Separation and recovery of critical metal ions using ionic liquids

Separation and purification of critical metal ions such as rare-earth elements (REEs), scandium and niobium from their minerals is difficult and often determines if extraction is economically and environmentally feasible. Solvent extraction is a commonly used metal-ion separation process, usually favored because of its simplicity, speed and wide scope, which is why it is often employed for separating trace metals from their minerals. However, the types of solvents widely used for the recovery of metal ions have adverse environmental impact. Alternatives to solvent extraction have been explored and advances in separation technologies have shown commercial establishment of liquid membranes as an alternative to conventional solvent extraction for the recovery of metals and other valuable materials. Liquid membrane transport incorporates solvent extraction and membrane separation in one continuously operating system. Both methods conventionally use solvents that are harmful to the environment, however, the introduction of ionic liquids (ILs) over the last decade is set to minimize the environmental impact of both solvent extraction and liquid membrane separation processes. ILs are a family of organic molten salts with low or negligible vapour pressure which may be formed below 100 ℃. Such liquids are also highly thermally stable and less toxic. Their ionic structure makes them thermodynamically favorable solvents for the extraction of metallic ions. The main aim of this article is to review the current achievements in the separation of REE, scandium, niobium and vanadium from their minerals, using ILs in either solvent extraction or liquid membrane processes. The mechanism of separation using ILs is discussed and the engineering constraints to their application are identified.     

Fabrication of ZnO nanorods using metal nanoparticles as growth nuclei

ZnO nanorods were produced by pulsed laser deposition (PLD). Drops of nanoparticle colloid (gold or silver) were placed on silica substrates to form growth nuclei. All nanoparticles were monocrystalline, with well-defined crystal surfaces and a negative electrical charge. The ZnO nanorods were produced in an off-axis PLD configuration at oxygen pressure of 5 Pa. The growth of the nanorods started from the nanoparticles in different directions, as one nanoparticle could become a nucleus for more than one nanorod. The low substrate temperature used indicates the absence of a catalyst during the growth of the nanorods. The diameters of the fabricated 1-D ZnO nanostructures were in the range of 50-120 nm and their length was determined by the deposition time.     

Preparation of AgX (X = Cl, I) nanoparticles using ionic liquids

Nanoparticles of silver halides have been prepared by mixing silver halide powder with a single liquid phase consisting of an ionic liquid, isooctane, n-decanol and water. Much higher nanoparticle concentrations may be formed with ionic liquids using this new simple method than are found with conventionally applied surfactants. This method also emphasizes the applicability of ionic liquids as versatile components in microemulsions and as solvents for the synthesis of nanomaterials. The effect on the nanoparticles of changing the composition of the liquid mixtures and the nature of the ionic liquid is analysed. High nanoparticle concentrations were only found with chloride based ionic liquids, indicating the importance of the ionic liquid anion in the mechanism of the reaction.     

Quantification of halide in ionic liquids using ion chromatography

The determination of chloride impurities in ionic liquids using ion chromatography is described. A wide range of cation-anion combinations may be analyzed using ion chromatography, including water-immiscible ionic liquids. For all ionic liquids studied, the limit of quantification for chloride was found to be below 8 ppm.     

硅材料固载离子液体挂载金属催化剂应用研究进展

离子液体具有独特的性质,将具有高表面积的硅材料用离子液体进行改性,再挂载金属化合物,可制得集离子液体中均相催化和固体非均相催化体系于一身的新型催化剂,用于多种有机反应.这些催化剂具有高效、高选择性、离子液体用量少、产品易分离和催化剂易回收等优点,因有望用于化工过程的固定床反应器而受到关注.本文综述了2005年以来硅材料固载离子液体挂载金属催化剂的应用研究成果.     

The controlled synthesis of stable gold nanoparticles in quaternary ammonium ionic liquids by simple heating

Stable gold nanoparticle (AuNP) colloids were synthesized in a class of quaternary ammonium-based room-temperature ionic liquids (QAILs), [Me(3)NC(2)H(4)OH](+)[Zn(n)Cl(2n + 1)](-) (n = 1 or 2), by heating in air at 135-145?°C. The QAIL was employed as a solvent, a reducing agent, and as a stabilizer. The size of the QAIL-AuNPs can be varied between 20 and 40 nm by changing the reaction temperature. A symproportionation reaction was employed to further decrease the size of the AuNPs by the addition of Au(3+) ions. The surface covering of QAIL on the AuNPs had a significant impact on their surface plasmon resonance (SPR), which was red-shifted. The AuNPs synthesized by this simple and environmentally friendly reaction can be realized in several minutes and also exhibit high stability and good reproducibility, providing a new facile approach to metal nanoparticle preparation.     

Decolorization of ionic liquids for spectroscopy

It has been widely recognized that although ionic liquids should be colorless, they are frequently not. Colored samples appear to be pure by most analytical techniques (e.g., NMR spectroscopy, mass spectrometry, HPLC, and ion chromatography), and there have been many attempts to identify the source of color in our own laboratories and others-after 20 years the best that can be said is that the impurities are at a very low level (probably parts per billion) with very high molar extinction coefficients. In this paper, we do not identify these impurities but describe a practical method for removing them for spectrochemical applications. We clearly note that the method is not "green", but we anticipate that it will only be applied to the small volumes of ionic liquids required for fundamental spectroscopic studies in academia but not in industrial processes.     

Fabrication of planar, layered nanoparticles using tri-layer resist templates

A simple and universal pathway to produce free multilayer synthetic nanoparticles is developed based on lithography, vapor phase deposition and a tri-layer resist lift-off and release process. The fabrication method presented in this work is ideal for production of a broad range of nanoparticles, either free in solution or still attached to an intact release layer, with unique magnetic, optical, radioactive, electronic and catalytic properties. Multi-modal capabilities are implicit in the layered architecture. As an example, directly fabricated magnetic nanoparticles are evaluated to illustrate the structural integrity of thin internal multilayers and the nanoparticle stability in aggressive biological environments, which is highly desired for biomedical applications.     

Fabrication of capped gold nanoparticles by using various amino acids

The production of gold nanoparticles (GNPs) by amino acid is one of the most attractive and interesting subjects in nanobiotechnology. In this study, amino acids have been utilised as a reducing agent and also an agent for capping GNPs. The GNPs were prepared using a reduction solution containing gold cations with optimum concentration of gold salt (5?mM), and also functionalised by glutamic acid, phenylalanine and tryptophan with optimum concentration of amino acids (25?mM). The optimum condition of gold solution and amino acids were achieved by ultraviolet–visible spectroscopy. The size of nanoparticles was obtained 5–20, 10–20 and 20–30?nm, respectively, by transmission electron microscopy and dynamic light scattering techniques. The results obtained from experimental and quantum calculations confirm that amino acids have strong bond while they have anion binding. Moreover, the free carboxylic groups of capped GNPs are one of the suitable and capable beads for binding biological agents. As a result, the medical applications of amino acids and proteins can be used as a practical method due to the strong interaction of peripheral amine groups with nanoparticles.     

Processing-structure–property relationships of SWNT–epoxy composites prepared using ionic liquids

Experimentally achieved mechanical properties of nanotube–epoxy composites fail to match theoretical expectations; shortcomings are mainly attributed to poor dispersion. The elastic modulus of a well-dispersed single walled carbon nanotube (SWNT)-ionic liquid-epoxy composite was evaluated in tension and compared to predictions by a micromechanics homogenization model. The model takes into account the mechanical properties of the constituent phases in addition to SWNT aspect ratio, spatial distribution, dispersion, and agglomeration. These parameters were evaluated using information obtained via scanning and transmission electron microscopy. The Young’s modulus of the composite shows excellent agreement with the model at low concentrations, while discrepancies at high SWNT concentrations are possibly due to composite processing limitations. At high concentrations the uncured composite mixture is above the rheological percolation threshold. As the polymer network reaches its maximum capacity for well-dispersed SWNTs, increasing volume fraction does not result in further significant reinforcing effects.     

Combined modeling and experimental studies of hydroxylated silica nanoparticles

Nanotechnology offers several opportunities to solve problems related with Oil and Gas industry. One of them is the possibility to use hard nanoparticles to control the wettability phenomena between the three-phase system (oil–water–minerals) at reservoir conditions of temperature, pressure, and salinity. Here, we present a combined experimental and modeling study of hydroxylated silica nanoparticles as candidate for improved oil recovery applications. In this work, we mainly focus on development of more realistic SiO₂-nanoparticle models and validating them against the experimental data. An efficient Monte Carlo scheme is proposed to generate realistic SiO₂ nanoparticle atomistic models (3–5 nm). Structural and spectroscopic properties such as Raman and Infrared were obtained through Molecular Dynamics (MD) calculations using a force field that mimics an ab initio data. We have also used Fourier transform infrared spectroscopy to identify chemical functional groups present in 5 nm unmodified (bare) silica nanoparticle dispersions. A good agreement between the MD simulations and experiments has been observed.     

Fabrication and actuation of ionic polymer metal composites patterned by combining electroplating with electroless plating

The novel fabrication technique that patterns the multiple electrodes of the ionic polymer metal composite actuators was developed to mimic the swimming and flapping locomotion of a living thing. The developed method is to combine electroplating with the electroless chemical reduction using the patterned mask. The advantages of this fabrication method are that the initial compositing between the polymer and platinum particles can be assured by the chemical reduction method, and the thickness of each electrode can be controlled easily and rapidly by electroplating. By using the fabricated actuator with a multiple degree of freedom, the oscillatory and undulatory waves of the flexible membrane actuator was generated and a twisting motion was also realized to verify the possibility of mimicking the fish-like locomotion. Present results show that this novel method combining electroplating with electroless plating can be a promising technique to easily pattern multiple electrodes and to implement the biomimetic motion of the polymer actuators with good mechanical bending performance.     

氨基酸离子液体应用研究进展

氨基酸离子液体是一类新型的功能化离子液体,除了具有常规离子液体的低蒸汽压、低熔点、宽液程、溶解性好和稳定性高等性质外,还具有很强的氢键网络结构、稳定的手性中心、双配位基团、生物兼容性和可生物降解等许多独特的性质。本文综述了近年来氨基酸离子液体在溶解生物质、气体吸收、手性分离、催化等方面的应用研究进展。     

Toxicity and biodegradability of imidazolium ionic liquids

Several bioassays have been carried out to analyze the toxicity and biodegradability of several imidazolium ionic liquids (ILs) in aqueous phase. The synthetized compounds consist of an imidazolium cation with two alkyl substituents in positions 3 (R1) and 1 (R2) and a counter-ion. The alkyl substituent R1 has been fixed as a methyl group and the effect of the alkyl chain length (C1-C8) of the other substituent (R2) has been tested. Moreover, the influence of diverse counter-ions A- (Cl-, PF6, XSO4-) has been analyzed. Acute toxicity and EC50 values of each compound in the aqueous solution have been determined by using the Microtox standard procedure. Biodegradability of IL has been determined by measuring BOD5 of aqueous samples containing IL and/or D-glucose and the IL residual content and/or d-glucose concentration after this assay. The viability of the microorganisms used in the BOD5 has been related to the ATP in the samples, measured by a bioluminescence assay. All the ILs tested were not biodegradable in the considered conditions. Besides, it was found that the shorter the chain length of side chain R2, the lower the toxic effect is. On the contrary, the anion has a little effect on the IL toxicity.     

离子液体在高分子合成中的应用

离子液体作为一种"绿色溶剂",具有很多独特的物理化学性能,可以应用于自由基聚合、阳离子聚合、配位聚合、电化学聚合等反应体系。本文阐述了离子液体的特点及合成方法,介绍了离子液体在高分子合成中的应用。     

Modification of magnetic properties of metal nanoparticles using nanotemplate approach

We demonstrate a nanotemplate approach by which different metal magnetic nanoparticles (Ni–Co, Ni–Fe and Co–Pt alloy particles) can be fabricated on a polyimide (PI) film. The process relies on the high interfacial energy between deposited metal and the PI film which forces the deposited metal film to preferentially nucleate on the pre-existing Ni seed particles. During subsequent thermal annealing, the deposited metal film coalesced onto the Ni seed particles to form a monolayer of magnetic nanoparticles on the PI film. Furthermore, the deposition/annealing can be repeated to change both size and constituent of the nanoparticles by introducing a different metal film during deposition. Potentially, any metal film can be deposited onto the Ni seed particles provided that the metal does not react with the Ni seed particles to create a monolayer of metal nanoisland structures with desire magnetic properties.     

Fabrication of coaxial metal nanocables using a self-assembled peptide nanotube scaffold

The design and fabrication of complex nanostructures with specific geometry and composition is one of the main challenges of nanotechnology. Here we demonstrate the devise of metal-insulator-metal, trilayered, coaxial nanocables. Such coaxial geometry may give rise to useful and unique electromagnetic properties. We have fabricated these nanostructures using a scaffold of self-assembled peptide nanotubes. Gold nanoparticles were bound to the surface of peptide nanotubes via a common molecular recognition element that was included in various linker peptides. This enabled us to promote site-specific metal reduction and to create the coaxial nanostructure. Using electron microscopy, 1H NMR spectra, and energy-dispersive X-ray analysis, we monitored the different steps within the process, gaining further understanding of its mechanism.     

Fabrication of size-controlled polyimide nanoparticles

Polyimide particles were fabricated through the two-steps imidization of poly(amic acid) particles prepared by using reprecipitation method. PAA and PI nanoparticles were all spherical, and the changes of particle size, its distribution, and morphology were not observed before and after the imidization. The preparation of PI nanoparticles size-controlled between ca. 20-500 nm was also achieved by changing the experimental conditions, temperature of the poor solvent, the composition of two kind of poor solvent, and PAA-NMP solution concentration.