Tunable membranes incorporating artificial water channels for high-performance brackish/low-salinity water reverse osmosis desalination.

Membrane-based technologies have a tremendous role in water purification and desalination. Inspired by biological proteins, artificial water channels (AWCs) have been proposed to overcome the permeability/selectivity trade-off of desalination processes. Promising strategies exploiting the AWC with angstrom-scale selectivity have revealed their impressive performances when embedded in bilayer membranes. Herein, we demonstrate that self-assembled imidazole-quartet (I-quartet) AWCs are macroscopically incorporated within industrially relevant reverse osmosis membranes. In particular, we explore the best combination between I-quartet AWC and m-phenylenediamine (MPD) monomer to achieve a seamless incorporation of AWC in a defect-free polyamide membrane. The performance of the membranes is evaluated by cross-flow filtration under real reverse osmosis conditions (15 to 20 bar of applied pressure) by filtration of brackish feed streams. The optimized bioinspired membranes achieve an unprecedented improvement, resulting in more than twice (up to 6.9 L⋅m-2⋅h-1⋅bar-1) water permeance of analogous commercial membranes, while maintaining excellent NaCl rejection (>99.5%). They show also excellent performance in the purification of low-salinity water under low-pressure conditions (6 bar of applied pressure) with fluxes up to 35 L⋅m-2⋅h-1 and 97.5 to 99.3% observed rejection.

Advanced stimuli-responsive membranes for smart separation.

Membranes have been extensively studied and applied in various fields owing to their high energy efficiency and small environmental impact. Further conferring membranes with stimuli responsiveness can allow them to dynamically tune their pore structure and/or surface properties for efficient separation performance. This review summarizes and discusses important developments and achievements in stimuli-responsive membranes. The most commonly utilized stimuli, including light, pH, temperature, ions, and electric and magnetic fields, are discussed in detail. Special attention is given to stimuli-responsive control of membrane pore structure (pore size and porosity/connectivity) and surface properties (wettability, surface topology, and surface charge), from the perspective of determining the appropriate membrane properties and microstructures. This review also focuses on strategies to prepare stimuli-responsive membranes, including blending, casting, polymerization, self-assembly, and electrospinning. Smart applications for separations are also reviewed as well as a discussion of remaining challenges and future prospects in this exciting field. This review offers critical insights for the membrane and broader materials science communities regarding the on-demand and dynamic control of membrane structures and properties. We hope that this review will inspire the design of novel stimuli-responsive membranes to promote sustainable development and make progress toward commercialization.

Investigating the thermal stability of metallic and non-metallic nanoparticles using a novel graphene oxide-based transmission electron microscopy heating-membrane.

In recent years, graphene has been explored as a heating membrane for studying high-temperature dynamics inside the transmission electron microscope (TEM) due to several limitations with the existing silicon nitride-based membrane. However, the transfer of monolayer graphene films for TEM experiments is challenging and requires many complicated steps with a minimum success rate. This work developed a novelin situheating platform by combining the graphene oxide (GO) flakes in the pre-patterned chips. The isolated GO flake was self-suspended between the metal electrodes by a simple drop-casting process. The GO was reduced and characterized using Raman and electron energy-loss spectroscopy. Furthermore, a GO-based heater was used to investigate the thermal stability of gold and silica nanoparticles. The gold nanoparticles evaporated non-uniformly and left an empty carbon shell, while silica disappeared uniformly by etching carbon support. We successfully demonstrated a GO flake as a heating membrane to study high temperature thermal dynamic reactions: melting/evaporation, agglomeration, Rayleigh instability, and formation/or removal of carbon in the nanoparticles.

Interfacial Polymerization of Zwitterionic Building Blocks for High-Flux Nanofiltration Membranes.

A simple scalable strategy is proposed to fabricate highly permeable antifouling nanofiltration membranes. Membranes with a selective thin polyamide layer were prepared via interfacial polymerization incorporating building blocks of zwitterionic copolymers. The zwitterionic copolymer, poly(aminopropyldimethylaminoethyl methacrylate)- co-poly(sulfobetaine methacrylate) with an average molecular weight of 6.1 kg mol-1, was synthesized in three steps: (i) polymerization of dimethylaminoethyl methacrylate to yield the base polymer by atom transfer radical polymerization (ATRP), (ii) fractional sulfobetainization via quaternization, and (iii) amination via quaternization. The effect of the zwitterionic polymer content on the polyamide surface characteristics, fouling resistance, and permeance is demonstrated. The zwitterion-modified membrane becomes more hydrophilic with lower surface roughness, as the zwitterionic polymer fraction increases. The excellent fouling resistance of the zwitterion-modified membrane was confirmed by the negligible protein adsorption and low bacteria fouling compared to a pristine membrane without zwitterionic segments. In addition, the zwitterion-modified membranes achieve a water permeation around 135 L m-2 h-1bar-1, which is 27-fold higher than that of the pristine membrane, along with good selectivity in the nanofiltration range, confirmed by the rejection of organic dyes. This permeance is about 10 times higher than that of other reported loose nanofiltration membranes with comparable dye rejection. The newly designed membrane is promising as a highly permeable fouling resistant cross-linked polyamide network for various water treatment applications.

Functionalized Nanochannels from Self-Assembled and Photomodified Poly(Styrene-b-Butadiene-b-Styrene).

Membranes are prepared by self-assembly and casting of 5 and 13 wt% poly(styrene-b-butadiene-b-styrene) (PS-b-PB-b-PS) copolymers solutions in different solvents, followed by immersion in water or ethanol. By controlling the solution-casting gap, porous films of 50 and 1 µm thickness are obtained. A gradient of increasing pore size is generated as the distance from the surface increased. An ordered porous surface layer with continuous nanochannels can be observed. Its formation is investigated, by using time-resolved grazing incident small angle X-ray scattering, electron microscopy, and rheology, suggesting a strong effect of the air-solution interface on the morphology formation. The thin PS-b-PB-b-PS ordered films are modified, by promoting the photolytic addition of thioglycolic acid to the polybutadiene groups, adding chemical functionality and specific transport characteristics on the preformed nanochannels, without sacrificing the membrane morphology. Photomodification increases fivefold the water permeance to around 2 L m-2 h-1 bar-1 , compared to that of the unmodified one. A rejection of 74% is measured for methyl orange in water. The membranes fabrication with tailored nanochannels and chemical functionalities can be demonstrated using relatively lower cost block copolymers. Casting on porous polyacrylonitrile supports makes the membranes even more scalable and competitive in large scale.

Carboxyl-functionalized nanochannels based on block copolymer hierarchical structures.

When building artificial nanochannels, having a scalable robust platform with controlled morphology is important, as well as having the option for final functionalization of the channels for the selective transport of water and proteins. We have previously developed asymmetric membranes that have a surface layer of very sharp pore size distribution, surface charge and pore functionalization. Here, a more complex bioinspired platform is reported. Hierarchical isotropic porous structures with spherical micrometer-sized cavities, interconnected by hexagonally ordered nanochannels, were prepared based on the phase separation of polystyrene-b-poly(t-butyl acrylate) block copolymers, following a nucleation and growth mechanism. The structure was imaged by scanning electron microscopy, which demonstrated a high density of ordered nanochannels. The hexagonal order formed by the self-assembly in solution was confirmed by small-angle X-ray scattering. The structure evolution was investigated by time-resolved grazing-incidence small-angle X-ray scattering. The assembled hydrophobic hierarchical structure was then converted to a hydrophilic structure by acid hydrolysis, leading to nanochannels covered by carboxylic groups and therefore convenient for water transport.

Self-Assembled Asymmetric Block Copolymer Membranes: Bridging the Gap from Ultra- to Nanofiltration.

The self-assembly of block copolymers is an emerging strategy to produce isoporous ultrafiltration membranes. However, thus far, it has not been possible to bridge the gap from ultra- to nanofiltration and decrease the pore size of self-assembled block copolymer membranes to below 5 nm without post-treatment. It is now reported that the self-assembly of blends of two chemically interacting copolymers can lead to highly porous membranes with pore diameters as small as 1.5 nm. The membrane containing an ultraporous, 60 nm thin separation layer can fully reject solutes with molecular weights of 600 g mol(-1) in aqueous solutions with a water flux that is more than one order of magnitude higher than the permeance of commercial nanofiltration membranes. Simulations of the membrane formation process by dissipative particle dynamics (DPD) were used to explain the dramatic observed pore size reduction combined with an increase in water flux.

Self-assembled isoporous block copolymer membranes with tuned pore sizes.

The combination of nonsolvent-induced phase separation and the self-assembly of block copolymers can lead to asymmetric membranes with a thin highly ordered isoporous skin layer. The effective pore size of such membranes is usually larger than 15 nm. We reduced the pore size of these membranes by electroless gold deposition. We demonstrate that the pore sizes can be controlled precisely between 3 and 20 nm leading to a tunable sharp size discrimination in filtration processes. Besides fractionation of nanoparticles and biomaterials, controlled drug delivery is an attractive potential application.

Biofilm rigidity, mechanics and composition in seawater desalination pretreatment employing ultrafiltration and microfiltration membranes.

The choice of appropriate biofilm control strategies in membrane systems for seawater desalination pretreatment relies on understanding the properties of the biofilm formed on the membrane. This study reveals how the biofilm composition, including both organic and inorganic, influenced the biofilm behavior under mechanical loading. The investigation was conducted on two Gravity-Driven Membrane reactors employing Microfiltration (MF) and Ultrafiltration (UF) membrane for the pretreatment of raw seawater. After a stabilization period of 20 days (Phase I), a biofilm behavior test was introduced (Phase II) to evaluate (i) biofilm deformation during the absence of permeation (i.e., relaxation) and (ii) biofilm resistance to detachment forces (i.e., air scouring). The in-situ monitoring investigation using Optical Coherence Tomography (OCT) revealed that the biofilms developed on MF and UF membrane presented a rigid structure in absence of filtration forces, limiting the application of relaxation and biofilm expansion necessary for cleaning. Moreover, under shear stress conditions, a higher reduction in biofilm thickness was observed for MF (-60%, from 84 to 34 µm) compared to UF (-30%, from 64 to 45 µm), leading to an increase of permeate flux (+60%, from 9.1 to 14.9 L/m2/h and +20 % from 7.8 to 9.5 L/m2/h, respectively). The rheometric analysis indicated that the biofilm developed on MF membrane had weaker mechanical strength, displaying lower storage modulus (-50 %) and lower loss modulus (-55 %) compared to UF. These differences in mechanical properties were linked to the lower concentration of polyvalent ions and the distribution of organic foulants (i.e., BB, LMW-N) found in the biofilm on the MF membrane. Moreover, in the presence of air scouring led to a slight difference in microbial community between UF and MF. Our findings provide valuable insight for future investigations aimed at engineer biofilm composition to optimize biofilm control strategies in membrane systems for seawater desalination pretreatment.

Porous Laser-Scribed Graphene Electrodes Modified with Zwitterionic Moieties: A Strategy for Antibiofouling and Low-Impedance Interfaces.

Laser-scribed graphene electrodes (LSGEs) are promising platforms for the development of electrochemical biosensors for point-of-care settings and continuous monitoring and wearable applications. However, the frequent occurrence of biofouling drastically reduces the sensitivity and selectivity of these devices, hampering their sensing performance. Herein, we describe a versatile, low-impedance, and robust antibiofouling interface based on sulfobetaine-zwitterionic moieties. The interface induces the formation of a hydration layer and exerts electrostatic repulsion, protecting the electrode surface from the nonspecific adsorption of various biofouling agents. We demonstrate through electrochemical and microscopy techniques that the modified electrode exhibits outstanding antifouling properties, preserving more than 90% of the original signal after 24 h of exposure to bovine serum albumin protein, HeLa cells, and Escherichia coli bacteria. The promising performance of this antifouling strategy suggests that it is a viable option for prolonging the lifetime of LSGEs-based sensors when operating on complex biological systems.

Precision ion separation via self-assembled channels.

Selective nanofiltration membranes with accurate molecular sieving offer a solution to recover rare metals and other valuable elements from brines. However, the development of membranes with precise sub-nanometer pores is challenging. Here, we report a scalable approach for membrane fabrication in which functionalized macrocycles are seamlessly oriented via supramolecular interactions during the interfacial polycondensation on a polyacrylonitrile support layer. The rational incorporation of macrocycles enables the formation of nanofilms with self-assembled channels holding precise molecular sieving capabilities and a threshold of 6.6 ångström, which corresponds to the macrocycle cavity size. The resulting membranes provide a 100-fold increase in selectivity for Li+/Mg2+ separation, outperforming commercially available and state-of-the-art nanocomposite membranes for lithium recovery. Their performance is further assessed in high-recovery tests under realistic nanofiltration conditions using simulated brines or concentrated seawater with various Li+ levels and demonstrates their remarkable potential in ion separation and Li+ recovery applications.

Polycage membranes for precise molecular separation and catalysis.

The evolution of the chemical and pharmaceutical industry requires effective and less energy-intensive separation technologies. Engineering smart materials at a large scale with tunable properties for molecular separation is a challenging step to materialize this goal. Herein, we report thin film composite membranes prepared by the interfacial polymerization of porous organic cages (POCs) (RCC3 and tren cages). Ultrathin crosslinked polycage selective layers (thickness as low as 9.5 nm) are obtained with high permeance and strict molecular sieving for nanofiltration. A dual function is achieved by combining molecular separation and catalysis. This is demonstrated by impregnating the cages with highly catalytically active Pd nanoclusters ( ~ 0.7 nm). While the membrane promotes a precise molecular separation, its catalytic activity enables surface self-cleaning, by reacting with any potentially adsorbed dye and recovering the original performance. This strategy opens opportunities for the development of other smart membranes combining different functions and well-tailored abilities.

Efficient and reliable encapsulation for perovskite/silicon tandem solar modules.

Perovskite/silicon tandem solar cells have a tremendous potential to boost renewable electricity production thanks to their very high performance combined with promising cost structure. However, for actual field deployment, any solar cell technology needs to be assembled into modules, where the associated processes involve several challenges that may affect both the performance and stability of the devices. For instance, due to its hygroscopic nature, ethylene vinyl acetate (EVA) is incompatible with perovskite-based photovoltaics. To circumvent this issue, we investigate here two alternative encapsulant polymers for the packaging of perovskite/silicon tandems into minimodules: a thermoplastic polyurethane (TPU) and a thermoplastic polyolefin (TPO) elastomer. To gauge their impact on tandem-module performance and stability, we performed two internationally established accelerated module stability tests (IEC 61215): damp heat exposure and thermal cycling. Finally, to better understand the thermomechanical properties of the two encapsulants and gain insight into their relation to the thermal cycling of encapsulated tandems, we performed a dynamic mechanical thermal analysis. Our understanding of the packaging process of the tandem module provides useful insights for the development of commercially viable perovskite photovoltaics.

Nanoporous membrane fabrication by nanoimprint lithography for nanoparticle sieving.

An isoporous membrane with strictly controlled pore size, shape and distribution could provide an efficient, precise and mild sieving of particles in nanotechnology and biomedical applications. However there is a lack of highly porous polymeric membranes combining isoporosity and high permeance in the range below 500 nm. Track-etched membranes are practically the only commercial option. Membranes prepared by phase inversion typically have a broad pore size distribution. Most nanofabrication methods have limited the preparation of membranes with pores in the micrometer range. In this work, we present a nanotechnology-based fabrication methodology to manufacture a stable and flexible nanoporous polymeric membrane with 300 nm isopores using UV nanoimprint lithography. The highly porous membrane has a pore density of 4 × 109 pores per cm2 and stable permeance of 108 000 L m-2 h-1 bar-1. Uniform ZIF-8 nanoparticles were synthesized and the isoporous membrane successfully demonstrated as high as 100% rejection and size-based sieving performance of nanoparticles.

Polytriazole membranes with ultrathin tunable selective layer for crude oil fractionation.

The design of materials and their manufacture into membranes that can handle industrial conditions and separate complex nonaqueous mixtures are challenging. We report a versatile strategy to fabricate polytriazole membranes with 10-nanometer-thin selective layers containing subnanometer channels for the separation of hydrocarbons. The process involves the use of the classical nonsolvent-induced phase separation method and thermal cross-linking. The membrane selectivity can be tuned to the lower end of the typical nanofiltration range (200 to 1000 gram mole-1). The polytriazole membrane can enrich up to 80 to 95% of the hydrocarbon content with less than 10 carbon atoms (140 gram mole-1). These membranes preferentially separate paraffin over aromatic components, making them suitable for integration in hybrid distillation systems for crude oil fractionation.

Hydrophobic polyamide nanofilms provide rapid transport for crude oil separation.

Hydrocarbon separation relies on energy-intensive distillation. Membrane technology can offer an energy-efficient alternative but requires selective differentiation of crude oil molecules with rapid liquid transport. We synthesized multiblock oligomer amines, which comprised a central amine segment with two hydrophobic oligomer blocks, and used them to fabricate hydrophobic polyamide nanofilms by interfacial polymerization from self-assembled vesicles. These polyamide nanofilms provide transport of hydrophobic liquids more than 100 times faster than that of conventional hydrophilic counterparts. In the fractionation of light crude oil, manipulation of the film thickness down to ~10 nanometers achieves permeance one order of magnitude higher than that of current state-of-the-art hydrophobic membranes while retaining comparable size- and class-based separation. This high permeance can markedly reduce plant footprint, which expands the potential for using membranes made of ultrathin nanofilms in crude oil fractionation.

From micelle supramolecular assemblies in selective solvents to isoporous membranes.

The supramolecular assembly of PS-b-P4VP copolymer micelles induced by selective solvent mixtures was used to manufacture isoporous membranes. Micelle order in solution was confirmed by cryo-scanning electron microscopy in casting solutions, leading to ordered pore morphology. When dioxane, a solvent that interacts poorly with the micelle corona, was added to the solution, polymer-polymer segment contact was preferential, increasing the intermicelle contact. Immersion in water gave rise to asymmetric porous membranes with exceptional pore uniformity and high porosity. The introduction of a small number of carbon nanotubes to the casting solution improved the membrane stability and the reversibility of the gate response in the presence of different pH values.

Naturally Extracted Hydrophobic Solvent and Self-Assembly in Interfacial Polymerization.

Pharmaceutical, chemical, and food industries are actively implementing membrane nanofiltration modules in their processes to separate valuable products and recover solvents. Interfacial polymerization (IP) is the most widely used method to produce thin-film composite membranes for nanofiltration and reverse osmosis processes. Although membrane processes are considered green and environmentally friendly, membrane fabrication has still to be further developed in such direction. For instance, the emission of volatile solvents during membrane production in the industry has to be carefully controlled for health reasons. Greener solvents are being proposed for phase-separation membrane manufacture. For the IP organic phase, the proposition of greener alternatives is in an early stage. In this work, we demonstrate the preparation of a high-performing composite membrane employing zero vapor pressure and naturally extracted oleic acid as the IP organic phase. Its long hydrophobic chain ensures intrinsic low volatility and acid monomer dissolution, while the polar head induces a unique self-assembly structure during the film formation. Membranes prepared by this technique were selective for small molecules with a molecular weight cutoff of 650 g mol-1 and a high permeance of ∼57 L m-2 h-1 bar-1.

Enzyme catalysis coupled with artificial membranes towards process intensification in biorefinery- a review.

In this review, for the first time, the conjugation of the major types of enzymes used in biorefineries and the membrane processes to develop different configurations of MBRs, was analyzedfor the production of biofuels, phytotherapics and food ingredients. In particular, the aim is to critically review all the works related to the application of MBR in biorefinery, highlighting the advantages and the main drawbacks which can interfere with the development of this system at industrial scale. Alternatives strategies to overcome main limits will be also described in the different application fields, such as the use of biofunctionalized magnetic nanoparticles associated with membrane processes for enzyme re-use and membrane cleaning or the membrane fouling control by the use of integrated membrane process associated with MBR.

Microfluidic Integrated Organic Electrochemical Transistor with a Nanoporous Membrane for Amyloid-ß Detection.

Alzheimer's disease (AD) is a neurodegenerative disorder associated with a severe loss in thinking, learning, and memory functions of the brain. To date, no specific treatment has been proven to cure AD, with the early diagnosis being vital for mitigating symptoms. A common pathological change found in AD-affected brains is the accumulation of a protein named amyloid-ß (Aß) into plaques. In this work, we developed a micron-scale organic electrochemical transistor (OECT) integrated with a microfluidic platform for the label-free detection of Aß aggregates in human serum. The OECT channel-electrolyte interface was covered with a nanoporous membrane functionalized with Congo red (CR) molecules showing a strong affinity for Aß aggregates. Each aggregate binding to the CR-membrane modulated the vertical ion flow toward the channel, changing the transistor characteristics. Thus, the device performance was not limited by the solution ionic strength nor did it rely on Faradaic reactions or conformational changes of bioreceptors. The high transconductance of the OECT, the precise porosity of the membrane, and the compactness endowed by the microfluidic enabled the Aß aggregate detection over eight orders of magnitude wide concentration range (femtomolar-nanomolar) in 1 µL of human serum samples. We expanded the operation modes of our transistors using different channel materials and found that the accumulation-mode OECTs displayed the lowest power consumption and highest sensitivities. Ultimately, these robust, low-power, sensitive, and miniaturized microfluidic sensors helped to develop point-of-care tools for the early diagnosis of AD.