Ionization behavior of nanoporous polyamide membranes.

Escalating global water scarcity necessitates high-performance desalination membranes, for which fundamental understanding of structure-property-performance relationships is required. In this study, we comprehensively assess the ionization behavior of nanoporous polyamide selective layers in state-of-the-art nanofiltration (NF) membranes. In these films, residual carboxylic acids and amines influence permeability and selectivity by imparting hydrophilicity and ionizable moieties that can exclude coions. We utilize layered interfacial polymerization to prepare physically and chemically similar selective layers of controlled thickness. We then demonstrate location-dependent ionization of carboxyl groups in NF polyamide films. Specifically, only surface carboxyl groups ionize under neutral pH, whereas interior carboxyl ionization requires pH >9. Conversely, amine ionization behaves invariably across the film. First-principles simulations reveal that the low permittivity of nanoconfined water drives the anomalous carboxyl ionization behavior. Furthermore, we report that interior carboxyl ionization could improve the water-salt permselectivity of NF membranes over fourfold, suggesting that interior charge density could be an important tool to enhance the selectivity of polyamide membranes. Our findings highlight the influence of nanoconfinement on membrane transport properties and provide enhanced fundamental understanding of ionization that could enable novel membrane design.

Polymeric Microcapsules as Robust Mimics of Emulsion Liquid Membranes for Selective Ion Separations.

Selective ion separations are increasingly needed to combat water scarcity, recover resources from wastewater, and enable the efficient recycling of electronics waste. Emulsion liquid membranes (ELMs) have received interest due to rapid kinetics, high selectivities, and low solvent requirements but are too unstable for industrial usage. We demonstrate that polymeric microcapsules can serve as robust, solvent-free mimics of ELMs. As a proof of concept, we incorporated the copper-selective ligand Lix 84-I in the walls of microcapsules formed from a commercial polystyrene-b-polybutadiene-b-polystyrene triblock polymer. The microcapsules were formed from a double-emulsion template, resulting in particles typically 20-120 µm in diameter that encapsulated even smaller droplets of a dilute (≤0.5 M) H2SO4 solution. Batch experiments demonstrated facilitated-transport behavior, with equilibrium reached in as little as 10 min for microcapsules with 1% ligand, and with ∼15-fold selectivity for Cu2+ over Ni2+. Furthermore, the microcapsules could be packed readily in columns for flow-through operation, thus enabling near-complete Cu2+ removal in ∼2 min under certain conditions, recovery of Cu2+ by flowing through fresh dilute H2SO4, and reuse for at least 10 cycles. The approach in this work can serve as a template for using selective ligands to enable robust and simple flow-through processes for a variety of selective ion separations.

Functionalized Polymersomes from a Polyisoprene-Activated Polyacrylamide Precursor.

Self-assembled polymer nanoparticles have tremendous potential in biomedical and environmental applications. For all applications, tailored polymer chemistries are critical. In this study, we demonstrate a precursor approach in which an activated, organic solvent-soluble block polymer precursor is modified through mild postpolymerization modifications to access new polymer structures. We synthesized and characterized poly(isoprene)-block-poly(di-Boc acrylamide) diblock polymers. This activated-acrylamide-based polymer was then reacted with amines or reductants in the absence of catalysts to yield the hydrophilic blocks polyacrylamide, poly(hydroxypropylene), and poly(N-ethyl acrylamide). The resulting amphiphilic block polymers self-assembled in water to form polymersomes, as confirmed by cryo-electron microscopy and confocal microscopy. The approach also enables simple functionalization with specialized ligands, which we demonstrated by tagging polymers with an amino-fluorophore and imaging by confocal microscopy. We expect that the methodologies established in this study will open doors to new and useful solution nanostructures with surface chemistries that can be optimized for various applications.

Enhanced antibacterial activity through the controlled alignment of graphene oxide nanosheets.

The cytotoxicity of 2D graphene-based nanomaterials (GBNs) is highly important for engineered applications and environmental health. However, the isotropic orientation of GBNs, most notably graphene oxide (GO), in previous experimental studies obscured the interpretation of cytotoxic contributions of nanosheet edges. Here, we investigate the orientation-dependent interaction of GBNs with bacteria using GO composite films. To produce the films, GO nanosheets are aligned in a magnetic field, immobilized by cross-linking of the surrounding matrix, and exposed on the surface through oxidative etching. Characterization by small-angle X-ray scattering and atomic force microscopy confirms that GO nanosheets align progressively well with increasing magnetic field strength and that the alignment is effectively preserved by cross-linking. When contacted with the model bacterium Escherichia coli, GO nanosheets with vertical orientation exhibit enhanced antibacterial activity compared with random and horizontal orientations. Further characterization is performed to explain the enhanced antibacterial activity of the film with vertically aligned GO. Using phospholipid vesicles as a model system, we observe that GO nanosheets induce physical disruption of the lipid bilayer. Additionally, we find substantial GO-induced oxidation of glutathione, a model intracellular antioxidant, paired with limited generation of reactive oxygen species, suggesting that oxidation occurs through a direct electron-transfer mechanism. These physical and chemical mechanisms both require nanosheet penetration of the cell membrane, suggesting that the enhanced antibacterial activity of the film with vertically aligned GO stems from an increased density of edges with a preferential orientation for membrane disruption. The importance of nanosheet penetration for cytotoxicity has direct implications for the design of engineering surfaces using GBNs.

Monte Carlo Simulations of Framework Defects in Layered Two-Dimensional Nanomaterial Desalination Membranes: Implications for Permeability and Selectivity.

Two-dimensional nanomaterial (2-D NM) frameworks, especially those comprising graphene oxide, have received extensive research interest for membrane-based separation processes and desalination. However, the impact of horizontal defects in 2-D NM frameworks, which stem from nonuniform deposition of 2-D NM flakes during layer build-up, has been almost entirely overlooked. In this work, we apply Monte Carlo simulations, under idealized conditions wherein the vertical interlayer spacing allows for water permeation while perfectly excluding salt, on both the formation of the laminate structure and molecular transport through the laminate. Our simulations show that 2-D NM frameworks are extremely tortuous (tortuosity ≈103), with water permeability decreasing from 20 to <1 L m-2 h-1 bar-1 as thickness increased from 8 to 167 nm. Additionally, we find that framework defects allow salt to percolate through the framework, hindering water-salt selectivity. 2-D NM frameworks with a packing density of 75%, representative of most 2-D NM membranes, are projected to achieve <92% NaCl rejection at a water permeability of <1 L m-2 h-1 bar-1, even with ideal interlayer spacing. A high packing density of 90%, which to our knowledge has yet to be achieved, could yield comparable performance to current desalination membranes. Maximizing packing density is therefore a critical technical challenge, in addition to the already daunting challenge of optimizing interlayer spacing, for the development of 2-D NM membranes.

A Path to Ultraselectivity: Support Layer Properties To Maximize Performance of Biomimetic Desalination Membranes.

Reverse osmosis (RO) has become a premier technology for desalination and water purification. The need for increased selectivity has incentivized research into novel membranes, such as biomimetic membranes that incorporate the perfectly selective biological water channel aquaporin or synthetic water channels like carbon nanotubes. In this study, we consider the performance of composite biomimetic membranes by projecting water permeability, salt rejection, and neutral-solute retention based on the permeabilities of the individual components, particularly the water channel, the amphiphilic bilayer matrix, and potential support layers that include polymeric RO, nanofiltration (NF), and porous ultrafiltration membranes. We find that the support layer will be crucial in the overall performance. Selective, relatively low-permeability supports minimize the negative impact of defects in the biomimetic layer, which are currently the main performance-limiting factor for biomimetic membranes. In particular, RO membranes as support layers would enable >99.85% salt rejection at ∼10000-fold greater biomimetic-layer defect area than for porous supports. By fundamentally characterizing neutral-solute permeation through RO and NF membranes, we show that RO membranes as support layers would enable high rejection of organic pollutants based on molecular size, overcoming the rapid permeation of hydrophobic solutes through the biomimetic layer. A biomimetic membrane could also achieve exceptionally high boron rejections of ∼99.7%, even with 1% defect area in the biomimetic layer. We conclude by discussing the implications of our findings for biomimetic membrane design.

Co-Casting Highly Selective Dual-Layer Membranes with Disordered Block Polymer Selective Layers.

Highly selective and water permeable dual-layer ultrafiltration (UF) membranes comprising a disordered poly(methyl methacrylate-stat-styrene)-block-poly(lactide) selective layer and a polysulfone (PSF) support layer were fabricated using a co-casting technique. A dilute solution of diblock polymer was spin coated onto a solvent-swollen PSF layer, rapidly heated to dry and disorder the block polymer layer, and subsequently immersed into an ice water coagulation bath to kinetically trap the disordered state in the block polymer selective layer and precipitate the support layer by nonsolvent-induced phase separation. Subsequent removal of the polylactide block generated porous membranes suitable for UF. The permeability of these dual-layer membranes was modulated by tuning the concentration of the PSF casting solution, while the size-selectivity was maintained because of the narrow pore size distribution of the self-assembled block polymer selective layer. Elimination of the thermal annealing step resulted in a dramatic increase in the water permeability without adversely impacting the size-selectivity, as the disordered nanostructure present in the concentrated casting solution was kinetically trapped upon rapid drying. The co-casting strategy outlined in this work may enable the scalable fabrication of block polymer membranes with both high permeability and high selectivity.

Capillary-driven desalination in a synthetic mangrove.

According to the cohesion-tension theory, mangrove trees desalinate salty water using highly negative pressure (or tension) that is generated by evaporative capillary forces in mangrove leaves. Here, we demonstrate a synthetic mangrove that mimics the main features of the natural mangrove: capillary pumping (leaves), stable water conduction in highly metastable states (stem), and membrane desalination (root). When using nanoporous membranes as leaves, the maximum osmotic pressures of saline feeds (10 to 30 bar) allowing pure water uptake precisely correspond to expected capillary pressures based on the Young-Laplace equation. Hydrogel-based leaves allow for stable operation and desalination of hypersaline solutions with osmotic pressures approaching 400 bar, fivefold greater than the pressure limits of conventional reverse osmosis. Our findings support the applicability of the cohesion-tension theory to desalination in mangroves, provide a new platform to study plant hydraulics, and create possibilities for engineered membrane separations using large, passively generated capillary pressures.

Next-Generation Ultrafiltration Membranes Enabled by Block Polymers.

Reliable and equitable access to safe drinking water is a major and growing challenge worldwide. Membrane separations represent one of the most promising strategies for the energy-efficient purification of potential water sources. In particular, porous membranes are used for the ultrafiltration (UF) of water to remove contaminants with nanometric sizes. However, despite exhibiting excellent water permeability and solution processability, existing UF membranes contain a broad distribution of pore sizes that limit their size selectivity. To maximize the potential utility of UF membranes and allow for precise separations, improvements in the size selectivity of these systems must be achieved. Block polymers represent a potentially transformative solution, as these materials self-assemble into well-defined domains of uniform size. Several different strategies have been reported for integrating block polymers into UF membranes, and each strategy has its own set of materials and processing considerations to ensure that uniform and continuous pores are generated. This Review aims to summarize and critically analyze the chemistries, processing techniques, and properties required for the most common methods for producing porous membranes from block polymers, with a particular focus on the fundamental mechanisms underlying block polymer self-assembly and pore formation. Critical structure-property-performance metrics will be analyzed for block polymer UF membranes to understand how these membranes compare to commercial UF membranes and to identify key research areas for continued improvements. This Review is intended to inform readers of the capabilities and current challenges of block polymer UF membranes, while stimulating critical thought on strategies to advance these technologies.

Pathways and Challenges for Biomimetic Desalination Membranes with Sub-Nanometer Channels.

Transmembrane protein channels, including ion channels and aquaporins that are responsible for fast and selective transport of water, have inspired membrane scientists to exploit and mimic their performance in membrane technologies. These biomimetic membranes comprise discrete nanochannels aligned within amphiphilic matrices on a robust support. While biological components have been used directly, extensive work has also been conducted to produce stable synthetic mimics of protein channels and lipid bilayers. However, the experimental performance of biomimetic membranes remains far below that of biological membranes. In this review, we critically assess the status and potential of biomimetic desalination membranes. We first review channel chemistries and their transport behavior, identifying key characteristics to optimize water permeability and salt rejection. We compare various channel types within an industrial context, considering transport performance, processability, and stability. Through a re-examination of previous vesicular stopped-flow studies, we demonstrate that incorrect permeability equations result in an overestimation of the water permeability of nanochannels. We find in particular that the most optimized aquaporin-bearing bilayer had a pure water permeability of 2.1 L m-2 h-1 bar-1, which is comparable to that of current state-of-the-art polymeric desalination membranes. Through a quantitative assessment of biomimetic membrane formats, we analytically show that formats incorporating intact vesicles offer minimal benefit, whereas planar biomimetic selective layers could allow for dramatically improved salt rejections. We then show that the persistence of nanoscale defects explains observed subpar performance. We conclude with a discussion on optimal strategies for minimizing these defects, which could enable breakthrough performance.

Permselectivity limits of biomimetic desalination membranes.

Water scarcity and inadequate membrane selectivity have spurred interest in biomimetic desalination membranes, in which biological or synthetic water channels are incorporated in an amphiphilic bilayer. As low channel densities (0.1 to 10%) are required for sufficient water permeability, the amphiphilic bilayer matrix will play a critical role in separation performance. We determine selectivity limits for biomimetic membranes by studying the transport behavior of water, neutral solutes, and ions through the bilayers of lipid and block-copolymer vesicles and projecting performance for varying water channel densities. We report that defect-free biomimetic membranes would have water/salt permselectivities ~108-fold greater than current desalination membranes. In contrast, the solubility-based permeability of lipid and block-copolymer bilayers (extending Overton's rule) will result in poor rejection of hydrophobic solutes. Defect-free biomimetic membranes thus offer great potential for seawater desalination and ultrapure water production, but would perform poorly in wastewater reuse. Potential strategies to limit neutral solute permeation are discussed.