Search Results (42)

Membrane capacitive deionization (MCDI) is an electrochemical ion separation process that combines ion-exchange membranes (IEMs) with porous carbon electrodes to enhance desalination efficiency and address the limitations of conventional capacitive deionization (CDI). In this study, a cation-exchange membrane (CEM) embedded with a metal–organic framework (MOF) was developed to effectively separate monovalent and multivalent cations in influent solutions via MCDI. To fabricate CEMs with high monovalent ion selectivity, ZIF-8 was incorporated into sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO) at various weight ratios. The resulting membranes were systematically characterized using diverse electrochemical methods. The ZIF-8-embedded CEMs demonstrated a sieving effect based on differences in ion size and hydration energy, achieving excellent permselectivity for monovalent ions. MCDI tests using the prepared CEMs showed a Na⁺ ion removal rate exceeding 99% in Na⁺/Mg²⁺ and Na⁺/Ca²⁺ mixed feed solutions, outperforming a commercial membrane (CSE, Astom Corp., Tokyo, Japan), which achieved a removal rate of 94.1%. These findings are expected to provide valuable insights for advancing not only MCDI but also other electro-membrane processes capable of selectively separating specific ions. Full article

The widespread application of electrodialysis is constrained by the high cost of ion exchange membranes, necessitating the development of affordable alternatives. This study focuses on the fabrication and performance evaluation of cation exchange membranes made from polyethersulfone (PES) and sulfonated polyethersulfone (sPES). Membranes were synthesized through phase inversion with varying solvent evaporation times, using N-Methyl-2-Pyrrolidone (NMP) as the solvent. The structural and functional modifications were confirmed using FTIR, XPS, and AFM techniques. Performance tests identified optimal electrodialysis results for PES membranes with a 3 h solvent evaporation time and for sPES membranes with a 1 h evaporation time. Under varying operational conditions, including applied voltage, flow rates, and feed solutions, sPES membranes demonstrated superior performance, underscoring their potential for cost-effective brackish water desalination applications. Full article

The objective of this study is to evaluate the degradation of end-of-life BWRO membranes sourced from a factory in France by analyzing their water permeability, roughness, and chemical composition in order to diagnose the level of degradation incurred during their first life cycle in water softening. Following this, two new applications for the end-of-life BWRO membranes were investigated: (i) as ultrafiltration membranes (UF) for domestic effluent treatment and (ii) as cation exchange membranes (CEM) for use in fungal microbial fuel cells (FMFC). The UF membrane was renovated with an acetic acid treatment and, subsequently, used for domestic effluent filtration. The cation exchange membrane was developed in two steps: (i) chlorine treatment and (ii) the deposition of an Amer Sil layer, a functional coating formed by an interpenetrating polymer network (IPN) made of sulfonated polyether sulfone (S-PES) in a cross-linked matrix of acrylic acid and divinylbenzene. Full article

Electrodialysis (ED) has already been applied to recover nickel in galvanizing processes, allowing nickel recovery and the production of a treated effluent with demineralized water quality. However, the growth in ED use is still limited by the production and commercialization of ion-selective membranes, currently limited to a few large companies. Therefore, this paper presents the development of homogeneous cationic and anionic membranes made from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) for ED use. Cationic membranes were prepared by the sulfonation reaction of PPO under different experimental conditions (PPO:H₂SO₄ molar ratio and reaction time). Anionic membranes were prepared by the bromination reaction of PPO, followed by the amination reaction. The membranes were characterized for their chemical and electrochemical properties, including ion exchange capacity, conductivity, thermal stability, and surface morphology. The optimal conditions for cationic membrane sulfonation were achieved with a 1:4.4 PPO:H₂SO₄ molar ratio, and a reaction time of 0.5 h. For anionic membranes, the best results were obtained with bromination, with a PPO:NBS (N-Bromosuccinimide) molar ratio of 1:0.5, followed by 14 days of amination. Overall, 91.8% chloride, 90.9% sulfate, and 85.5% nickel ion extraction was achieved, highlighting PPO as a promising polymer for the development of anionic and cationic ion-selective membranes for ED. Full article

The combination of ion exchange membranes with carbon quantum dots (CQDs) is a promising field that could lead to significant advances in water treatment. Composite membranes formed by sulfonated poly(ether ether ketone) (SPEEK) with embedded CQDs were used for the detection and removal of heavy metal ions, such as lead and cadmium, from water. SPEEK is responsible for the capture of heavy metals based on the cation exchange mechanism, while CQDs detect their contamination by exhibiting changes in fluorescence. Water-insoluble “red” carbon quantum dots (rCQDs) were synthesized from p-phenylenediamine so that their photoluminescence was shifted from that of the polymer matrix. CQDs and the composites were characterized by several techniques: FTIR, Raman, UV/VIS, photoluminescence, XPS spectroscopies, and AFM microscopy. The heavy metal ion concentration was analyzed by inductively coupled plasma–optical emission spectroscopy (ICP-OES). The concentration ranges were 10.8–0.1 mM for Pb²⁺ and 10.0–0.27 mM for Cd²⁺. SPEEK/rCQDs showed a more pronounced turn-off effect for lead. The composite achieved 100% removal efficiency for lead and cadmium when the concentration was below a half of the ion exchange capacity of SPEEK. The regeneration of membranes in 1 M NaCl was also studied. A second order law was effective to describe the kinetics of the process. Full article

Ammonia is a promising carbon-free fuel, but current methods to produce ammonia are energy intensive. New methods are thereby needed, with one promising method being electrochemical nitrogen reduction cells. Efficient cell operation requires robust catalysts but also efficient membrane separators that permit the selective transport of ions while minimizing the transport of the products across the cell. Commercial membranes have an unknown morphology which makes designing improved cells challenging. To address this problem, we synthesized a series of membranes with controlled crosslinking density and chemical composition to understand their impact on ammonium transport. Higher crosslinking density led to lower ammonium permeability. At the highest crosslinking density, similar ammonium permeability was observed independent of the water volume fraction and hydrophobicity of the monomers. These results suggest new directions to develop membranes with reduced ammonium crossover to improve the efficiency of these electrochemical cells. Full article

Cation exchange membranes (CEMs) play a significant role in the transition to a more sustainable/green society. They are important components for applications such as water electrolysis, artificial photosynthesis, electrodialysis and fuel cells. Their synthesis, however, is far from being sustainable, affecting safety, health and the environment. This review discusses and evaluates the possibilities of synthesizing CEMs that are more sustainable and green. First, the concepts of green and sustainable chemistry are discussed. Subsequently, this review discusses the fabrication of conventional perfluorinated CEMs and how they violate the green/sustainability principles, eventually leading to environmental and health incidents. Furthermore, the synthesis of green CEMs is presented by dividing the synthesis into three parts: sulfonation, material selection and solvent selection. Innovations in using gaseous SO3 or gas–liquid interfacial plasma technology can make the sulfonation process more sustainable. Regarding the selection of polymers, chitosan, cellulose, polylactic acid, alginate, carrageenan and cellulose are promising alternatives to fossil fuel-based polymers. Finally, water is the most sustainable solvent and many biopolymers are soluble in it. For other polymers, there are a limited number of studies using green solvents. Promising solvents are found back in other membrane, such as dimethyl sulfoxide, Cyrene™, Rhodiasolv^® PolarClean, TamiSolve NxG and γ-valerolactone. Full article

Novel composite membranes employing a poly(ether-block-amide) (PEBAX) copolymer and sulfonated montmorillonite (S-MMT) as a filler were developed. The ratio of polyether to polyamide blocks was investigated using PEBAX 2533 and PEBAX 4533 based on the membrane properties and performance. Additionally, the effect of the changing filler ratio was monitored. The interaction between the S-MMT as nanofiller and the polymer matrix of PEBAX2533 and PEBAX4533 as well as the crystalline nature and thermal and mechanical stability of the composite membranes were evaluated using Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and tensile test. The composite membrane with 7 wt.% S-MMT showed the highest water uptake of 21% and 16% and an acceptable swelling degree of 16% and 9% for PEBAX 2533 and PEBAX 4533 composite membranes, respectively. In terms of water uptake and ion exchange capacity at room temperature, the new un-protonated membranes are superior to un-protonated Nafion. Meanwhile, with the same S-MMT content, the ion conductivity of PEBAX 2533 and PEBAX 4533 composite membranes is 2 and 1.6 mS/cm, and their ion exchange capacity is 0.9 and 1.10 meq/g. Full article

Fluorinated proton-exchange membranes (PEMs) based on graft copolymers of dehydrofluorinated polyvinylidene fluoride (D-PVDF), 3-sulfopropyl acrylate (SPA), and 1H, 1H, 2H-perfluoro-1-hexene (PFH) were prepared via free radical copolymerization and characterized for fuel cell application. The membrane morphology and physical properties were studied via small-(SAXS) and wide-angle X-ray scattering (WAXS), SEM, and DSC. It was found that the crystallinity degree is 17% for PEM-RCF (co-polymer with SPA) and 16% for PEM-RCF-2 (copolymer with SPA and PFH). The designed membranes possess crystallite grains of 5–6 nm in diameter. SEM images reveal a structure with open pores on the surface of diameters from 20 to 140 nm. Their transport and electrochemical characterization shows that the lowest membrane area resistance (0.9 Ωcm²) is comparable to perfluorosulfonic acid PEMs (such as Nafion^®) and polyvinylidene fluoride (PVDF) based CJMC cation-exchange membranes (ChemJoy Polymer Materials, China). Key transport and physicochemical properties of new and commercial membranes were compared. The PEM-RCF permeability to NaCl diffusion is rather high, which is due to a relatively low concentration of fixed sulfonate groups. Voltammetry confers that the electrochemical behavior of new PEM correlates to that of commercial cation-exchange membranes, while the ionic conductivity reveals an impact of the extended pores, as in track-etched membranes. Full article

The present work discusses the influence of the thickness of MF-4SK perfluorinated sulfonic cation-exchange membranes on their electrotransport properties in hydrochloric acid solutions. It is found that diffusion permeability and conductivity are primarily determined with the specific water content of the membranes and increase with their increase. Analysis of the contribution of reverse diffusion through the membrane to the value of the limiting current shows that it can reach 20% for membranes with a thickness of 60 μm. A study of the characteristics of the fuel cell with perfluorinated membranes of different thicknesses shows that the membrane thickness affects both the ohmic resistance of the membrane-electrode assembly and the diffusion limitations of proton transport in polymer electrolytes. Full article

The hydration of ions and charge groups controls electro mass transfer through ion exchange systems. The self-diffusion and local mobility of water molecules as well as lithium cations in poly (4-styrenesulfonic acid) and its lithium, sodium and cesium salts were investigated for the first time using pulsed-field gradient NMR (PFG NMR) and NMR relaxation techniques. The temperature dependences of the water molecule and Li⁺ cation self-diffusion coefficients exhibited increasing self-diffusion activation energy in temperature regions below 0 °C, which is not due to the freezing of parts of the water. The self-diffusion coefficients of water molecules and lithium cations, as measured using PFG NMR, are in good agreement with the self-diffusion coefficients calculated based on Einstein’s equation using correlation times obtained from spin-lattice relaxation data. It was shown that macroscopic water molecules’ and lithium cations’ transfer is controlled by local particles jumping between neighboring sulfonated groups. These results are similar to the behavior of water and cations in sulfonic cation exchanger membranes and resins. It was concluded that polystyrenesulfonic acid is appropriate model of the ionogenic part of membranes based on this polymer. Full article

To achieve high throughput, low-pressure drops, and high adsorption capacity of Cr(VI) and Pb(II) in industrial wastewater treatment, cellulose membranes containing cationic and anionic groups were fabricated, respectively. In this process, cost-effective cotton fabrics were oxidized using sodium periodate, followed by quaternary ammonium or sulfonation modifications. The chemical composition, surface morphology, and thermal and mechanical properties of the cellulose membranes were investigated by ATR-FTIR, solid-state NMR, SEM, TGA, and tensile experiments. Quaternary ammonium, aldehyde, and sulfonate groups were distributed on the cationic/anionic cellulose fibers as adsorption sites, which issue remarkable adsorption capability to the cellulose membranes. The highly toxic Cr(VI) and Pb(II) ions were used to challenge the adsorption capacity of the cationic and anionic cellulose membranes, respectively. The maximum adsorption capacities of Cr(VI) and Pb(II) ions were 61.7 and 63.7 mg/g, respectively, suggested by Langmuir isotherms, kinetics, and thermodynamics in the static experiments. The dynamic adsorption capability of cationic cellulose membranes against Cr(VI) ions was determined and compared with that of commercially available anionic-exchange membranes. Spiral wound filtration cartridges were fabricated by cationic and anionic cellulose membranes, respectively, and were used to adsorb Cr(VI) and Pb(II) from lab-made wastewater, respectively. The cationic cellulose cartridge can purify 4.4 L of wastewater containing 1.0 mg/L of Cr(VI) ions with a 100% removal ratio, while the pressure drop was retained at 246 Pa. Similarly, the anionic cellulose cartridge exhibited even more impressive adsorption capability; the removal ratio against Pb(II) was 99% when 8.6 L of 1.0 mg/L of Pb(II) ions containing wastewater was treated, and the pressure drop was retained at 234 Pa. A composite cartridge fabricated by the integration of cationic and anionic cellulose membranes was successfully employed to purify the wastewater containing Cr(VI) and Pb(II) simultaneously. The possible adsorption mechanism was proposed, and the recycling ability of the cellulose membranes was also discussed. Full article

The interconnection of ionogenic channel structure, cation hydration, water and ionic translational mobility was revealed in Nafion and MSC membranes based on polyethylene and grafted sulfonated polystyrene. A local mobility of Li⁺, Na⁺ and Cs⁺ cations and water molecules was estimated via the ¹H, ⁷Li, ²³Na and ¹³³Cs spin relaxation technique. The calculated cation and water molecule self-diffusion coefficients were compared with experimental values measured using pulsed field gradient NMR. It was shown that macroscopic mass transfer is controlled by molecule and ion motion near sulfonate groups. Lithium and sodium cations whose hydrated energy is higher than water hydrogen bond energy move together with water molecules. Cesium cations in possession of low hydrated energy are directly jumping between neighboring sulfonate groups. Cation Li⁺, Na⁺ and Cs⁺ hydration numbers (h) in membranes were calculated from ¹H chemical shift water molecule temperature dependences. The values calculated from the Nernst–Einstein equation and the experimental conductivity values were close to each other in Nafion membranes. In MSC membranes, calculated conductivities were one order of magnitude more compared to the experimental ones, which is explained by the heterogeneity of the membrane pore and channel system. Full article

The possibility of using various types of ion-exchange membranes in diffusion dialysis for the separation of sulfuric acid and nickel sulfate has been evaluated. The process of the dialysis separation of a real waste solution from an electroplating facility containing 252.3 g/L of sulfuric acid, 20.9 g/L of nickel ions and small amounts of zinc, iron, copper ions, etc. has been studied. Heterogeneous cation-exchange membrane containing sulfonic groups and heterogeneous anion-exchange membranes with different thicknesses (from 145 μm to 550 μm) and types of fixed groups (four samples with quaternary ammonium base and one sample with secondary and tertiary amines) have been used. The diffusion fluxes of sulfuric acid, nickel sulfate, and the total and osmotic fluxes of the solvent have been determined. The use of a cation-exchange membrane does not allow the separation of the components, since the fluxes of both components are low and comparable in magnitude. The use of anion-exchange membranes makes it possible to efficiently separate sulfuric acid and nickel sulfate. Anion-exchange membranes with quaternary ammonium groups are more effective in the diffusion dialysis process, while the thin membrane turns out to be the most effective. Full article

The features of the electrochemical behavior of experimental heterogeneous ion-exchange membranes with different mass fractions of sulfonated cation-exchange resin (from 45 to 65 wt%) have been studied by voltammetry during electrodialysis. Electromembrane systems with 0.01 M NaCl solution and with a mixed 0.01 M NaCl + 0.05 M phenylalanine (Phe) solution have been investigated. A significant influence of the ion-exchanger content on the parameters of current-voltage curves (CVCs) was established for the first time. Electrodialysis of the sodium chloride solution revealed a decrease in the length of the limiting current plateau and in the resistances of the second and third sections of the CVCs with an increase in the resin content in the membrane. The fact of the specific shape of the CVCs of all studied cation-exchange membrane samples in mixed solutions of the mineral salt and the amino acid was established. A specific feature of current-voltage curves is the presence of two plateaus of the limiting current and two values of the limiting current, respectively. This phenomenon in electromembrane systems with neutral amino acids has not been found before. The value of the first limiting current is determined by cations of the mineral salt, which are the main current carriers in the system. The presence of the second plateau and the corresponding second limiting current is due to the appearance of additional carriers due to the ability of phenylalanine as an organic ampholyte to participate in protolytic reactions. In the cation-exchange electromembrane system with the phenylalanine containing solution, two mechanisms of H⁺/OH⁻ ion generation through water splitting and acid dissociation are shown. The possibility of the generation of H⁺/OH⁻ ions at the enriched solution/cation-exchange membrane interface during electrodialysis of amino acid containing solutions is shown for the first time. The results of this study can be used to improve the process of electromembrane demineralization of neutral amino acid solutions by both targeted selection or the creation of new membranes and the selection of effective current operating modes. Full article