Search Results (63)

In this paper, polymer inclusion membranes (PIMs) were created using poly(vinyl chloride)-based alkyl sulfonic acid derivatives as ion carriers and dioctyl terephthalate as a plasticizer for the selective separation of Pb(II), Cu(II), and Cd(II) ions from aqueous nitrate solutions. The ion carriers were dinonylnaphthalenesulfonic acid (DNNSA) and nonylbenzenesulfonic acid (NBSA). The influence of the carrier and the plasticizer concentration in the membrane on the transport efficiency was investigated. For the PIM system, 15% wt. of carrier (DNNSA, NBSA), 20% wt. of plasticizer, and 65% wt. of polymer poly(vinyl chloride) PVC were the optimal proportions, with which the process was the most effective. Research on the transport kinetics has shown that the transport of Pb(II) ions through PIMs containing acidic carriers adheres to a first-order kinetics equation, which is characteristic of a facilitated transport mechanism. The activation parameter for these processes suggests that the high performance of these ion carriers is associated with the immobilization of the carrier within the membrane. It was found that PIMs based on DNNSA facilitate the selective separation of Pb(II)/Cu(II) and Pb(II)/Cd(II) mixtures, achieving high separation factors. Full article

Polymer inclusion membranes (PIMs) have been reported to be useful for the selective separation of numerous metal ions, with multiple applications in areas such as analytical chemistry, water quality monitoring, water treatment, and metal recovery. This review aims to update the recent advancements related to PIM technology in metal ion separation, with a particular emphasis on environmentally friendly production and applications. PIMs have many advantages over classical liquid–liquid extraction, such as excellent selectivity, ease of use with simultaneous extraction and back-extraction, stability, and reusability. PIMs typically consist of a base polymer, a carrier, and, if necessary, a plasticizer, and can therefore be tailored to specific analytes and specific matrices. Consequently, numerous studies have been carried out to develop PIMs for specific applications. In analytical chemistry, PIMs have been used mostly for analyte preconcentration, matrix separation, speciation analysis, and sensing. They can be used as passive sampling tools or integrated into automated water monitoring systems. PIMs are also widely studied for the extraction and purification of valuable metals in the frame of the circular economy, as well as for wastewater treatment. Even if they are a greener alternative to classical metal extraction, their production still requires petroleum-based polymers and toxic and volatile solvents. In recent years, there has been a clear trend to replace classical polymers with biodegradable and bio-sourced polymers and to replace the production of PIMs using toxic solvents with those based on green solvents or without solvents. According to the published literature, environmentally friendly PIM-based techniques are a highly recommended area of future research for metal ion separation directed toward a wide range of applications. Full article

Selective separation of hydroxylamine (HA) from metal ions to prepare high-purity HA remains a challenge. In this study, given that HA can react with carbonyl compounds, TTA (thenoyltrifluoroacetone) was screened as a carrier to prepare the polymer inclusion membrane (PIM), which was used to separate HA from metal and inorganic acid ions. The experimental results demonstrated that the PIM exhibited good selectivity for HA. During the PIM process, the proton gradient served as a driving force to transport NH₂OH(I). The electrodialysis (ED) process was used to efficiently and continuously provide proton gradient without introducing other ions, which coupled with PIM to separate HA. Under the optimum conditions, the separation factors of NH₂OH(I)/Na(I) and NH₂OH(I)/K(I) were 30.81 and 35.11; the purity of HA was 99.4%, indicating that the PIM-ED process can be used for high-purity preparation of HA. Full article

The room temperature ionic liquid trihexyl(tetradecyl)phosphonium decanoate ([P₆₆₆₁₄][Dec]) was employed in the liquid-liquid extraction of Co(II) from hydrochloric acid solutions in the presence of Ni(II). The extraction performance in liquid-liquid separations showed a strong dependence on the acid content of the feed aqueous solution. The best performance in terms of extracted cobalt and selectivity was obtained when the feed contained a HCl concentration above 6 M On the contrary, when the experiment was performed in absence of HCl, a lower extraction and Co/Ni selectivity were obtained. This behavior has been rationalized by considering the protonation of the [Dec]⁻ anion and the different Co(II)/Ni(II) speciation in HCl media. Moreover, polymer inclusion membranes (PIMs) were prepared using PVC and [P₆₆₆₁₄][Dec] at different weight rations. Only the PIM formulated with a 30:70/PVC:[P₆₆₆₁₄][Dec] weight ratio demonstrated effective extraction of Co(II) from the HCl solution. The extraction efficiency and selectivity of the PIM was comparable to that from biphasic liquid experiments at 8 M HCl. The results of this study constitute a promising background for further practical developments of carboxylate-based ILs applied in Co/Ni separations. Full article

In this study, an ionic liquid-based polymer inclusion membrane (IL-PIM) made of (50% polymer-50% CyphosIL104) was used to extract and separate the rare earth elements (REEs) Y, La, Nd, and Sm in chloride solutions. The effect of extraction time and pH was studied to optimize the extraction and separation conditions. The four REEs were effectively extracted at pH 4–5 from both single and mixed metals solutions. However, at pH 2, only Y was extracted. The recovery of the extracted REEs from the loaded PIM was achieved using HNO₃ and H₂SO₄. In the case of La, it was quantitatively back-extracted with H₂SO₄ after a contact time of 1 h, while up to 4 h was necessary to recover 70% of the extracted Y, Sm, and Nd. Extraction isotherms were studied, and the Freundlich isotherm model was the most adequate to describe the interaction between the PIM and the REEs. Finally, the developed PIM was investigated for the extraction of REEs from mixtures containing other metals, which showed great selectivity for the REEs. Full article

This article reports on the extraction of palladium(II) from hydrochloric acid (HCl) solutions using polymer inclusion membranes (PIMs) containing tetrabutylammonium bromide (TBAB) as the ion carrier. The membranes were based on cellulose triacetate (CTA) as the polymer support. The main aim of this study is to determine the possibility of TBAB’s application as the effective ion carrier/extractant of Pd(II) from hydrochloric acid solutions. At first, the effect of the hydrochloric acid concentration in the aqueous phase on palladium(II) extraction was investigated. Next, cellulose triacetate membranes with TBAB as the carrier were prepared and applied for the recovery of Pd(II) from HCl solutions. As a result of the investigations, the optimal composition of the receiving phase was determined to be 0.5 M thiourea in 0.1 M hydrochloric acid. The effect of the acid concentration in the source phase was investigated. The results show a linear decrease in the permeability coefficient and initial flux of palladium(II) with an increase in the hydrochloric acid concentration in the source phase. The separation of Pd(II) from Pt(IV) from the hydrochloric acid solution was also studied. The transport rate of Pd(II) was higher than Pt(IV). The separation coefficient S_Pd/Pt was 1.3. The results show that transport through PIMs with TBAB can be used as an effective method to recover Pd(II) from hydrochloric acid, especially at a low concentration of this acid. Full article

The effective purification of aqueous solutions of methylene blue dye was tested using polymer inclusion membranes (PIMs) that contained cellulose triacetate (CTA) as a polymer base, o-nitrophenyl octyl ether (o-NPOE) as a plasticizer, and meso-tetra methyl tetrakis-[methyl-2-(4-acetlphenoxy)] calix[4]pyrrole (KP) as a carrier. Scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy were used to define the microstructure and surface of PIMs. Experimental results showed that, with an increased concentration of methylene blue in an aqueous solution, the removal percentage also increased. Further observation showed that the flux increased with the rise in the source phase pH values from 3 to 10. The carrier and plasticizer content in the membrane significantly influenced the membrane’s transport properties. The optimal composition of the membrane in percent by weight for KP was 74% plasticizer; 18% support, and 8% carrier. The maximum MB removal (93.10%) was achieved at 0.10 M HCl solution as the receiving phase. It was shown that the membrane with optimal composition showed good reusability and enabled the easy and spontaneous separation of methylene blue from aqueous solutions. Full article

This study investigated the influence of various plasticizers commonly used in the manufacture of polymer inclusion membranes (PIMs), such as 2-nitrophenyl octyl ether (NPOE), phthalates, adipates, and sebacates on the mechanical, thermal, and transport properties of membranes. Additionally, butyl stearate (BTS), chosen for its non-toxic nature compared to phthalates and its cost-effectiveness relative to adipates and sebacates, was evaluated as a plasticizer in PIMs for the first time. All plasticizers were incorporated in PIMs made of either cellulose triacetate (CTA) or poly(vinyl chloride) (PVC) as the base polymers and the task-specific ionic liquid trioctylmethylammonium thiosalicylate (TOMATS) as the carrier. The plasticizers were found to significantly affect the characteristics of membrane hydrophilicity, mechanical flexibility, and thermal stability. Transport experiments using Hg(II) as a model target ion revealed that, for CTA-based PIMs, the plasticizer did not significantly affect transport efficiency. However, for PVC-based PIMs, BTS exhibited better efficiency when compared to NPOE. These findings highlight the potential of BTS as an attractive alternative to currently used plasticizers in PVC-based PIM formulations. Full article

The systematic increase in the use of rare earth elements (REEs) in various technologically advanced products around the world (e.g., in electronic devices), the growing amount of waste generated by the use of high-tech materials, and the limited resources of naturally occurring REE ores resulted in an intensive search for effective and environmentally safe methods for recovering these elements. Among these methods, techniques based on the application of various types of liquid membranes (LMs) play an important role, primarily due to their high efficiency, the simplicity of membrane formation and use, the utilization of only small amounts of environmentally hazardous reagents, and the possibility of simultaneous extraction and back-extraction and reusing the membranes after regeneration. However, because both primary and secondary sources (e.g., waste) of REEs are usually complex and contain a wide variety of components, and the selectivity and efficiency of LMs depend on many factors (e.g., the composition and form of the membrane, nature of the recovered ions, composition of the feed and stripping phases, etc.), new membranes are being developed that are “tailored” to the properties of the recovered rare earth elements and to the character of the solution in which they occur. This review describes the latest achievements (since 2019) related to the recovery of a range of REEs with the use of various liquid membranes (supported liquid membranes (SLMs), emulsion liquid membranes (ELMs), and polymer inclusion membranes (PIMs)), with particular emphasis on methods that fall within the trend of eco-friendly solutions. Full article

The selective extraction of metals from aqueous solutions is a very important stage in the hydrometallurgical processing of metallic waste. Leach solutions are usually a multicomponent mixture. The main impurity of aqueous solutions obtained after leaching using inorganic acids is iron. In this work, the membrane separation of iron(III) from nickel(II), cobalt(II), and lithium(I) was studied. The facilitated transport of metal ions using polymer inclusion membranes (PIMs) with tetrabutylammonium bromide (TBAB) as an ion carrier under various conditions was analyzed in detail. Several factors, such as the ion carrier concentration in the membrane as well as the effect of the inorganic acid concentration in the source/receiving phases on the kinetic parameters, were investigated. The results show that ionic liquid TBAB is a very selective ion carrier of Fe(III) towards Ni(II), Co(II), and Li(I). Full article

A partial least squares (PLS) quantitative chemometric method based on the analysis of the mid-Fourier transform infrared spectroscopy (MID-FTIR) spectrum of polymer inclusion membranes (PIMs) used for the extraction of Cr(VI) from aqueous media is developed. The system previously optimized considering the variables membrane composition, extraction time, and pH, is characterized in terms of its adsorption isotherm, distribution coefficient, extraction percent, and enrichment factor. A Langmuir-type adsorption behavior with K_L = 2199 cm³/mmol, q_max = 0.188 mmol/g, and 0 < R_L < 1 indicates that metal adsorption is favorable. The characterization of the extraction reaction is performed as well, showing a 1:1 Cr(VI):Aliquat 336 ratio, in agreement with solvent extraction data. The principal component analysis (PCA) of the PIMs reveals a complex pattern, which is satisfactorily simplified and related to Cr(VI) concentrations through the use of a variable selection method (iPLS) in which the bands in the ranges 3451–3500 cm⁻¹ and 3751–3800 cm⁻¹ are chosen. The final PLS model, including the 100 wavelengths selected by iPLS and 10 latent variables, shows excellent parameter values with root mean square error of calibration (RMSEC) of 3.73115, root mean square error of cross-validation (RMSECV) of 6.82685, bias of −1.91847 × 10⁻¹³, cross-validation (CV) bias of 0.185947, R² Cal of 0.98145, R² CV of 0.940902, recovery% of 104.02 ± 4.12 (α = 0.05), sensitivity% of 0.001547 ppb, analytical sensitivity (γ) of 3.8 ppb, γ⁻¹: 0.6 ppb⁻¹, selectivity of 0.0155, linear range of 5.8–100 ppb, limit of detection (LD) of 1.9 ppb, and limit of quantitation (LQ) of 5.8 ppb. The developed PIM sensor is easy to implement as it requires few manipulations and a reduced number of chemical compounds in comparison to other similar reported systems. Full article

A unique facilitation on the transport flux of Cu(II) was investigated by using modified polymer inclusion membranes (PIMs). LIX^®84I-based polymer inclusion membranes (LIX^®-based PIMs) using poly(vinyl chloride) (PVC) as support, 2-nitrophenyl octyl ether (NPOE) as plasticizer and Lix84I as carrier were modified by reagents with different polar groups. The modified LIX^®-based PIMs showed an increasing transport flux of Cu(II) with the help of ethanol or Versatic acid 10 modifiers. The metal fluxes with the modified LIX^®-based PIMs were observed varying with the amount of modifiers, and the transmission time was cut by half for the modified LIX^®-based PIM cast with Versatic acid 10. The physical–chemical characteristics of the prepared blank PIMs with different Versatic acid 10 were further characterized by using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), contract angle measurements and electro-chemical impedance spectroscopy (EIS). The characterization results indicated that the modified LIX^®-based PIMs cast with Versatic acid 10 appeared to be more hydrophilic with increasing membrane dielectric constant and electrical conductivity that allowed better accessibility of Cu(II) across PIMs. Hence, it was deduced that hydrophilic modification might be a potential method to improve the transport flux of the PIM system. Full article

Five mathematical models for transport description in polymer inclusion membranes (PIMs) were presented and compared via regression analysis. The applicability of the models was estimated through the examination of experimental data of Zn(II), Cd(II), Pb(II), and Cu(II) ions transported by typical carriers. In four kinetic models, a change in the feed and stripping solution volume was taken into account. The goodness of fit was compared using the standard error of the regression, Akaike information criterion (AIC), Bayesian (Schwarz) information criterion (BIC), and Hannan–Quinn information criterion (HQC). The randomness distribution in the data was confirmed via a nonparametric runs test. Based on these quantities, appropriate models were selected. Full article

Pollution of the environment, including water resources, is currently one of the greatest challenges due to emerging new contaminants of anthropogenic origin. Of particular concern are emerging organic pollutants such as pharmaceuticals, endocrine disruptors, and pesticides, but also other industrial pollutants, for example, synthetic dyes. The growing demand for environmentally friendly and economical methods of removing emerging contaminants and synthetic dyes from wastewater resulted in increased interest in the possibility of using techniques based on the application of polymer inclusion membranes (PIMs) for this purpose. PIM-based techniques are promising methods for eliminating emerging contaminants and synthetic dyes from aqueous solutions, including wastewater, due to high efficiency, membranes versatility, ease/low cost of preparation, and high selectivity. This review describes the latest developments related to the removal of various emerging contaminants and synthetic dyes from aqueous solutions using PIMs over the past few years, with particular emphasis on research aimed at increasing the effectiveness and selectivity of PIMs, which may contribute to wider use of these methods in the future. Full article

The growing demand for environmentally friendly and economical methods of removing toxic metal ions from polluted waters and for the recovery of valuable noble metal ions from various types of waste, which are often treated as their secondary source, has resulted in increased interest in techniques based on the utilization of polymer inclusion membranes (PIMs). PIMs are characterized by many advantages (e.g., the possibility of simultaneous extraction and back extraction, excellent stability and high reusability), and can be adapted to the properties of the removed target analyte by appropriate selection of carriers, polymers and plasticizers used for their formulation. However, the selectivity and efficiency of the membrane process depends on many factors (e.g., membrane composition, nature of removed metal ions, composition of aqueous feed solution, etc.), and new membranes are systematically designed to improve these parameters. Numerous studies aimed at improving PIM technology may contribute to the wider use of these methods in the future on an industrial scale, e.g., in wastewater treatment. This review describes the latest achievements related to the removal of various metal ions by PIMs over the past 3 years, with particular emphasis on solutions with potential industrial application. Full article