Designing polymeric membranes with coordination chemistry for high-precision ion separations.

State-of-the-art polymeric membranes are unable to perform the high-precision ion separations needed for technologies essential to a circular economy and clean energy future. Coordinative interactions are a mechanism to increase sorption of a target species into a membrane, but the effects of these interactions on membrane permeability and selectivity are poorly understood. We use a multilayered polymer membrane to assess how ion-membrane binding energies affect membrane permeability of similarly sized cations: Cu2+, Ni2+, Zn2+, Co2+, and Mg2+. We report that metals with higher binding energy to iminodiacetate groups of the polymer more selectively permeate through the membrane in multisalt solutions than single-salt solutions. In contrast, weaker binding species are precluded from diffusing into the polymer membrane, which leads to passage proportional to binding energy and independent of membrane thickness. Our findings demonstrate that selectivity of polymeric membranes can markedly increase by tailoring ion-membrane binding energy and minimizing membrane thickness.

Membrane Materials for Selective Ion Separations at the Water-Energy Nexus.

Synthetic polymer membranes are enabling components in key technologies at the water-energy nexus, including desalination and energy conversion, because of their high water/salt selectivity or ionic conductivity. However, many applications at the water-energy nexus require ion selectivity, or separation of specific ionic species from other similar species. Here, the ion selectivity of conventional polymeric membrane materials is assessed and recent progress in enhancing selective transport via tailored free volume elements and ion-membrane interactions is described. In view of the limitations of polymeric membranes, three material classes-porous crystalline materials, 2D materials, and discrete biomimetic channels-are highlighted as possible candidates for ion-selective membranes owing to their molecular-level control over physical and chemical properties. Lastly, research directions and critical challenges for developing bioinspired membranes with molecular recognition are provided.

Precisely Engineered Photoreactive Titanium Nanoarray Coating to Mitigate Biofouling in Ultrafiltration.

To combat biofouling on membranes, diverse nanostructures of titanium dioxide (TiO2) have emerged as effective antimicrobial coatings due to TiO2's abilities to transport charge and photoinduce oxidation. However, TiO2 composite polymeric membranes synthesized using traditional methods of growing crystals have proven chemically unstable, with loss of coating and diminishing antimicrobial performance. Thus, new fabrication methods to enhance durability and efficacy should be considered. In this work, we propose a stepwise approach to construct a stable, uniform TiO2 nanoarray of regularly spaced, aligned crystals on the surface of a polytetrafluoroethylene ultrafiltration membrane using precisely controlled atomic layer deposition (ALD) followed by solvothermal deposition. We demonstrate that ALD can uniformly seed TiO2 nanoparticles on the membrane surface with atomic-scale precision. Subsequently, solvothermal deposition assembles and aligns a uniform TiO2 nanoarray forest. In the presence of sunlight, this TiO2 nanoarray effectively inactivates any deposited bacteria, increasing flux recovery after membrane cleaning. By systematically investigating this antimicrobial activity, we found that TiO2 both physically damages cell membranes as well as produces reactive oxygen species in the presence of sunlight that inactivate bacteria. Our study provides an effective bottom-up synthesis scheme to optimize and tailor antifouling TiO2 coatings for ultrafiltration and other surfaces for a wide range of applications.

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.

Concentration and Recovery of Dyes from Textile Wastewater Using a Self-Standing, Support-Free Forward Osmosis Membrane.

Forward osmosis (FO) can potentially treat textile wastewaters with less fouling than pressure-driven membrane processes such as reverse osmosis and nanofiltration. However, conventional FO membranes with asymmetric architecture experience severe flux decline caused by internal concentration polarization and fouling as dye molecules accumulate on the membrane surface. In this study, we present a new strategy for concentrating dye by using a self-standing, support-free FO membrane with a symmetric structure. The membrane was fabricated by a facile solution-casting approach based on a poly(triazole- co-oxadiazole- co-hydrazine) (PTAODH) skeleton. Due to its dense architecture, ultrasmooth surface, and high negative surface charge, the PTAODH membrane exhibits excellent FO performance with minimal fouling, low reverse salt flux, and negligible dye passage to the draw solution side. Cleaning with a 40% alcohol solution, after achieving a concentration factor of ∼10, resulted in high flux recovery ratio (98.7%) for the PTAODH membrane, whereas significant damage to the active layers of two commercial FO membranes was observed. Moreover, due to the existence of cytotoxic oxadiazole and triazole moieties in the polymer structure, our PTAODH membrane exhibited an outstanding antibacterial property with two model bacteria. Our results demonstrate the promising application of the symmetric PTAODH membrane for the concentration of textile wastewaters and its superior antifouling performance compared to state-of-the-art commercial FO 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.