Composite Membranes Research Articles

Composite ultrathin membranes for clarification and primary recovery of biobased itaconic acid from fermentation broths

Itaconic acid is a biobased organic acid with clear potential to become a relevant renewable building-block chemical. However, to compete with petrochemical processes, the production cost of biobased processes, particularly the downstream processing contribution, needs to be reduced. In this work, composite membranes comprising ultrathin films of crosslinked poly[(o-cresyl glycidyl ether)-co-formaldehyde] and branched polyethyleneimine on mixed cellulose ester supports were developed for application in the primary recovery of itaconic acid from fermentation broths. In contrast to commercial and literature-reported counterparts, these membranes exhibit low itaconic acid rejections over a wide range of pH, ionic strength, organic acid concentration and operating pressure. Moreover, these membranes can efficiently recover itaconic acid from clarified fermentation broth as well as unclarified fermentation broth of Pichia pastoris cultivations, with average rejections below 15 % recorded over 8 h of operation. Lastly, the performance of these membranes was compared to literature-reported strategies for primary recovery of biobased organic acids. The efficient recovery of itaconic acid from unclarified fermentation broth opens the possibility to perform clarification and primary recovery simultaneously, thus simplifying the downstream processing of biobased itaconic acid considerably.

Development and investigation of a multilayer PDMS/zeolite composite membrane for CO2 separation applications

This work aims to investigate and develop a concept for CO2 separation based on PDMS/SSZ–13 (high-Si CHA) composite membranes. Firstly, an Al2O3 support was coated with SSZ-13 zeolite layer, then to increase the performance of the membrane, a Polydimethylsiloxane layer was effectively deposited homogeneously to cover the cracks and defects of the zeolite layer. The results of single gas permeation measurements displayed a notable increase in ideal CO2/CH4 selectivity up to 428 at the lowest PDMS concentration of 0.5 vol%. Moreover, a coating time of 10 min preserved CO2 permeance while increasing CO2/CH4 selectivity from 5 to 120. A twentyfold increase in CO2/CH4 selectivity was noted with mixed gas permeation without a reduction in CO2 permeance. Quantitative and qualitative microscopic analyses were also carried out on the coated membrane to better understand its morphology and microstructure. The outcomes indicated that PDMS layer decreased the permeation of N2 and CH4 and enhanced surface affinity toward CO2, resulting in reduced defects in the zeolite membranes and enhanced selectivity for CO2/N2 and CO2/CH4.

Constructing high-performance nanofiltration membranes using nanofiber supports: Effects of structural stability and polyvinyl alcohol interlayers

Nanofiber supports are promising candidates for constructing high-performance nanofiltration (NF) membranes due to their unique interconnected pores and high porosity. Conventional nanofiber supports usually possess excessive surface roughness and low structural stabilities, influencing the formation of polyamide separation layers. However, research on the effects of nanofiber support properties on the NF membrane performances is relatively few. In this study, we systematically evaluated the effects of structural properties of the nanofiber supports on the performances of the fabricated thin-film nanofiber composite (TFNC) NF membranes. The polyimide (PI) support with heat-pressing post-treatments owns a smooth surface and high structural stability due to the welding and compaction of the PI nanofibers. This promoted the formation of a polyamide separation layer with high smoothness and low fouling tendencies. Consequently, the mechanical strength and long-term operation stability of the TFNC-PI NF membrane were much stronger than that of the membranes with polyacrylonitrile (PAN) and PVDF nanofiber supports. Membrane performance analyses illustrated that the TFNC NF membranes possess notable higher water permeance while slight lower salt rejection than the commercial NF membrane. Compared to TFNC-PAN NF membranes (18∼20 L m-2h−1 bar−1), the water permeance of the structurally stable TFNC-PI NF membrane was relatively low (15–16 L m-2h−1 bar−1) due to its smaller surface filtration area and membrane pore size. Further attempts illustrated that constructing interlayers with 2 wt% polyvinyl alcohol (PVA) coating solutions resulted in the formation of clear and regular Turing structures in the polyamide surface layer. It notably enhanced the water permeance of the membrane by ∼30 % without compromising the salt rejection capability of the membrane. This study provides fundamental insights into the effects of nanofiber support properties on NF performance and feasible pathways to construct high-performance TFNC NF membranes.

Enhanced properties of a positive-charged nanofiltration membrane containing quaternarized chitosan through second interfacial polymerization for the removal of salts and pharmaceuticals.

Nanofiltration (NF) membrane technology has been widely used in the removal of salts and trace organic pollutants, such as pharmaceuticals and personal care products (PPCPs), due to its superiority. A positive-charged composite NF membrane with an active skin layer was prepared by polyethyleneimine (PEI), trimethyl benzene chloride, and quaternate chitosan (HTCC) through second interfacial polymerization on the polyethersulfone ultrafiltration membrane. The physicochemical properties of the nanocomposite membrane were investigated using surface morphology, hydrophilicity, surface charge, and molecular weight cut-off (MWCO). The influence of the concentration and reaction time of PEI and HTCC was documented. The optimized membrane had a MWCO of about 481 Da and possessed a pure water permeability of 25.37 L·m-2·h-1·MPa-1. The results also exhibited salt rejection ability as MgCl2 > CaCl2 > MgSO4 > Na2SO4 > NaCl > KCl, showing a positive charge on the fabricated membrane. In addition, the membrane had higher rejection to atenolol, carbamazepine, amlodipine, and ibuprofen at 89.46, 86.02, 90.12, and 77.21%, respectively. Moreover, the anti-fouling performance and stability of the NF membrane were also improved.

Synergistic Interface Platforms: Designing Superhydrophilic Conductive Nanoparticle‐Decorated Nanofibrous Membranes

AbstractIn today's technological landscape, advancing methods for producing conductive membranes that simplify and streamline the development of advanced interface materials is crucial. This study introduces a versatile and innovative method for fabricating superhydrophilic, conductive nanofibrous membranes based on the in situ synthesis of polypyrrole nanoparticles on poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) electrospun fibers. The composite membranes morphologically exhibit a particle‐decorated nanofibrous configuration, with polypyrrole nanoparticles distributed along the individual fibers' surface. The nanoparticle‐nanofiber configuration shows distinctive properties; electrochemically, the electrospun mats demonstrate excellent inherent electrical conductivity, good cyclic and high electrochemical stability, and low resistance. Furthermore, the amphiphilic and superhydrophilic behavior, achieved through nanotopography, porosity and interactions between the intrinsically conductive polymer and the PVDF‐HFP fibers, enables efficient uptake of polar and nonpolar analytes. The membranes also demonstrate good in vitro cell viability of both murine and human fibroblasts. Given its efficient interaction with liquids and omnidirectional 360‐degree conductivity, this material emerges as an excellent candidate for use as a biocompatible, multifunctional interface layer. The produced nanoparticle‐nanofibrous membrane materials offer a promising platform for interface applications, featuring enhanced spatiotemporal configurations and wide‐ranging applicability.

PVC plasticized membranes modified with Fe3O4 nanoparticles for potentiometric sensing of sulfate

Potentiometric sensing is one of the most wide spread platforms for analysis of aqueous solutions. The development of potentiometric sensors for hydrophilic anions such as sulfate, phosphate and bicarbonate is a challenging problem, since their high hydration energy results in a low affinity for non-polar polymer membranes – a standard material for potentiometric sensor production.In this study we propose a new type of polymeric sensor membranes for ion-selective sensors with pronounced selectivity to hydrophilic anions. The membranes are based on inorganic Fe3O4 nanoparticles (NP) embedded into plasticized poly(vinyl chloride). Six different formulations of membranes with various combinations of Fe3O4 nanoparticles and other membrane-active components were synthesized and characterized with a wide range of physico-chemical methods. Contact angle measurements, FTIR spectra, SEM and AFM imaging, magnetization hysteresis curves, ZFC/FC studies were performed. The obtained results proved the formation of nanocomposites and demonstrated a structure with “cavities” in membranes with embedded nanoparticles. Potentiometric sensitivity and selectivity of the developed sensors in aqueous solutions of SO42−, HPO42−, HCO3−, H2PO4−, NO3− and Cl−anions were studied. The developed sensors showed high sensitivity to sulfate ion (-22 mV/dec in the concentration range from 10−5 to 10−3 M) and low sensitivity to the typical interfering anions – chloride and nitrate (-14 mV/dec). The optimized sensor membrane composition demonstrated sulfate selectivity higher than that of commercially available ion-selective sensor formulations. The novel sensors were tested for quantification of SO42− in real samples of natural mineral water and the obtained content of sulfate was in a good agreement with the reference data (relative error < 3 %)

Benzenesulfonamide-Functionalized Electrospun Polysulfone as an Antibacterial Support Layer of Thin-Film Composite Pressure-Retarded Osmosis Membrane: Fabrication and Performance Evaluation

Benzenesulfonamide-Functionalized Electrospun Polysulfone as an Antibacterial Support Layer of Thin-Film Composite Pressure-Retarded Osmosis Membrane: Fabrication and Performance Evaluation

Synthesis and Characterization of Enhanced Proton-Conducting Nafion&lt;sup&gt;® &lt;/sup&gt;117- Silica Composite Membranes for Fuel Cell Applications

Nafion®/silica nanocomposite membranes were prepared by impregnation method from Nafion® 117 and sol-gel pre-synthesized n-octadecyl-trimethoxy silane (C18TMS) coated silica nanoparticles. The scanning electron microscope (SEM) of pristine silica particles displayed monodispersed nanospheres with diameters ranging from 150-350 nm; while Brunauer-Emmett-Teller (BET) analysis presented 760 m2/g BET surface area, a micropore-mesopore bimodal distribution of micropore systems with respective pore volume at 14.6 Å and 17.0 Å (2.01 x 10-3 cm3/g.Å), as well as the prolific mesopores centered at 29.5 Å (5.64 x 10-2 cm3/g.Å). Characterization of Nafion® 117 based membranes on SEM, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and x-ray diffraction (XRD), and tensile stress exhibited varying surface morphology with silica loadings, structural interaction between membrane support and the ion exchanger, thermal stabilities (up to 330 °C), crystalline nature, and reasonable mechanical stability of nanocomposite membranes. The maximum water uptake (44.8 %) and proton conductivity of (1.14 x10-2 S/cm) were obtained on low Nafion®/SiO2 (5%) loaded membrane. While both composite membranes displayed the improved reduction in methanol permeability, 2.43x10-07 cm2/s at 80 °C was obtained with high Nafion®/SiO2 (10%) loading. Improved water uptake and proton conductivity substantiate the high ion exchange capacity (IEC) of 1.81 meq.g-1 when compared to IEC of 0.93 meq.g-1 [pristine Nafion®] and 1.46 meq.g-1 [Nafion®/SiO2 (10%)]. The increase in IEC value may be due to the high acid functionalization of additional sulfonic acid groups surrounded by hydrophilic segments of nanosilica, which improves the properties of the membrane. The high proton conductivity coupled with great water retention capabilities indicated that the Nafion®/SiO2 nanocomposite membranes could be utilized as proton exchange membranes for medium temperature methanol fuel cells. Keywords: Fuel cells; nanocomposite membrane; SiO2 nanofillers; methanol permeability; ion exchange capacity

Ultrasensitive Label-Free Electrochemical Immunosensor for Carbohydrate Antigen-125 (CA125) Employing Cu(II)-Polyethyleneimine (PEI)/Silica Nanoparticle@Overoxidized Polypyrrole (OPPy)/Multi-Walled Carbon Nanotubes (MWNTs) Hybrid Nanomaterial

Novel electroactive nanotags of Cu(II) functionalized polyethylenimine (PEI)/SiO2 nanoparticles (abbreviated as Cu2+/PEI/SiO2 NPs) were conveniently synthesized using a strong coordination reaction between Cu(II) and the multi-amino groups of PEI. These electroactive nanotags were easily coated on the overoxidized polypyrrole (OPPy) modified Nafion/multi-walled carbon nanotubes (abbreviated as Nafion/MWNTs) electrode surface through Cu-N bonds and strong electrostatic interactions. The Cu2+/PEI/SiO2 NPs@OPPy/MWNTs hybrid nanomaterial was formed without the addition of extra membrane-forming substances. The experimental results demonstrate that the OPPy/MWNTs composite membrane coupled with electrocatalytic Cu(Tris)4 2+ complexes in tris(hydroxymethyl)aminomethane (Tris)-HCl buffer medium amplified the electrochemical signals of nanotags based on the mutual synergistic effects. As an application, a label-free electrochemical immunosensor for epithelial ovarian cancer biomarker-carbohydrate antigen-125 (CA125) was constructed by covalently immobilizing CA125 antibody onto the hybrid nanomaterial modified electrode. With the increasing concentrations of CA125 antigen, different decreases in the electrochemical signals of the nanotags were observed due to the formation of antigen-antibody immune complexes. The electrochemical immunosensor showed a linear relationship from 0.001 to 500 U·mL−1 for CA125 with a detection limit of 3.4 × 10−4 U·mL−1. In addition, the proposed immunosensor was applied to the determination of CA125 in human serum with satisfactory results.

Scalable Preparation of Ultraselective and Highly Permeable Fully Aromatic Polyamide Nanofiltration Membranes for Antibiotic Desalination.

Membranes are important in the pharmaceutical industry for the separation of antibiotics and salts. However, its widespread adoption has been hindered by limited control of the membrane microstructure (pore architecture and free-volume elements), separation threshold, scalability, and operational stability. In this study, 4,4',4'',4'''-methanetetrayltetrakis(benzene-1,2-diamine) (MTLB) as prepared as a molecular building block for fabricating thin-film composite membranes (TFCMs) via interfacial polymerization. The relatively large molecular size and rigid molecular structure of MTLB, along with its non-coplanar and distorted conformation, produced thin and defect-free selective layers (~27 nm) with ideal microporosities for antibiotic desalination. These structural advantages yielded an unprecedented high performance with a water permeance of 45.2 L m-2 h-1 bar-1 and efficient antibiotic desalination (NaCl/adriamycin selectivity of 422). We demonstrated the feasibility of the industrial scaling of the membrane into a spiral-wound module (with an effective area of 2.0 m2). This module exhibited long-term stability and performance that surpassed those of state-of-the-art membranes used for antibiotic desalination. This study provides a scientific reference for the development of high-performance TFCMs for water purification and desalination in the pharmaceutical industry.

Enhancing Escherichia coli abiotic stress resistance through ornithine lipid formation

Escherichia coli is a common host for biotechnology and synthetic biology applications. During growth and fermentation, the microbes are often exposed to stress conditions, such as variations in pH or solvent concentrations. Bacterial membranes play a key role in response to abiotic stresses. Ornithine lipids (OLs) are a group of membrane lipids whose presence and synthesis have been related to stress resistance in bacteria. We wondered if this stress resistance could be transferred to bacteria not encoding the capacity to form OLs in their genome, such as E. coli. In this study, we engineered different E. coli strains to produce unmodified OLs and hydroxylated OLs by expressing the synthetic operon olsFC. Our results showed that OL formation improved pH resistance and increased biomass under phosphate limitation. Transcriptome analysis revealed that OL-forming strains differentially expressed stress- and membrane-related genes. OL-producing strains also showed better growth in the presence of the ionophore carbonyl cyanide 3-chlorophenylhydrazone (CCCP), suggesting reduced proton leakiness in OL-producing strains. Furthermore, our engineered strains showed improved heterologous violacein production at phosphate limitation and also at low pH. Overall, this study demonstrates the potential of engineering the E. coli membrane composition for constructing robust hosts with an increased abiotic stress resistance for biotechnology and synthetic biology applications.Key points• Ornithine lipid production in E. coli increases biomass yield under phosphate limitation.• Engineered strains show an enhanced production phenotype under low pH stress.• Transcriptome analysis and CCCP experiments revealed reduced proton leakage.

Efficient removal of Cr(VI) from wastewater by composite adsorptive membrane modified with polyethyleneimine (PEI)

The development of an efficient and economical method to remove the toxic Cr(VI) from water is a global challenge. This study developed a new composite adsorptive membrane by combining polyacrylonitrile (PAN) as a substrate with crosslinked polyethyleneimine (PEI) to efficiently remove Cr(VI) from wastewater. After optimizing the preparation conditions of the material, the Cr(VI) removal by PEI/GMA@PAN was investigated using batch adsorption and longer-term filtration experiments. The composite adsorptive membrane exhibited a high adsorption capacity, reaching a maximum of 89.16 mg/g, along with fast adsorption kinetics that achieved equilibrium within 100 min for Cr(VI) removal. Even in the presence of coexisting ions, PEI/GMA@PAN membrane maintained a high efficiency in removing Cr(VI). The removal mechanism mainly relied on electrostatic interactions and the reduction of Cr(VI) to Cr(III). Notably, long-term filtration experiments substantiated the membrane's effectiveness in removing Cr(VI) from synthetic wastewater, with an impressive treatment volume of 342 L/m2. The optimized PEI/GMA@PAN membrane also demonstrated low PEI leaching across a wide pH range and the potential for re-utilization through four-round cycles, underscoring its promising applicability in wastewater treatment. Therefore, the newly synthesized composite membranes show potential for the removal of Cr(VI) from wastewater.

Sea and brackish water desalination through a novel PVDF-PTFE composite hydrophobic membrane by vacuum membrane distillation

The present study aims to evaluate the performance of porous hydrophobic Polyvinylidene fluoride − Polytetrafluoroethylene (PVDF-PTFE) composite membranes for desalination by vacuum membrane distillation (VMD) technique. The effect of operating parameters such as feed NaCl concentration (10,000 to 40,000 mg/L), feed temperature (50 °C to 80 °C), and downstream pressure (80 to 120 mmHg) on water permeation rate was studied. The increase in feed temperature enhanced the water permeation rate due to a rise in driving force across the membrane. For a constant downstream pressure of 80 mmHg, feed temperature of 80 °C and feed flow rate of 80 L/h, the membrane exhibited a maximum water flux of 3 kg/m2h with 99.86% salt rejection when aqueous NaCl concentration of 10,000 mg/L was charged as feed. Membrane characterization was performed using various analytical tools to determine physico-chemical properties such as pore size, structural elucidation, thermal stability, crystallinity, and hydrophobicity of the membrane material. Further, a temperature and concentration polarization coefficient-based analysis was performed by solving the mass and heat transport model equations using MATLAB software. The proposed research study promotes the application of VMD for recovering potable water from highly saline sea/brackish water and alleviates brine disposal issues.

Biofouling mitigation of Nb2AlC and Mo3AlC2 MXene-precursors doped polyether sulfone mixed matrix membranes for pathogen microorganisms

This study explores the incorporation of Nb2AlC and Mo3AlC2 MAX phases, known for their nano-layered structure, into polyether sulfone (PES) membranes to enhance their antifouling and permeability properties for pathogen microorganism filtration against bovine serum albumin (BSA) and Escherichia coli (E. coli). The composite membranes were characterized for their structural and morphological properties, and their performance in mitigating biofouling was evaluated. The structural characterizations have been performed for all the prepared MAX phases and corresponding composite membranes. The antioxidant ability of Nb2AlC and Mo3AlC2 MAX phases was defined by the DPPH radical scavenging assay, and the highest antioxidant ability was found to be 59.35 %, while 53.69 % scavenging potential was recorded at 100 mg/L. The percentage scavenging ability was raised with an increase in concentrations. The antimicrobial properties of MAX phases, evaluated as the minimum inhibitory concentration, were stated against several pathogen microorganisms. The tested compounds of Nb2AlC and Mo3AlC2 composites containing MAX phases exhibited excellent chemical nuclease activity, and it was determined that Nb2AlC caused double strand DNA cleavage activity while Mo3AlC2 induced the complete fragmentation of the DNA molecule. Biofilm inhibition of Nb2AlC and Mo3AlC2 MAX phases was studied against Staphylococcus aureus, and Pseudomonas aeruginosa and the maximum biofilm inhibition of Nb2AlC and Mo3AlC2 MAX phases was found to be 77.15 % and 69.07 % against S. aureus and also 69.74 % and 65.01 % against P. aeruginosa. Furthermore, Nb2AlC and Mo3AlC2 MAX phases demonstrated excellent E. coli growth inhibition of 100 % at 125 and 250 mg/L.

A review on the design and fabrication of polydimethylsiloxane thin-film composite membranes (TFCMs) for alcohol permselective pervaporation

Pervaporation-based membrane technology have gained increasing interest due to their energy efficiency and environmental sustainability. Polydimethylsiloxane (PDMS) thin-film composite membranes (TFCMs) have emerged as promising candidates for alcohol permselective applications. Compared to the development of pervaporation membrane for water purification, the optimization progress with the ethanol recovery membrane has been fairly slow and fails to meet requirements of bio-alcohol production. Despite the continuous efforts on membrane materials, the role of structural, physicochemical properties for the forming progress of selective layer on substrate is not a well-attended topic. This paper summarized the design and construction considerations of PDMS composite membranes for pervaporation from the viewpoint of the transport resistance model, including the effect of selective layer, support layer, and intermediate layer, to deeply understand and precisely regulate the preparation process. We high light the key role of crosslinking and spreading of PDMS on porous support layer in membrane fabrication. The structure-activity relationship between the separation performance of transport structure with the membrane solution properties, substrate pore structure, and the fabrication methods was discussed in detail. It was indicated that the challenges for the TFCMs applied on a pilot or industrial scale include the thickness control, coating and curing time optimization, and solvent issue. Finally, it was expected for further research to optimize the membrane fabrication process, develop novel advanced membrane materials and to explore complex and potential applications the new requirements in industry.

Scalable, Interfacially Synthesized, Covalent-Organic Framework (COF)-Based Thin-Film Composite (TFC) Hollow Fiber Membranes for Organic Solvent Nanofiltration (OSN).

Covalent organic frameworks have great potential for energy-efficient molecular sieving-based separation. However, it remains challenging to implement COFs as an alternative membrane material due to the lack of a scalable and cost-effective fabrication mechanism. This work depicts a new method for fabricating a scalable in situ COF hollow fiber (HF) membrane by an interfacial polymerization (IP) approach at room temperature. The 2D COF film was constructed on a polyacrylonitrile HF substrate using aldehyde (1,3,5-trimethylphloroglucinol, Tp) and amine (4,4'-azodianiline (Azo) and 4,4',4″-(1,3,5-triazine- 2,4,6-triyl) trianiline (Tta)) as precursors. The COF membrane on the PAN substrate showed 99% rejection of Direct red-80 with remarkable solvent permeance. The rejection analysis revealed that the structural aspects of the solute molecule play a major role in rejection rather than the molecular weight. We further optimized the precursor concentrations to improve the permeation performance of the resulting membrane. The durability study reveals excellent stability of the membrane toward organic solvents. This study also demonstrated the easy scalability of the membrane fabrication approach. The approach was further extrapolated to fabricate a cation-based COF membrane. These charged membranes exhibited an enhanced rejection performance. Finally, this approach can facilitate industrially challenging molecular sieving applications using COF-based membranes.

Polylactic acid/ zinc oxide decorated multi-wall carbon nanotubes fibrous membranes and their applications in oil-water separation

The frequent occurrence of oil spills and oily wastewater leakage has increased the demand for oil-water separation materials with good hydrophobicity. Herein, a novel polylactic acid composite fibrous membrane is reported to address this problem. The zinc oxide decorated multi-wall carbon nanotubes were synthesized via the hydrothermal reaction and composited with polylactic acid to prepare a series of fibrous membranes via electrospinning. The wetting behavior of the prepared fibrous membranes conformed to Cassie's equation, proving that the introduced zinc oxide-decorated multi-wall carbon nanotubes enhanced the surface roughness of the prepared fibrous membranes. Such rough surfaces of the fibrous membranes have enhanced the hydrophobicity and increased the water contact angle to 138.5° (in air) and 159.3° (under oil), respectively. The oil uptake of the prepared fibrous membranes has reached 73.2 g/g. The prepared fibrous membrane was able to absorb oil on the water surface, underwater, or emulsion. Therefore, the prepared polylactic acid/zinc oxide-decorated multi-wall carbon nanotubes fibrous membrane can be a good candidate material for treating oily wastewater.

Porous Ceramic Metal-Based Flow Battery Composite Membrane.

In metal-based flow battery, membranes significantly impact energy conversion efficiency and security. Unfortunately, damages to the membrane occur due to gradual accumulation of metal dendrites, causing short circuits and shortening cycle life. Herein, we developed a rigid hierarchical porous ceramic flow battery composite membrane with a sub-10-nm-thick polyelectrolyte coating to achieve high ion selectivity and conductivity, to restrain dendrite, and to realize long cycle life and high areal capacity. An aqueous zinc-iron flow battery prepared using this membrane achieved an outstanding energy efficiency of >80%, exhibiting excellent long-term stability (over 1000 h) and extremely high areal capacity (260 mAh cm-2). Low-field nuclear magnetic resonance (NMR) spectroscopy, small-angle X-ray scattering, in situ infrared spectroscopy, solid-state NMR analysis, and nano-computed tomography revealed that the rigid hierarchical pore structures and numerous hydrogen bonding networks in the membrane contributed to the stable operation and superior battery performance. This study contributes to the development of next-generation metal-based flow battery membranes for energy and power generation.

Leveraging Janus Substrates as a Confined "Interfacial Reactor" to Synthesize Ultrapermeable Polyamide Nanofilms.

Porous substrates act as open "interfacial reactors" during the synthesis of polyamide composite membranes via interfacial polymerization. However, achieving a thin and dense polyamide nanofilm with high permeance and selectivity is challenging when using a conventional substrate with uniform wettability. To overcome this limitation, we propose the use of Janus porous substrates as confined interfacial reactors to decouple the local monomer concentration from the total monomer amount during interfacial polymerization. By manipulating the location of the hydrophilic/hydrophobic interface in a Janus porous substrate, we can precisely control the monomer solution confined within the hydrophilic layer without compromising its concentration. The hydrophilic surface ensures the uniform distribution of monomers, preventing the formation of defects. By employing Janus substrates fabricated through single-sided deposition of polydopamine/polyethyleneimine, we significantly reduce the thickness of the polyamide nanofilms from 88.4 to 3.8 nm by decreasing the thickness of the hydrophilic layer. This reduction leads to a remarkable enhancement in water permeance from 7.2 to 52.0 l/m2·h·bar while still maintaining ~96% Na2SO4 rejection. The overall performance of this membrane surpasses that of most reported membranes, including state-of-the-art commercial products. The presented strategy is both simple and effective, bringing ultrapermeable polyamide nanofilms one step closer to practical separation applications.

Porous Ceramic Metal‐Based Flow Battery Composite Membrane

AbstractIn metal‐based flow battery, membranes significantly impact energy conversion efficiency and security. Unfortunately, damages to the membrane occur due to gradual accumulation of metal dendrites, causing short circuits and shortening cycle life. Herein, we developed a rigid hierarchical porous ceramic flow battery composite membrane with a sub‐10‐nm‐thick polyelectrolyte coating to achieve high ion selectivity and conductivity, to restrain dendrite, and to realize long cycle life and high areal capacity. An aqueous zinc‐iron flow battery prepared using this membrane achieved an outstanding energy efficiency of &gt;80%, exhibiting excellent long‐term stability (over 1000 h) and extremely high areal capacity (260 mAh cm−2). Low‐field nuclear magnetic resonance (NMR) spectroscopy, small‐angle X‐ray scattering, in situ infrared spectroscopy, solid‐state NMR analysis, and nano‐computed tomography revealed that the rigid hierarchical pore structures and numerous hydrogen bonding networks in the membrane contributed to the stable operation and superior battery performance. This study contributes to the development of next‐generation metal‐based flow battery membranes for energy and power generation.