Manin, Andrey Dmitrievich

Lysova A.A., Manin A.D., Golubenko D.V., Ponomarev I.I., Altynov V.A., Hilal N., Yaroslavtsev A.B.

Yurova P.A., Stenina I.A., Manin A.D., Golubenko D.V., Yaroslavtsev A.B.

Surface modification of heterogeneous MA-41 anion-exchange membranes with cerium oxide particles, including those with a surface functionalized with phosphoric acid groups, was carried out. The resulting composite membranes were characterized by SEM, TGA, IR spectroscopy, and voltammetry. For membranes in various ionic forms, their conductivity, the number of anion transfers, as well as the selective permeability coefficients of singly and doubly charged anions in the process of electrodialysis desalting were determined. The modifying layer of cerium oxide practically does not change the conductivity of the membranes, but increases their selectivity to singly charged anions. Thus, the value of the selective permeability coefficient $$P({\text{C}}{{{\text{l}}}^{ - }}{\text{/SO}}_{4}^{{2 - }})$$ of the modified MA-41 membrane increases from 0.82 to 1.01, and $$P({\text{NO}}_{3}^{ - }{\text{/SO}}_{4}^{{2 - }})$$ increases from 1.38 to 1.60.

Golubenko D.V., Manin A.D., Wu L., Xu T., Yaroslavtsev A.B.

The scientific community has shown great interest in the selectivity of anion-exchange membranes (AEMs), particularly regarding their ability to monovalent-ions selective transport. In this work, we have studied the selectivity of an original anion-exchange membrane and a layer-by-layer (LbL) surface-modified membrane in the electrodialysis (ED) desalination of sodium chloride and sodium sulfate mixture in a lab-scale cell. The effect of various experimental factors on the desalination process and the selectivity of the separation of ions with different charges, such as the composition of the concentrate compartment, electrolyte concentrations in the concentrate and diluate compartments (0.004–0.5 M), the specific current value (0.82–9.0 mA/cm2), the desalination time, and the stirring of solution were considered. To explain the observed patterns, diffusion experiments and numerical simulations using the COMSOL® software package were carried out. Our findings demonstrate that the method chosen for conducting the benchmark desalination of a mixture of chlorides and sulfates can significantly affect the values of the selectivity coefficients and the accuracy of their determination for both standard and surface-modified membranes. For the latter, varying the desalination conditions leads to improved P(Cl/SO4) due to modification of up to 40 %.

Manin A., Golubenko D., Novikova S., Yaroslavtsev A.

The possibility of targeted change of the properties of ion exchange membranes by incorporation of various nanoparticles into the membranes is attracting the attention of many research groups. Here we studied for the first time the influence of cerium phosphate nanoparticles on the physicochemical and transport properties of commercial anion exchange membranes based on quaternary ammonium-functionalized polystyrenes, such as heterogeneous Ralex® AM and pseudo-homogeneous Neosepta® AMX. The incorporation of cerium phosphate on one side of the membrane was performed by precipitation from absorbed cerium ammonium nitrate (CAN) anionic complex with ammonium dihydrogen phosphate or phosphoric acid. The structures of the obtained hybrid membranes and separately synthesized cerium phosphate were investigated using FTIR, P31 MAS NMR, EDX mapping, and scanning electron microscopy. The modification increased the membrane selectivity to monovalent ions in the ED desalination of an equimolar mixture of NaCl and Na2SO4. The highest selectivities of Ralex® AM and Neosepta® AMX-based hybrid membranes were 4.9 and 7.7, respectively. In addition, the modification of Neosepta® membranes also increased the resistance to a typical anionic surfactant, sodium dodecylbenzenesulfonate.

Manin A.D., Golubenko D.V., Yurova P.A., Yaroslavtsev A.B.

To improve the selectivity of cation-exchange membranes to the transfer of lithium with respect to magnesium during the electrodialysis desalination of lithium and magnesium sulfates solutions, the surface of a commercial cation-exchange membrane based on sulfated polystyrene was modified with cerium(III, IV) and zirconium phosphates. Upon incorporation of phosphate particles, the Li/Mg selectivity coefficients of the membranes increased up to 113%.

Golubenko D.V., Manin A.D., Wang Y., Xu T., Yaroslavtsev A.B.

Recently, the selectivity of ion-exchange membranes and its control have been the subject of numerous fundamental and applied studies. This paper reports an enhanced monovalent anion selectivity of hybrid membrane based on the FujiFilm® Type I anion-exchange membrane and in situ synthesized cerium phosphate (CeP) with a gradient distribution over the membrane thickness. The Cl/SO 4 -selectivity coefficient ( P(Cl/SO 4 ) ) of hybrid membranes reached 6.2. The effect of modification on the Cl/SO 4 selectivity passed through a minimum as the total concentration of the external solution increased from 0.04 M to 1 M. For low concentration electrolytes, Cl/SO 4 -selectivity improving was attributed to partial neutralization of positive fixed charges by negative fixed charges of cerium phosphate, which causes an effective decrease of ion-exchange capacity and reduction of electrostatic selectivity factor favouring sulfate transport; for high concentration electrolytes, to the formation of narrow transport channel between the surface of the inorganic nanoparticle and the pore wall, which causes a decrease of sulfate transport due to the size sieving effect. The hybrid membranes and cerium phosphate were characterized using ATR FTIR and 31 P MAS NMR spectroscopy, XRD analysis and scanning electron microscopy with EDX microanalysis. • Monovalent ion selectivity of AEMs was improved by cerium phosphate modification. • Up to a 55% increase in the Cl/SO4-selectivity coefficient was observed. • Selectivity improvement depends on the external electrolyte concentration. • It is assumed that a change in the separation mechanism causes this dependence.

Li A., Wu Y., Wu Q., Zhao R., Zhong Z., Yang R., Liu Y., Xia X., Zuo K.

Bozorov Y., Turaev K., Alikulov R., Karimov M., Muminov B., Berdimurodov E., Eliboev I., Demir M., Yusuff A.S., Elangovan N.

Rosentreter H., Scope C., Oddoy T., Lerch A., Meier-Haack J.

Jie Lim Z., Kho M., Chen X., Goh K.B.

Elozeiri A.A., Dykstra J.E., Lammertink R.G., Rijnaarts H.H.

Chinello D., Post J., de Smet L.C.

Cha Y.Y., Lee C., Kim H., Lee G.G., Nam S.E., Lee J.S.

With the surge in electric vehicle sales, managing spent batteries has become critical. The significant rare metal content in batteries has driven interest in recovering these metals from industrial wastewater. Electrodialysis (ED) stands out for its eco-friendliness, low energy consumption, and compatibility with other technologies. This review highlights recent advancements in ED, including integrating nanofiltration (NF) for enhanced selectivity and diffusion dialysis (DD) for pretreatment to improve conductivity and energy efficiency. Innovations in ion exchange membranes (IEMs), such as monovalent-selective and functionalized membranes, have boosted ion separation performance. Strategies like bipolar membrane ED (BMED) and chelating agents enhance recovery efficiency, while anti-fouling techniques like pulsed electric fields and surface modifications prolong membrane lifespan. Energy efficiency improvements include optimizing electrical systems and adopting multistage or selective ED setups. Scaling ED systems for industrial applications involves addressing challenges like resistance and leakage through advanced design and monitoring. Despite progress, further innovation is needed to improve selectivity, reduce fouling, and enhance system reliability. By advancing materials and integrating complementary technologies, ED can serve as a sustainable solution for recovering rare metal ions and treating wastewater, aligning with circular economy goals.

Lysova A.A., Manin A.D., Golubenko D.V., Ponomarev I.I., Altynov V.A., Hilal N., Yaroslavtsev A.B.

Ponomarev I.I., Volkova Y.A., Skupov K.M., Vtyurina E.S., Ponomarev I.I.

Interphase boundary interactions are essential for high-temperature polymer electrolyte membrane fuel cell membrane electrode assembly (MEA) operation. Interactions between the self-phosphorylating polybenzimidazole (PBI)-6F coating on a carbon nanofiber electrode and the self-phosphorylating proton-conducting membrane during MEA operation would improve the cell performance. The presented approach represents a novel path for the development of a PBI membrane-based MEA.

He R., Li W., Zhu J., He T.

Ahmad M., Ahmed M., Ali A., Wani T.A., Khalid K., Ali I.

Yurova P.A., Stenina I.A., Manin A.D., Golubenko D.V., Yaroslavtsev A.B.

Heterogeneous anion-exchange MA-41 membranes were surface modified with cerium oxide, incl. that with a surface functionalized with phosphoric acid groups. Composite membranes were characterized by SEM, TGA, IR spectroscopy, and voltammetry; their conductivity in various ionic forms, anion transfer numbers, and selectivity coefficients for the separation of singly and doubly charged anions during electrodialysis desalination were determined. The modifying layer of cerium oxide practically does not change conductivity of the composite membranes, but increases their monovalent selectivity. E.g., the P(Cl /SO42–) selectivity of the modified MA-41 membrane increases from 0.82 to 1.01, and the P(NO3 /SO42–) selectivity – from 1.38 to 1.60.

Liao J., Wang T., Xu Y., Zhang Q., Tang Y., Mu J., Ang E.H., Yao Y., Xu Y., Shen J.

Mono-valent selective ion-exchange membrane, as the core component of selective electrodialysis (SED), has received extensive attention. In this work, we report a mono-valent selective anion-exchange membrane (AEM), which was fabricated with distorted poly(aryl ether sulfone) and decorated with bifunctional side-chains providing anion exchange groups and hydrophobic segments. By tuning the length of the hydrophobic side-chains, the nanophase separation within AEMs was finely tuned, evidenced by an ionic cluster size of about 0.47 nm from SAXS analysis. The optimized AEM (PAES-TA-7 AEM) shows a very low water swelling ratio of 6.4%, signaling good dimensional stability. The perm-selectivity () of PAES-TA-7 AEM during ED reached 107 at 2.5 mA∙cm−2 (ion flux: 2.69 × 10−8 mol·cm−2·s−1 at 90 min) significantly exceeding that of the commercial Neosepta ACS (11; 2.08 × 10−8 mol·cm−2·s−1). It is inferred that the ion channels, resulting from nanophase separation between the side-chains and the backbone, as well as the free volume cavity created by the distorted backbone, significantly contribute to the smooth transport of the Cl– ions through the AEM with less resistance. As a result, it is believed that this work offers a useful strategy to advance the monovalent anion-selective membranes.

Ivanets A.I., Razumovskaya D.V., Prozorovich V.G., Kouznetsova T.F.

Adsorbents based on lithium manganese double oxides Li1.33Mn1.67O4 with a spinel structure were synthesized using the sol–gel method. The influence of temperature during synthesis and conversion to the H-form, as well as the conditions of the adsorption experiment, on the adsorption capacity of the resulting adsorbents was investigated. It was found that increasing the synthesis temperature of Li1.33Mn1.67O4 oxides from 500 to 600 °C leads to a decrease in the adsorption capacity for Li+ ions from 6.60 to 1.62 mmol g−1 at an adsorption temperature of 50 °C.

Faddeev N.A., Kuriganova A.B., Leontyev I.N., Smirnova N.V.

The platinum catalysts based on carbon black and carbon nanotubes supports have been obtained via pulse alternating current technique. The synthesized Pt/C catalysts showed better electric transport characteristics and the carbon monoxide poisoning resistance in comparison with the commercial Pt/C owing to both the size of the platinum nanoparticles and their agglomeration on the support surface, and the morphology of the carbon support.

Lu C., Chen Z., Wu Y., Zhang Y., Wang F., Hu C., Qu J.

Golubenko D.V., Manin A.D., Wu L., Xu T., Yaroslavtsev A.B.

The scientific community has shown great interest in the selectivity of anion-exchange membranes (AEMs), particularly regarding their ability to monovalent-ions selective transport. In this work, we have studied the selectivity of an original anion-exchange membrane and a layer-by-layer (LbL) surface-modified membrane in the electrodialysis (ED) desalination of sodium chloride and sodium sulfate mixture in a lab-scale cell. The effect of various experimental factors on the desalination process and the selectivity of the separation of ions with different charges, such as the composition of the concentrate compartment, electrolyte concentrations in the concentrate and diluate compartments (0.004–0.5 M), the specific current value (0.82–9.0 mA/cm2), the desalination time, and the stirring of solution were considered. To explain the observed patterns, diffusion experiments and numerical simulations using the COMSOL® software package were carried out. Our findings demonstrate that the method chosen for conducting the benchmark desalination of a mixture of chlorides and sulfates can significantly affect the values of the selectivity coefficients and the accuracy of their determination for both standard and surface-modified membranes. For the latter, varying the desalination conditions leads to improved P(Cl/SO4) due to modification of up to 40 %.

Tekinalp Ö., Zimmermann P., Burheim O.S., Deng L.

Removing halide ions from wastewater and industrial effluents is crucial to eliminating their potential risks to human health, ecosystems, and industrial operations. However, conventional techniques for this process are inefficient and have severe drawbacks, including the use of hazardous chemicals, secondary pollution, and increased costs. Utilizing monovalent selective anion exchange membranes (AEMs) in electrodialysis has emerged as an effective solution for separating halide ions from sulfate-rich solutions. This review presents the recent progress, applications, and future prospects of this method, elucidates the principles underlying monovalent selectivity in AEMs, provides an overview of AEM membrane materials and preparation methods, and addresses the impacts of electrodialysis operating conditions on halide removing processes, such as current density, flow rate, pH, and stack design. Existing challenges and recognized gaps, such as complexities in solution composition, membrane stability concerns, insufficient consideration of operational factors, and limitations in modeling, demanding further efforts in this field are also presented. Overcoming these hurdles necessitates a focused approach involving material and membrane design, in-depth exploration of solution dynamics, better operational understanding, and the application of advanced modeling techniques. Effectively addressing these challenges holds the potential to notably amplify the efficiency and efficacy of electrodialysis in mitigating halide ion pollution in sulfate-rich solutions.

Chinello D., Post J., de Smet L.C.

In this study we investigated the selective separation of nitrate from chloride using newly designed PVDF-based anion-exchange membranes. Five membranes were successfully manufactured by casting, each containing a different PVDF concentration (from 0 to 50 % w/w). A polyaromatic anion-exchange polymer was used as a binder. Experimental data shows that the binder had no impact on the nitrate selectivity while increasing the PVDF concentration enhanced nitrate transport. The membrane with a 50 % w/w PVDF content (PVDF-50), exhibited a nearly double selectivity than a commercial membrane (Neosepta AMX). However, we also found that the membrane electrical resistance increased with the PVDF concentration. As the nitrate selectivity was found to be independent of the membrane thickness, selective boundary layer effects were ruled out, suggesting that the ion selectivity was mainly driven by the increased affinity between the anion and the membrane, with less hydrated ions more favourably transported. To confirm this hypothesis, PVDF-50 was tested using a multi-ion solution, including bromide and fluoride. This equimolar solution experiment indicated a direct correlation between ion selectivity and hydration energy of the ion species. Lastly, we investigated the transport of divalent ions through the hybrid membrane, showing a 10 % transport for sulfate.

Kabir M.M., Sabur G.M., Akter M.M., Nam S.Y., Im K.S., Tijing L., Shon H.K.

The water industries (WIN) are now approaching towards sustainability of resource use, recovery process, and water and energy management based on the circular economy (CRE) framework. Thus, the integration of electrodialysis (ED) technology in the WIN with a CRE paradigm should be recommended for ensuring the sustainability of ED desalination, resource, and energy recovery (EDDRER). According to the literature review, and to the best of our knowledge, there is no systematic study devoted to the sustainable EDDRER; hence a comprehensive and critical knowledge generation of EDDRER is essential for further technological advancements of ED. Consequently, this review paper investigated the plausible incorporation of ED in the WIN for a CRE of EDDRER. The recent progress of EDDRER has been described comprehensively and critically. Moreover, an all-inclusive techno-economics and environmental sustainability analysis of EDDRER from WIN for a CRE has been carried out. This paper marks the first instance in which energy recovery techniques employing ED have been reported and critically discussed. In addition, the latest case studies of EDDRER in the WIN have been discussed critically, and the significant scaling-up issues of EDDRER have been assessed based on the state-of-the-art recent scientific findings. Furthermore, the potential mitigation measures for the scaling-up issues have also been addressed. This study is the first comprehensive assessment of EDDRER from WIN for a closed-loop economy. The novel insights of this study could be essential for the development of a sustainable CRE-based EDDRER process for WIN to attain sustainable development goals (SDGs).

Safronova E.Y., Lysova A.A.

The progress of modern technologies and the requirements imposed on the production ecology demand the development of new ion-exchange membrane polymer materials with a set of desired properties. These materials are used in liquid and gas separation and purification systems, chemical and electrochemical syntheses, and alternative energetics. Membrane materials based on perfluorosulfonic acid polymers (PFSA) possess a set of characteristics necessary for their practical application: high ionic conductivity and selectivity and good chemical stability, strength, and elasticity. This review addresses the microstructure of PFSA membranes and its change induced by water and solvent uptake and discusses the features of ion and gas transport, mechanical properties, and the dependence of a number of parameters on polymer chain length and ionic form.

Abdullah R., Astira D., Widiyanto A.R., Dharma H.N., Hidayat A.R., Santoso L., Sulistiono D.O., Rahmawati Z., Gunawan T., Jaafar J., Kusumawati Y., Othman M.H., Fansuri H.

Wastewater treatment has emerged as the most effective method for addressing the scarcity of clean water, which is expected to cause a worldwide crisis in the near future. The membrane bioreactor (MBR) is a cutting-edge technology that combines membrane filtration with biological activity in the form of microorganisms. MBR has been considered the most efficient approach so far owing to its high effluent and relatively small space requirements. The membrane constituent material is an important aspect of producing MBR with maximum process performance. This study extensively evaluated the application of polymers, ceramics, and mixed matrix membranes (MMM) in wastewater treatment performance. MMM has better performance due to its hydrophilic nature, good chemical, mechanical, and thermal stability, and ease of synthesis. Various types of filler in MMM for MBR applications are also discussed, including metals, metal oxides, carbon, MOF, silica, and zeolite. The addition of fillers in the polymer matrix has been able to improve the characteristics of the membrane, including water flux, rejection of pollutants, and resistance to fouling. Subsequently, several important parameters of MMM that affect the performance of MBR, including hydrophilicity, surface charge, surface roughness, module, pore characteristics, and filler charge, have been reviewed. An investigation of the performance of the MBR, such as activated sludge characteristics, operating conditions, and fouling phenomena, is presented. Lastly, this review describes the challenges and perspectives of developing MMM-based MBR in the future.

Gangrade A.S., Tusi B., Ghosh P.C., Holdcroft S.

This study presents an investigation on the monovalent/divalent ion permselectivity of anion exchange ionenes, a distinct class of solid polymer polyelectrolytes having cationic fixed charge groups located directly on the polymer backbone, rather than being pendant. These ionenes are commercially available as Aemion® AEMs and are based on hexamethyl-p-terphenyl poly (bibenzimidazolium) (HMT-PMBI). Monovalent/divalent permselectivity values of four Aemion® membranes of different thickness and ion exchange capacity were determined via electrodialysis in a mixed electrolyte system comprising chloride/sulfate anions. To fully understand the transport phenomena in these materials, ion transport properties were studied in conjunction with water uptake and ionic conductance. When the AEMs were exposed to mixed chloride/sulfate solutions, their water uptake significantly increased compared to purely chloride containing solutions, and the concentration of fixed charge groups in the AEMs consequently decreased. We find that thicker ionenes with lower IEC exhibit the highest permselectivity. The data also reveal that thinner AEMs yield a greater ionic flux loss and decreased permselectivity values, particularly in case of lower IEC AEMs. Surprisingly, despite its low water uptake and high resistance, commercial Selemion AMV possesses lower permselectivity than low IEC ionene-based Aemion® AEMs, which we explain on the basis of the highly tortuous internal morphology of low water content ionenes. Permselectivity-to-resistance ratio values are an order of magnitude higher for low IEC ionenes when compared with high IEC ionenes and Selemion AMV.

Eliseev A.A., Gurianov K.E., Poyarkov A.A., Komkova M.A., Sadilov I.S., Chumakov A.P., Petukhov D.I.

Mends E.A., Chu P.

The increasing adoption of lithium in clean energy technologies has promoted significant development of novel and environmentally sustainable techniques for lithium extraction from secondary sources. In this review, we evaluate seawater and geothermal brines as potential secondary lithium resources for supplementing the rising demand. The review examines relevant literature to understand key aspects pertaining to lithium extraction from these systems in which the fundamental chemistry, the efficacy of different potential extraction techniques, and the associated impacts of each technique are critically reviewed. The extensive research in conventional closed basin brines is utilized as a baseline to demonstrate the current research progress, providing guidelines for future research direction in lithium extraction from seawater and geothermal brines. Based on the literature, it is suggested that sorption and ion-exchange will have high potential for prospective lithium extraction from aqueous resources like salars, seawater, and geothermal brines, and that the integration of activated carbon materials or microorganisms with these techniques will enhance the selectivity of lithium extraction from aqueous resources.

Manin A., Golubenko D., Novikova S., Yaroslavtsev A.

The possibility of targeted change of the properties of ion exchange membranes by incorporation of various nanoparticles into the membranes is attracting the attention of many research groups. Here we studied for the first time the influence of cerium phosphate nanoparticles on the physicochemical and transport properties of commercial anion exchange membranes based on quaternary ammonium-functionalized polystyrenes, such as heterogeneous Ralex® AM and pseudo-homogeneous Neosepta® AMX. The incorporation of cerium phosphate on one side of the membrane was performed by precipitation from absorbed cerium ammonium nitrate (CAN) anionic complex with ammonium dihydrogen phosphate or phosphoric acid. The structures of the obtained hybrid membranes and separately synthesized cerium phosphate were investigated using FTIR, P31 MAS NMR, EDX mapping, and scanning electron microscopy. The modification increased the membrane selectivity to monovalent ions in the ED desalination of an equimolar mixture of NaCl and Na2SO4. The highest selectivities of Ralex® AM and Neosepta® AMX-based hybrid membranes were 4.9 and 7.7, respectively. In addition, the modification of Neosepta® membranes also increased the resistance to a typical anionic surfactant, sodium dodecylbenzenesulfonate.

Dang C., Helal A.S., Zhu L., Xu G., Zhu M.

Sharma P.P., Mohammed S., Aburabie J., Hashaikeh R.

This paper proposes the use of monovalent selective electrodialysis technology to concentrate the valuable sodium chloride (NaCl) component present in seawater reverse osmosis (SWRO) brine for direct utilization in the chlor-alkali industry. To enhance monovalent selectivity, a polyamide selective layer was fabricated on commercial ion exchange membranes (IEMs) through interfacial polymerization (IP) of piperazine (PIP) and 1,3,5-Benzenetricarbonyl chloride (TMC). The IP-modified IEMs were characterized using various techniques to investigate changes in chemical structure, morphology, and surface charge. Ion chromatography (IC) analysis showed that the divalent rejection rate was more than 90% for IP-modified IEMs, compared to less than 65% for commercial IEMs. Electrodialysis results demonstrated that the SWRO brine was successfully concentrated to 14.9 g/L NaCl at a power consumption rate of 3.041 kWh/kg, indicating the advantageous performance of the IP-modified IEMs. Overall, the proposed monovalent selective electrodialysis technology using IP-modified IEMs has the potential to provide a sustainable solution for the direct utilization of NaCl in the chlor-alkali industry.

Tekinalp Ö., Zimmermann P., Holdcroft S., Burheim O.S., Deng L.

The selective separation of metal species from various sources is highly desirable in applications such as hydrometallurgy, water treatment, and energy production but also challenging. Monovalent cation exchange membranes (CEMs) show a great potential to selectively separate one metal ion over others of the same or different valences from various effluents in electrodialysis. Selectivity among metal cations is influenced by both the inherent properties of membranes and the design and operating conditions of the electrodialysis process. The research progress and recent advances in membrane development and the implication of the electrodialysis systems on counter-ion selectivity are extensively reviewed in this work, focusing on both structure–property relationships of CEM materials and influences of process conditions and mass transport characteristics of target ions. Key membrane properties, such as charge density, water uptake, and polymer morphology, and strategies for enhancing ion selectivity are discussed. The implications of the boundary layer at the membrane surface are elucidated, where differences in the mass transport of ions at interfaces can be exploited to manipulate the transport ratio of competing counter-ions. Based on the progress, possible future R&D directions are also proposed.

Pismenskaya N., Rybalkina O., Solonchenko K., Pasechnaya E., Sarapulova V., Wang Y., Jiang C., Xu T., Nikonenko V.

Innovative ion exchange membranes have become commercially available in recent years. However, information about their structural and transport characteristics is often extremely insufficient. To address this issue, homogeneous anion exchange membranes with the trade names ASE, CJMA-3 and CJMA-6 have been investigated in NaxH(3−x)PO4 solutions with pH 4.4 ± 0.1, 6.6 and 10.0 ± 0.2, as well as NaCl solutions with pH 5.5 ± 0.1. Using IR spectroscopy and processing the concentration dependences of the electrical conductivity of these membranes in NaCl solutions, it was shown that ASE has a highly cross-linked aromatic matrix and mainly contains quaternary ammonium groups. Other membranes have a less cross-linked aliphatic matrix based on polyvinylidene fluoride (CJMA-3) or polyolefin (CJMA-6) and contain quaternary amines (CJMA-3) or a mixture of strongly basic (quaternary) and weakly basic (secondary) amines (CJMA-6). As expected, in dilute solutions of NaCl, the conductivity of membranes increases with an increase in their ion-exchange capacity: CJMA-6 < CJMA-3 << ASE. Weakly basic amines appear to form bound species with proton-containing phosphoric acid anions. This phenomenon causes a decrease in the electrical conductivity of CJMA-6 membranes compared to other studied membranes in phosphate-containing solutions. In addition, the formation of the neutral and negatively charged bound species suppresses the generation of protons by the “acid dissociation” mechanism. Moreover, when the membrane is operated in overlimiting current modes and/or in alkaline solutions, a bipolar junction is formed at the CJMA- 6/depleted solution interface. The CJMA-6 current-voltage curve becomes similar to the well-known curves for bipolar membranes, and water splitting intensifies in underlimiting and overlimiting modes. As a result, energy consumption for electrodialysis recovery of phosphates from aqueous solutions almost doubles when using the CJMA-6 membrane compared to the CJMA-3 membrane.