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Nanofiltration (NF) membranes have been widely applied in many important environmental applications, including water softening, surface/groundwater purification, wastewater treatment, and water reuse. In recent years, a new class of piperazine (PIP)-based NF membranes featuring a crumpled polyamide layer has received considerable attention because of their great potential for achieving dramatic improvements in membrane separation performance. Since the report of novel crumpled Turing structures that exhibited an order of magnitude enhancement in water permeance (

In this work, a conductive thin film composite forward osmosis (TFC-FO) membrane was firstly prepared via vacuum filtering MXenes nanolayer on the outer surface of polyethersulfone membrane followed by interfacial polymerization in the other side. Moreover, its feasibility of mitigating organic fouling under electric field was evaluated. Results indicated that the addition of MXenes greatly reduced the electric resistance of membrane from 2.1 × 1012 to 46.8 Ω, enhanced the membrane porosity and promoted the membrane performance in terms of the ratio of water flux to reverse salt flux. The modified TFC-FO membrane presented the optimal performance with 0.47 g/m2 loading amount of MXenes. Organic fouling experiments using sodium alginate (SA) and bovine serum albumin (BSA) as representative demonstrated that the introduction of MXenes could effectively enhance the anti-fouling ability of TFC-FO membrane under the electric field of 2 V. The interelectron repulsion hindered organic foulants attaching into membrane surface and thus effectively alleviated the membrane fouling. More importantly, the modified TFC-FO membrane showed good stability during the fouling experiment of 10 h. In all, our work proved that introducing MXenes into the porous layer of support is feasible to alleviate organic fouling of FO membrane.

The permeance and selectivity of a reverse osmosis (RO) membrane are governed by its ultrathin polyamide film, yet the growth of this critical film during interfacial polymerization (IP) has not been fully understood. This study investigates the evolution of a polyamide nanofilm at the aqueous/organic interface over time. Despite its thickness remaining largely constant (∼15 nm) for the IP reaction time ranging from 0.5 to 60 min, the density of the polyamide nanofilm increased from 1.25 to 1.36 g cm

Despite increasing sustainable water purification, current desalination membranes still suffer from insufficient permeability and treatment efficiency, greatly hindering extensive practical applications. In this work, we provide a new membrane design protocol and molecule-level mechanistic understanding of vapor transport for the treatment of hypersaline waters via a membrane distillation process by rationally fabricating more robust metal-based carbon nanotube (CNT) network membranes, featuring a superhydrophobic superporous surface (80.0 ± 2.3% surface porosity). With highly permeable ductile metal hollow fibers as substrates, the construction of a superhydrophobic (water contact angle ∼170°) CNT network layer endows the membranes with not only almost perfect salt rejection (over 99.9%) but a promising water flux (43.6 L·m

Interlayered thin-film nanocomposite (TFNi) membranes have been shown to achieve enhanced water permeance as a result of the gutter effect. Nevertheless, some studies report impaired separation performance after the inclusion of an interlayer. In this study, we resolve the competing mechanisms of water transport in the transverse direction vs that in the normal direction. To enable easy comparison, carbon nanotube (CNT)-incorporated TFNi membranes with an identical polyamide rejection layer but different interlayer thicknesses were investigated. While increasing the thickness of the CNT interlayer facilitates water transport in the transverse direction (therefore improving the gutter effect), it simultaneously increases its hydraulic resistance in the normal direction. An optimal water permeance of 13.0 ± 0.7 L m

A random 2D nanochannel orientation in a polyamide membrane provides superior membrane permeability and selectivity to a horizontally aligned one.

This article reviews organic photocatalyst hydrogen evolution reaction (HER), discussing the excitonic behaviour and improvement strategies. It also covers progress in organic photocatalysts, and assesses HER efficiency and stability.

In recent decades, nanofiltration (NF) is considered as a promising separation technique to produce drinking water from different types of water source. In this paper, we comprehensively reviewed the progress of NF-based drinking water treatment, through summarizing the development of materials/fabrication and applications of NF membranes in various scenarios including surface water treatment, groundwater treatment, water reuse, brackish water treatment, and point of use applications. We not only summarized the removal of target major pollutants (e.g., hardness, pathogen, and natural organic matter), but also paid attention to the removal of micropollutants of major concern (e.g., disinfection byproducts, per- and polyfluoroalkyl substances, and arsenic). We highlighted that, for different applications, fit-for-purpose design is needed to improve the separation capability for target compounds of NF membranes in addition to their removal of salts. Outlook and perspectives on membrane fouling control, chlorine resistance, integrity, and selectivity are also discussed to provide potential insights for future development of high-efficiency NF membranes for stable and reliable drinking water treatment.

There has been a growing interest in water purification by graphene oxide (GO) laminate membranes due to their exceptional hydrophilicity, high throughput, and extraordinary separation performance originating from their two-dimensional and well-defined nanostructure. However, the swelling and stability in an aqueous environment are areas of concern for the GO laminate membranes. Here, a novel methylimidazolium ionic liquid-reduced GO (mimG)-assembled GO laminate membrane (mimG-GO) with remarkable stability was fabricated by a vacuum-assisted strategy for water purification. Methylimidazolium-based ionic liquid-reduced graphene oxide (mimG) was prepared by a facile nucleophilic ring-opening mechanism. Fabricated membranes were thoroughly characterized for stability, structural, permeance, and rejection properties in an aqueous environment. A combination of cationic mimG and GO nanosheets improves membrane stability in the aqueous environment via cation-π interactions and creates nanofluidic channels for facile water transport while yielding significant enhancement in the salt and dye separation performance. The pore size and the number of nanofluidic channels were precisely controlled via material deposition and laminate thickness to remove salts from water. The mimG-GO laminate membrane containing 72.2 mg m

Three-dimensional (3D) microfibrillar network represents an important structural design for various natural tissues and synthetic aerogels. Despite extensive efforts, achieving high mechanical properties for synthetic 3D microfibrillar networks remains challenging. Here, we report ultrastrong polymeric aerogels involving self-assembled 3D networks of aramid nanofiber composites. The interactions between the nanoscale constituents lead to assembled networks with high nodal connectivity and strong crosslinking between fibrils. As revealed by theoretical simulations of 3D networks, these features at fibrillar joints may lead to an enhancement of macroscopic mechanical properties by orders of magnitude even with a constant level of solid content. Indeed, the polymeric aerogels achieved both high specific tensile modulus of ~625.3 MPa cm3 g−1 and fracture energy of ~4700 J m−2, which are advantageous for diverse structural applications. Furthermore, their simple processing techniques allow fabrication into various functional devices, such as wearable electronics, thermal stealth, and filtration membranes. The mechanistic insights and manufacturability provided by these robust microfibrillar aerogels may create further opportunities for materials design and technological innovation.

Cosolvent-assisted interfacial polymerization (IP) can effectively enhance the separation performance of thin film composite (TFC) reverse osmosis (RO) membranes. However, the underlying mechanisms regulating the formation of their polyamide (PA) rejection films remain controversial. The current study reveals two essential roles of cosolvents in the IP reaction: (1) directly promoting interfacial vaporization with their lower boiling points and (2) increasing the solubility of

The potential coexistence and interaction of bromine and polyamide membranes during membrane-based water treatment prompts us to investigate the effect of bromine on membrane performance. For fully aromatic polyamide membrane NF90 exposed under a mild bromination condition (10 mg/L), bromine incorporation resulted in more negatively charged (-13 vs -25 mV) and hydrophobic (55.2 vs 58.9°) surfaces and narrower pore channels (0.3 vs 0.29 nm). The permeabilities of water and neutral solutes were reduced by 64 and 69-87%, respectively, which was attributed to the decreased effective pore radius and hydrophilicity. NaCl permeability was reduced by 90% as a synergistic result of enhanced size exclusion and charge repulsion. The further exposure (100 and 500 mg/L bromine) resulted in a more hydrophobic surface (61.7 and 65.5°) and the minor further reduction for water and solute permeabilities (1-9%). Compared with chlorine, the different incorporation efficiency and properties (e.g., atomic size, hydrophilicity) of bromine resulted in opposite trends and/or different degrees for the variation of physicochemical properties and filtration performance of membranes. The bromine incorporation, the shift and disappearance of three characteristic bands, and the increased O/N ratio and calcium content indicated the degradation pathways of N-bromination and bromination-promoted hydrolysis under mild bromination conditions (480 mg/L·h). The further ring-bromination occurred after severe bromine exposure (4800-24,000 mg/L·h). The semi-aromatic polyamide membrane NF270 underwent a similar but less significant deteriorated filtration performance compared with NF90, which requires a different explanation.

Poly- and perfluoroalkyl substances (PFASs) have caused severe public concerns due to their toxicity and extensive occurrence in the aquatic environment. This study reports a highly porous amine-fu...

Papermaking industry discharges large quantities of wastewater and waste gas, whose treatment is limited by extra chemicals requirements, insufficient resource recovery and high energy consumption. Herein, a chemical self-sufficiency zero liquid discharge (ZLD) system, which integrates nanofiltration, bipolar membrane electrodialysis and membrane contactor (NF-BMED-MC), is designed for the resource recovery from wastewater and waste gas. The key features of this system include: 1) recovery of NaCl from pretreated papermaking wastewater by NF, 2) HCl/NaOH generation and fresh water recovery by BMED, and 3) CO

Membrane fouling is the obstacle that limits the practical application of membranes in efficient oil/water separation. The main reason for membrane fouling is the deposition of the dispersed phase (e.g., oil) on the membrane surface based on the sieving effect. The key challenge for solving the fouling problem is to achieve fouling removal via rationally considering hydrodynamics and interfacial science. Herein, a poly(vinylidene fluoride) membrane with a dual-scale hyperporous structure and rational wettability is designed to achieve a continuous "nonfouling" separation for oil/water emulsions via membrane demulsification. The membrane is fabricated via dual-phase separation (vapor and nonsolvent) and modified by in situ polymerization of poly(hydroxyethyl methylacrylate) (contact angle 59 ± 1°). The membrane shows stable permeability (1078 ± 50 Lm-2h-1bar-1) and high separation efficiency (>99.0%) in 2 h of continuous cross-flow without physicochemical washing compared to superwetting membranes. The permeation is composed of two distinct immiscible liquid phases via coalescence demulsification. The surface shearing and pore throat collision coalescence demulsification mechanism is proposed, and rational interface wettability facilitates the foulant/membrane interaction for "nonfouling" separation. Beyond superwetting surfaces, a new strategy for achieving "nonfouling" emulsion separation by designing membranes with a dual-scale hyperporous structure and rational wettability is provided.

Lead (Pb) is a typical contaminant in water with adverse effects on human health. Hong Kong’s incident of drinking water contamination by Pb in 2015 caused severe public concerns regarding drinking water safety. Conventional treatment methods for Pb removal generally require electricity, chemical dosage, and considerable time and space, which significantly restrict their use for rapid water purification under emergency situations. In this study, a polyvinyl alcohol/polyacrylic acid (PVA/PAA) composite nanofibrous membrane was developed for the rapid and effective removal of Pb from water. The PVA/PAA membrane had a high water permeability of 550 L/m2/h/kPa - 710 L/m2/h/kPa, which allowed the filtration to be driven by gravity (e.g. with a water height of 10.0 cm). The membrane showed consistently high removal efficiency of Pb (> 95%) with a volumetric loading up to 3000 L/m2. This high removal efficiency was attributed to the combined effects of complexing and electrostatic attraction between Pb and PAA. An esculent citric acid was used to regenerate the exhausted PVA/PAA membrane. The regenerated membrane maintained its removal efficiency of Pb over a five-cycle filtration. These results imply that the PVA/PAA composite membrane can be repeatedly used in electricity-free filtration devices for rapid elimination of Pb under emergency situations.

The separation properties of polyamide reverse osmosis and nanofiltration membranes, widely applied for desalination and water reuse, are constrained by the permeability-selectivity upper bound. Although thin-film nanocomposite (TFN) membranes incorporating nanomaterials exhibit enhanced water permeance, their rejection is only moderately improved or even impaired due to agglomeration of nanomaterials and formation of defects. A novel type of TFN membranes featuring an interlayer of nanomaterials (TFNi) has emerged in recent years. These novel TFNi membranes show extraordinary improvement in water flux (e.g., up to an order of magnitude enhancement) along with better selectivity. Such enhancements can be achieved by a wide selection of nanomaterials, ranging from nanoparticles, one-/two-dimensional materials, to interfacial coatings. The use of nanostructured interlayers not only improves the formation of polyamide rejection layers but also provides an optimized water transport path, which enables TFNi membranes to potentially overcome the longstanding trade-off between membrane permeability and selectivity. Furthermore, TFNi membranes can potentially enhance the removal of heavy metals and micropollutants, which is critical for many environmental applications. This review critically examines the recent developments of TFNi membranes and discusses the underlying mechanisms and design criteria. Their potential environmental applications are also highlighted.

It remains challenging for graphene oxide (GO) membranes to achieve highly efficient performance and sufficient stability for aqueous molecule/ion precise separations. Herein, a molecular-level rational structure design protocol was proposed to develop ceramic-based graphene oxide framework (GOF) membranes with significantly enhanced sieving performance and stability for efficient removal of salts and micropollutants. Via a molecular cross-linking strategy, interlayered nanochannels between GO nanosheets can be rationally designed, featuring precisely tailorable channel size, promising surface chemistries and remarkably robust stability suitable for aqueous separation. Due to a significantly decreased nanochannel size, cross-linking of TU (thiourea) molecule significantly improved monovalent salt rejection (95.6% for NaCl), outperforming existing state-of-the-art GO-based, commercial organic nanofiltration and emerging two-dimensional MoS2 membranes, while moderately decreasing water permeability. In comparison, the GOF membranes cross-linked with MPD (m-phenylenediamine) exhibited a simultaneous increase in permeability and rejection for both salts and micropollutants (21.0% and 53.3% enhancement for chloramphenicol (CAP) solution), breaking their conventional trade-off issue. Cross-linking mechanism indicates that more robust nanochannels were formed by stronger covalent bonds via dehydration condensation between amine (TU/MPD) and carboxyl groups (GO), and nucleophilic addition between amine (TU/MPD) and epoxy groups (GO). Molecule/ion separation mechanism involved size sieving (steric hindrance), electrostatic interaction, Donnan effect, and partial dehydration effect. This work provides a novel protocol for rationally designing size and surface chemistry of highly robust GO nanochannels at a subnanometer level to construct water-stable functional GOF membranes with enhanced sieving performance for water treatment applications.

Membrane-based water reuse through reverse osmosis (RO) and nanofiltration (NF) faces a critical challenge from organic micropollutants (OMPs). Conventional polyamide RO and NF membranes often lack adequate selectivity to achieve sufficient removal of toxic and harmful OMPs in water. Tailoring membrane chemistry and structure to allow highly selective removal of OMPs has risen as an important topic in membrane-based water reuse. However, a critical literature gap remains to be addressed: how to design membranes for more selective removal of OMPs. In this review, we critically analyzed the roles of membrane chemistry and structure on the removal of OMPs and highlighted opportunities and strategies toward more selective removal of OMPs in the context of water reuse. Specifically, we statistically analyzed rejection of OMPs by conventional polyamide membranes to illustrate their drawbacks on OMPs removal, followed by a discussion on the underlying fundamental mechanisms. Corresponding strategies to tailor membrane properties for improving membrane selectivity against OMPs, including surface modification, nanoarchitecture construction, and deployment of alternative membrane materials, were systematically assessed in terms of water permeance, OMPs rejection, and water-OMPs selectivity. In the end, we discussed the potential and challenges of various strategies for scale-up in real applications.

Transition metal dichalcogenide membranes exhibit good antiswelling properties but poor water desalination property. Here, a one-step covalent functionalization of MoS

Conventional separation membranes suffer from evitable fouling and flux decrease for water treatment applications. Herein, a novel protocol of electro-enhanced membrane separation is proposed for the efficient treatment of microsized emulsions (∼1 μm) by rationally designing robust electroresponsive copper metallic membranes, which could mitigate oil fouling and coenhance permeance (from ∼1026 to ∼2516 L·m

While reverse osmosis (RO) is the leading technology to address the global challenge of water scarcity through desalination and potable reuse of wastewater, current RO membranes fall short in rejecting certain harmful constituents from seawater (e.g., boron) and wastewater [e.g., N -nitrosodimethylamine (NDMA)]. In this study, we develop an ultraselective polyamide (PA) membrane by enhancing interfacial polymerization with amphiphilic metal-organic framework (MOF) nanoflakes. These MOF nanoflakes horizontally align at the water/hexane interface to accelerate the transport of diamine monomers across the interface and retain gas bubbles and heat of the reaction in the interfacial reaction zone. These mechanisms synergistically lead to the formation of a crumpled and ultrathin PA nanofilm with an intrinsic thickness of ~5 nm and a high cross-linking degree of ~98%. The resulting PA membrane delivers exceptional desalination performance that is beyond the existing upper bound of permselectivity and exhibited very high rejection (>90%) of boron and NDMA unmatched by state-of-the-art RO membranes.

Widespread applications of reverse osmosis (RO)-based processes call for high-performance thin-film composite (TFC) membranes. In this study, a TFC membrane by incorporating an ultrathin 2D metal–o...

Interlayered thin-film nanocomposite membranes (TFNi) are an emerging type of membranes with great potential to overcome the permeability-selectivity upper bound of conventional thin-film composite (TFC) nanofiltration and reverse osmosis membranes. However, the exact roles of the interlayer and the corresponding mechanisms leading to enhanced separation performance of TFNi membranes remain poorly understood. This study reports a polydopamine (PDA)-intercalated TFNi nanofiltration membrane (PA-PSF2, PDA coating time of 2 h) that possessed nearly an order of magnitude higher water permeance (14.8 ± 0.4 Lm-2 h-1 bar-1) than the control TFC membrane (PA-PFS0, 2.4 ± 0.5 Lm-2 h-1 bar-1). The TFNi membrane further showed enhanced rejection toward a wide range of inorganic salts and small organic molecules (including antibiotics and endocrine disruptors). Detailed mechanistic investigation reveals that the membrane separation performance was enhanced due to both the direct "gutter" effect of the PDA interlayer and its indirect effects resulting from enhanced polyamide formation on the PDA-coated substrate, with the "gutter" effect playing a more dominant role. This study provides a mechanistic and comprehensive framework for the future development of TFNi membranes.

Treatment of highly saline wastewaters via conventional technology is a key challenging issue, which calls for efficient desalination membranes featuring high flux and rejection, low fouling, and excellent stability. Herein, we report a high-strength and flexible electro-conductive stainless steel-carbon nanotube (SS-CNT) membrane, exhibiting significantly enhanced anticorrosion and antifouling ability via a microelectrical field-coupling strategy during membrane distillation. The membrane substrates exhibited excellent mechanical strength (244.2 ± 9.8 MPa) and ductility, thereby overcoming the critical bottleneck of brittleness of traditional inorganic membranes. By employing a simple surface activation followed by self-catalyzed chemical vapor deposition, CNT was grown in situ on SS substrates via a tip-growth mechanism to finally form robust superhydrophobic SS-CNT membrane. To address the challenging issues of significant corrosion and fouling, using a negative polarization microelectrical field-coupling strategy, simultaneously enhanced antifouling and anticorrosion performance was realized for treatment of organic high salinity waters while exhibiting stable high flux and rejection via an electrostatic repulsion and electron supply mechanism. This application-oriented rational design protocol can be potentially used to extend toward high performance composite membranes derived from other electro-conductive metal substrates functionally decorated with CNT network and to other applications in water treatment.

Removal of pharmaceutically active compounds (PhACs) is of great importance in wastewater reclamation due to their potent negative impacts on human health. Typical polyamide nanofiltration (NF) membranes are negatively charged, which compromises their rejection rate of positively charged PhACs. Herein, we propose to rationally design a novel thin-film nanocomposite (TFN) NF membrane featuring a dually charged metal organic framework (MOF) to effectively remove both positively and negatively charged PhACs. Ethylenediamine (ED) was grafted to the coordinately unsaturated metal sites inside the MIL-101(Cr). The resulting ED-MIL-101(Cr) contained both strong positively charged amine groups inside its channels and negatively charged carboxyl groups at its surface. This dually charged nature of the MOF nanoparticles enabled the ED-MIL-101(Cr)-containing TFN membrane to achieve high rejection rates (mostly90%) for both positively (terbutaline, atenolol, fluoxetine) and negatively charged PhACs (ketoprofen, diclofenac, bezafibrate). At the same time, the ED-MIL-101(Cr) TFN membrane had greatly improved water permeance (140% over the control membrane with MOF loading). Calculations based on density functional theory further confirmed the large energy barrier for the migration of both negatively and positively charged PhACs across the nanochannels of ED-MIL-101(Cr). This study highlights a promising potential of dually charged MOF-TFN membranes for efficient removal of trace organic contaminants in wastewater reclamation.

Rational design of a high-performance defect-free polyamide (PA) layer on a robust ceramic substrate is challenging for forward osmosis (FO) water treatment applications. In this study, we first demonstrated a robust ceramic-based thin-film composite (TFC) FO membrane by engineering a novel nanocomposite interlayer of titanium dioxide and carbon nanotube (TiO2/CNT). The structural morphologies and properties were systematically characterized for different substrates (without interlayer, with TiO2 interlayer, or with TiO2/CNT interlayer) and the corresponding ceramic-based TFC-FO membranes. Introduction of low roughness nanocomposite interlayers with decreased pore size created an interface with improved surface characteristics, favoring the formation of a defect-free nanovoid-containing PA layer with high cross-linking degree. The resulting ceramic-based FO membrane had a water permeability of approximately 2 L/(m2 h bar) and a NaCl rejection of 98%, showing simultaneous enhancements in both compared to the control membrane without an interlayer. Mechanism analysis indicates that such a special nanocomposite interlayer not only provided more active sites for the formation of a thinner defect-free nanovoid-containing PA layer without penetration into substrate but also acted as a highly porous three-dimensional network structure for rapid water transport. This work provides a novel protocol for rational design and fabrication of a high-performance multilayered inorganic FO membrane as well as extended applications in water treatment with enhanced performance.

Recent studies show that the surface morphology of a thin film composite (TFC) polyamide membrane depends strongly on its porous substrate. Nevertheless, the underlining mechanisms and the effects on membrane separation performance remain controversial. To dissect the exact role of pore properties, we synthesized TFC polyamide membranes on polycarbonate substrates with cylindrical track-etched pores (PCTE) of well-defined pore size ranging from 10 to 800 nm. Leaf-like roughness features were most prominent for polyamide films formed on substrates of intermediate pore sizes (80 and 100 nm). Smaller pores inhibited leaf-like features as a result of insufficient storage of m-phenylenediamine (MPD) monomers for the interfacial reaction, whereas larger pores resulted in diminished surface roughness due to the lack of confinement to the interfacially degassed nanobubbles. Substrate porosity plays a critical role on membrane water permeability, while smaller pores with greater pore density are favored to improve membrane rejection. TFC polyamide membranes prepared on sponge-like poly(ether sulfone) and polysulfone substrates exhibit better water permeability and salt rejection compared to the PCTE-TFC membranes thanks to the simultaneously enhanced confinement and MPD storage effects. The mechanistic insights gained in this study reveal the huge potential of substrate design toward high-performance TFC RO membranes.