure-function relationship of cytochrome c (Cyt-c) dissolved in ILs. We have found that DCH18C6 enables transfer of Lys-rich proteins into ILs via supramolecular complexation. The hydrophobicity and functional groups of ILs have a great influence on protein partitioning, and a hydroxyl group-containing IL with DCH18C6 is capable of the quantitative partitioning of Cyt-c. On the other hand, protein transfer using conventional organic solvents is negligibly small. UV-visible, CD, and resonance Raman spectroscopic characterizations indicate that the sixth ligand Met 80 in the heme group of the Cyt-c-DCH18C6 complex in IL is replaced by other amino acid residues of the peptide chain and that a non-natural, six-coordinate, low-spin ferric heme structure is induced in IL. Solubilization of Cyt-c in IL causes the environmental change of the heme vicinity of Cyt-c, which triggers the functional conversion of Cyt-c from an electron-transfer protein to peroxidase. The Cyt-c-DCH18C6 complex in IL provides remarkably high peroxidase activity compared with native Cyt-c, because of enhancement of the affinity for H2O2.

Feasibility of Ionic Liquids as Alternative Separation Media for Industrial Solvent Extraction Processes

Extraction of rare earth metals into ionic liquids (ILs) from aqueous solutions was investigated using octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) as an extractant. Use of ILs greatly enhanced the extraction efficiency and selectivity of CMPO for metal ions compared to when n-dodecane was used as the extracting solvent. The extraction mechanism has been studied by slope analysis and extraction tests, and these confirmed that the metal extraction proceeds via a cation-exchange mechanism. Furthermore, stripping of metals from ILs into an aqueous phase by complexing agents and recycling of the extracting ILs phase was successfully accomplished.

The Electrolysis of Molten Antimony Sulfide

Adding redox activity into ionic liquids (ILs) extends their practical roles beyond an inert ionic conductor or electrolyte for applications in electrochemical energy storage. Especially for supercapatteries, redox ILs are desirable because they can contribute to increasing the charge storage capacity by merging the capacitive and Nernstian storage mechanisms without compromising their intrinsic wide potential windows. Several prospects of redox ILs are identified and discussed for optimising performance in supercapatteries.