Ion and Water Dynamics in the Transition from Dry to Wet Conditions in Salt-Doped PEG.

The influence of the water content on ion and water transport mechanisms in polymer membranes under low to moderate hydration conditions remains poorly understood. In this study, we combine ion and water diffusivity (PFG-NMR) measurements with atomistic molecular dynamics simulations to better understand transport processes in hydrated salt-doped poly(ethylene glycol). Above the water percolation threshold, the experimental and simulated diffusivities are in good agreement with the free volume transport models. At low hydration levels, unlike dry systems, ion diffusion cannot be described by polymer segmental dynamics alone. We rationalize such observations by the interplay between ion-water and ion-polymer solvation of cations and between ion-water and cation-anion interactions for anions. Further, we demonstrate that a two-state model combining ion-water solvation and free volume transport can describe water dynamics across the entire hydration range of interest. Our findings provide a more encompassing analysis of ion and water transport in hydrated polyelectrolytes, specifically in the low hydration regime.

Accounting for Ion Pairing Effects on Sulfate Salt Sorption in Cation Exchange Membranes.

Ion exchange membranes (IEMs) are frequently used in water treatment and electrochemical applications, with their ion separation properties largely governed by equilibrium ion partitioning between a membrane and contiguous solution. Despite an expansive literature on IEMs, the influence of electrolyte association (i.e., ion pairing) on ion sorption remains relatively unexplored. In this study, salt sorption in two commercial cation exchange membranes equilibrated with 0.01-1.0 M MgSO4 and Na2SO4 is investigated experimentally and theoretically. Association measurements of salt solutions using conductometric experiments and the Stokes-Einstein approximation show significant concentrations of ion pairs in MgSO4 and Na2SO4 relative to those in simple electrolytes (i.e., NaCl), which is consistent with prior studies of sulfate salts. The Manning/Donnan model, developed and validated for halide salts in previous studies, substantially underpredicts sulfate sorption measurements, presumably due to ion pairing effects not accounted for in this established theory. These findings suggest that ion pairing can enhance salt sorption in IEMs due to partitioning of reduced valence species. By reformulating the Donnan and Manning models, a theoretical framework for predicting salt sorption in IEMs that explicitly considers electrolyte association is developed. Remarkably, theoretical predictions of sulfate sorption are improved by over an order of magnitude by accounting for ion speciation. In some cases, good quantitative agreement is observed between theoretical and experimental values for external salt concentrations between 0.1 and 1.0 M using no adjustable parameters.

The Donnan potential revealed.

Selective transport of solutes across a membrane is critical for many biological, water treatment and energy conversion and storage systems. When a charged membrane is equilibrated with an electrolyte, an unequal distribution of ions arises between phases, generating the so-called Donnan electrical potential at the solution/membrane interface. The Donnan potential results in the partial exclusion of co-ion, providing the basis of permselectivity. Although there are well-established ways to indirectly estimate the Donnan potential, it has been widely reported that it cannot be measured directly. Here we report the first direct measurement of the Donnan potential of an ion exchange membrane equilibrated with salt solutions. Our results highlight the dependence of the Donnan potential on external salt concentration and counter-ion valence, and show a reasonable agreement with current theoretical models of IEMs, which incorporate ion activity coefficients. By directly measuring the Donnan potential, we eliminate ambiguities that arise from limitations inherent in current models.

Engineering Li/Na selectivity in 12-Crown-4-functionalized polymer membranes.

Lithium is widely used in contemporary energy applications, but its isolation from natural reserves is plagued by time-consuming and costly processes. While polymer membranes could, in principle, circumvent these challenges by efficiently extracting lithium from aqueous solutions, they usually exhibit poor ion-specific selectivity. Toward this end, we have incorporated host-guest interactions into a tunable polynorbornene network by copolymerizing 1) 12-crown-4 ligands to impart ion selectivity, 2) poly(ethylene oxide) side chains to control water content, and 3) a crosslinker to form robust solids at room temperature. Single salt transport measurements indicate these materials exhibit unprecedented reverse permeability selectivity (∼2.3) for LiCl over NaCl-the highest documented to date for a dense, water-swollen polymer. As demonstrated by molecular dynamics simulations, this behavior originates from the ability of 12-crown-4 to bind Na+ ions more strongly than Li+ in an aqueous environment, which reduces Na+ mobility (relative to Li+) and offsets the increase in Na+ solubility due to binding with crown ethers. Under mixed salt conditions, 12-crown-4 functionalized membranes showed identical solubility selectivity relative to single salt conditions; however, the permeability and diffusivity selectivity of LiCl over NaCl decreased, presumably due to flux coupling. These results reveal insights for designing advanced membranes with solute-specific selectivity by utilizing host-guest interactions.

Origins of Lithium/Sodium Reverse Permeability Selectivity in 12-Crown-4-Functionalized Polymer Membranes.

Direct lithium extraction via membrane separations has been fundamentally limited by lack of monovalent ion selectivity exhibited by conventional polymeric membranes, particularly between sodium and lithium ions. Recently, a 12-Crown-4-functionalized polynorbornene membrane was shown to have the largest lithium/sodium permeability selectivity observed in a fully aqueous system to date. Using atomistic molecular dynamics simulations, we reveal that this selectivity is due to strong interactions between sodium ions and 12-Crown-4 moieties, which reduce sodium ion diffusivity while leaving lithium ion mobility relatively unaffected. Moreover, the ion diffusivities in the membrane, when scaled by their respective solution diffusivities and free ion fractions, can be collapsed to an almost universal relationship depending on solvent volume fraction.

Water Treatment: Are Membranes the Panacea?

Alongside the rising global water demand, continued stress on current water supplies has sparked interest in using nontraditional source waters for energy, agriculture, industry, and domestic needs. Membrane technologies have emerged as one of the most promising approaches to achieve water security, but implementation of membrane processes for increasingly complex waters remains a challenge. The technical feasibility of membrane processes replacing conventional treatment of alternative water supplies (e.g., wastewater, seawater, and produced water) is considered in the context of typical and emerging water quality goals. This review considers the effectiveness of current technologies (both conventional and membrane based), as well as the potential for recent advancements in membrane research to achieve these water quality goals. We envision the future of water treatment to integrate advanced membranes (e.g., mixed-matrix membranes, block copolymers) into smart treatment trains that achieve several goals, including fit-for-purpose water generation, resource recovery, and energy conservation.

Designing Solute-Tailored Selectivity in Membranes: Perspectives for Water Reuse and Resource Recovery.

Treatment of nontraditional source waters (e.g., produced water, municipal and industrial wastewaters, agricultural runoff) offers exciting opportunities to expand water and energy resources via water reuse and resource recovery. While conventional polymer membranes perform water/ion separations well, they do not provide solute-specific separation, a key component for these treatment opportunities. Herein, we discuss the selectivity limitations plaguing all conventional membranes, which include poor removal of small, neutral solutes and insufficient discrimination between ions of the same valence. Moreover, we present synthetic approaches for solute-tailored selectivity including the incorporation of single-digit nanopores and solute-selective ligands into membranes. Recent progress in these areas highlights the need for fundamental studies to rationally design membranes with selective moieties achieving desired separations.