The high concentration of chloride ions in desulphurization wastewater is the primary limiting factor for its reusability. Monovalent anion selective electrodialysis (S-ED) enables the selective removal of chloride ions, thereby facilitating the reuse of desulfurization wastewater. In this study, different concentrations of NaCl and Na2SO4 were used to simulate different softened desulfurization wastewater. The effects of current density and NaCl and Na2SO4 concentration on ion flux, permselectivity (PSO42-Cl-) and specific energy consumption were studied. The results show that Selemion ASA membrane exhibits excellent permselectivity for Cl- and SO42-, with a significantly lower flux observed for SO42- compared to Cl-. Current density exerts a significant influence on ion flux; as the current density increases, the flux of SO42- also increases but at a lower rate than that of Cl-, resulting in an increase in permselectivity. When the current density reaches 25 mA/cm2, the permselectivity reaches a maximum of 50.4. The increase in NaCl concentration leads to a decrease in the SO42- flux; however, the permselectivity is reduced due to the elevated Cl-/SO42- ratio. The SO42- flux increases with the increase in Na2SO4 concentration, while the permselectivity increases with the decrease in Cl-/SO42- ratio.

Ion-exchange membranes (IEMs) are widely used in water, energy, and environmental applications, but transport models to accurately simulate ion permeation are currently lacking. This study presents a theoretical framework to predict ionic conductivity of IEMs by introducing an analytical model for condensed counterion mobility to the Donnan-Manning model. Modeling of condensed counterion mobility is enabled by the novel utilization of a scaling relationship to describe screening lengths in the densely charged IEM matrices, which overcame the obstacle of traditional electrolyte chemistry theories breaking down at very high ionic strength environments. Ionic conductivities of commercial IEMs were experimentally characterized in different electrolyte solutions containing a range of mono-, di-, and trivalent counterions. Because the current Donnan-Manning model neglects the mobility of condensed counterions, it is inadequate for modeling ion transport and significantly underestimated membrane conductivities (by up to ≈5× difference between observed and modeled values). Using the new model to account for condensed counterion mobilities substantially improved the accuracy of predicting IEM conductivities in monovalent counterions (to as small as within 7% of experimental values), without any adjustable parameters. Further adjusting the power law exponent of the screen length scaling relationship yielded reasonable precision for membrane conductivities in multivalent counterions. Analysis reveals that counterions are significantly more mobile in the condensed phase than in the uncondensed phase because electrostatic interactions accelerate condensed counterions but retard uncondensed counterions. Condensed counterions still have lower mobilities than ions in bulk solutions due to impedance from spatial effects. The transport framework presented here can model ion migration a priori with adequate accuracy. The findings provide insights into the underlying phenomena governing ion transport in IEMs to facilitate the rational development of more selective membranes.

The resurgence in designing polyelectrolyte membrane (PEM) materials has propound grid-scale electrochemical energy storage devices. Herein, we report on studies corroborating the synergistic influence of ionic domain microstructure modification and intercalation of telechelic bis-piperidinium-functionalized graphene oxide (GO) to fabricate stable bifunctional membranes from sulfonated poly(2,6-dimethyl-1,4-phenylene ether) (sPPE) for efficient anthrarufin-based alkaline redox flow batteries. A critically long-lasting quest on alkaline stability and -OH conductivity dilemma in hydrocarbon-based PEMs is meticulously resolved via a bifunctional ion-conducting matrix. Preferential studies on hydrophilic domain distribution in sPPE suggest that, with high microphase homogeneity, higher specific capacity retentions are achievable during galvanostatic charge-discharge (GCD) analysis. Moreover, the low-capacity issues were overcome by improving the redoxolyte-membrane interface affinities incorporating bis-piperidinium-bearing graphene oxide (bis-QGO). Consequently, at 1.0 and 2.0 wt % intercalation of bis-QGO, the bifunctional polyelectrolyte membranes (BFPMs) impart lowest overpotentials of 93 mV (for BFPM-1.0) and ∼100 mV (for BFPM-2.0) which are ∼43 and 40% lower than that of Nafion-117 (i.e., ∼164 mV). Furthermore, the efficiency of BFPMs, viz., the Coulombic, voltage, and energy efficiencies, was ∼95-98%, ∼85%, and ≥80% at 20 mA cm-2, respectively. In long-cycling operations, the GCD profile evidenced ∼99% efficiency retention over 450 cycles and illustrated reproducible rate capability. Finally, the polarization studies of BFPMs revealed ∼54% higher peak power density (87.5 mW cm-2) delivery than Nafion-117 (∼57 mW cm-2). We believe that this strategic designing approach could offer newer and simple avenues to avail high-performance BFPMs at low intercalation loads for alkaline electrochemical energy storage and related applications.

For the first time, based on the joint application of the fine-porous and cell models, a theoretical analysis of the changing transport and structural characteristics of heterogeneous polymeric ion-exchange membranes (IEMs) MK-40, MA-40, and MA-41 after exposure to elevated temperatures in water and aggressive media (H2SO4 and NaOH solutions), as well as after long-term processing in electrodialyzers of various types, was carried out. The studied membranes are composites of ion-exchange polymers with polyethylene and nylon reinforcing mesh. The external influences provoke the aging of IEMs and the deterioration of their characteristics. The transport properties of IEMs are quantitatively described using five physicochemical parameters: counterion diffusion and equilibrium distribution coefficients in the membrane, characteristic exchange capacity, which depends on the microporosity of ion-exchanger particles, and macroscopic porosity at a known exchange capacity of IEMs. Calculations of the physicochemical parameters of the membranes were performed according to a specially developed fitting technique using the experimental concentration dependences of integral diffusion permeability and specific electrical conductivity, and their model analogs. This made it possible to identify and evaluate changes in the membrane micro- and macrostructure and examine the process of artificial aging of the IEM polymer material due to the abovementioned external impacts.

The possible effects of ionizing radiation on four commercial membranes, which are typically used as electrolytes in fuel cells supplying energy to a huge variety of medical implantable devices, were studied. These devices could obtain energy from the biological environment through a glucose fuel cell, which could be a good candidate to replace conventional batteries as a power source. In these applications, materials with high radiation stability for the fuel cell elements would be disabled. The polymeric membrane is one of the key elements in fuel cells. Membrane swelling properties are very important because they affect the fuel cell\'s performance. For this reason, the swelling behaviors of various samples of each membrane irradiated with different doses were analyzed. Each sample was irradiated with a typical dose of a conventional radiotherapy treatment, and the regular conditions of the biological working environment were simulated. The target was to examine the possible effect of the received radiation on the membranes. The results show that the ionizing radiation influenced their swelling properties, as well as that dimensional changes were dependent on the existence of reinforcement, be it internal or external, in the membrane structure.

A high-performing bipolar membrane (BPM) was fabricated using functionalized polysulfones as the ion-exchange layers (IELs) and two-dimensional (2D) V2O5-nanosheets blended with polyvinyl alcohol (PVA) as the water dissociation catalyst (WDC) at the interfacial layer. The composite BPM showed a low resistance of 0.79 Ω cm2, confirming the good contact between the IEL and WDC, much needed for the ionic conductivity. It also demonstrated high water dissociation performance with a water dissociation voltage of 1.11 V corresponding to a current density of 1.02 mA/cm2 in the presence of a 1 M NaCl electrolytic solution. The functionalization of the polysulfone with -SO3- and R4N+ groups successfully resulted in the increase of hydrophilicity of the polymer, thereby increasing the water uptake capacity of the membranes. The blending of 2D V2O5 nanosheets with PVA proved to be an effective WDC, as confirmed by the increased conductivity and efficiency of the water dissociation (WD) reaction. The 2D V2O5-ns have great potential toward water adsorption onto its surface, thereby interacting with the water molecules, weakening the bonding force of water, and dissociating it into H+ and OH-. The transportation of coions across the membranes and generation of protons and hydroxyl ions at the interfacial layer are correlated with the change in the pH of the catholyte and anolyte as a function of current density during the WD reaction. The high performance of the composite BPM (BPM_VO-ns) was demonstrated at a higher current density of 100 mA/cm2 with a WD resistance of 0.027 Ω cm2. The durability was tested by subjecting it to 45 h of run at lower (1.02 mA/cm2) and higher (100 mA/cm2) current densities which display a negligible change in the interlayer voltage. Thus, the fabricated composite BPMs pave the way to be utilized for efficient and durable WD reactions under neutral electrolytic conditions.

This study investigates the influence of co-existing ions on the salinity gradient power generation performance of the reverse electrodialysis (RED) using three different commercial ion exchange membrane pairs. The feed solutions, including the mixture of two different salts, were prepared with 90 wt.% of NaCl and 10 wt.% of LiCl, KCl, CaCl2, MgCl2 or Na2SO4 by keeping the salt ratio between high concentrate solution and low concentrate solution constant as 1:30 (g/g) at various flow velocities (50, 125 and 200 mL/min). It was observed that the divalent ions exhibited a negative impact on the performance of the RED system due to their high valence and low ionic mobility depending on their high hydrated radius and low diffusion coefficients compared to those of the monovalent ions. On the other hand, the effect of the monovalent ions differed according to the properties of ion exchange membranes used in the RED stack. When the power generation performances of ion exchange membrane pairs employed in the RED stack were compared, it was considered that Neosepta AMX and CMX membranes provided the highest power density due to their low membrane thicknesses, low electrical resistances, and relatively high ion exchange capacities compared to other two commercial ion exchange membrane pairs.

In this study, the characteristic frequencies of the electrochemical impedance of ion-exchange membrane systems constituted by the membrane and two diffusion boundary layers adjacent to the membrane were investigated. Approximations of the impedance of the Randles equivalent electric circuit in multiple frequency ranges were considered, and the characteristic frequencies of the zeros and poles of orders ½ and 1 were derived. The characteristic geometric frequencies, those associated with the interfacial charge transfer and the diffusive transport processes, as well as those associated with the transitions between processes, were identified by means of analytical expressions.

Emerging technologies in nanotechnology and biomedical engineering have led to an increase in the use of implantable biomedical devices. These devices are currently battery powered which often means they must be surgically replaced during a patient\'s lifetime. Therefore, there is an important need for a power source that could provide continuous, stable power over a prolonged time. Reverse electrodialysis (RED) based biopower cells have been previously used to generate continuous power from physiologically relevant fluids; however, the low salinity gradient that exists within the body limited the performance of the biopower cell. In this study, a miniaturized RED biopower cell design coupled with a salt cartridge was evaluated for boosting the salt concentration gradient supplied to RED in situ. For the salt cartridge, polysulfone (PSf) hollow fibers were prepared in-house and saturated with NaCl solutions to deliver salt and thereby enhance the concentration gradient. The effect of operational parameters including solution flow rate and cartridge salt concentration on salt transport performance was evaluated. The results demonstrated that the use of the salt cartridge was able to increase the salt concentration of the RED inlet stream by 74% which in turn generated a 3-fold increase in the open circuit voltage (OCV) of the biopower cell. This innovative adaptation of the membrane-based approach into portable power generation could help open new pathways in various biomedical applications.

The global temperature increase must be limited to below 1.5 °C to alleviate the worst effects of climate change. Electrocatalytic CO2 reduction (ECO2 R) to generate chemicals and feedstocks is considered one of the most promising technologies to cut CO2 emission at an industrial level. However, despite decades of studies, advances at the laboratory scale have not yet led to high industrial deployment rates. This Review discusses practical challenges in the industrial chain that hamper the scaling-up deployment of the ECO2 R technology. Faradaic efficiencies (FEs) of about 100 % and current densities above 200 mA cm-2 have been achieved for the ECO2 R to CO/HCOOH, and the stability of the electrolysis system has been prolonged to 2000 h. For ECO2 R to C2 H4 , the maximum FE is over 80 %, and the highest current density has reached the A cm-2 level. Thus, it is believed that ECO2 R may have reached the stage for scale-up. We aim to provide insights that can accelerate the development of the ECO2 R technology.