Origin of Limiting and Overlimiting Currents in Bipolar Membranes.

Bipolar membranes (BPMs), a special class of ion exchange membranes with the unique ability to electrochemically induce either water dissociation or recombination, are of growing interest for environmental applications including eliminating chemical dosage for pH adjustment, resource recovery, valorization of brines, and carbon capture. However, ion transport within BPMs, and particularly at its junction, has remained poorly understood. This work aims to theoretically and experimentally investigate ion transport in BPMs under both reverse and forward bias operation modes, taking into account the production or recombination of H+ and OH-, as well as the transport of salt ions (e.g., Na+, Cl-) inside the membrane. We adopt a model based on the Nernst-Planck theory, that requires only three input parameters─membrane thickness, its charge density, and pK of proton adsorption─to predict the concentration profiles of four ions (H+, OH-, Na+, and Cl-) inside the membrane and the resulting current-voltage curve. The model can predict most of the experimental results measured with a commercial BPM, including the observation of limiting and overlimiting currents, which emerge due to particular concentration profiles that develop inside the BPM. This work provides new insights into the physical phenomena in BPMs and helps identify optimal operating conditions for future environmental applications.

Recent advances and prospects in electrochemical coupling technologies for metal recovery from water.

With the development of our society, the desire to recover valuable metal resources from metal-containing wastewaters or natural water bodies is becoming increasingly stronger nowadays. To overcome the limitations of single techniques, coupling technologies with synergistic effects are attracting increasing attention regarding metal resource recovery from water with particular interest in electrochemical coupling technologies in view of the advantages of electrochemical methods. This state-of-the-art review comprehensively presented the mechanisms and performance of electrochemical coupling systems for metal recovery from water. To give a clear overview of current research trends, technologies coupled with electrochemical processes can be categorized into six main types: electrochemical techniques, membrane modules, adsorption/extraction techniques, sonication technologies, energy supply techniques and others. The electrochemical coupling system has shown synergistic advantages (e.g., improving metal recovery efficiency, reducing energy consumption) over single technologies. We then discuss the remaining challenges, present corresponding solutions, and put forward future directions for current electrochemical coupled systems towards metal recovery. This review is conducive to broadening the potential applications of electrochemical coupling processes for metal recovery and sustainable water treatment.

Modeling micropollutant removal by nanofiltration and reverse osmosis membranes: considerations and challenges.

Organic micropollutants (OMPs) in drinking water constitute a potential risk to human health; therefore, effective removal of these pollutants is required. Nanofiltration (NF) and reverse osmosis (RO) are promising membrane-based technologies to remove OMPs. In NF and RO, the rejection of OMPs depends on the properties and characteristics of the membrane, the solute, and the solution. In this review, we discuss how these properties can be included in models to study and predict the rejection of OMPs. Initially, an OMP classification is proposed to capture the relevant properties of 58 OMPs. Following the methodology described in this study, more and new OMPs can be easily included in this classification. The classification aims to increase the comprehension and mechanistic understanding of OMP removal. Based on the physicochemical principles used to classify the 58 OMPs, it is expected that other OMPs in the same groups will be similarly rejected. From this classification, we present an overview of the rejection mechanisms involved in the removal of specific OMP groups. For instance, we discuss the removal of OMPs classified as perfluoroalkyl substances (e.g., perfluorooctanoic acid, PFOA). These substances are highly relevant due to their human toxicity at extremely low concentration as well as their persistence and omnipresence in the environment. Finally, we discuss how the rejection of OMPs can be predicted by describing both the membrane-solution interface and calculating the transport of solutes inside the membrane. We illustrate the importance and impact of different rejection mechanisms and interfacial phenomena on OMP removal and propose an extended Nernst-Plank equation to calculate the transport of solutes across the membrane due to convection, diffusion, and electromigration. Finally, we show how the theory discussed in this review leads to improved predictions of OMP rejection by the membranes.

Theory of oil fouling for microfiltration and ultrafiltration membranes in produced water treatment.

Due to the complexity of oil-in-water emulsions, the existing literature is still missing a mathematical tool that can describe membrane fouling in a fully quantitative manner on the basis of relevant fouling mechanisms. HYPOTHESIS: In this work, a quantitative model that successfully describes cake layer formation and pore blocking is presented. We propose that the degree of pore blocking is determined by the membrane contact angle and the resulting surface coverage, while the cake layer is described by a mass balance and a cake erosion flux. VALIDATION: The model is validated by comparison to experimental data from previous works (Dickhout et al. 2019; Virga et al., 2020) where membrane type, surfactant type and salinity were varied. Most input parameters could be directly taken from the experimental conditions, while four fitting parameters were required. FINDINGS: The experimental data can be well described by the model which was developed to provide insight into the dominant fouling mechanisms. Moreover, where existing models usually assume that pore blocking precedes cake layer formation, here we find that cake layer formation can start and occur while the degree of pore blocking is still increasing, in line with the more dynamic nature of oil droplets filtration. These new conceptual advances in the field of colloid and interface science open up new pathways for membrane fouling understanding, prevention and control.

Salt and Water Transport in Reverse Osmosis Membranes: Beyond the Solution-Diffusion Model.

Understanding the salt-water separation mechanisms of reverse osmosis (RO) membranes is critical for the further development and optimization of RO technology. The solution-diffusion (SD) model is widely used to describe water and salt transport in RO, but it does not describe the intricate transport mechanisms of water molecules and ions through the membrane. In this study, we develop an ion transport model for RO, referred to as the solution-friction model, by rigorously considering the mechanisms of partitioning and the interactions among water, salt ions, and the membrane. Ion transport through the membrane is described by the extended Nernst-Planck equation, with the consideration of frictions between the species (i.e., ion, water, and membrane matrix). Water flow through the membrane is governed by the hydraulic pressure gradient and the friction between the water and membrane matrix as well as the friction between water and ions. The model is validated using experimental measurements of salt rejection and permeate water flux in a lab-scale, cross-flow RO setup. We then investigate the effects of feed salt concentration and hydraulic pressure on salt permeability, demonstrating strong dependence of salt permeability on feed salt concentration and applied pressure, starkly disparate from the SD model. Lastly, we develop a framework to analyze the pressure drop distribution across the membrane, demonstrating that cross-membrane transport dominates the overall pressure drop in RO, in marked contrast to the SD model that assumes no pressure drop across the membrane.

Electrochemical removal of amphoteric ions.

Several harmful or valuable ionic species present in seawater, brackish water, and wastewater are amphoteric, weak acids or weak bases, and, thus, their properties depend on local water pH. Effective removal of these species can be challenging for conventional membrane technologies, necessitating chemical dosing of the feedwater to adjust pH. A prominent example is boron, which is considered toxic in high concentrations and often requires additional membrane passes to remove during seawater desalination. Capacitive deionization (CDI) is an emerging membraneless technique for water treatment and desalination, based on electrosorption of salt ions into charging microporous electrodes. CDI cells show strong internally generated pH variations during operation, and, thus, CDI can potentially remove pH-dependent species without chemical dosing. However, development of this technique is inhibited by the complexities inherent to the coupling of pH dynamics and ion properties in a charging CDI cell. Here, we present a theoretical framework predicting the electrosorption of pH-dependent species in flow-through electrode CDI cells. We demonstrate that such a model enables insight into factors affecting species electrosorption and conclude that important design rules for such systems are highly counterintuitive. For example, we show both theoretically and experimentally that for boron removal, the anode should be placed upstream and the cathode downstream, an electrode order that runs counter to the accepted wisdom in the CDI field. Overall, we show that to achieve target separations relying on coupled, complex phenomena, such as in the removal of amphoteric species, a theoretical CDI model is essential.

Desalination of Complex Multi-Ionic Solutions by Reverse Osmosis at Different pH Values, Temperatures, and Compositions.

For a thorough mechanistic understanding of reverse osmosis (RO), data on ion retention obtained by desalination of multi-ionic solutions are needed. In this paper, we show how to obtain such data under controlled laboratory conditions at any nonextreme pH. For that, we propose a simple method where we use N2 and CO2 gas control to set the composition of a gas phase in equilibrium with the feedwater solution. By increasing the CO2 partial pressure, the pH of the solution will decrease and vice versa. We applied this method of CO2 gas control to extend and validate an existing data set on ion retention of multi-ionic brackish water with 10 different ionic species, whereas conditions in the prior data set were slightly uncontrolled; in our new analysis, we performed experiments at precisely controlled pH and temperature. We run experiments at pH 6.73 and pH 7.11 and in a temperature range of T = 15-31 °C. Our results show that when pH is decreased, or temperature increased, the ion retention of most ions decreases. We also tested the influence of the Na+ to Ca2+ concentration ratio in this multi-ionic solution on ion retention at pH 6.73 and T ∼ 31 °C. We noticed that this ratio has a larger effect on ion retention for cations than for anions. We compare our data with the earlier reported data and describe similarities and differences. The improved data set will be an important tool for future development of accurate and validated RO ion transport models. Such RO models that describe desalination performance in detail are important for successful commercial application of the RO technology. We also discuss a relevant preparation method for water slightly oversaturated with barely soluble CaCO3 by solution preparation at high CO2 pressure, after which the solution is brought to the required pH by the N2 and CO2 gas control method.

Multicomponent mass transport modeling of water desalination by reverse osmosis including ion pair formation.

Reverse Osmosis (RO) is one of the main membrane technologies currently used for the desalination of seawater and brackish water to produce freshwater. However, the mechanism of transport and separation of ions in RO membranes is not yet fully understood. Besides acid-base reactions (i.e., including the H+-ion), at high concentrations, the salt ions can associate and form ion pairs. In this study, we investigate how to include the formation of these ion pairs in the extended Donnan steric partitioning pore model. We study the desalination of a water source where three ion pairs can be formed (NaCl, MgCl+, and MgCl2) and also include water self-dissociation and the carbonate system. The model assumes infinitely fast reactions, which means that the participating ions are locally at chemical equilibrium with one another. A square stoichiometric reaction matrix composed of active species, moieties, and reactions is formulated. As the final constraint equation, we use the charge balance. The model predicts profiles in concentration, flux, and reaction rates across the membrane for all species and calculates the retention per group of ions. Ion pair formation has an influence on the fluxes of individual ions and therefore influences the retention of ions.

Layering of bidisperse charged nanoparticles in sedimentation.

Bidisperse mixtures of charged nanoparticles form separate layers upon centrifugation as a result of minimization of the system's free energy in sedimentation-diffusion equilibrium. Different factors were investigated experimentally for their effects on the layering, and are supported by theoretical calculations of the full sedimentation profiles. Surprisingly, lighter/smaller nanoparticles can even sink below heavier/larger ones when the particle surface charge is carefully tuned. This study provides deeper insights into the control of layering in polydisperse particle mixtures during sedimentation.

Surfactant-dependent critical interfacial tension in silicon carbide membranes for produced water treatment.

During fossil oil extraction, a complex water stream known as produced water (PW), is co-extracted. Membrane treatment makes PW re-use possible, but fouling and oil permeation remain major challenges. In this work, membrane fouling and oil retention of Synthetic PW stabilized with a cationic, anionic, zwitterionic or nonionic surfactant, were studied at various surfactant and salt concentrations. We discuss our results in the framework of the Young-Laplace (YL) equation, which predicts for a given membrane, pressure and oil-membrane contact angle, a critical interfacial tension (IFT) below which oil permeation should occur. We observe such a transition from high to low oil retention with decreasing IFT for the anionic (SDS), cationic (CTAB) and non-ionic (TX) surfactant, but at significantly higher critical IFTs than predicted by YL. On the other side, for the zwitterionic DDAPS we do not observe a drop in oil retention, even at the lowest IFT. The discrepancy between our findings and the critical IFT predicted by YL can be explained by the difference between the measured contact angle and the effective contact angle at the wall of the membrane pores. This leads to a surfactant-dependent critical IFT. Additionally, our results point out that zwitterionic surfactants even at the lowest IFT did not present a critical IFT and exhibited low fouling and low oil permeation.

Selective adsorption of nitrate over chloride in microporous carbons.

Activated carbon is the most common electrode material used in electrosorption processes such as water desalination with capacitive deionization (CDI). CDI is a cyclic process to remove ions from aqueous solutions by transferring charge from one electrode to another. When multiple salts are present in a solution, the removal of each ionic species can be different, resulting in selective ion separations. This ion selectivity is the result of combined effects, such as differences in the hydrated size and valence of the ions. In the present work, we study ion selectivity from salt mixtures with two different monovalent ions, chloride and nitrate. We run adsorption experiment in microporous carbons (i.e., without applying a voltage), as well as electrosorption experiments (i.e., based on applying a voltage between two carbon electrodes). Our results show that i) during adsorption and electrosorption, activated carbon removes much more nitrate than chloride; ii) at equilibrium, ion selectivity does not depend strongly on the composition of the water, but does depend on charging voltage in CDI; and iii) during electrosorption, ion selectivity is time-dependent. We modify the amphoteric Donnan model by including an additional affinity of nitrate to carbon. We find good agreement between our experimental results and the theory. Both show very high selectivity towards nitrate over chloride, [Formula: see text] ∼10, when no voltage is applied, or when the voltage is low. The selectivity gradually decreases with increasing charging voltage to [Formula: see text] ∼6 at Vch = 1.2 V. Despite this decrease, the affinity-effect for nitrate continues to play an important role also at a high voltage. In general, we can conclude that our work provides new insights in the importance of carbon-ion interactions for electrochemical water desalination.

Performance metrics for the objective assessment of capacitive deionization systems.

In the growing field of capacitive deionization (CDI), a number of performance metrics have emerged to describe the desalination process. Unfortunately, the separation conditions under which these metrics are measured are often not specified, resulting in optimal performance at minimal removal. Here we outline a system of performance metrics and reporting conditions that resolves this issue. Our proposed system is based on volumetric energy consumption (Wh/m3) and throughput productivity (L/h/m2) reported for a specific average concentration reduction, water recovery, and feed salinity. To facilitate and rationalize comparisons between devices, materials, and operation modes, we propose a nominal standard separation of removing 5 mM from a 20 mM NaCl feed solution at 50% water recovery. We propose this particular separation as a standard, but emphasize that the rationale presented here applies irrespective of separation details. Using our proposed separation, we compare the desalination performance of a flow-through electrode (fte-CDI) cell and a flow between membrane (fb-MCDI) device, showing how significantly different systems can be compared in terms of generally desirable desalination characteristics. In general, we find that performance analysis must be considered carefully so to not allow for ambiguous separation conditions or the maximization of one metric at the expense of another. Additionally, for context and clarity, we discuss a number of important underlying performance indicators and cell characteristics that are not performance measures in and of themselves but can be examined to better understand differences in performance.

Wettability of Amphoteric Surfaces: The Effect of pH and Ionic Strength on Surface Ionization and Wetting.

We present a novel theory to predict the contact angle of water on amphoteric surfaces, as a function of pH and ionic strength. To validate our theory, experiments were performed on two commonly used amphoteric materials, alumina (Al2O3) and titania (TiO2). We find good agreement at all pH values, and at different salt concentrations. With increasing salt concentration, the theory predicts the contact angle-pH curve to get steeper, while keeping the same contact angle at pH = PZC (point of zero charge), in agreement with data. Our model is based on the amphoteric 1-p K model and includes the electrostatic free energy of an aqueous system as well as the surface energy of a droplet in contact with the surface. In addition, we show how our theory suggests the possibility of a novel responsive membrane design, based on amphoteric groups. At pH ∼ PZC, this membrane resists flow of water but at slightly more acidic or basic conditions the wettability of the membrane pores may change sufficiently to allow passage of water and solutes. Moreover, these membranes could act as active sensors that only allow solutions of high ionic strength to flow through in wastewater treatment.

Energy consumption in capacitive deionization - Constant current versus constant voltage operation.

In the field of Capacitive Deionization (CDI), it has become a common notion that constant current (CC) operation consumes significantly less energy than constant voltage operation (CV). Arguments in support of this claim are that in CC operation the endpoint voltage is reached only at the end of the charging step, and thus the average cell voltage during charging is lower than the endpoint voltage, and that in CC operation we can recover part of the invested energy during discharge. Though these arguments are correct, in the present work based on experiments and theory, we conclude that in operation of a well-defined CDI cycle, this does not lead, for the case we analyze, to the general conclusion that CC operation is more energy efficient. Instead, we find that without energy recovery there is no difference in energy consumption between CC and CV operation. Including 50% energy recovery, we find that indeed CC is more energy efficient, but also in CV much energy can be recovered. Important in the analysis is to precisely define the desalination objective function, such as that per unit total operational time -including both the charge and discharge steps- a certain desalination quantity and water recovery must be achieved. Another point is that also in CV operation energy recovery is possible by discharge at a non-zero cell voltage. To aid the analysis we present a new method of data representation where energy consumption is plotted against desalination. In addition, we propose that one must analyze the full range of combinations of cycle times, voltages and currents, and only compare the best cycles, to be able to conclude which operational mode is optimal for a given desalination objective. We discuss three methods to make this analysis in a rigorous way, two experimental and one combining experiments and theory. We use the last method and present results of this analysis.

Theory of water treatment by capacitive deionization with redox active porous electrodes.

Capacitive deionization (CDI) for water treatment, which relies on the capture of charged species to sustain the electrical double layers (EDLs) established within porous electrodes under an applied electrical potential, can be enhanced by the chemical attachment of fixed charged groups to the porous electrode electrodes (ECDI). It has recently been demonstrated that further improvements in capacity and energy storage can be gained by functionalization of the electrode surfaces with redox polymers in which the charge on the electrodes can be modulated through Faradaic reactions under different cell voltages in a capacitive process that can be called "Faradaic CDI" (FaCDI). Here, we extend recent mathematical models developed for the characterization of CDI and ECDI systems to incorporate the redox mediated contributions by allowing for the variable chemical charges generated by reactions in FaCDI. The lumped model developed here assumes the spacer channel is well-mixed with uniform electrosorption in each electrode. We demonstrate that the salt adsorption performance characterization of the fixed chemical charge ECDI and variable chemical charge FaCDI materials can be unified within a common theoretical framework based on the point of zero charge (PZC) of the electrode material. In the latter case the PZC is determined by the equilibrium potentials of the redox couples immobilized on the porous electrodes. The new model is able to predict the experimentally observed enhanced and inverted performance of CDI cells, and illuminates the benefit of choosing redox active materials for water treatment applications. The deionization performance of FaCDI cells is shown to be superior to that of CDI and ECDI systems with equilibrium adsorption capacities 50-100% higher than attained with CDI systems, and at smaller cell voltages, depending on the redox potentials of the Faradaic moieties.

Reversible thermodynamic cycle analysis for capacitive deionization with modified Donnan model.

It is a widely accepted principle that a thermodynamically reversible desalination process should consume the Gibbs free energy of separation. This principle has been shown in reverse osmosis and has important practical implications in reducing its energy consumption. Capacitive deionization (CDI) with carbon electrodes, a desalination process based on electrical double layer (EDL) formation, should also follow such a principle when it operates in a thermodynamically reversible way. Inspired by a previous thermodynamic analysis on a three-stage reversible CDI process using the Gouy-Chapman-Stern model, we conducted a thermodynamic analysis of a four-stage reversible CDI cycle using the modified Donnan model. This analysis better reflects the cyclic nature of practical CDI operations and account for the significant EDL overlap in nanosized micropores of realistic CDI electrodes. Our analysis of CDI cycles with different separations and final discharge voltages shows that the electrical work to complete a four-stage cycles is numerically exactly identical to the Gibbs free energy of separation, as long as the cycle is operated in a thermodynamically reversible manner.

Coulometry and Calorimetry of Electric Double Layer Formation in Porous Electrodes.

Coulometric measurements on salt-water-immersed nanoporous carbon electrodes reveal, at a fixed voltage, a charge decrease with increasing temperature. During far-out-of-equilibrium charging of these electrodes, calorimetry indicates the production of both irreversible Joule heat and reversible heat, the latter being associated with entropy changes during electric double layer (EDL) formation in the nanopores. These measurements grant experimental access-for the first time-to the entropic contribution of the grand potential; for our electrodes, this amounts to roughly 25% of the total grand potential energy cost of EDL formation at large applied potentials, in contrast with point-charge model calculations that predict 100%. The coulometric and calorimetric experiments show a consistent picture of the role of heat and temperature in EDL formation and provide hitherto unused information to test against EDL models.

Theory of pH changes in water desalination by capacitive deionization.

In electrochemical water desalination, a large difference in pH can develop between feed and effluent water. These pH changes can affect the long-term stability of membranes and electrodes. Often Faradaic reactions are implicated to explain these pH changes. However, quantitative theory has not been developed yet to underpin these considerations. We develop a theory for electrochemical water desalination which includes not only Faradaic reactions but also the fact that all ions in the water have different mobilities (diffusion coefficients). We quantify the latter effect by microscopic physics-based modeling of pH changes in Membrane Capacitive Deionization (MCDI), a water desalination technology employing porous carbon electrodes and ion-exchange membranes. We derive a dynamic model and include the following phenomena: I) different mobilities of various ions, combined with acid-base equilibrium reactions; II) chemical surface charge groups in the micropores of the porous carbon electrodes, where electrical double layers are formed; and III) Faradaic reactions in the micropores. The theory predicts small pH changes during desalination cycles in MCDI if we only consider phenomena I) and II), but predicts that these pH changes can be much stronger if we consider phenomenon III) as well, which is in line with earlier statements in the literature on the relevance of Faradaic reactions to explain pH fluctuations.

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes.

Linear sweep and cyclic voltammetry techniques are important tools for electrochemists and have a variety of applications in engineering. Voltammetry has classically been treated with the Randles-Sevcik equation, which assumes an electroneutral supported electrolyte. In this paper, we provide a comprehensive mathematical theory of voltammetry in electrochemical cells with unsupported electrolytes and for other situations where diffuse charge effects play a role, and present analytical and simulated solutions of the time-dependent Poisson-Nernst-Planck equations with generalized Frumkin-Butler-Volmer boundary conditions for a 1:1 electrolyte and a simple reaction. Using these solutions, we construct theoretical and simulated current-voltage curves for liquid and solid thin films, membranes with fixed background charge, and cells with blocking electrodes. The full range of dimensionless parameters is considered, including the dimensionless Debye screening length (scaled to the electrode separation), Damkohler number (ratio of characteristic diffusion and reaction times), and dimensionless sweep rate (scaled to the thermal voltage per diffusion time). The analysis focuses on the coupling of Faradaic reactions and diffuse charge dynamics, although capacitive charging of the electrical double layers is also studied, for early time transients at reactive electrodes and for nonreactive blocking electrodes. Our work highlights cases where diffuse charge effects are important in the context of voltammetry, and illustrates which regimes can be approximated using simple analytical expressions and which require more careful consideration.

Produced water treatment by membranes: A review from a colloidal perspective.

While the world faces an increased scarcity in fresh water supply, it is of great importance that water from industry and waste streams can be treated for re-use. One of the largest waste streams in the oil and gas industry is produced water. After the phase separation of oil and gas, the produced water is left. This mixture contains dissolved and dispersed hydrocarbons, surfactants, clay particles and salts. Before this water can be used for re-injection, irrigation or as industrial water, it has to be treated. Conventional filtration techniques such as multi media filters and cartridge filters, are able to remove the majority of the contaminants, but the smallest, stabilized oil droplets (<10µm) remain present in the treated water. In recent years, research has focused on membranes to remove these small oil droplets, because this technology requires no frequent replacement of filters and the water quality after treatment is better. Membranes however suffer from fouling by the contaminants in produced water, leading to a lower clean water flux and increased energy costs. Current research on produced water treatment by membranes is mainly focused on improving existing processes and developing fouling-resistant membranes. Multiple investigations have determined the importance of different factors (such as emulsion properties and operating conditions) on the fouling process, but understanding the background of fouling is largely absent. In this review, we describe the interaction between the membrane and a produced water emulsion from a colloidal perspective, with the aim to create a clear framework that can lead to much more detailed understanding of membrane fouling in produced water treatment. Better understanding of the complex interactions at the produced water/membrane interface is essential to achieve more efficient applications.