Forward Osmosis Membranes: The Significant Roles of Selective Layer.

Forward osmosis (FO) is a promising separation technology to overcome the challenges of pressure-driven membrane processes. The FO process has demonstrated profound advantages in treating feeds with high salinity and viscosity in applications such as brine treatment and food processing. This review discusses the advancement of FO membranes and the key membrane properties that are important in real applications. The membrane substrates have been the focus of the majority of FO membrane studies to reduce internal concentration polarization. However, the separation layer is critical in selecting the suitable FO membranes as the feed solute rejection and draw solute back diffusion are important considerations in designing large-scale FO processes. In this review, emphasis is placed on developing FO membrane selective layers with a high selectivity. The effects of porous FO substrates in synthesizing high-performance polyamide selective layer and strategies to overcome the substrate constraints are discussed. The role of interlayer in selective layer synthesis and the benefits of nanomaterial incorporation will also be reviewed.

The coming of age of water channels for separation membranes: from biological to biomimetic to synthetic.

Water channels are one of the key pillars driving the development of next-generation desalination and water treatment membranes. Over the past two decades, the rise of nanotechnology has brought together an abundance of multifunctional nanochannels that are poised to reinvent separation membranes with performances exceeding those of state-of-the-art polymeric membranes within the water-energy nexus. Today, these water nanochannels can be broadly categorized into biological, biomimetic and synthetic, owing to their different natures, physicochemical properties and methods for membrane nanoarchitectonics. Furthermore, against the backdrop of different separation mechanisms, different types of nanochannel exhibit unique merits and limitations, which determine their usability and suitability for different membrane designs. Herein, this review outlines the progress of a comprehensive amount of nanochannels, which include aquaporins, pillar[5]arenes, I-quartets, different types of nanotubes and their porins, graphene-based materials, metal- and covalent-organic frameworks, porous organic cages, MoS2, and MXenes, offering a comparative glimpse into where their potential lies. First, we map out the background by looking into the evolution of nanochannels over the years, before discussing their latest developments by focusing on the key physicochemical and intrinsic transport properties of these channels from the chemistry standpoint. Next, we put into perspective the fabrication methods that can nanoarchitecture water channels into high-performance nanochannel-enabled membranes, focusing especially on the distinct differences of each type of nanochannel and how they can be leveraged to unlock the as-promised high water transport potential in current mainstream membrane designs. Lastly, we critically evaluate recent findings to provide a holistic qualitative assessment of the nanochannels with respect to the attributes that are most strongly valued in membrane engineering, before discussing upcoming challenges to share our perspectives with researchers for pathing future directions in this coming of age of water channels.

Emerging Materials for Mixed-Matrix Membranes.

This Special Issue, entitled "Emerging Materials for Mixed-Matrix Membranes" was introduced to cover the recent progress in the development of materials for mixed-matrix membranes (MMMs) with potential application in fields such as sea water desalination, gas separation, pharmaceutical separation, wastewater treatment and the removal of pathogenic (viruses and bacteria) microorganisms as well as solvents and resource recovery [...].

Bio-inspired super liquid-repellent membranes for membrane distillation: Mechanisms, fabrications and applications.

With the aggravation of the global water crisis, membrane distillation (MD) for seawater desalination and hypersaline wastewater treatment is highlighted due to its low operating temperature, low hydrostatic pressure, and theoretically 100% rejection. However, some issues still impede the large-scale applications of MD technology, such as membrane fouling, scaling and unsatisfactory wetting resistance. Bio-inspired super liquid-repellent membranes have progressed rapidly in the past decades and been considered as one of the most promising approaches to overcome the above problems. This review for the first time systematically summarizes and analyzes the mechanisms of different super liquid-repellent surfaces, their preparation and modification methods, and anti-wetting/fouling/scaling performances in the MD process. Firstly, the topology theories of in-air superhydrophobic, in-air omniphobic and underwater superoleophobic surfaces are illustrated using different models. Secondly, the fabrication methods of various super liquid-repellent membranes are classified. The merits and demerits of each method are illustrated. Thirdly, the anti-wetting/fouling/scaling mechanisms of super liquid-repellent membranes are summarized. Finally, the conclusions and perspectives of the bio-inspired super liquid-repellent membranes are elaborated. It is anticipated that the systematic review herein can provide readers with foundational knowledge and current progress of super liquid-repellent membranes, and inspire researchers to overcome the challenges up ahead.

Recent Progress in Mixed-Matrix Membranes for Hydrogen Separation.

Membrane separation is a compelling technology for hydrogen separation. Among the different types of membranes used to date, the mixed-matrix membranes (MMMs) are one of the most widely used approaches for enhancing separation performances and surpassing the Robeson upper bound limits for polymeric membranes. In this review, we focus on the recent progress in MMMs for hydrogen separation. The discussion first starts with a background introduction of the current hydrogen generation technologies, followed by a comparison between the membrane technology and other hydrogen purification technologies. Thereafter, state-of-the-art MMMs, comprising emerging filler materials that include zeolites, metal-organic frameworks, covalent organic frameworks, and graphene-based materials, are highlighted. The binary filler strategy, which uses two filler materials to create synergistic enhancements in MMMs, is also described. A critical evaluation on the performances of the MMMs is then considered in context, before we conclude with our perspectives on how MMMs for hydrogen separation can advance moving forward.

Enhanced Performance of Carbon Molecular Sieve Membranes Incorporating Zeolite Nanocrystals for Air Separation.

Three different zeolite nanocrystals (SAPO-34, PS-MFI and ETS-10) were incorporated into the polymer matrix (Matrimid® 5218) as polymer precursors, with the aim of fabricating mixed-matrix carbon molecular sieve membranes (CMSMs). These membranes are investigated for their potential for air separation process. Based on our gas permeation results, incorporating porous materials is feasible to improve O2 permeability, owing to the creation of additional porosities in the resulting mixed-matrix CMSMs. Owing to this, the performance of the CMSM with 30 wt% PS-MFI loading is able to surpass the upper bound limit. This study demonstrates the feasibility of zeolite nanocrystals in improving O2/N2 separation performance in CMSMs.

Recent Progress in One- and Two-Dimensional Nanomaterial-Based Electro-Responsive Membranes: Versatile and Smart Applications from Fouling Mitigation to Tuning Mass Transport.

Membrane technologies are playing an ever-important role in the field of water treatment since water reuse and desalination were put in place as alternative water resources to alleviate the global water crisis. Recently, membranes are becoming more versatile and powerful with upgraded electroconductive capabilities, owing to the development of novel materials (e.g., carbon nanotubes and graphene) with dual properties for assembling into membranes and exerting electrochemical activities. Novel nanomaterial-based electrically responsive membranes have been employed with promising results for mitigating membrane fouling, enhancing membrane separation performance and self-cleaning ability, controlling membrane wettability, etc. In this article, recent progress in novel-nanomaterial-based electrically responsive membranes for application in the field of water purification are provided. Thereafter, several critical drawbacks and future outlooks are discussed.

2D Material Based Advanced Membranes for Separations in Organic Solvents.

2D materials have shown high potentials for fabricating next-generation membranes. To date, extensive studies have focused on the applications of 2D material membranes in gas and aqueous media. Recently, compelling opportunities emerge for 2D material membranes in separation applications in organic solvents because of their unique properties, such as ultrathin mono- to few-layers, outstanding chemical resistance toward organic solvents. Hence, this review aims to provide a timely overview of the current state-of-the-art of 2D material membranes focusing on their applications in organic solvent separations. 2D material membranes fabricated using graphene materials and a few representative nongraphene-based 2D materials, including covalent organic frameworks and MXenes, are summarized. The key membrane design strategies and their effects on separation performances in organic solvents are also examined. Last, several perspectives are provided in terms of the critical challenges for 2D material membranes, including standardization of membrane performance evaluation, improving understandings of separation mechanisms, managing the trade-off of permeability and selectivity, issues related to application versatility, long-term stability, and fabrication scalability. This review will provide a useful guide for researchers in creating novel 2D material membranes for advancing new separation techniques in organic solvents.

Author Correction: Scalable synthesis of hierarchically structured carbon nanotube-graphene fibres for capacitive energy storage.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

MXene Materials for Designing Advanced Separation Membranes.

MXenes are emerging rapidly as a new family of multifunctional nanomaterials with prospective applications rivaling that of graphenes. Herein, a timely account of the design and performance evaluation of MXene-based membranes is provided. First, the preparation and physicochemical characteristics of MXenes are outlined, with a focus on exfoliation, dispersion stability, and processability, which are crucial factors for membrane fabrication. Then, different formats of MXene-based membranes in the literature are introduced, comprising pristine or intercalated nanolaminates and polymer-based nanocomposites. Next, the major membrane processes so far pursued by MXenes are evaluated, covering gas separation, wastewater treatment, desalination, and organic solvent purification. The potential utility of MXenes in phase inversion and interfacial polymerization, as well as layer-by-layer assembly for the preparation of nanocomposite membranes, is also critically discussed. Looking forward, exploiting the high electrical conductivity and catalytic activity of certain MXenes is put into perspective for niche applications that are not easily achievable by other nanomaterials. Furthermore, the benefits of simulation/modeling approaches for designing MXene-based membranes are exemplified. Overall, critical insights are provided for materials science and membrane communities to navigate better while exploring the potential of MXenes for developing advanced separation membranes.

Realizing small-flake graphene oxide membranes for ultrafast size-dependent organic solvent nanofiltration.

Membranes for organic solvent nanofiltration (OSN) or solvent-resistant nanofiltration (SRNF) offer unprecedented opportunities for highly efficient and cost-competitive solvent recovery in the pharmaceutical industry. Here, we describe small-flake graphene oxide (SFGO) membranes for high-performance OSN applications. Our strategy exploits lateral dimension control to engineer shorter and less tortuous transport pathways for solvent molecules. By using La3+ as a cross-linker and spacer for intercalation, the SFGO membrane selective layer was stabilized, and size-dependent ultrafast selective molecular transport was achieved. The methanol permeance was up to 2.9-fold higher than its large-flake GO (LFGO) counterpart, with high selectivity toward three organic dyes. More importantly, the SFGO-La3+ membrane demonstrated robust stability for at least 24 hours under hydrodynamic stresses that are representative of realistic OSN operating conditions. These desirable attributes stem from the La3+ cross-linking, which forms uniquely strong coordination bonds with oxygen-containing functional groups of SFGO. Other cations were found to be ineffective.

Metallicity-Dependent Ultrafast Water Transport in Carbon Nanotubes.

Carbon nanotubes (CNTs) with hydrophobic and atomically smooth inner channels are promising for building ultrahigh-flux nanofluidic platforms for energy harvesting, health monitoring, and water purification. Conventional wisdom is that nanoconfinement effects determine water transport in CNTs. Here, using full-atomistic molecular dynamics simulations, it is shown that water transport behavior in CNTs strongly correlates with the electronic properties of single-walled CNTs (metallic (met) vs semiconducting (s/c)), which is as dominant as the effect of nanoconfinement. Three pairs of CNTs (i.e., (8,8)met , 10.85 Å vs (9,7)s/c , 10.88 Å; (9,8)s/c , 11.53 Å vs (10,7)met , 11.59 Å; and (9,9)met , 12.20 Å vs (10,8)s/c , 12.23 Å) are used to investigate the roles of diameter and metallicity. Specifically, the (9,8)s/c can restrict the hydrogen-bonding-mediated structuring of water and give the highest reduction in carbon-water interaction energy, providing an extraordinarily high water flux, around 250 times that of the commercial reverse osmosis membranes and approximately fourfold higher than the flux of the state-of-the-art boron nitrate nanotubes. Further, the high performance of (9,8)s/c is also reproducible when embedded in lipid bilayers as synthetic high-water flux porins. Given the increasing availability of high-purity CNTs, these findings provide valuable guides for realizing novel CNT-enhanced nanofluidic systems.

Leveraging Nanocrystal HKUST-1 in Mixed-Matrix Membranes for Ethylene/Ethane Separation.

The energy-intensive ethylene/ethane separation process is a key challenge to the petrochemical industry. HKUST-1, a metal-organic framework (MOF) which possesses high accessible surface area and porosity, is utilized in mixed-matrix membrane fabrication to investigate its potential for improving the performance for C2H4/C2H6 separation. Prior to membrane fabrication and gas permeation analysis, nanocrystal HKUST-1 was first synthesized. This step is critical in order to ensure that defect-free mixed-matrix membranes can be formed. Then, polyimide-based polymers, ODPA-TMPDA and 6FDA-TMPDA, were chosen as the matrices. Our findings revealed that 20 wt% loading of HKUST-1 was capable of improving C2H4 permeability (155% for ODPA-TMPDA and 69% for 6FDA-TMPDA) without excessively sacrificing the C2H4/C2H6 selectivity. The C2H4 and C2H6 diffusivity, as well as solubility, were also improved substantially as compared to the pure polymeric membranes. Overall, our results edge near the upper bound, confirming the effectiveness of leveraging nanocrystal HKUST-1 filler for performance enhancements in mixed-matrix membranes for C2H4/C2H6 separation.

Hierarchically Structured Janus Membrane Surfaces for Enhanced Membrane Distillation Performance.

Commercial hydrophobic poly(vinylidene fluoride) (PVDF) membranes are vulnerable to membrane fouling and pore wetting, hampering the use of membrane distillation (MD) for the treatment of surfactant- and oil-containing feed streams. To address these challenges, we designed novel Janus membranes with multilevel roughness to mitigate foulant adhesion and prevent pore wetting. Specifically, fouling- and wetting-resistant Janus MD membranes with hierarchically structured surfaces were tailored via a facile technique that involved oxidant-induced dopamine polymerization followed by in situ immobilization of silver nanoparticles (AgNPs) on commercial PVDF hollow fiber substrates. These membranes demonstrated outstanding antifouling properties and salt rejection performances in comparison to membranes with single-level structures. We ascribed the membranes' excellent performances to the coupled effects of improved surface hydrophilicity and self-healing mechanism brought about by AgNPs. Furthermore, the newly engineered membranes exhibited antibacterial properties in Bacillus acidicola solutions as evidenced by clear inhibition zones observed on a confocal laser scanning microscope. The development of hierarchically structured Janus MD membranes with multilevel roughness paves a way to mitigate membrane fouling and pore wetting caused by low-surface-tension feed streams in the MD process.

Harnessing Filler Materials for Enhancing Biogas Separation Membranes.

Biogas is an increasingly attractive renewable resource, envisioned to secure future energy demands and help curb global climate change. To capitalize on this resource, membrane processes and state-of-the-art membranes must efficiently recover methane (CH4) from biogas by separating carbon dioxide (CO2). Composite (a.k.a. mixed-matrix) membranes, prepared from common polymers and rationally selected/engineered fillers, are highly promising for this application. This review comprehensively examines filler materials that are capable of enhancing the CO2/CH4 separation performance of polymeric membranes. Specifically, we highlight novel synthetic strategies for engineering filler materials to develop high-performance composite membranes. Besides, as the matrix components (polymers) of composite membranes largely dictate the overall gas separation performances, we introduce a new empirical metric, the "Filler Enhancement Index" ( Findex), to aid researchers in assessing the effectiveness of the fillers from a big data perspective. The Findex systematically decouples the effect of polymer matrices and critically evaluates both conventional and emerging fillers to map out a future direction for next-generation (bio)gas separation membranes. Beyond biogas separation, this review is of relevance to a broader community with interests in composite membranes for other gas separation processes, as well as water treatment applications.

High-performance nanocomposite membranes realized by efficient molecular sieving with CuBDC nanosheets.

Two-dimensional (2-D) CuBDC nanosheets (ns-CuBDC) with high-aspect-ratios were deliberately paired with polymers possessing high free volumes to fabricate high performance gas separation membranes. Owing to the molecular sieving effect of the filler, a small ns-CuBDC loading (2-4 wt%) could significantly improve the CO2/CH4 selectivities of membranes, resulting in performances that surpass the upper bound limit for polymer membranes.

A hierarchically porous nickel-copper phosphide nano-foam for efficient electrochemical splitting of water.

Electrochemical splitting of water to produce oxygen (O2) and hydrogen (H2) through a cathodic hydrogen evolution reaction (HER) and an anodic oxygen evolution reaction (OER) is a promising green approach for sustainable energy supply. Here we demonstrated a porous nickel-copper phosphide (NiCuP) nano-foam as a bifunctional electrocatalyst for highly efficient total water splitting. Prepared from a bubble-templated electrodeposition method and subsequent low-temperature phosphidization, NiCuP has a hierarchical pore structure with a large electrochemical active surface area. To reach a high current density of 50 mA cm-2, it requires merely 146 and 300 mV with small Tafel slopes of 47 and 49 mV dec-1 for HER and OER, respectively. The total water splitting test using NiCuP as both the anode and cathode showed nearly 100% Faradic efficiency and surpassed the performances of electrode pairs using commercial Pt/C and IrO2 catalysts under our test conditions. The high activity of NiCuP can be attributed to (1) the conductive NiCu substrates, (2) a large electrochemically active surface area together with a combination of pores of different sizes, and (3) the formation of active Ni/Cu oxides/hydroxides while keeping a portion of more conductive Ni/Cu phosphides in the nano-foam. We expect the current catalyst to enable the manufacturing of affordable water splitting systems.

Bacterial physiology is a key modulator of the antibacterial activity of graphene oxide.

Carbon-based nanomaterials have a great potential as novel antibacterial agents; however, their interactions with bacteria are not fully understood. This study demonstrates that the antibacterial activity of graphene oxide (GO) depends on the physiological state of cells for both Gram-negative and -positive bacteria. GO susceptibility of bacteria is the highest in the exponential growth phase, which are in growing physiology, and stationary-phase (non-growing) cells are quite resistant against GO. Importantly, the order of GO susceptibility of E. coli with respect to the growth phases (exponential ≫ decline > stationary) correlates well with the changes in the envelope ultrastructures of the cells. Our findings are not only fundamentally important but also particularly critical for practical antimicrobial applications of carbon-based nanomaterials.

Sandwich-Architectured Poly(lactic acid)-Graphene Composite Food Packaging Films.

Biodegradable food packaging promises a more sustainable future. Among the many different biopolymers used, poly(lactic acid) (PLA) possesses the good mechanical property and cost-effectiveness necessary of a biodegradable food packaging. However, PLA food packaging suffers from poor water vapor and oxygen barrier properties compared to many petroleum-derived ones. A key challenge is, therefore, to simultaneously enhance both the water vapor and oxygen barrier properties of the PLA food packaging. To address this issue, we design a sandwich-architectured PLA-graphene composite film, which utilizes an impermeable reduced graphene oxide (rGO) as the core barrier and commercial PLA films as the outer protective encapsulation. The synergy between the barrier and the protective encapsulation results in a significant 87.6% reduction in the water vapor permeability. At the same time, the oxygen permeability is reduced by two orders of magnitude when evaluated under both dry and humid conditions. The excellent barrier properties can be attributed to the compact lamellar microstructure and the hydrophobicity of the rGO core barrier. Mechanistic analysis shows that the large rGO lateral dimension and the small interlayer spacing between the rGO sheets have created an extensive and tortuous diffusion pathway, which is up to 1450-times the thickness of the rGO barrier. In addition, the sandwiched architecture has imbued the PLA-rGO composite film with good processability, which increases the manageability of the film and its competency to be tailored. Simulations using the PLA-rGO composite food packaging film for edible oil and potato chips also exhibit at least eight-fold extension in the shelf life of these oxygen and moisture sensitive food products. Overall, these qualities have demonstrated the high potential of a sandwich-architectured PLA-graphene composite film for food packaging applications.

Synergism of Water Shock and a Biocompatible Block Copolymer Potentiates the Antibacterial Activity of Graphene Oxide.

Graphene oxide (GO) is promising in the fight against pathogenic bacteria. However, the antibacterial activity of pristine GO is relatively low and concern over human cytotoxicity further limits its potential. This study demonstrates a general approach to address both issues. The developed approach synergistically combines the water shock treatment (i.e., a sudden decrease in environmental salinity) and the use of a biocompatible block copolymer (Pluronic F-127) as a synergist co-agent. Hypoosmotic stress induced by water shock makes gram-negative pathogens more susceptible to GO. Pluronic forms highly stable nanoassemblies with GO (Pluronic-GO) that can populate around bacterial envelopes favoring the interactions between GO and bacteria. The antibacterial activity of GO at a low concentration (50 µg mL(-1) ) increases from <30% to virtually complete killing (>99%) when complemented with water shock and Pluronic (5 mg mL(-1) ) at ≈2-2.5 h of exposure. Results suggest that the enhanced dispersion of GO and the osmotic pressure generated on bacterial envelopes by polymers together potentiate GO. Pluronic also significantly suppresses the toxicity of GO toward human fibroblast cells. Fundamentally, the results highlight the crucial role of physicochemical milieu in the antibacterial activity of GO. The demonstrated strategy has potentials for daily-life bacterial disinfection applications, as hypotonic Pluronic-GO mixture is both safe and effective.