Achieving superiorly high heat-dimensional stability,high strength,and good electrochemical performance for electrospun separators in power lithium-ion battery through building unique condensed structure based on polyimide and poly (m-phenylene isophthalamide)

It is still a challenge for simultaneously achieving high heat resistance, high strength and outstanding electrochemical performance for separators in power lithium-ion battery (PLB). Herein, new high performance electrospun separators are developed through building unique structure based on polyimide (PI) and poly (m-phenylene isophthalamide) (PMIA). Orthogonal tests (4⁴) show that the magnitude order of electrospinning factors on the morphology of membrane is concentration>injection rate>receiving distance>voltage. With the optimum factors, the electrospun membrane (PI/PMIA) was prepared, which was further pressed at 100°C for 10 min to get treated membrane (H-PI/PMIA). Interestingly, the comprehensive performance of PI/PMIA is not a simple combination of those of PI and PMIA; instead, PI/PMIA has much better thermal and mechanical properties than both PI and PMIA, proving that PI/PMIA has a synergistic effect. PI/PMIA and H-PI/PMIA not only have good ionic conductivity and electrochemical stability, but also have superiorly high properties including dimensional stability (thermal shrinkage temperature>300°C), tensile strengths (24.1 MPa for PI/PMIA, 34.3 MPa for H-PI/PMIA) and capacity retentions (97.9%, 99.2%) compared with electrospun membranes for PLBs reported in the literature so far (SCI database). The mechanism behind these attractive performances is discussed from condensed structure of membranes.     

The influence of poly(3,4-ethylenedioxythiophene) modification on the transport properties and fuel cell performance of Nafion-117 membranes

Nafion-117/PEDOT composite membranes were synthesized by in situ chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) using ammonium persulfate as an oxidant. The polymerization of EDOT in Nafion membranes for various EDOT/oxidant treatment sequences was studied for the first time. PEDOT introduction leads to a slight decrease in both the ion-exchange capacity and water uptake of the composite membranes, as well as to an increase in cationic transport. Membranes initially treated with an oxidant exhibit better conductivity and lower hydrogen permeability. The effect of both modification of Nafion-117 membranes by PEDOT and hot-pressing of hydrogen-oxygen membrane-electrode assemblies (MEAs) on the performance of proton-exchange membrane fuel cells was studied. The maximum power density of the fabricated MEAs increases 1.5-fold: from 510 (for a pristine Nafion-117 membrane) to 810 mW cm⁻² (for a membrane modified by PEDOT). The current density at a voltage of 0.4 V reaches 1248 and 2246 mA cm⁻², respectively.     

Influence of deposited amine-functionalized Si-MCM-41 in polyacrylonitrile electrospun membranes applied for separation of water in oil emulsions

Among several oil/water emulsion separation technologies, the utilization of nanoparticle-decorated membranes with diverse functionalities has received considerable attention in recent years, particularly if the antifouling capacity can be improved. In this article, we propose a new membrane based on surface-hydrolyzed polyacrylonitrile electrospun membranes and/or decorated with amine-functionalized Si-MCM-41 nanoparticles to be used as oil/water emulsion separation treatment and to determine their antifouling ability. X-Ray photoelectron spectrometry, attenuated total reflectance Fourier transform infrared spectroscopy, and toluidine blue O assay, scanning electron microscopy, contact angle measurements for oil under water and thermogravimetry were used for characterizing the membranes and an assay of permeability was developed to quantify the diffusion of oil molecules across the electrospun membrane. The electrospun and/or decorated membranes showed an underwater oleophobic wettability, which can separate oil-in-water emulsions with 87% separation efficiency, results of fouling experiments, evaluated in terms of rejection and flux recovery ratio, exhibited good antifouling ability, but the membrane decoration process did not lead to superior outcomes compared with undecorated membranes.     

Continuum electrostatic approach for evaluating positions and interactions of proteins in a bilayer membrane

Orientations of proteins in the membranes are crucial to their function and stability. Unfortunately the exact positions of these proteins in the lipid bilayer are mostly undetermined. Here, the spatial orientation of membrane proteins within the lipid membrane was evaluated using a Poisson–Boltzmann solvent continuum approach to calculate the electrostatic free energy of the protein solvation at various orientations in an implicit bilayer. The solvation energy was obtained by computing the difference in electrostatic energies of the protein in water and in lipid/water environments, treating each as an implicit solvent model. The optimal position of transmembrane proteins (TMP) in a lipid bilayer is identified by the minimum in the “downhill” pathway of the solvation energy landscape. The energy landscape pattern was considerably conserved in various TMP classes. Evaluation of the position of 1060 membrane proteins from the orientations of proteins in membranes (OPM) database revealed that most of the polytopic and β-barrel proteins were in good agreement with those of the OPM database. The study provides a useful scheme for estimating the membrane solvation energy made by lipid-exposed amino acids in membrane proteins. In addition, our results tested with the bacterial potassium channel model demonstrated the potential usefulness of the approach in assessing the quality of membrane protein models. The present approach should be applicable for constructing transmembrane proteins–lipid configuration suitable for membrane protein simulations and will have utility for the structural modeling of membrane proteins.     

Promote Intratumoral Drug Release and Penetration to Counteract Docetaxel-Induced Metastasis by Photosensitizer-Modified Red Blood Cell Membrane-Coated Nanoparticle

The red blood cell membrane (RBCm) provides tight protection, lowers the immunogenicity, and prolongs the circulation time of drugs in vivo when acting as the coating of drug delivery systems. However, the cellular uptake and release of drugs are hindered by RBCm. Docetaxel (DTX) is the first-line medicine for treating triple-negative breast cancer (TNBC), but it induces tumor metastasis. To solve these dilemmas, in this study, the photosensitizer 1,1-dioctadecyl-3,3,3,3-tetramethylindotricarbocyanine iodide (DiR)-modified RBCm (DM) is prepared, which is coated onto a hybrid micelle consisting of the prodrugs of DTX and the anti-metastasis agent calcitriol (CTL), obtaining a nanoparticle, named HDC-DM. In a 4T1 tumor-bearing mouse model, after injecting HDC-DM, the intratumoral DTX and CTL concentrations are increased by 1.7 and 2.5 times compared with the free drug groups. After irradiating tumors with near-infrared laser, DiR elicits the photothermal effect, triggering the rupture of RBCm and drug release, promoting drug penetration in tumors, and inducing immunogenic cell death. The tumor growth inhibition rate is 77%, and the formation of lung metastases is reduced by 82%, with good biocompatibility. It is suggested that the combination of phototherapy, chemotherapy, and anti-metastatic therapy using HDC-DM is expected to be a powerful strategy for treating TNBC.     

Ultrahigh Energy Storage Capacitors Based on Freestanding Single-Crystalline Antiferroelectric Membrane/PVDF Composites

Inorganic/organic dielectric composites are very attractive for high energy density electrostatic capacitors. Usually, linear dielectric and ferroelectric materials are chosen as inorganic fillers to improve energy storage performance. Antiferroelectric (AFE) materials, especially single-crystalline AFE oxides, have relatively high efficiency and higher density than linear dielectrics or ferroelectrics. However, adding single-crystalline AFE oxides into polymers to construct composite with improved energy storage performance remains elusive. In this study, high-quality freestanding single-crystalline PbZrO₃ membranes are obtained by a water-soluble sacrificial layer method. They exhibit classic AFE behavior and then 2D–2D type PbZrO₃/PVDF composites with the different film thicknesses of PbZrO₃ (0.1-0.4 µm) is constructed. Their dielectric properties and polarization response improve significantly as compared to pure PVDF and are optimized in the PbZrO₃(0.3 µm)/PVDF composite. Consequently, a record-high energy density of 43.3 J cm⁻³ is achieved at a large breakdown strength of 750 MV m⁻¹. Phase-field simulation indicates that inserting PbZrO₃ membranes effectively reduces the breakdown path. Single-crystalline AFE oxide membranes will be useful fillers for composite-based high-power capacitors.     

Self-Standing Covalent Organic Framework Membranes for H2/CO2 Separation

Covalent organic frameworks (COFs) are proposed as promising candidates for engineering advanced molecular sieving membranes due to their precise pore sizes, modifiable pore environment, and superior stability. However, COFs are insoluble in common solvents and do not melt at high temperatures, which presents a great challenge for the fabrication of COF-based membranes (COFMs). Herein, for the first time, a new synthetic strategy is reported to prepare continuous and intact self-standing COFMs, including 2D N-COF membrane and 3D COF-300 membrane. Both COFMs show excellent selectivity of H₂/CO₂ mixed gas (13.8 for N-COF membrane and 11 for COF-300 membrane), and especially ultrahigh H₂ permeance (4319 GPU for N-COF membrane and 5160 GPU for COF-300 membrane), which is superior to those of COFMs reported so far. It should be noted that the overall separation performance of self-standing COFMs exceeds the Robeson upper bound. Furthermore, a theoretical study based on Grand Canonical Monte Carlo (GCMC) simulation is performed to explain the excellent separation of H₂/CO₂ through COFMs. Thus, this facile preparation method will provide a broad prospect for the development of self-standing COFMs with highly efficient H₂ purification.     

Defect Engineering of MOF-Based Membrane for Gas Separation

Metal–organic frameworks (MOFs) are highly versatile materials that have been identified as promising candidates for membrane-based gas separation applications due to their uniformly narrow pore windows and virtually unlimited structural and chemical features. Defect engineering of MOFs has opened new opportunities for manipulating MOF structures, providing a simple yet efficient approach for enhancing membrane separation. However, the utilization of this strategy to tailor membrane microstructures and enhance separation performance is still in its infancy. Thus, this summary aims to provide a guideline for tailoring defective MOF-based membranes. Recent developments in defect engineering of MOF-based membranes will be discussed, including the synthesis strategies for defective MOFs, the effects of defects on the gas adsorption properties, gas transport mechanisms, and recently reported defective MOF-based membranes. Furthermore, the emerging challenges and future prospects will be outlined. Overall, defect engineering offers an exciting opportunity to improve the performance of MOF-based gas membranes. However, there is still a long way to go to fully understand the influence of defects on MOF properties and optimize the design of MOF-based membranes for specific gas separation applications. Nonetheless, continued research in this field holds great promise for the development of next-generation membrane-based gas separation technologies.     

Aperture-Adjustable and Repairable Metal-Based MOFs Catalysis Membrane for Water Purification

Precise adjustment of the pore size, damage repair, and efficient cleaning is all challenges for the wider application of inorganic membranes. This study reports a simple strategy of combining dry-wet spinning and electrosynthesis to fabricate stainless-steel metal–organic framework composite membranes characterized by customizable pore sizes, targeted reparability, and high catalytic activity for membrane cleaning. The membrane pore size can be precisely customized in the range of 14–212 nm at nanoscale, and damaged membranes can be repaired by targeted treatment in 120 s. In addition, advanced oxidation processes can be used to quickly clean the membrane and achieve 98% flux recovery. The synergistic actions of the membrane matrix and the selective layer increase the adsorption energy of active sites to oxidant, shorten the electron transfer cycle, and enhance the overall catalytic performance. This study can provide a new direction for the development of advanced membranes for water purification and high-efficiency membrane cleaning methods.     

Ultra-Thin Single-Particle-Layer Sodium Beta-Alumina-Based Composite Polymer Electrolyte Membrane for Sodium-Metal Batteries

Inorganic/organic composite polymer electrolytes (CPEs) with good flexibility and electrode contact have been pursued for solid−state sodium-metal batteries. However, the application of CPEs for high energy density solid−state sodium-metal batteries is still limited by the low Na⁺ conductivity, large thickness, and low ion transference number. Herein, an ultra-thin single-particle-layer (UTSPL) composite polymer electrolyte membrane with a thickness of ≈20 µm straddled by a sodium beta−alumina ceramic electrolyte (SBACE) is presented. A ceramic Na⁺-ion electrolyte that bridges or percolates across an ultra-thin and flexible polymer membrane provides: 1) the strength and flexibility from the polymer membrane, 2) excellent electrolyte/electrode interfacial contact, and 3) a percolation path for Na⁺-ion transfer. Owing to this novel design, the obtained UTSPL-35SBACE membrane exhibits a high Na⁺-ion conductivity of 0.19 mS cm⁻¹ and a transference number of 0.91 at room temperature, contributing to long−term cycling stability of symmetric sodium cells with a small overpotential. The assembled quasi-solid-state cell with the as−prepared UTSPL-35SBACE membrane displays superior cycling performance with a discharge capacity of 105 mAh g⁻¹ at 0.5 °C rate after 100 cycles and excellent rate performance (82 mAh g⁻¹ at 5 °C rate) at room temperature with the potassium manganese hexacyanoferrate (KMHCF)@CNTs/CNFs cathode, where KMHCF refers to potassium manganese hexacyanoferrate.