Electrosorption Integrated with Bipolar Membrane Water Dissociation: A Coupled Approach to Chemical-free Boron Removal.

Boron removal from aqueous solutions has long persisted as a technological challenge, accounting for a disproportionately large fraction of the chemical and energy usage in seawater desalination and other industrial processes like lithium recovery. Here, we introduce a novel electrosorption-based boron removal technology with the capability to overcome the limitations of current state-of-the-art methods. Specifically, we incorporate a bipolar membrane (BPM) between a pair of porous carbon electrodes, demonstrating a synergized BPM-electrosorption process for the first time. The ion transport and charge transfer mechanisms of the BPM-electrosorption system are thoroughly investigated, confirming that water dissociation in the BPM is highly coupled with electrosorption of anions at the anode. We then demonstrate effective boron removal by the BPM-electrosorption system and verify that the mechanism for boron removal is electrosorption, as opposed to adsorption on the carbon electrodes or in the BPM. The effect of applied voltage on the boron removal performance is then evaluated, revealing that applied potentials above ∼1.0 V result in a decline in process efficiency due to the increased prevalence of detrimental Faradaic reactions at the anode. The BPM-electrosorption system is then directly compared with flow-through electrosorption, highlighting key advantages of the process with regard to boron sorption capacity and energy consumption. Overall, the BPM-electrosorption shows promising boron removal capability, with a sorption capacity >4.5 µmol g-C-1 and a corresponding specific energy consumption of <2.5 kWh g-B-1.

Partitioning of mobile ions between ion exchange polymers and aqueous salt solutions: importance of counter-ion condensation.

Equilibrium partitioning of ions between a membrane and a contiguous external solution strongly influences transport properties of polymeric membranes used for water purification and energy generation applications. This study presents a theoretical framework to quantitatively predict ion sorption from aqueous electrolytes (e.g., NaCl, MgCl2) into charged (i.e., ion exchange) polymers. The model was compared with experimental NaCl, MgCl2, and CaCl2 sorption data in commercial cation and anion exchange membranes. Ion sorption in charged polymers was modeled using a thermodynamic approach based on Donnan theory coupled with Manning's counter-ion condensation theory to describe non-ideal behavior of ions in the membrane. Ion activity coefficients in solution were calculated using the Pitzer model. The resulting model, with no adjustable parameters, provides remarkably good agreement with experimental values of membrane mobile salt concentration. The generality of the model was further demonstrated using literature data for ion sorption of various electrolytes in charged polymers, including HCl sorption in Nafion.

Nanoscale transport enables active self-assembly of millimeter-scale wires.

Active self-assembly processes exploit an energy source to accelerate the movement of building blocks and intermediate structures and modify their interactions. A model system is the assembly of biotinylated microtubules partially coated with streptavidin into linear bundles as they glide on a surface coated with kinesin motor proteins. By tuning the assembly conditions, microtubule bundles with near millimeter length are created, demonstrating that active self-assembly is beneficial if components are too large for diffusive self-assembly but too small for robotic assembly.

Ion-capture electrodialysis using multifunctional adsorptive membranes.

Technologies that can efficiently purify nontraditional water sources are needed to meet rising global demand for clean water. Water treatment plants typically require a series of costly separation units to achieve desalination and the removal of toxic trace contaminants such as heavy metals and boron. We report a series of robust, selective, and tunable adsorptive membranes that feature porous aromatic framework nanoparticles embedded within ion exchange polymers and demonstrate their use in an efficient, one-step separation strategy termed ion-capture electrodialysis. This process uses electrodialysis configurations with adsorptive membranes to simultaneously desalinate complex water sources and capture diverse target solutes with negligible capture of competing ions. Our methods are applicable to the development of efficient and selective multifunctional separations that use adsorptive membranes.

A Single-Ion Conducting Borate Network Polymer as a Viable Quasi-Solid Electrolyte for Lithium Metal Batteries.

Lithium-ion batteries have remained a state-of-the-art electrochemical energy storage technology for decades now, but their energy densities are limited by electrode materials and conventional liquid electrolytes can pose significant safety concerns. Lithium metal batteries featuring Li metal anodes, solid polymer electrolytes, and high-voltage cathodes represent promising candidates for next-generation devices exhibiting improved power and safety, but such solid polymer electrolytes generally do not exhibit the required excellent electrochemical properties and thermal stability in tandem. Here, an interpenetrating network polymer with weakly coordinating anion nodes that functions as a high-performing single-ion conducting electrolyte in the presence of minimal plasticizer, with a wide electrochemical stability window, a high room-temperature conductivity of 1.5 × 10-4 S cm-1 , and exceptional selectivity for Li-ion conduction (tLi+ = 0.95) is reported. Importantly, this material is also flame retardant and highly stable in contact with lithium metal. Significantly, a lithium metal battery prototype containing this quasi-solid electrolyte is shown to outperform a conventional battery featuring a polymer electrolyte.

Functionalized Porous Aromatic Frameworks as High-Performance Adsorbents for the Rapid Removal of Boric Acid from Water.

This study demonstrates that functionalized, highly porous polymers are promising for the adsorptive capture of boric acid, a neutral contaminant that is difficult to remove from seawater using conventional reverse osmosis membranes. Appending N-methyl-d-glucamine (NMDG) to the pore walls of high-surface-area porous aromatic frameworks (PAFs) yields the adsorbents PAF-1-NMDG and P2-NMDG in a simple two-step synthesis. The boron-selective PAFs demonstrate adsorption capacities that are up to 70% higher than those of a commercial boron-selective resin, Amberlite IRA743, and markedly faster adsorption rates, owing to their higher NMDG loadings and greater porosities relative to the resin. Remarkably, PAF-1-NMDG is able to reduce the boron concentration in synthetic seawater from 2.91 to <0.5 ppm in less than 3 min at an adsorbent loading of only 0.3 mg mL-1 . The boron adsorption rate constants of both frameworks, determined via a pseudo-second-order rate model, represent the highest values reported in the literature-in most cases orders of magnitude higher than those of other boron-selective adsorbents. The frameworks can also be readily regenerated via mild acid/base treatment and maintain constant boron adsorption capacities for at least 10 regeneration cycles. These results highlight the numerous advantages of PAFs over traditional porous polymers in water treatment applications.

Predicting Salt Permeability Coefficients in Highly Swollen, Highly Charged Ion Exchange Membranes.

This study presents a framework for predicting salt permeability coefficients in ion exchange membranes in contact with an aqueous salt solution. The model, based on the solution-diffusion mechanism, was tested using experimental salt permeability data for a series of commercial ion exchange membranes. Equilibrium salt partition coefficients were calculated using a thermodynamic framework (i.e., Donnan theory), incorporating Manning's counterion condensation theory to calculate ion activity coefficients in the membrane phase and the Pitzer model to calculate ion activity coefficients in the solution phase. The model predicted NaCl partition coefficients in a cation exchange membrane and two anion exchange membranes, as well as MgCl2 partition coefficients in a cation exchange membrane, remarkably well at higher external salt concentrations (>0.1 M) and reasonably well at lower external salt concentrations (<0.1 M) with no adjustable parameters. Membrane ion diffusion coefficients were calculated using a combination of the Mackie and Meares model, which assumes ion diffusion in water-swollen polymers is affected by a tortuosity factor, and a model developed by Manning to account for electrostatic effects. Agreement between experimental and predicted salt diffusion coefficients was good with no adjustable parameters. Calculated salt partition and diffusion coefficients were combined within the framework of the solution-diffusion model to predict salt permeability coefficients. Agreement between model and experimental data was remarkably good. Additionally, a simplified version of the model was used to elucidate connections between membrane structure (e.g., fixed charge group concentration) and salt transport properties.

Maximizing the right stuff: The trade-off between membrane permeability and selectivity.

Increasing demands for energy-efficient separations in applications ranging from water purification to petroleum refining, chemicals production, and carbon capture have stimulated a vigorous search for novel, high-performance separation membranes. Synthetic membranes suffer a ubiquitous, pernicious trade-off: highly permeable membranes lack selectivity and vice versa. However, materials with both high permeability and high selectivity are beginning to emerge. For example, design features from biological membranes have been applied to break the permeability-selectivity trade-off. We review the basis for the permeability-selectivity trade-off, state-of-the-art approaches to membrane materials design to overcome the trade-off, and factors other than permeability and selectivity that govern membrane performance and, in turn, influence membrane design.

Charged Polymer Membranes for Environmental/Energy Applications.

Ion exchange membranes are used in various membrane-based processes (e.g., electrodialysis, fuel cells). Charged solute transport is largely governed by the charged groups on the polymer backbone. In this review, fundamental relationships describing salt permeability and ionic conductivity, as well as water permeability, in charged polymers are developed within the framework of the Nernst-Planck and solution-diffusion models. The influence of fixed charge groups and polymer structure on water sorption and diffusion is discussed. Current understanding of ion partitioning in charged polymers, focusing on the use of thermodynamic models (i.e., Donnan theory) to describe such phenomena, is summarized. Ion diffusivity data from the literature are interpreted using a model developed by Mackie and Meares to assess relative and absolute effects of the polymer and fixed charge groups on ion diffusivity. Furthermore, membrane requirements for several important technologies are listed. Knowledge gaps and opportunities for fundamental research are also discussed.

Chemically enhancing block copolymers for block-selective synthesis of self-assembled metal oxide nanostructures.

We report chemical modification of self-assembled block copolymer thin films by ultraviolet light that enhances the block-selective affinity of organometallic precursors otherwise lacking preference for either copolymer block. Sequential precursor loading and reaction facilitate formation of zinc oxide, titanium dioxide, and aluminum oxide nanostructures within the polystyrene domains of both lamellar- and cylindrical-phase modified polystyrene-block-poly(methyl methacrylate) thin film templates. Near-edge X-ray absorption fine structure measurements and Fourier transform infrared spectroscopy show that photo-oxidation by ultraviolet light creates Lewis basic groups within polystyrene, resulting in an increased Lewis base-acid interaction with the organometallic precursors. The approach provides a method for generating both aluminum oxide patterns and their corresponding inverses using the same block copolymer template.