Critical Mineral Separations: Opportunities for Membrane Materials and Processes to Advance Sustainable Economies and Secure Supplies.

Sustainable energy solutions and electrification are driving increased demand for critical minerals. Unfortunately, current mineral processing techniques are resource intensive, use large quantities of hazardous chemicals, and occur at centralized facilities to realize economies of scale. These aspects of existing technologies are at odds with the sustainability goals driving increased demand for critical minerals. Here, we argue that the small footprint and modular nature of membrane technologies position them well to address declining concentrations in ores and brines, the variable feed concentrations encountered in recycling, and the environmental issues associated with current separation processes; thus, membrane technologies provide new sustainable pathways to strengthening resilient critical mineral supply chains. The success of creating circular economies hinges on overcoming diverse barriers across the molecular to infrastructure scales. As such, solving these challenges requires the convergence of research across disciplines rather than isolated innovations.

Thermodynamics of Li+-Crown Ether Interactions in Aqueous Solvent.

Lithium ion-based batteries are ubiquitous in modern technology due to applications in personal electronics and high-capacity storage for electric vehicles. Concerns about lithium supply and battery waste have prompted interest in lithium recycling methods. The crown ether 12-crown-4 has been studied for its abilities to form stable complexes with lithium ions (Li+). In this paper, molecular dynamics simulations are applied to examine the binding properties of a 12-crown-4-Li+ system in aqueous solution. It was found that 12-crown-4 did not form stable complexes with Li+ in aqueous solution due to the binding geometry which was prone to interference by surrounding water molecules. In addition, the binding properties of sodium ions (Na+) to 12-crown-4 are examined for comparison. Subsequently, calculations were performed with the crown ethers 15-crown-5 and 18-crown-6 to study their complexation with Li+ as well as Na+. It was determined that binding was unfavorable for both types of ions for all three crown ethers tested, though 15-crown-5 and 18-crown-6 showed a marginally greater affinity for Li+ than 12-crown-4. Metastable minima present in the potential of mean force for Na+ render binding marginally more likely there. We discuss these results in the context of membrane-based applications of crown ethers for Li+ separations.

Dual-Functional Nanofiltration Membranes Exhibit Multifaceted Ion Rejection and Antifouling Performance.

Charged functional groups are often incorporated onto the surface of nanofiltration (NF) membranes to facilitate the selective rejection of multivalent ions over monovalent ions. However, since fouling-resistant surfaces tend to be electrically neutral, the incorporation of charged functionality exacerbates membrane fouling. Multifunctional Janus membrane architectures, which incorporate chemically distinct domains over their cross section, provide a strategy for balancing the competing demands associated with making fouling-resistant, ion rejecting NF membranes. Here, through the controlled exposure of poly(trifluoroethyl methacrylate-co-oligo-(ethylene glycol) methyl ether methacrylate-co-(3-azido-2-hydroxypropyl methacrylate)) copolymer substrates to a series of reactive solutions containing alkyne-terminated molecules, the process for creating dual-functional membranes by using the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction was analyzed. Under the appropriate conditions, the CuAAC reaction propagates into the copolymer substrate as a front. This phenomenon results in a process for creating layered domains of distinct functionality whereby the distribution of antifouling zwitterionic moieties and ion rejecting sulfonate moieties can be modified by manipulating the exposure time. The ion rejection and fouling propensity for a family of dual-functional membranes was examined. For short initial reaction times, which introduced a thin antifouling layer on top of an ion rejection layer, the rejection of 1 mM K2SO4, 87%, was comparable to the value for full charge control membranes, 90%. Moreover, when exposed to a fouling solution containing bovine serum albumin (BSA), these dual-functional membranes exhibited an 18% decline in normalized flux and recovered 99% of their flux upon rinsing with water. In comparison, the full charge membranes exhibited a 44% decline in normalized flux and recovered 65% of their flux upon washing. As such, the results demonstrate that the controlled functionalization process reported here is capable of balancing antifouling and ion rejection capabilities. Furthermore, the versatile nature of the click chemistry mechanism at the center of this process offers a means by which to design and fabricate multifunctional membranes for numerous future applications.

Rapid fabrication of precise high-throughput filters from membrane protein nanosheets.

Biological membranes are ideal for separations as they provide high permeability while maintaining high solute selectivity due to the presence of specialized membrane protein (MP) channels. However, successful integration of MPs into manufactured membranes has remained a significant challenge. Here, we demonstrate a two-hour organic solvent method to develop 2D crystals and nanosheets of highly packed pore-forming MPs in block copolymers (BCPs). We then integrate these hybrid materials into scalable MP-BCP biomimetic membranes. These MP-BCP nanosheet membranes maintain the molecular selectivity of the three types of ß-barrel MP channels used, with pore sizes of 0.8 nm, 1.3 nm, and 1.5 nm. These biomimetic membranes demonstrate water permeability that is 20-1,000 times greater than that of commercial membranes and 1.5-45 times greater than that of the latest research membranes with comparable molecular exclusion ratings. This approach could provide high performance alternatives in the challenging sub-nanometre to few-nanometre size range.

100th Anniversary of Macromolecular Science Viewpoint: Integrated Membrane Systems.

Membranes fabricated from self-assembled materials are one recent example of how polymer science has been leveraged to advance membrane technology. Due to their well-defined nanostructures, the performance of membranes made from these materials is pushing the boundaries of size-selective filtration. Still, there remains a need for higher performance and more selective membranes. The advent of functional membrane platforms that rely on mechanisms beyond steric hindrance (e.g., charge-selective membranes and membrane sorbents) is one approach to realize improved solute-solute selectivity and further advance membrane technology. To date, the lab-scale demonstration of these platforms has often relied on fabrication schemes that require extended processing times. However, in order to translate lab-scale demonstrations to larger-scale implementation, it is critical that the rate of the functionalization scheme is reconciled with membrane manufacturing rates. In this viewpoint, it is postulated that substrates lined by reactive moieties that are amenable to postfabrication modification would enable the production of membranes with controlled nanostructures while providing access to a diverse array of pore wall chemistries. A comparison of reaction and manufacturing rates suggests that mechanisms that exhibit second-order reaction rate constants of at least 1 M-1 s-1 are needed for roll-to-roll processing. Furthermore, for mechanisms that exhibit rate constants greater than 300 M-1 s-1, it may be possible to integrate multiple functional domains over the membrane surface such that useful properties emerge. These multifunctional systems can expand the capabilities of membranes when the patterned chemistries interact at the heterojunctions between domains (e.g., Janus and charge-patterned mosaic membranes) or if they exhibit cooperative responses to external operating conditions (e.g., membrane pumps).

Interfacial Junctions Control Electrolyte Transport through Charge-Patterned Membranes.

Distinct transport mechanisms emerge when nanostructured substrates are patterned with multiple chemistries. For example, charge-patterned mosaic membranes possess surfaces functionalized with discrete domains of both positive and negative charge. These oppositely charged domains provide pathways for both the cation and anion from a dissolved salt to permeate through the membrane without violating the macroscopic constraint of electroneutrality. Here, by systematically varying the geometry and size of the charge pattern, we elucidate the molecular interactions that promote the transport of salts under the action of pressure-driven flow. For patterns that consist of equivalent areal coverages of positively charged and negatively charged domains, the effects of the geometric parameters were encapsulated in a single variable, the interfacial packing density, that quantified the fraction of the membrane surface covered by junctions between oppositely charged domains. Experimentally, the transport of symmetric electrolytes (i.e., KCl and MgSO4) increased with the value of the interfacial packing density, while the interfacial packing density did not significantly affect the transport of asymmetric electrolytes (i.e., K2SO4 and MgCl2). Simulations of the electrical potential near the membrane surface demonstrate that for symmetric electrolytes the structural charge heterogeneity reduces the barrier to ion partitioning, thereby promoting salt transport through the membranes. For asymmetric electrolytes, the charge heterogeneity skews the local availability of ions from the stoichiometric ratio of the salt, thus hindering salt transport. These findings demonstrate the promise of accessing transport mechanisms, which could find utility in a diverse range of chemical separations and sensing applications, through chemical patterning of membranes.

Publisher Correction: Achieving high permeability and enhanced selectivity for Angstrom-scale separations using artificial water channel membranes.

The original version of this Article contained an error in the spelling of the author Woochul Song, which was incorrectly given as Woochul C. Song. This has been corrected in both the PDF and HTML versions of the Article.

Achieving high permeability and enhanced selectivity for Angstrom-scale separations using artificial water channel membranes.

Synthetic polymer membranes, critical to diverse energy-efficient separations, are subject to permeability-selectivity trade-offs that decrease their overall efficacy. These trade-offs are due to structural variations (e.g., broad pore size distributions) in both nonporous membranes used for Angstrom-scale separations and porous membranes used for nano to micron-scale separations. Biological membranes utilize well-defined Angstrom-scale pores to provide exceptional transport properties and can be used as inspiration to overcome this trade-off. Here, we present a comprehensive demonstration of such a bioinspired approach based on pillar[5]arene artificial water channels, resulting in artificial water channel-based block copolymer membranes. These membranes have a sharp selectivity profile with a molecular weight cutoff of ~ 500 Da, a size range challenging to achieve with current membranes, while achieving a large improvement in permeability (~65 L m-2 h-1 bar-1 compared with 4-7 L m-2 h-1 bar-1) over similarly rated commercial membranes.

Facile Synthesis of a Pentiptycene-Based Highly Microporous Organic Polymer for Gas Storage and Water Treatment.

Rigid H-shaped pentiptycene units, with an intrinsic hierarchical structure, were employed to fabricate a highly microporous organic polymer sorbent via Friedel-Crafts reaction/polymerization. The obtained microporous polymer exhibits good thermal stability, a high Brunauer-Emmett-Teller surface area of 1604 m2 g-1, outstanding CO2, H2, and CH4 storage capacities, as well as good adsorption selectivities for the separation of CO2/N2 and CO2/CH4 gas pairs. The CO2 uptake values reached as high as 5.00 mmol g-1 (1.0 bar and 273 K), which, along with high adsorption selectivity values (e.g., 47.1 for CO2/N2), make the pentiptycene-based microporous organic polymer (PMOP) a promising sorbent material for carbon capture from flue gas and natural gas purification. Moreover, the PMOP material displayed superior absorption capacities for organic solvents and dyes. For example, the maximum adsorption capacities for methylene blue and Congo red were 394 and 932 mg g-1, respectively, promoting the potential of the PMOP as an excellent sorbent for environmental remediation and water treatment.

Polymeric Ion Pumps: Using an Oscillating Stimulus To Drive Solute Transport in Reactive Membranes.

The development of membranes that separate molecules on the basis of chemical factors, rather than physical factors, is one promising approach to meeting the demand for membranes that are more selective. In this study, the design of multifunctional, pH-responsive membranes that selectively pump a target solute is detailed. The membranes consist of two functional components: a gate layer made from an amine-functionalized copolymer and a reactive matrix lined by iminodiacetic acid groups that bind divalent cations reversibly. These two chemistries exhibit concurrent changes in the cation binding affinity and gate permeability in response to the pH value of the surrounding solution such that when the membranes are exposed to an oscillating pH, the combination drives a facilitated transport mechanism that pumps ions. In mixed solute systems, calcium permeated through the membrane four times faster than sucrose in the presence of an oscillating pH even though the solutes possess similar hydrodynamic sizes and permeated through the membrane at the same rate when the pH value was constant. The development of polymeric ion pumps was guided by a model that provided several critical insights. First, the solute binding capacity and thickness of the membrane define the asymptotic limit for enhanced selectivity. Second, the maximum enhancement in selectivity is realized in the limit of infinitely rapid oscillations. The multifunctional membranes discussed here provide a platform for the development of processes that can fractionate molecules of similar size but varying chemistry.

High-Affinity Detection and Capture of Heavy Metal Contaminants using Block Polymer Composite Membranes.

Adsorptive membranes offer one possible solution to the challenge of removing and recovering heavy metal ion contaminants and resources from water supplies. However, current membrane-based sorbents suffer from low binding affinities, leading to issues when contaminants are present at trace concentrations or when the source waters have a high concentration of background electrolytes that compete for open binding sites. Here, these challenges are addressed in the design of a highly permeable (i.e., permeability of ∼2.8 × 104 L m-2 h-1 bar-1) sorbent platform based on polysulfone and polystyrene-b-poly(acrylic acid) composite membranes. The membranes possess a fully interconnected network of poly(acrylic acid)-lined pores, which enables the surface chemistry to be tailored through sequential attachment of polyethylenimine brushes and metal-binding terpyridine ligands. The polyethylenimine brushes increase the saturation capacity, while the addition of terpyridine enables high-affinity binding to a diversity of transition metal ions (i.e., Pd2+, Cd2+, Hg2+, Pb2+, Zn2+, Co2+, Ni2+, Fe2+, Nd3+, and Sm3+). This platform removes these metal contaminants from solution with a sorbent capacity of 1.2 mmol g-1 [based on Cu2+ uptake]. The metal capture performance of the functionalized membranes persists in spite of high concentrations of competitive ions, with >99% removal of Pb2+ and Cd2+ ions from artificial groundwater and seawater solutions. Breakthrough experiments demonstrate the efficient purification of feed solutions containing multiple heavy metal ions under dynamic flow conditions. Finally, fluorescence quenching of the terpyridine moiety upon metal ion complexation offers an in situ probe to monitor the extent of sorbent saturation with a Stern-Volmer association constant of 2.9 × 104 L mol-1. The permeability, capacity, and affinity of these membranes, with high-density display of a metal-binding ligand, offer a chemically tailored platform to address the challenges that arise in ensuring clean water.

Nanoporous Block Polymer Thin Films Functionalized with Bio-Inspired Ligands for the Efficient Capture of Heavy Metal Ions from Water.

Heavy metal contamination of water supplies poses a serious threat to public health, prompting the development of novel and sustainable treatment technologies. One promising approach is to molecularly engineer the chemical affinity of a material for the targeted removal of specific molecules from solution. In this work, nanoporous polymer thin films generated from tailor-made block polymers were functionalized with the bio-inspired moieties glutathione and cysteamine for the removal of heavy metal ions, including lead and cadmium, from aqueous solutions. In a single equilibrium stage, the films achieved removal rates of the ions in excess of 95%, which was consistent with predictions based on the engineered material properties. In a flow-through configuration, the thin films achieved an even greater removal rate of the metal ions. Furthermore, in mixed ion solutions the capacity of the thin films, and corresponding removal rates, did not demonstrate any reduction due to competitive adsorption effects. After such experiments the material was repeatedly regenerated quickly with no observed loss in capacity. Thus, these membranes provide a sustainable platform for the efficient purification of lead- and cadmium-contaminated water sources to safe levels. Moreover, their straightforward chemical modifications suggest that they could be engineered to treat sources containing other recalcitrant environmental contaminants as well.

Block Polymer Membranes Functionalized with Nanoconfined Polyelectrolyte Brushes Achieve Sub-Nanometer Selectivity.

The well-defined nanostructure of membranes manufactured from self-assembled block polymers enables highly selective separations; however, recent efforts to push the pore size of block polymer-based membranes to the lower end of the size spectrum have only been moderately successful for a variety of reasons. For instance, the conformational changes of the stimuli-responsive functional groups lining the pore walls of some block polymer membranes result in varied pore sizes that limit their operational range. Here, we overcome this challenge through the directed design of the third moiety of an A-B-C triblock polymer. The use of this macromolecular design paradigm allows for the preparation of a 500 nm thick polyisoprene-b-polystyrene-b-poly(2-acrylamido-ethane-1,1-disfulonic acid) (PI-PS-PADSA) coating atop a hollow fiber membrane support. This nanoporous test bed, which exhibits an average pore radius of 1 nm, demonstrates an extremely high solute selectivity by fully gating solutes that have only an 8 Å size difference, a separation that is based solely on a sieving mechanism. Furthermore, the nanoscale structural characteristics of the solvated PADSA pore walls are elucidated by quantifying the rejection of neutral solutes and calculating the hydraulic permeability values in solutions of high ionic strength (1 mM ≤ I ≤ 3 M) and over a broad range of solution pH (1 ≤ pH ≤ 13). These key results provide a solid foundation for defining structure-property-performance relationships in the emerging area of nanoporous triblock polymer thin films. Moreover, the successful demonstration of the test bed separation device offers a tangible means by which to manufacture next-generation nanofiltration membranes that require a robust performance profile over a dynamic range of conditions.

A Method for the Efficient Fabrication of Multifunctional Mosaic Membranes by Inkjet Printing.

Most conventional membrane systems are based on size-selective materials that permeate smaller molecules and retain larger ones. However, membranes that can permeate larger molecules more rapidly than smaller ones could find widespread utilization in multiple arenas of technology. Charge mosaic membranes are one example of such a system. Due to their unique nanostructure, which consists of discrete oppositely charged domains, charge mosaics are capable of permeating large dissolved salts more rapidly than smaller water molecules. Here, we present a combined inkjet printing and template synthesis technique to prepare charge mosaic membranes in a rapid and straightforward manner and demonstrate the unique transport properties that result from the mosaic membrane design. Poly(vinyl alcohol)-based composite inks containing poly(diallyldimethylammonium chloride) or poly(sodium 4-styrenesulfonate) were used to pattern positively charged or negatively charged domains, respectively, on the surface of a polycarbonate track-etched membrane with 30 nm pores. The ability to control the net surface charge of the mosaic membranes through the rational deposition of oppositely charged materials was demonstrated and confirmed through nanostructural characterization, electrokinetic measurements, and piezodialysis experiments. Namely, mosaic membranes that possessed an overall neutral charge (i.e., membranes that had equal coverage of positively and negatively charged domains) were capable of enriching the concentration of potassium chloride in the solution that permeated through the membrane. These membranes can be deployed in the many established and emerging nanoscale technologies that rely on the selective transport and separation of ionic solutes from solution. Furthermore, because of the flexibility provided by the membrane fabrication platform, the efforts reported in this work can be extended to other mosaic designs with myriad other functional components.

Unusually Stable Hysteresis in the pH-Response of Poly(Acrylic Acid) Brushes Confined within Nanoporous Block Polymer Thin Films.

Stimuli-responsive soft materials are a highly studied field due to their wide-ranging applications; however, only a small group of these materials display hysteretic responses to stimuli. Moreover, previous reports of this behavior have typically shown it to be short-lived. In this work, poly(acrylic acid) (PAA) chains at extremely high grafting densities and confined in nanoscale pores displayed a unique long-lived hysteretic behavior caused by their ability to form a metastable hydrogen bond network. Hydraulic permeability measurements demonstrated that the conformation of the PAA chains exhibited a hysteretic dependence on pH, where different effective pore diameters arose in a pH range of 3 to 8, as determined by the pH of the previous environment. Further studies using Fourier transform infrared (FTIR) spectroscopy demonstrated that the fraction of ionized PAA moieties depended on the thin film history; this was corroborated by metal adsorption capacity, which demonstrated the same pH dependence. This hysteresis was shown to be persistent, enduring for days, in a manner unlike most other systems. The hypothesis that hydrogen bonding among PAA units contributed to the hysteretic behavior was supported by experiments with a urea solution, which disrupted the metastable hydrogen bonded state of PAA toward its ionized state. The ability of PAA to hydrogen bond within these confined pores results in a stable and tunable hysteresis not previously observed in homopolymer materials. An enhanced understanding of the polymer chemistry and physics governing this hysteresis gives insight into the design and manipulation of next-generation sensors and gating materials in nanoscale applications.

Template Synthesis of Nanostructured Polymeric Membranes by Inkjet Printing.

The fabrication of functional nanomaterials with complex structures has been serving great scientific and practical interests, but current fabrication and patterning methods are generally costly and laborious. Here, we introduce a versatile, reliable, and rapid method for fabricating nanostructured polymeric materials. The novel method is based on a combination of inkjet printing and template synthesis, and its utility and advantages in the fabrication of polymeric nanomaterials is demonstrated through three examples: the generation of polymeric nanotubes, nanowires, and thin films. Layer-by-layer-assembled nanotubes can be synthesized in a polycarbonate track-etched (PCTE) membrane by printing poly(allylamine hydrochloride) and poly(styrenesulfonate) sequentially. This sequential deposition of polyelectrolyte ink enables control over the surface charge within the nanotubes. By a simple change of the printing conditions, polymeric nanotubes or nanowires were prepared by printing poly(vinyl alcohol) in a PCTE template. In this case, the high-throughput nature of the method enables functional nanomaterials to be generated in under 3 min. Furthermore, we demonstrate that inkjet printing paired with template synthesis can be used to generate patterns comprised of chemically distinct nanomaterials. Thin polymeric films of layer-by-layer-assembled poly(allylamine hydrochloride) and poly(styrenesulfonate) are printed on a PCTE membrane. Track-etched membranes covered with the deposited thin films reject ions and can potentially be utilized as nanofiltration membranes. When the fabrication of these different classes of nanostructured materials is demonstrated, the advantages of pairing template synthesis with inkjet printing, which include fast and reliable deposition, judicious use of the deposited materials, and the ability to design chemically patterned surfaces, are highlighted.

Nanostructured Membranes from Triblock Polymer Precursors as High Capacity Copper Adsorbents.

Membrane adsorbers are a proposed alternative to packed beds for chromatographic separations. To date, membrane adsorbers have suffered from low binding capacities and/or complex processing methodologies. In this work, a polyisoprene-b-polystyrene-b-poly(N,N-dimethylacrylamide) (PI-PS-PDMA) triblock polymer is cast into an asymmetric membrane that possesses a high density of nanopores (d ∼ 38 nm) at the upper surface of the membrane. Exposing the membrane to a 6 M aqueous hydrochloric acid solution converts the PDMA brushes that line the pore walls to poly(acrylic acid) (PAA) brushes, which are capable of binding metal ions (e.g., copper ions). Using mass transport tests and static binding experiments, the saturation capacity of the PI-PS-PAA membrane was determined to be 4.1 ± 0.3 mmol Cu(2+) g(-1). This experimental value is consistent with the theoretical binding capacity of the membranes, which is based on the initial PDMA content of the triblock polymer precursor and assumes a 1:1 stoichiometry for the binding interaction. The uniformly sized nanoscale pores provide a short diffusion length to the binding sites, resulting in a sharp breakthrough curve. Furthermore, the membrane is selective for copper ions over nickel ions, which permeate through the membrane over 10 times more rapidly than copper during the loading stage. This selectivity is present despite the fact that the sizes of these two ions are nearly identical and speaks to the chemical selectivity of the triblock polymer-based membrane. Furthermore, addition of a pH 1 solution releases the bound copper rapidly, allowing the membrane to be regenerated and reused with a negligible loss in binding capacity. Because of the high binding capacities, facile processing method implemented, and ability to tailor further the polymer brushes lining the pore walls using straightforward coupling reactions, these membrane adsorbers based on block polymer precursors have potential as a separation media that can be designed to a variety of specific applications.

Preparation of Chemically-Tailored Copolymer Membranes with Tunable Ion Transport Properties.

Membranes derived from copolymer materials are a promising platform due to their straightforward fabrication and small yet tunable pore structures. However, most current applications of these membranes are limited to the size-selective filtration of solutes. In this study, to advance the utility of copolymer membranes beyond size-selective filtrations, a poly(acrylonitrile-r-oligo(ethylene glycol) methyl ether methacrylate-r-glycidyl methacrylate) (P(AN-r-OEGMA-r-GMA)) copolymer is used to fabricate membranes that can be chemically modified via straightforward schemes. The P(AN-r-OEGMA-r-GMA) copolymer is cast into asymmetric membranes using a nonsolvent induced phase separation technique. Then, the surface charge of the membrane is modified to tailor its performance for nanofiltration applications. The oxirane groups of the glycidyl methacrylate (GMA) moiety that line the pore walls of the membrane allows for both positively charged and negatively charged moieties to be introduced directly without any prior activation. Notably, the highly size-selective nanostructure of the copolymer materials is retained throughout the functionalization processes. Specifically, amine moieties are attached to the pore walls using the aminolysis of the oxirane groups. The resulting amine-functionalized membrane is positively charged and rejects up to 87% of the salt dissolved in a 10 mM magnesium chloride feed solution. Further modification of the amine-functionalized membrane with 4-sulfophenyl isothiocyanate results in pore walls lined by sulfonic acid moieties. These negatively charged membranes reject up to 90% of a 10 mM sodium sulfate feed solution. Throughout the modification scheme, the membrane permeability remains equal to 1.5 L m(-2) h(-1) bar(-1) and the rejection of neutral solutes (i.e., sucrose and poly(ethylene oxide)) is consistent with the membrane having a single well-defined pore diameter of ∼5 nm. The performance of the membrane as a function of ion valence number, solution pH, and ionic strength is investigated.

Mixed mosaic membranes prepared by layer-by-layer assembly for ionic separations.

Charge mosaic membranes, which possess distinct cationic and anionic domains that traverse the membrane thickness, are capable of selectively separating dissolved salts from similarly sized neutral solutes. Here, the generation of charge mosaic membranes using facile layer-by-layer assembly methodologies is reported. Polymeric nanotubes with pore walls lined by positively charged polyethylenimine moieties or negatively charged poly(styrenesulfonate) moieties were prepared via layer-by-layer assembly using track-etched membranes as sacrificial templates. Subsequently, both types of nanotubes were deposited on a porous support in order to produce mixed mosaic membranes. Scanning electron microscopy demonstrates that the facile deposition techniques implemented result in nanotubes that are vertically aligned without overlap between adjacent elements. Furthermore, the nanotubes span the thickness of the mixed mosaic membranes. The effects of this unique nanostructure are reflected in the transport characteristics of the mixed mosaic membranes. The hydraulic permeability of the mixed mosaic membranes in piezodialysis operations was 8 L m(-2) h(-1) bar(-1). Importantly, solute rejection experiments demonstrate that the mixed mosaic membranes are more permeable to ionic solutes than similarly sized neutral molecules. In particular, negative rejection of sodium chloride is observed (i.e., the concentration of NaCl in the solution that permeates through a mixed mosaic membrane is higher than in the initial feed solution). These properties illustrate the ability of mixed mosaic membranes to permeate dissolved ions selectively without violating electroneutrality and suggest their utility in ionic separations.

Ultrafiltration of uranyl peroxide nanoclusters for the separation of uranium from aqueous solution.

Uranyl peroxide cluster species were produced in aqueous solution by the treatment of uranyl nitrate with hydrogen peroxide, lithium hydroxide, and potassium chloride. Ultrafiltration of these cluster species using commercial sheet membranes with molecular mass cutoffs of 3, 8, and 20 kDa (based on polyethylene glycol) resulted in U rejection values of 95, 85, and 67% by mass, respectively. Ultrafiltration of untreated uranyl nitrate solutions using these membranes resulted in virtually no rejection of U. These results demonstrate the ability to use the filtration of cluster species as a means for separating U from solutions on the basis of size. Small-angle X-ray scattering, Raman spectroscopy, and electrospray ionization mass spectrometry confirmed the presence of uranyl peroxide cluster species in solution and were used to characterize their size, shape, and dispersity.