Tunable molecular transport and sieving enabled by covalent organic framework with programmable surface charge

Molecular separation is critical to mitigating the issues of water contamination and shortage and currently focuses on the use of framework materials fabricated by special building blocks. However, developing a simple and tunable synthesis methodology for materials with alternative permeation and selectivity remains challenging. Here, we fabricate a series of nanochannel membranes composed of uniform spherical covalent organic frameworks (COFs). Diversified spherical COFs have diameters ranging from ∼150 to ∼800 nm, therefore demonstrating a programmable surface charge distribution from −24 to −63 mV. COF membranes with tailor-made surface charge enable different surface energy levels and allow increasing water permeation of 15.5 to 34.5 L m⁻² h⁻¹ bar⁻¹. Furthermore, COFs can also act as filters, achieving up to 99.7% rejection and separation of the opposite charged dyes. We expect these COFs with tunable surface charge to be applicable to variety of fields, including sieving, batteries, and water treatments.     

Multifunctional Polymer/Porous Boron Nitride Nanosheet Membranes for Superior Trapping Emulsified Oils and Organic Molecules

Effective oil/water separation and removal of organic molecules from water are of worldwide importance for water source protection. Multifunctional sorbent materials with excellent sorption capacity, stability, and recyclability properties need to be developed. Here, flexible and multifunctional polymer/porous boron nitride nanosheets (BNNSs) membranes with high water permeability, exhibiting high effectiveness and stability in the purification of simulated wastewater tainted with either oil/water emulsion or organic molecules, are reported. Remarkably, the flexible nature of these porous membranes enables simplicity of operation for water remediation processing and ease of post‐processing collection. The composite membrane also displays a remarkably high permeability of 8 × 10⁴ L μm m⁻² h⁻¹ bar⁻¹, roughly three orders of magnitude higher than pure polymer, and excellent filter efficiencies for the pharmaceuticals ciprofloxacin, chlortetracycline, and carbamazepine (up to 14.2 L g⁻¹ of BNNSs in the composite membrane for a concentration of 10 mg L⁻¹ ciprofloxacin) and the dye methylene blue (up to 9.3 L g⁻¹ of BNNSs in the composite membrane at a concentration of 30 mg L⁻¹). Exhausted membranes can be readily rejuvenated by simple washing with retention of their high‐performance characteristics. The results demonstrate the potential efficacy and practicality of these membranes for water cleaning.     

Two-Dimensional Interlayer Space Induced Horizontal Transformation of Metal–Organic Framework Nanosheets for Highly Permeable Nanofiltration Membranes

Laminar membranes comprising graphene oxide (GO) and metal–organic framework (MOF) nanosheets benefit from the regular in-plane pores of MOF nanosheets and thus can support rapid water transport. However, the restacking and agglomeration of MOF nanosheets during typical vacuum filtration disturb the stacking of GO sheets, thus deteriorating the membrane selectivity. Therefore, to fabricate highly permeable MOF nanosheets/reduced GO (rGO) membranes, a two-step method is applied. First, using a facile solvothermal method, ZnO nanoparticles are introduced into the rGO laminate to stabilize and enlarge the interlayer spacing. Subsequently, the ZnO/rGO membrane is immersed in a solution of tetrakis(4-carboxyphenyl)porphyrin (H₂TCPP) to realize in situ transformation of ZnO into Zn-TCPP in the confined interlayer space of rGO. By optimizing the transformation time and mass loading of ZnO, the obtained Zn-TCPP/rGO laminar membrane exhibits preferential orientation of Zn-TCPP, which reduces the pathway tortuosity for small molecules. As a result, the composite membrane achieves a high water permeance of 19.0 L m⁻² h⁻¹ bar⁻¹ and high anionic dye rejection (>99% for methyl blue).     

Fabrication of a Cation Exchange Membrane with Largely Reduced Anion Permeability for Advanced Aqueous K-ion Battery in an Alkaline-Neutral Electrolyte Decoupling System

Herein, an efficient method to prepare sulfonated polyether ether ketone (SPEEK) based cation exchange membranes (CEMs) is developed, where polyethersulfone (PES) is used as an additive. The optimized membrane of 30 wt.%PES/SPEEK-M exhibits a rather low anion permeability and a high ionic conductivity of 9.52 mS cm⁻¹ together with low volume swelling in water. Meanwhile, tensile strength of the membrane is as high as 31.4 MPa with a tensile strain of 162%. As separators for aqueous K-ion batteries (AKIBs) with decoupled gel electrolytes (Zn anode in alkaline and Prussian blue (FeHCF) cathode in neutral). Discharge voltage of the AKIB can reach 2.3 V. Meanwhile, Zn dendrites can be effectively suppressed in the gel anolyte. Specific capacities of the FeHCF cathode are 116.7 mAh g⁻¹ at 0.3 A g⁻¹ (close to its theoretical value), and 95.0 mAh g⁻¹ at 1.0 A g⁻¹, indicating good rate performance. Capacity retention of the cathode is as high as 91.2% after 1000 cycles’ cycling owing to the well remained neutral environment of the catholyte. There is almost no pH change for the catholyte after cycling, indicating good anion-blocking or cation-selecting ability of the 30 wt.%PES/SPEEK-M, much better than other membranes.     

Versatile Magnetic Mesoporous Carbon Derived Nano-Adsorbent for Synchronized Toxic Metal Removal and Bacterial Disinfection from Water Matrices

Contamination of water resources by toxic metals and opportunistic pathogens remains a serious challenge. The development of nano-adsorbents with desired features to tackle this problem is a continuously evolving field. Here, magnetic mesoporous carbon nanospheres grafted by antimicrobial polyhexamethylene biguanidine (PHMB) are reported. Detailed mechanistic investigations reveal that the electrostatic stabilizer modified magnetic nanocore interfaced mesoporous shell can be programmatically regulated to tune the size and related morphological properties. The core–shell nano-adsorbent shows tailorable shell thickness (≈20–55 nm), high surface area (363.47 m² g⁻¹), pore volume (0.426 cm³ g⁻¹), radially gradient pores (11.26 nm), and abundant biguanidine functionality. Importantly, the nano-adsorbent has high adsorption capacity for toxic thallium (Tl(I) ions (≈559 mg g⁻¹), excellent disinfection against Staphylococcus aureus and Escherichia coli (>99.99% at 2 and 2.5 µg mL⁻¹), ultrafast disinfection kinetics rate (>99.99% within ≈4 min), and remarkable regeneration capability when exposed to polluted water matrices. The Tl(I) removal is attributed to surface complexation and physical adsorption owing to open ended mesopores, while disinfection relies on contact of terminal biguanidines with phospholipid head groups of membrane. The significance of this work lies in bringing up effective synchronic water purification technology to combat pathogenic microorganisms and toxic metal.     

High Ion Conductive and Selective Membrane Achieved through Dual Ion Conducting Mechanisms

Conventional ion-selective membranes, that is ion-exchange and porous membranes, are unable to perform high conductivity and selectivity simultaneously due to the contradictions between their ion selecting and conducting mechanisms. In this work, a bifunctional ion-selective layer is developed via the combination of nanoporous boron nitride (PBN) and ion exchange groups from Nafion to achieve high ion conductivity through dual ion conducting mechanisms as well as high ion selectivity. A template-free method is adopted to synthesize flake-like PBN, which is further enmeshed with Nafion resin to form the bifunctional layer coated onto a porous polyetherimide membrane. The double-layer membrane exhibits excellent ion selectivity (1.49 × 10⁸ mS cm⁻³ min), which is 22 times greater than that of the pristine porous polyetherimide membrane, with outstanding ion conductivity (64 mS cm⁻¹). In a vanadium flow battery, the double-layer membrane achieves a high Coulombic efficiency of 97% and outstanding energy efficiency of 91% at 40 mA cm⁻² with a stable cycling performance for over 700 cycles at 100 mA cm⁻². PBN with ion exchange groups may therefore offer a potential solution to the limitation between ion selectivity and conductivity in ion-selective membranes.     

Selective Permeation of Water through Angstrom-Channel Graphene Membranes for Bioethanol Concentration

Graphene-based laminate membranes have been theoretically predicted to selectively transport ethanol from ethanol–water solution while blocking water. Here, robust angstrom-channel graphene membranes (ACGMs) fabricated by intercalating carbon sheets derived from chitosan into thermally reduced graphene oxide (GO) sheets are reported. ACGMs with robust and continuous slit-shaped pores (an average pore size of 3.9 Å) are investigated for the dehydration of ethanol. Surprisingly, only water permeates through ACGMs in the presence of aqueous ethanol solution. For the water-ethanol mixture containing 90 wt% ethanol, water can selectively permeate through ACGMs with a water flux of 63.8 ± 3.2 kg m⁻² h⁻¹ at 20 °C and 389.1 ± 19.4 kg m⁻² h⁻¹ at 60 °C, which are over two orders of magnitude higher than those of conventional pervaporation membranes. This means that ACGMs can effectively operate at room temperature. Moreover, the ethanol can be fast concentrated to high purity (up to 99.9 wt%). Therefore, ACGMs are very promising for production of bioethanol with high efficiency, thus improving its process sustainability.     

Comparison of tertiary treatment by nanofiltration and reverse osmosis for water reuse in denim textile industry

The wastewaters resulting from different baths of a dyeing factory specialized in denim fabric are collected and treated by an activated sludge plant. This study investigated the coupling of activated sludge treatment with either nanofiltration (NF) or reverse osmosis (RO) to recycle water and reuse it in the process. We first conducted NF experiments with a HL membrane in different configurations: dead end and cross-flow for flat sheets and also in spiral wound form. Results on water permeation and salt rejection show that performances are configuration dependent. Then, for the study of the NF/RO textile wastewater treatment, experiments were conducted with spiral wound membranes in order to be closest to the industrial configuration. After analyzing the removal efficiencies of suspended solids and chemical oxygen demand (COD) of the treatment plant, we conducted NF experiments using an HL2514TF spiral wound membrane preceded by ultrafiltration (UF) treatment. We used as well an RO membrane (AG2514TF) to compare performances in water yield and quality for the same pumping costs. The results show that NF allows higher yield, while respecting the Tunisian standard of water reuse (COD < 90 mg L⁻¹). Above 9 bar, the TDS rejection reaches 60% and the hardness is lower than the factory constraint (100 mg L⁻¹ CaCO₃), allowing the reuse of the water in the process.     

Effects of ion beam surface modification on water absorption characteristics of perfluorosulfonic acid membranes

The dynamic behavior of water within ion beam (10 keV Ar⁺, 1.0 × 10¹⁶–1.2 × 10¹⁷ ions/cm²) modified perfluorosulfonic acid (PFSA) membranes was investigated at room temperature by combining direct-current (DC) resistance with alternative-current (AC) impedance methods under a water-saturated air atmosphere. The bulk impedance in existing surface sulfonate groups (SO₃⁻) decreased approximately one order of magnitude as a result of Ar⁺ ion irradiation compared to the unirradiated membrane. The enhancement in the proton conductivity results in an improvement of the water absorption characteristics at the Ar⁺ ion-modified surface which showed large superficies as well as hydrophilic radicals. These results can be explained in base of a relative increase in both the water content of the membrane and the change in the interactions of water molecules with sulfonate group at the interface on the proton-transfer process.     

Ultrathin Ultralow-Platinum Catalyst Coated Membrane for Proton Exchange Membrane Fuel Cells

Catalyst coated membrane (CCM) is the core component of proton exchange membrane fuel cells and is routinely fabricated by spraying Pt/C slurries onto membrane, resulting in low activity and thick catalyst layer (CL, 5–10 µm) with an unaffordable Pt loading of 0.2–0.4 mg cm⁻² and a large mass transfer resistance at cathode. Highly active ultrathin ultralow-Pt CL (UUCL) is urgently required, but remains rare. Herein, wet-chemical direct growth of UUCLs on both sides of membrane to achieve integrated ultrathin ultralow-Pt catalyst coated membranes (UUCCMs) with a cathodic CL thickness of 79.7 ± 15.0 nm and a Pt loading of 20.2 ± 1.6 µg cm⁻² is reported. The key to this unique fabrication is the release of proton from membrane to regioselectively initiate the growth of interconnected Pd nanoneedle clusters array on membrane, followed by high-density deposition of Pt nanoparticles on Pd (Pt/Pd UUCLs). The single cell of UUCCMs exhibits the highest mass peak power density of 59.9 W mg_Pt,Cathode⁻¹ in the literature. The exceptional activity originates from high electrochemically active surface area, remarkable oxygen reduction reaction activity closely correlated with strain, and electronic effect at Pt/Pd interface, as well as improved mass transfer and optimal water management.     

Trapped Pore Waters in the Open Proton Channel HV1

The voltage-gated proton channel, H_V1, is crucial for innate immune responses. According to alternative hypotheses, protons either hop on top of an uninterrupted water wire or bypass titratable amino acids, interrupting the water wire halfway across the membrane. To distinguish between both hypotheses, the water mobility for the putative case of an uninterrupted wire is estimated. The predicted single-channel water permeability 2.3 × 10⁻¹² cm³ s⁻¹ reflects the permeability-governing number of hydrogen bonds between water molecules in single-file configuration and pore residues. However, the measured unitary water permeability does not confirm the predicted value. Osmotic deflation of reconstituted lipid vesicles reveals negligible water permeability of the H_V1 wild-type channel and the D174A mutant open at 0 mV. The conductance of 1400 H⁺ s⁻¹ per wild-type channel agrees with the calculated diffusion limit for a ≈2 Å capture radius for protons. Removal of a charged amino acid (D174) at the pore mouth decreases H⁺ conductance by reducing the capture radius. At least one intervening amino acid contributes to H⁺ conductance while interrupting the water wire across the membrane.     

One-step fabrication of soot particle-embedded fibrous membranes for solar distillation using candle burning-assisted electrospinning

Solar distillation, a promising technique for water purification and desalination, requires photothermal materials to efficiently convert solar energy into heat. In this study, a novel method is proposed wherein fresh carbonaceous (soot) particles, as a photothermal material, are embedded into electrospun fibrous membranes by burning candles (to produce soot) and electrospinning of polymer material simultaneously. The proposed method can produce several types of membranes with various particle positions (interior or exterior) in the polymer fiber. The particle positions were adjusted by changing the introduction points of particles using a polymer jet. Polymer fibers with diameters of several hundred nanometers were fabricated. Experiments revealed that the soot particle position did not influence the photothermal conversion performance of the membranes. The fabricated membrane could improve the heat localization up to 194.5% and exhibited water distillation and desalination rates as high as 1.60 and 1.55 kg m⁻²h⁻¹, respectively, under 1-sun solar light irradiation. The proposed method opens a new route for the functionalization of polymer membranes.     

Adsorptive separation and photocatalytic degradation of methylene blue dye on titanate nanotube powders prepared by hydrothermal process using metal Ti particles as a precursor

Titanate nanotube powders (TNTPs) with the twofold removal ability, i.e. adsorptive separation and photocatalytic degradation, are synthesized under hydrothermal conditions using metal Ti particles as a precursor in the concentrated alkaline solution, and their morphology, structure, adsorptive and photocatalytic properties are investigated. Under hydrothermal conditions, the titanate nanotubes (TNTs) with pore diameter of 3-4 nm are produced on the surface of metal Ti particles, and stacked together to form three-dimensional (3D) network with porous structure. The TNTPs synthesized in the autoclave at 130 °C for 24 h exhibits a maximum adsorption capability of about 197 mg g⁻¹ in the neutral methylene blue (MB) solution (40 mg L⁻¹) within 90 min, the adsorption process can be described by pseudo second-order kinetics model. Especially, in comparison with the adsorptive and the photocatalytic processes are performed in turn, about 50 min can be saved through synchronously utilizing the double removal ability of TNTPs when the removal ratio of MB approaches 95% in MB solution (40 mg L⁻¹) at a solid-liquid (S/L) ratio of 1:8 under ultraviolet (UV) light irradiation. These 3D TNTPs with the twofold removal properties and easier separation ability for recycling use show promising prospect for the treatment of dye pollutants from wastewaters in future industrial application.     

Preparation of zeolite T membranes by microwave-assisted in situ nucleation and secondary growth

Zeolite T membranes were firstly prepared on the α-Al₂O₃ tubes by microwave-assisted in situ nucleation and secondary growth. The obtained membranes were characterized by XRD, SEM, single gas permeation, and pervaporation (PV). In the PV dehydration of ethanol and 2-propanol, the as-synthesized membranes displayed high separation performance. For the 90 wt.% alcohol/water mixtures at 338 K, the water flux reached 1.23 kg m^− 2 h^− 1 for the dehydration of ethanol and 1.52 kg m^− 2 h^− 1 for the dehydration of 2-propanol; both separation factors were higher than 10, 000.     

Solar-Powered Interfacial Evaporation and Deicing Based on a 3D-Printed Multiscale Hierarchical Design

Solar-powered interfacial heating has emerged as a sustainable technology for hybrid applications with minimal carbon footprints. Aerogels, hydrogels, and sponges/foams are the main building blocks for state-of-the-art photothermal materials. However, these conventional three-dimensional (3D) structures and related fabrication technologies intrinsically fail to maximize important performance-enhancing strategies and this technology still faces several performance roadblocks. Herein, monolithic, self-standing, and durable aerogel matrices are developed based on composite photothermal inks and ink-extrusion 3D printing, delivering all-in-one interfacial steam generators (SGs). Rapid prototyping of multiscale hierarchical structures synergistically reduce the energy demand for evaporation, expand actual evaporation areas, generate massive environmental energy input, and improve mass flows. Under 1 sun, high water evaporation rates of 3.74 kg m⁻² h⁻¹ in calm air and 25.3 kg m⁻² h⁻¹ at a gentle breeze of 2 m s⁻¹ are achieved, ranking among the best-performing solar-powered interfacial SGs. 3D-printed microchannels and hydrophobic modification deliver an icephobic surface of the aerogels, leading to self-propelled and rapid removal of ice droplets. This work shines light on rational fabrication of hierarchical photothermal materials, not merely breaking through the constraints of solar-powered interfacial evaporation and clean water production, but also discovering new functions for photothermal interfacial deicing.     

High Virus Removal by Self‐Organized Nanostructured 2D Liquid‐Crystalline Smectic Membranes for Water Treatment

To obtain high quality of drinking water free from biocontaminants is especially important issue. A new strategy employing smectic liquid‐crystalline ionic membranes exhibiting 2D structures of layered nanochannels for water treatment is proposed for efficient virus removal and sufficient water flux. The smectic A (SmA) liquid‐crystalline membranes obtained by in situ polymerization of an ionic mesogenic monomer are examined for removal of three distinct viruses with small size: Qβ bacteriophage, MS2 bacteriophage, and Aichi virus. The semi‐bilayer structure of the SmA significantly obstructs the virus penetration with an average log reduction value of 7.3 log₁₀ or the equivalent of reducing 18 million viruses down to 1. Furthermore, the layered nanochannels of the SmA liquid crystal allow efficient water permeation compared to other types of liquid‐crystalline membrane consisting of nanopores.     

Thin Film Composite Membranes as a New Category of Alkaline Water Electrolysis Membranes

Alkaline water electrolysis (AWE) is considered a promising technology for green hydrogen (H₂) production. Conventional diaphragm-type porous membranes have a high risk of explosion owing to their high gas crossover, while nonporous anion exchange membranes lack mechanical and thermochemical stability, limiting their practical application. Herein, a thin film composite (TFC) membrane is proposed as a new category of AWE membranes. The TFC membrane consists of an ultrathin quaternary ammonium (QA) selective layer formed via Menshutkin reaction-based interfacial polymerization on a porous polyethylene (PE) support. The dense, alkaline-stable, and highly anion-conductive QA layer prevents gas crossover while promoting anion transport. The PE support reinforces the mechanical and thermochemical properties, while its highly porous and thin structure reduces mass transport resistance across the TFC membrane. Consequently, the TFC membrane exhibits unprecedentedly high AWE performance (1.16 A cm⁻² at 1.8 V) using nonprecious group metal electrodes with a potassium hydroxide (25 wt%) aqueous solution at 80 °C, significantly outperforming commercial and other lab-made AWE membranes. Moreover, the TFC membrane demonstrates remarkably low gas crossover, long-term stability, and stack cell operability, thereby ensuring its commercial viability for green H₂ production. This strategy provides an advanced material platform for energy and environmental applications.     

Calcinable Polymer Membrane with Revivability for Efficient Oily‐Water Remediation

Fouling of polymeric membranes remains a major challenge for long‐term operation of oily‐water remediation. The common reclamation methods to recycle fouled membranes have the issues of either incomplete degradation of organic pollutants or damage to filter membranes. Here, a calcinable polymer membrane with effective reclamation after fouling is reported, which shows full recovery of the original oil/water separation efficiency. The membrane is made of polysulfonamide/polyacrylonitrile fibers by emulsion electrospinning, followed by hydrothermal decoration of TiO₂ nanoparticles. The bonding structured fibrous membrane displays outstanding thermal stability in air (400 °C), strong acid/alkali resistance (at the pH range from 1 to 13), and robust tensile strength. As a result, the chemically fouled polymeric membrane can be easily reclaimed without decreasing in separation performance and mechanical properties by annealing treatment. As a proof‐of‐concept, the as‐prepared membrane is integrated into a wastewater separation tank, which achieves a high water flux over 3000 L m^?2 h^?1 and oil rejection efficiency of 99.6% for various oil‐in‐water emulsions. The presented strategy on membrane fabrication is believed to be an effective remedy for membrane fouling, and should apply in a wider field of filtration industry.     

Electric-Field-Induced Ionic Sieving at Planar Graphene Oxide Heterojunctions for Miniaturized Water Desalination

Layered graphene oxide membranes (GOMs) offer a unique platform for precise sieving of small ions and molecules due to controlled sub-nanometer-wide interlayer distance and versatile surface chemistry. Pristine and chemically modified GOMs effectively block organic dyes and nanoparticles, but fail to exclude smaller ions with hydrated diameters less than 9 Å. Toward sieving of small inorganic salt ions, a number of strategies are proposed by reducing the interlayer spacing down to merely several angstroms. However, one critical challenge for such compressed GOMs is the extremely low water flux (<0.1 Lm⁻² h⁻¹ bar⁻¹) that prevents these innovative nanomaterials from being used in real-world applications. Here, a planar heterogeneous graphene oxide membrane (PHGOM) with both nearly perfect salt rejection and high water flux is reported. Horizontal ion transport through oppositely charged GO multilayer lateral heterojunction exhibits bi-unipolar transport behavior, blocking the conduction of both cations and anions. Assisted by a forward electric field, salt concentration is depleted in the near-neutral transition area of the PHGOM. In this situation, deionized water can be extracted from the depletion zone. Following this mechanism, a high rejection rate of 97.0% for NaCl and water flux of 1529 Lm⁻² h⁻¹ bar⁻¹ at the outlet via an inverted T-shaped water extraction mode are achieved.     

Composite Solid Electrolyte with Continuous and Fast Organic–Inorganic Ion Transport Highways Created by 3D Crimped Nanofibers@functional Ceramic Nanowires

A 3D crimped sulfonated polyethersulfone-polyethylene oxide(C-SPES/PEO) nanofiber membrane and long-range lanthanum cobaltate(LaCoO₃) nanowires are collectively doped into a PEO matrix to acquire a composite solid electrolyte (C-SPES-PEO-LaCoO₃) for all-solid-state lithium metal batteries(ASSLMBs). The 3D crimped structure enables the fiber membrane to have a large porosity of 90%. Therefore, under the premise of strongly guaranteeing the mechanical properties of C-SPES-PEO-LaCoO₃, the ceramic nanowires conveniently penetrated into the 3D crimped SPES nanofiber without being blocked, which can facilitate fast ionic conductivity by forming 3D continuous organic–inorganic ion transport pathways. The as-prepared electrolyte delivers an excellent ionic conductivity of 2.5 × 10⁻⁴ S cm⁻¹ at 30 °C. Density functional theory calculations indicate that the LaCoO₃ nanowires and 3D crimped C-SPES/PEO fibers contribute to Li⁺ movement. Particularly, the LiFePO₄/C-SPES-PEO-LaCoO₃ /Li and NMC811/C-SPES-PEO-LaCoO₃/Li pouch cell have a high initial discharge specific capacity of 156.8 mAh g⁻¹ and a maximum value of 176.7 mAh g⁻¹, respectively. In addition, the universality of the penetration of C-SPES/PEO nanofibers to functional ceramic nanowires is also reflected by the stable cycling performance of ASSLMBs based on the electrolytes, in which the LaCoO₃ nanowires are replaced with Gd-doped CeO₂ nanowires. The work will provide a novel approach to high performance solid-state electrolytes.