Recycling the High-Salinity Textile Wastewater by Quercetin-Based Nanofiltration Membranes with Minimal Water and Energy Consumption.

Effective recovery of dyes and salts from textile wastewater by nanofiltration (NF) remains a serious challenge due to the high consumption of water and energy caused by the limited performance of the available membranes. Herein, a novel strategy is described to prepare loose polyester NF membranes by using renewable quercetin as the aqueous monomer for fractionation of high salinity textile wastewater with minimal water and energy consumption. Compared with NF270, taken as the reference membrane, the QE-0.2/TMC-0.2 membrane significantly improved the efficiency for dye/salt fractionation by 288%. The water consumption was also decreased by 42.9%. The efficiency is attributed to an ultrahigh water permeance of 198 ± 2.1 L-1 m-2 h-1 bar-1 with a high selectivity of 123 (extremely low NaCl rejection of 1.6% and high Congo red rejection of 99.2%). The optimal quercetin-based membrane had an ultrathin separation layer of about 39 ± 1.2 nm with good hydrophilicity and negative charge density. Moreover, this work includes a novel method of comparison with a theoretically ideal membrane, which shows that both the energy and water consumption are near their theoretical minimum. This strategy is expected to save energy and minimize carbon emissions for membrane-based wastewater treatment systems.

Scalable Fabrication of Crystalline COF Membranes from Amorphous Polymeric Membranes.

Covalent organic framework (COF) membranes hold potential for widespread applicability, but scalable fabrication is challenging. Here, we demonstrate the disorder-to-order transformation from amorphous polymeric membrane to crystalline COF membrane via monomer exchange. Solution processing is used to prepare amorphous membrane and the replacing monomer is selected based on the chemical and thermodynamical stability of the final framework. Reversible imine bonds allow the extraneous monomers to replace the pristine monomers within amorphous membrane, driving the transformation from disordered network to ordered framework. Incorporation of intramolecular hydrogen bonds enables the crystalline COF to imprint the amorphous membrane morphology. The COF membranes harvest proton conductivity up to 0.53 S cm-1 at 80 °C. Our strategy bridges amorphous polymeric and crystalline COF membranes for large-scale fabrication of COF membranes and affords guidance on materials processing.

Ultrastrong and Tough Urushiol-Based Ionic Conductive Double Network Hydrogels as Flexible Strain Sensors.

Ionic conductive hydrogels have attracted increasing research interest in flexible electronics. However, the limited resilience and poor fatigue resistance of current ionic hydrogels significantly restrict their practical application. Herein, an urushiol-based ionic conductive double network hydrogel (PU/PVA-Li) was developed by one-pot thermal initiation polymerization assisted with freeze-thaw cycling and subsequent LiCl soaking. Such a PU/PVA-Li hydrogel comprises a primary network of covalently crosslinked polyurushiol (PU) and a secondary network formed by physically crosslinked poly(vinyl alcohol) (PVA) through crystalline regions. The obtained PU/PVA-Li hydrogel demonstrates exceptional mechanical properties, including ultrahigh strength (up to 3.4 MPa), remarkable toughness (up to 1868.6 kJ/m3), and outstanding fatigue resistance, which can be attributed to the synergistic effect of the interpenetrating network structure and dynamic physical interactions between PU and PVA chains. Moreover, the incorporation of LiCl into the hydrogels induces polymer chain contraction via ionic coordination, further enhancing their mechanical strength and resilience, which also impart exceptional ionic conductivity (2.62 mS/m) to the hydrogels. Based on these excellent characteristics of PU/PVA-Li hydrogel, a high-performance flexible strain sensor is developed, which exhibits high sensitivity, excellent stability, and reliability. This PU/PVA-Li hydrogel sensor can be effectively utilized as a wearable electronic device for monitoring various human joint movements. This PU/PVA-Li hydrogel sensor could also demonstrate its great potential in information encryption and decryption through Morse code. This work provides a facile strategy for designing versatile, ultrastrong, and tough ionic conductive hydrogels using sustainable natural extracts and biocompatible polymers. The developed hydrogels hold great potential as promising candidate materials for future flexible intelligent electronics.

Synthesis of Guanine/Vermiculite Two-Dimensional Nanocomposites for Wireless Humidity Sensing in Nut Storage Environment.

Two-dimensional (2D) nanostructures have the advantages of high specific surface area, easy surface functionalization, abundant active sites, and good compatibility with device integration and can be assembled into three-dimensional structures, which are key to the development of high-performance gas sensors. In this study, 2D vermiculite (VMT) nanosheets and guanine (G), two renewable resources with unique chemical structures, were organically combined to fully use the specificity of their molecular structures and functional activities. Driven by the regulation of 2D VMT nanosheets, guanine/vermiculite (G/VMT)-based 2D nanocomposites with controllable pore structure, multiple binding sites, and unobstructed mass transfer were designed and synthesized. The G/VMT nanocomposite material was used as a quartz crystal microbalance (QCM) electrode-sensitive film material to build a QCM-based humidity sensor. G/VMT-based QCM humidity sensor had good logarithmic linear relation (0.9971), high sensitivity (24.49 Hz/% relative humidity), low hysteresis (1.75% RH), fast response/recovery time (39/6 s), and good stability. Furthermore, with a QCM sensor and a specially designed wireless circuit, a wireless humidity detection system transmitting via Wi-Fi allows real-time monitoring of nut storage. This study presents an environmentally friendly, high-performance, miniature 2D nanocomposite sensor strategy for real-time monitoring.

Ultrathin Membranes for Separations: A New Era Driven by Advanced Nanotechnology.

Ultrathin membranes are at the forefront of membrane research, offering great opportunities in revolutionizing separations with ultrafast transport. Driven by advanced nanomaterials and manufacturing technology, tremendous progresses are made over the last 15 years in the fabrications and applications of sub-50 nm membranes. Here, an overview of state-of-the-art ultrathin membranes is first introduced, followed by a summary of the fabrication techniques with an emphasis on how to realize such extremely low thickness. Then, different types of ultrathin membranes, categorized based on their structures, that is, network, laminar, or framework structures, are discussed with a focus on the interplays among structure, fabrication methods, and separation performances. Recent research and development trends are highlighted. Meanwhile, the performances and applications of current ultrathin membranes for representative separations (gas separation and liquid separation) are thoroughly analyzed and compared. Last, the challenges in material design, structure construction, and coordination are given, in order to fully realize the potential of ultrathin membranes and facilitate the translation from scientific achievements to industrial productions.

Photo-tailored heterocrystalline covalent organic framework membranes for organics separation.

Organics separation for purifying and recycling environment-detrimental solvents is essential to sustainable chemical industries. Covalent organic framework (COF) membranes hold great promise in affording precise and fast organics separation. Nonetheless, how to well coordinate facile processing-high crystalline structure-high separation performance remains a critical issue and a grand challenge. Herein, we propose a concept of heterocrystalline membrane which comprises high-crystalline regions and low-crystalline regions. The heterocrystalline COF membranes are fabricated by a two-step procedure, i.e., dark reaction for the construction of high-crystalline regions followed by photo reaction for the construction of low-crystalline regions, thus linking the high-crystalline regions tightly and flexibly, blocking the defect in high-crystalline regions. Accordingly, the COF membrane exhibits sharp molecular sieving properties with high organic solvent permeance up to 44-times higher than the state-of-the-art membranes.

Charged Nanochannels in Covalent Organic Framework Membranes Enabling Efficient Ion Exclusion.

Controllable ion transport through nanochannels is crucial for biological and artificial membrane systems. Covalent organic frameworks (COFs) with regular and tunable nanochannels are emerging as an ideal material platform to develop synthetic membranes for ion transport. However, ion exclusion by COF membranes remains challenging because most COF materials have large-sized nanochannels leading to nonselective transport of small ions. Here we develop ionic COF membranes (iCOFMs) to control ion transport through charged framework nanochannels, the interior surfaces of which are covered with arrayed sulfonate groups to render superior charge density. The overlap of an electrical double layer in charged nanochannels blocks the entry of co-ions, narrows their passageways, and concomitantly restrains the permeation of counterions via the charge balance. These highly charged large-sized nanochannels within the iCOFM enable ion exclusion while maintaining intrinsically high water permeability. Our results reveal possibilities for controllable ion transport based on COF membranes for water purification, ionic separation, sensing, and energy conversion.

Assembling covalent organic framework membranes with superior ion exchange capacity.

Ionic covalent organic framework membranes (iCOFMs) hold great promise in ion conduction-relevant applications because the high content and monodispersed ionic groups could afford superior ion conduction. The key to push the upper limit of ion conductivity is to maximize the ion exchange capacity (IEC). Here, we explore iCOFMs with a superhigh ion exchange capacity of 4.6 mmol g-1, using a dual-activation interfacial polymerization strategy. Fukui function is employed as a descriptor of monomer reactivity. We use Brønsted acid to activate aldehyde monomers in organic phase and Brønsted base to activate ionic amine monomers in water phase. After the dual-activation, the reaction between aldehyde monomer and amine monomer at the water-organic interface is significantly accelerated, leading to iCOFMs with high crystallinity. The resultant iCOFMs display a prominent proton conductivity up to 0.66 S cm-1, holding great promise in ion transport and ionic separation applications.

Electrostatic-modulated interfacial polymerization toward ultra-permselective nanofiltration membranes.

Interfacial polymerization (IP) is a platform technology for ultrathin membranes. However, most efforts in regulating the IP process have been focused on short-range H-bond interaction, often leading to low-permselective membranes. Herein, we report an electrostatic-modulated interfacial polymerization (eIP) via supercharged phosphate-rich substrates toward ultra-permselective polyamide membranes. Phytate, a natural strongly charged organophosphate, confers high-density long-range electrostatic attraction to aqueous monomers and affords tunable charge density by flexible metal-organophosphate coordination. The electrostatic attraction spatially enriches amine monomers and temporally decelerates their diffusion into organic phase to be polymerized with acyl chloride monomers, triggering membrane sealing and inhibiting membrane growth, thus generating polyamide membranes with reduced thickness and enhanced cross-linking. The optimized nearly 10-nm-thick and highly cross-linked polyamide membrane displays superior water permeance and ionic selectivity. This eIP approach is applicable to the majority of conventional IP processes and can be extended to fabricate a variety of advanced membranes from polymers, supermolecules, and organic framework materials.

Weakly Humidity-Dependent Proton-Conducting COF Membranes.

State-of-the-art proton exchange membranes (PEMs) often suffer from significantly reduced conductivity under low relative humidity, hampering their efficient application in fuel cells. Covalent organic frameworks (COFs) with pre-designable and well-defined structures hold promise to cope with the above challenge. However, fabricating defect-free, robust COF membranes proves an extremely difficult task due to the poor processability of COF materials. Herein, a bottom-up approach is developed to synthesize intrinsic proton-conducting COF (IPC-COF) nanosheets (NUS-9) in aqueous solutions via diffusion and solvent co-mediated modulation, enabling a controlled nucleation and in-plane-dominated IPC-COF growth. These nanosheets allow the facile fabrication of IPC-COF membranes. IPC-COF membranes with crystalline, rigid ion nanochannels exhibit a weakly humidity-dependent conductivity over a wide range of humidity (30-98%), 1-2 orders of magnitude higher than that of benchmark PEMs, and a prominent fuel cell performance of 0.93 W cm-2 at 35% RH and 80 °C arising from superior water retention and Grotthuss mechanism-dominated proton conduction.

Author Correction: Metal-coordinated sub-10 nm membranes for water purification.

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

Covalent Organic Framework Nanosheets as Reactive Fillers To Fabricate Free-Standing Polyamide Membranes for Efficient Desalination.

Mixed matrix membranes (MMMs) have been increasingly utilized in membrane processes. Covalent organic frameworks (COFs) hold great promise as emergent nanofillers to fabricate high-performance MMMs; however, only few studies about COF materials in MMMs have been reported where COFs are all used as nonreactive fillers. Herein, we propose using -NH2-functionalized COF nanosheets as reactive fillers (rCON) to fabricate MMMs. rCON altered the morphology and chemistry of MMMs by controlling the diffusion rate of piperazine through hydrogen bonding prior to the interfacial polymerization process and inducing the creation of ridges in the MMMs with subsequent increase in surface area (∼24%). rCON was chemically cross-linked to the trimesoyl chloride through amide bonding, subsequently elevating the hydrophilicity (∼35%) and fouling resistance of MMMs. The presence of -NH2 groups elevated the rCON-PA compatibility, ensuring the high rCON loading of 5 wt % in the MMMs without sacrificing salt rejection. Accordingly, the PA-rCON MMMs exhibited a flux of 46.5 L m-2 h-1 bar-1, which is 6.8 times higher than that of the pristine PA membrane, with a high rejection rate of 93.5% for Na2SO4.

Metal-coordinated sub-10 nm membranes for water purification.

Ultrathin membranes with potentially high permeability are urgently demanded in water purification. However, their facile, controllable fabrication remains a grand challenge. Herein, we demonstrate a metal-coordinated approach towards defect-free and robust membranes with sub-10 nm thickness. Phytic acid, a natural strong electron donor, is assembled with metal ion-based electron acceptors to fabricate metal-organophosphate membranes (MOPMs) in aqueous solution. Metal ions with higher binding energy or ionization potential such as Fe3+ and Zr4+ can generate defect-free structure while MOPM-Fe3+ with superhydrophilicity is preferred. The membrane thickness is minimized to 8 nm by varying the ligand concentration and the pore structure of MOPM-Fe3+ is regulated by varying the Fe3+ content. The membrane with optimized MOPM-Fe3+ composition exhibits prominent water permeance (109.8 L m-2 h-1 bar-1) with dye rejections above 95% and superior stability. This strong-coordination assembly may enlighten the development of ultrathin high-performance membranes.

Author Correction: Metal-coordinated sub-10 nm membranes for water purification.

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

Zwitterionic materials for antifouling membrane surface construction.

UNLABELLED: Membrane separation processes are often perplexed by severe and ubiquitous membrane fouling. Zwitterionic materials, keeping electric neutrality with equivalent positive and negative charged groups, are well known for their superior antifouling properties and have been broadly utilized to construct antifouling surfaces for medical devices, biosensors and marine coatings applications. In recent years, zwitterionic materials have been more and more frequently utilized for constructing antifouling membrane surfaces. In this review, the antifouling mechanisms of zwitterionic materials as well as their biomimetic prototypes in cell membranes will be discussed, followed by the survey of common approaches to incorporate zwitterionic materials onto membrane surfaces including surface grafting, surface segregation, biomimetic adhesion, surface coating and so on. The potential applications of these antifouling membranes are also embedded. Finally, we will present a brief perspective on the future development of zwitterionic materials modified antifouling membranes. STATEMENT OF SIGNIFICANCE: Membrane fouling is a severe problem hampering the application of membrane separation technology. The properties of membrane surfaces play a critical role in membrane fouling and antifouling behavior/performance. Antifouling membrane surface construction has evolved as a hot research issue for the development of membrane processes. Zwitterionic modification of membrane surfaces has been recognized as an effective strategy to resist membrane fouling. This review summarizes the antifouling mechanisms of zwitterionic materials inspired by cell membranes as well as the popular approaches to incorporate them onto membrane surfaces. It can help form a comprehensive knowledge about the principles and methods of modifying membrane surfaces with zwitterionic materials. Finally, we propose the possible future research directions of zwitterionic materials modified antifouling membranes.