Layer-by-layer adsorption allows the creation of versatile functional coatings for ion exchange membranes, but the stability of the coating and resulting properties of modified membranes in their operation is a frequently asked question. This paper examines the changes in voltammetric curves of layer-by-layer coated cation exchange membranes and pH-metry of desalination chamber with a studied membrane and an auxiliary anion exchange membrane after short-term tests, including over-limiting current modes. The practical operation of the membranes did not affect the voltammetric curves, but enhanced the generation of H+ and OH− ions in a system with polyethylenimine modified membrane in Ca2+ containing solution. It is shown that a distinction between the voltammetric curves of the membranes modified and the different polyamines persists during the operation and that, in the case of polyethylenimine, there is an additional zone of growth of potential drop in voltammetric curves and stronger generation of H+ and OH− ions as indicated by pH-metry.

Insufficient understanding of transport mechanism of polybasic acid species (phosphoric, citric, malic, etc.) through anion-exchange membranes (AEMs) hinders the widespread use of electrodialysis for processing salt solutions of such acids, e.g. the recovery of phosphates from mixed solutions. In this paper, we present experimental current-voltage characteristics (CVC) and partial fluxes of H2PO4 ? and HPO42 ? across an AEM. These data are simulated using a mathematical model based on the Nernst-Planck-Poisson equations coupled with the kinetic equations for chemical reactions. The model describes the nonstationary transport of phosphate acid species through an AEM and adjacent solution diffusion boundary layers. It is shown that the proton-transfer reactions determine the occurrence of two limiting currents. The electric current sweep rate and the values of dissociation rate constants of acid anions largely affect the values of these limiting currents and generally the shape of the CVC. It is found that due to chemical reactions involving polybasic anions, the formation of their concentration profiles in the membrane occurs much slower than in the case of monobasic salts. Numerical simulation shows that a quasi-stationary CVC is possible only when the current sweep rate is such that measurements are carried out for at least 10 h.

The application of electrodialysis for tartrate stabilization and reagent-free acidity correction of wine and juices is attracting increasing interest. New aliphatic membranes CJMC-3 and CJMA-3 and aromatic membranes CSE and ASE were tested to determine their suitability for use in these electrodialysis processes and to evaluate the fouling of these membranes by wine components for a short (6–8 h) operating time. Using IR spectroscopy, optical indication and measurement of surface contact angles, the chemical composition of the studied membranes, as well as some details about their fouling by wine components, was clarified. The current–voltage charsacteristics, conductivity and water-splitting capacity of the membranes before and after electrodialysis were analyzed. We found that in the case of cation-exchange membranes, complexes of anthocyanins with metal ions penetrate into the bulk (CJMC-3) or are localized on the surface (CSE), depending on the degree of crosslinking of the polymer matrix. Adsorption of wine components by the surface of anion-exchange membranes CJMA-3 and ASE causes an increase in water splitting. Despite fouling under identical conditions of electrodialysis, membrane pair CJMC-3 and CJMA-3 provided 18 ± 1 tartrate recovery with 31 · 10−3 energy consumption, whereas CSE and ASE provided 20 ± 1% tartrate recovery with an energy consumption of 28 · 10−3 Wh, in addition to reducing the conductivity of wine by 20 ± 1%. The casting of aliphatic polyelectrolyte films on the surface of aromatic membranes reduces fouling with a relatively small increase in energy consumption and approximately the same degree of tartrate recovery compared to pristine CSE and ASE.

The creation of monovalent selective ion exchange membranes benefits the desalination of surface waters by removing interfering monovalent ions while preserving polyvalent ionic nutrients. Studies of a promising method of layer-by-layer adsorption of polymers for the creation of monovalent selective coatings note a significant effect of the number of formed layers and of the nature of the external layer on the properties of the resulting membranes. This article reports the changes in properties of layer-by-layer coated heterogeneous membranes occurring at increasing numbers of layers that are attributed to the supposed intermixing of polymers between the layers, namely dependence of limiting current densities determined from i-V curve, enhanced electroconvection that was attributed to the appearing electrical heterogeneity of the surface, and the decreasing monovalent selectivity in electrodialysis of mixed NaCl + CaCl2 solution (from 1.33 to about 1) between the samples with five and six to eight layers of polymers.

Layer-by-layer adsorption of polyelectrolytes with alternating charges of polar groups makes it possible to create functional coatings to increase the monovalent selectivity of ion exchange membranes. In this work the chronopotentiograms of MK-40 heterogeneous ion exchange membrane layer-by-layer coated with polyallylamine and with sodium polystyrene sulfonate are studied. It is shown that chronopotentiometry allows detecting a more pronounced second transition time, a decrease in the stationary potential drop and an increase in the amplitude of the oscillations of potential drop in the stationary sections of the chronopotentiograms of modified membranes, indicating the differences in the counterions transport between the supporting and the modified membranes that can be attributed to “expansion of the funnel” for the entry of electric current lines into the heterogeneous membrane after the application of the homogenizing layer and to enhancement of the development of electroconvection. An increase in the number of modifying layers from two to five does not lead to significant changes in the form of chronopotentiograms.

Agriculture is the world’s largest consumer of water accounting for about 70% of freshwater withdrawals. Faced with scarcity of pure water, it results in need in desalination to produce water for agricultural needs from brackish water, seawater or polluted sources. Widely used technologies reduce total salinity decreasing also the levels of calcium, magnesium, sulphates and phosphates required for normal growth of plants. Recently a layer-by-layer adsorption of charged polymers was proposed for creation of functional materials that would preferentially remove monovalent ions such as Na + and Cl − . Our previous studies demonstrated the creation of cation selective membrane basing on affordable heterogeneous cation exchange membrane that specifically separated Na + from Na + /Ca 2+ mixed solution during electrodialysis. Further characterization showed that, in addition to the expected increase in specific selectivity with respect to singly charged counterions, there was an increase in the overall selectivity with respect to counterions. We provide data from measurements of electrical conductivity, diffusion permeability, and the results of calculating the transport numbers of counterions, demonstrating an increase in selectivity.

The review describes the place of membrane methods in solving the problem of the recovery and re-use of biogenic elements (nutrients), primarily trivalent nitrogen NIII and pentavalent phosphorus PV, to provide the sustainable development of mankind. Methods for the recovery of NH4+ − NH3 and phosphates from natural sources and waste products of humans and animals, as well as industrial streams, are classified. Particular attention is paid to the possibilities of using membrane processes for the transition to a circular economy in the field of nutrients. The possibilities of different methods, already developed or under development, are evaluated, primarily those that use ion-exchange membranes. Electromembrane methods take a special place including capacitive deionization and electrodialysis applied for recovery, separation, concentration, and reagent-free pH shift of solutions. This review is distinguished by the fact that it summarizes not only the successes, but also the “bottlenecks” of ion-exchange membrane-based processes. Modern views on the mechanisms of NH4+ − NH3 and phosphate transport in ion-exchange membranes in the presence and in the absence of an electric field are discussed. The innovations to enhance the performance of electromembrane separation processes for phosphate and ammonium recovery are considered.

The formation of compositions from polymer layers can significantly increase the monovalent selectivity of ion-conducting materials used in membrane separation processes. It is known that the achieved selectivity strongly correlates with the charge of the upper polymer layer determined through its zeta potential. It is of interest to confirm the strict dependence of the zeta potential on the charge of the upper polymer layer for rough commercial membranes. In this work, we studied the zeta potentials of polyallylamine and sodium polystyrene sulfonate adsorbed on heterogeneous membrane in solutions with different charge numbers of the counterion. It is shown that such coatings are characterized by more negative values of zeta potentials in comparison with those known for smooth coatings and that, upon transition to doubly charged counterions, there is no surface recharge.

Electrodialysis (ED) is an attractive method of tartrate stabilization of wine due to its rapidity and reagentlessness. At the same time, fouling of ion-exchange membranes by the components of wine materials is still an unsolved problem. The effect of ethanol, polyphenols (mainly anthocyanins and proanthocyanidins) and saccharides (fructose) on the fouling of aliphatic ion-exchange membranes CJMA-6 and CJMC-5 (manufactured by Hefei Chemjoy Polymer Materials Co. Ltd., Hefei, China) was analyzed using model solutions. It was shown that the mechanism and consequences of fouling are different in the absence of an electric field and during electrodialysis. In particular, a layer of colloidal particles is deposited on the surface of the CJMA-6 anion-exchange membrane in underlimiting current modes. Its thickness increases with increasing current density, apparently due to the implementation of a trap mechanism involving tartaric acid anions, as well as protons, which are products of water splitting and “acid dissociation”. A successful attempt was made to clean CJMA-6 in operando by pumping a water-alcohol solution of KCl through the desalination compartment and changing electric field direction. It has been established that such a cleaning process suppresses the subsequent biofouling of ion-exchange membranes. In addition, selective recovery of polyphenols with high antioxidant activity is possible.

It is known that ammonium has a higher permeability through anion exchange and bipolar membranes compared to K+ cation that has the same mobility in water. However, the mechanism of this high permeability is not clear enough. In this study, we develop a mathematical model based on the Nernst–Planck and Poisson’s equations for the diffusion of ammonium chloride through an anion-exchange membrane; proton-exchange reactions between ammonium, water and ammonia are taken into account. It is assumed that ammonium, chloride and OH− ions can only pass through membrane hydrophilic pores, while ammonia can also dissolve in membrane matrix fragments not containing water and diffuse through these fragments. It is found that due to the Donnan exclusion of H+ ions as coions, the pH in the membrane internal solution increases when approaching the membrane side facing distilled water. Consequently, there is a change in the principal nitrogen-atom carrier in the membrane: in the part close to the side facing the feed NH4Cl solution (pH < 8.8), it is the NH4+ cation, and in the part close to distilled water, NH3 molecules. The concentration of NH4+ reaches almost zero at a point close to the middle of the membrane cross-section, which approximately halves the effective thickness of the diffusion layer for the transport of this ion. When NH3 takes over the nitrogen transport, it only needs to pass through the other half of the membrane. Leaving the membrane, it captures an H+ ion from water, and the released OH− moves towards the membrane side facing the feed solution to meet the NH4+ ions. The comparison of the simulation with experiment shows a satisfactory agreement.

The presence of membrane fouling is the main drawback in membrane processes, and it is related to the premature use and high cost for the replacement of membranes. Polyphenols in cranberry juice are associated with ion-exchange membrane fouling, and it results in a loss of these beneficial compounds in the juice when treated by membrane processes such as electrodialysis. In the present work, four heterogeneous or pseudohomogeneous cation-exchange membranes (CSE-fg, MK-40, CEM Type-II, and CJMC-5), different in terms of the polymer matrix (aromatic, aliphatic), exchange capacity, size, and location of meso and macropores, were studied to understand the impact of the membrane structure and physico-chemical properties on adsorption and desorption of phenolic compounds (anthocyanins and proanthocyanidins) from cranberry juice. It appeared from these results that MK-40, CEM Type-II, and CSE-fg were more prone to fouling due to their high ion-exchange capacity, their thickness, and the presence of meso and macropores in their structure. Indeed, electrostatic interactions occurred between fixed groups of membranes and polyphenolic ions. Desorption of the entire membrane and cryogenic grinding with pH adjusted to 10 allowed a better recovery of anthocyanins and proanthocyanidins (PACs), respectively, since hydroxide ions competed with polyphenols and membrane that induced desorption of polyphenols. In the future, this new knowledge will become the basis for a more sensible choice of membranes and for the development of protocols for extending their life cycle.

Ion exchange membranes covered with layers of polyelectrolytes of alternating charges are characterized by very high monovalent selectivity. This allows the use of such membranes for electrodialytic fractionation of multicomponent solutions. However, the very existence of the boundary at which differently charged layers come in contact can hinder a membrane’s effectiveness by limiting its ion permeability, raising levels of H+ and OH− ions (thus shifting the pH) and increasing the electrical resistance of the membrane, which leads to increased energy consumption. To test how these properties would be changed, we created cheap layer-by-layer-modified membranes based on the heterogeneous MK-40 membrane, on which we adsorbed layers of polyallylamine and sulfonated polystyrene. We created samples with 3, 4, and 5 layers of polyelectrolytes and characterized them. We showed that the application of layers did not decrease the efficiency of the membrane, since the electrical resistance of the modified samples, which increased after application of the first oppositely charged layer, declined with the application of the following layers and became comparable to that of the substrate, while their limiting current density was higher and the shift of pH of treated solution was low in magnitude and comparable with that of the substrate membrane.

Electrodialytic concentration of ammonium-containing liquid products of biochemical processing of municipal, industrial, and livestock wastewater is a promising method for obtaining cheap liquid fertilizers for agriculture. At the same time, it is known that electrodialysis of NH4Cl solutions fails to achieve the same high brine concentrations as in the case of other chlorides, for example, KCl. We show that the reason is high diffusion permeability of anion-exchange membranes (AEMs) to NH4Cl, which is due to the protonation–deprotonation reactions of ammonium coions during their transfer from an external solution to an internal AEM solution and vice versa. For the first time, a mathematical model of NH4Cl diffusion through AEM was proposed with allowance for these reactions. The experimental values of the diffusion permeability of an anion-exchange membrane AMX and a cation-exchange membrane CMX in NH4Cl and KCl solutions have been compared. between The results of calculating the diffusion permeability of the membrane AMX in NH4Cl solutions are in qualitative agreement with the experiment data.

Generation of H+ and OH- ions at anion-exchange membranes is a phenomenon, which substantially reduces the performance of a number of electromembrane processes, such as the wastewater treatment, fuel cell energy production and others. We show that the mechanisms of this phenomenon are different, when a Neosepta AMX anion-exchange membrane is bathed in a strong electrolyte solution (NaCl and KCl) or in an ampholyte solution (NaH2PO4, KH2PO4, KHT and KH(2)Cit). The H+ and OH- ions' generation in the case of strong electrolytes requires a voltage threshold (about 0.3 V of the corrected voltage not including ohmic contribution), which relates to a current close to the limiting current. The process occurs mainly through proton transfer reactions involving the membrane functional groups. In the case of ampholytes, this generation takes place without a threshold; this process is separated in space: the generation of H+ occurs at the depleted solution/membrane interface, that of OH- ions, at the membrane boundary with the enriched solution. Electrochemical impedance spectra (EIS) are used for the determination of the effective rate constants for the H+ and OH- ions' generation. Their values are compared with the rate constants calculated from the acid dissociation constants (K-a).

Despite the growing interest in pulsed electric field modes in membrane separation processes, there are currently not many works devoted to studying the effect of the surface properties and composition of ion-exchange membranes on their efficiency in these modes. In this paper, we have shown the effect of increasing mass transfer using different kinds of ion-exchange membranes (heterogeneous and homogeneous with smooth, undulated, and rough surfaces) during electrodialysis in the pulsed electric field modes at underlimiting and overlimiting currents. It was found that the maximum increment in the average current is achieved when the average potential corresponds to the right-hand edge of the limiting current plateau of the voltammetric curve, i.e., at the maximum resistance of the system in the DC mode. For the first time, the development of electroconvective vortices was visualized in pulsed electric field modes and it was experimentally shown that even at relatively low frequencies, a non-uniform concentration field is preserved at the time of a pause, which stimulates the rapid development of electroconvection when pulses are switched on again. In the case of relatively high pulse frequencies, the electroconvective vortices formed during a pulse lapse do not completely decay during a pause; they only slightly decrease in size.

It has been found that after 300 h of operation of AMX and AMX-Sb anion-exchange membranes (Astom, Japan) in overlimiting current regimes in the process of electrodialysis desalination of 0.02 M NaCl, NH4Cl, NaH2PO4, and KC4H5O6 (KHT) solutions, the limiting currents, $$i_{{\lim }}^{{\exp }}$$ , determined by graphic processing of current–voltage curves increase in the order NaCl < NaH2PO4 < KHT. Their increments relative to those for the “fresh” membrane are 33, 90, and 128%, respectively. The growth in $$i_{{\lim }}^{{\exp }}$$ is accompanied by an increase in the thickness of the samples occurring in the NaH2PO4 and KHT solutions. In the case of NH4Cl, the values of $$i_{{\lim }}^{{\exp }}$$ decrease. It has been shown that a small decrease in counterion transport numbers during membrane operation has almost no effect on the values of limiting currents. The main contribution to the increase in $$i_{{\lim }}^{{\exp }}$$ is apparently made by electroconvection, which develops according to the mechanism of electroosmosis of the first kind. Its development is facilitated by the growth in the number and size of free-standing micrometer-sized cavities on the surface of anion-exchange membranes, the area and linear dimensions of which increase in the order NaCl < NaH2PO4 < KHT. These cavities are formed as a result of enhancement of electrochemical degradation of the ion-exchange material and the inert filler polyvinyl chloride at the membrane/solution interface in ampholyte solutions.

Electrodialysis (ED) with ion-exchange membranes is a promising method for the extraction of phosphates from municipal and other wastewater in order to obtain cheap mineral fertilizers. Phosphorus is transported through an anion-exchange membrane (AEM) by anions of phosphoric acid. However, which phosphoric acid anions carry the phosphorus in the membrane and the boundary solution, that is, the mechanism of phosphorus transport, is not yet clear. Some authors report an unexpectedly low current efficiency of this process and high energy consumption. In this paper, we report the partial currents of H2PO4−, HPO42−, and PO43− through Neosepta AMX and Fujifilm AEM Type X membranes, as well as the partial currents of H2PO4− and H+ ions through a depleted diffusion layer of a 0.02 M NaH2PO4 feed solution measured as functions of the applied potential difference across the membrane under study. It was shown that the fraction of the current transported by anions through AEMs depend on the total current density/potential difference. This was due to the fact that the pH of the internal solution in the membrane increases with the growing current due to the increasing concentration polarization (a lower electrolyte concentration at the membrane surface leads to higher pH shift in the membrane). The HPO42− ions contributed to the charge transfer even when a low current passed through the membrane; with an increasing current, the contribution of the HPO42− ions grew, and when the current was about 2.5 ilimLev (ilimLev was the theoretical limiting current density), the PO43− ions started to carry the charge through the membrane. However, in the feed solution, the pH was 4.6 and only H2PO4− ions were present. When H2PO4− ions entered the membrane, a part of them transformed into doubly and triply charged anions; the H+ ions were released in this transformation and returned to the depleted diffusion layer. Thus, the phosphorus total flux, jP (equal to the sum of the fluxes of all phosphorus-bearing species) was limited by the H2PO4− transport from the bulk of feed solution to the membrane surface. The value of jP was close to ilimLev/F (F is the Faraday constant). A slight excess of jP over ilimLev/F was observed, which is due to the electroconvection and exaltation effects. The visualization showed that electroconvection in the studied systems was essentially weaker than in systems with strong electrolytes, such as NaCl.