Organic Membrane Research Articles

Phosphorylated Covalent Organic Framework Membranes Toward Ultrafast Single Lithium-Ion Transport.

Developing all-solid-state electrolytes, the chips for lithium-metal batteries, with superior electrochemical and mechanical properties awaitsthe disruptive materials. Herein, ionic covalent organic framework membranes are explored as solid-state electrolytes for single Li+ conduction. In the membrane, the anion groups act as Li+ transporter, determining Li+ binding capacity and releasing ability, whereas the oxygen-containing groups act as Li+ co-transporter, creating relay sites between adjacent Li+ transporters for rapid hopping. The membrane exhibits an unprecedented Li+ conductivity of 1.7 mS cm-1 with a Li+-transference number close to unity at room temperature. Additionally, the membrane possesses high flexibility, low interfacial resistance, and excellent cycling performance at room temperature. This work paves an unprecedented path for the advancement of next-generation Li+ conductors in solid-state electrolytes.

Organic Solvent Nanofiltration Membrane with In Situ Constructed Covalent Organic Frameworks as Separation Layer

Organic solvent nanofiltration (OSN) technology is advantageous for separating mixtures of organic solutions owing to its low energy consumption and environmental friendliness. Covalent organic frameworks (COFs) are good candidates for enhancing the efficiency of solvent transport and ensuring precise molecular sieving of OSN membranes. In this study, p-phenylenediamine (Pa) and 1,3,5-trimethoxybenzene (Tp) are used to construct, in situ, a TpPa COF skin layer via interfacial polymerization (IP) on a polyimide substrate surface. After subsequent crosslinking and activation steps, a kind of TpPa/polyimide (PI) OSN membrane is obtained. Under optimized fabrications, this OSN membrane exhibits an ethanol permeance of 58.0 LMH/MPa, a fast green FCF (FGF) rejection of 96.2%, as well as a pure n-hexane permeance of 102.0 LMH/MPa. Furthermore, the TpPa/PI OSN membrane exhibits good solvent resistance, which makes it suitable for the separation, purification, and concentration of organic solvents.

Polyamide-Crystalline Covalent Organic Framework Dual-Layer Nanofiltration Membrane with Improved Ion Selectivity

Polyamide-Crystalline Covalent Organic Framework Dual-Layer Nanofiltration Membrane with Improved Ion Selectivity

Molecular Weaving Towards Flexible Covalent Organic Framework Membranes for Efficient Gas Separations.

Covalent organic frameworks (COFs) exhibit considerable potential in gas separations owing to their remarkable stability and tunable pore structures. Nevertheless, their application as gas separation membranes is hindered by limited size-sieving capabilities and poor processability. In this study, we propose a novel molecular weaving strategy that combines hydroxyl polymers and 2D TpPa-SO3H COF nanosheets, achieving high gas separation efficiency. Driven by the strong electrostatic interactions, the hydroxyl chains thread through the COF pores, effectively weaving and assembling the composites to achieve exceptional flexibility and high mechanical strength. The penetrated chains also reduce the effective pore size of COFs, and combined with the "secondary confinement effect" stemming from abundant CO2 sorption sites in the channels, the PVA@TpPa-SO3H membrane demonstrates a remarkable H2 permeance of 1267.3 GPU and an H2/CO2 selectivity of 43, surpassing the 2008 Robson upper bound limit. This facile strategy holds promise for the manufacture of large-area COF-based membranes for small-sized gas separations.

Molecular Weaving Towards Flexible Covalent Organic Framework Membranes for Efficient Gas Separations

AbstractCovalent organic frameworks (COFs) exhibit considerable potential in gas separations owing to their remarkable stability and tunable pore structures. Nevertheless, their application as gas separation membranes is hindered by limited size‐sieving capabilities and poor processability. In this study, we propose a novel molecular weaving strategy that combines hydroxyl polymers and 2D TpPa−SO3H COF nanosheets, achieving high gas separation efficiency. Driven by the strong electrostatic interactions, the hydroxyl chains thread through the COF pores, effectively weaving and assembling the composites to achieve exceptional flexibility and high mechanical strength. The penetrated chains also reduce the effective pore size of COFs, and combined with the “secondary confinement effect” stemming from abundant CO2 sorption sites in the channels, the PVA@TpPa−SO3H membrane demonstrates a remarkable H2 permeance of 1267.3 GPU and an H2/CO2 selectivity of 43, surpassing the 2008 Robson upper bound limit. This facile strategy holds promise for the manufacture of large‐area COF‐based membranes for small‐sized gas separations.

Rapid preparation and mechanism investigation of covalent organic framework membranes by 3D printing based on electrostatic spraying

Covalent organic framework (COF) has great advantages in the field of membrane separation, but the efficient and convenient preparation of COF membranes is still a challenge. Herein, we propose a novel method with green solvent for the preparation of COF membranes based on electrostatic spraying, which can be successfully prepared within 10 min, forming the TpPa COF with a pore size of 1.8 nm. Molecular dynamics simulations demonstrate that electrostatic spraying enhances the reaction rate by lowering the energy barrier and increasing the movement of reacting monomers. Atomization of the solvent in electrostatic spraying causes the rapid volatilization of the solvent, resulting in supersaturation of the generated TpPa, precipitation and crystallization, and promotes the formation of TpPa COF structure. The optimal COF membrane for the separation of Congo red wastewater is prepared by adjusting the voltage, concentration, and spraying time, with selectivity of Na2SO4 for Congo Red attaining 118 and water permeance reaching 70.2 L m-2 h-1 bar-1. This work not only elaborates the membrane preparation mechanism in the electrostatic spraying process, but also greatly shortens the time of COF membrane preparation compared to the traditional method (2–3 days), which contributes to the possibility for practical application of COF membranes.

Recent Advances in Metal–Organic Framework-Based Ion-Selective Nanofluidic Membranes: Fabrication and Applications

Recent Advances in Metal–Organic Framework-Based Ion-Selective Nanofluidic Membranes: Fabrication and Applications

Enhancing CO2/N2 and CO2/CH4 Separation Properties of PES/SAPO-34 Membranes Using Choline Chloride-Based Deep Eutectic Solvents as Additives

CO2 separation is an important environmental method mainly used in reducing CO2 emissions to mitigate anthropogenic climate change. The use of mixed-matrix membranes (MMMs) arrives as a possible answer, combining the high selectivity of inorganic membranes with high permeability of organic membranes. However, the combination of these materials is challenging due to their opposing nature, leading to poor interactions between polymeric matrix and inorganic fillers. Many additives have been tested to reduce interfacial voids, some of which showed potential in dealing with compatibility problems, but most of them lack further studies and optimization. Deep eutectic solvents (DESs) have emerged as IL substitutes since they are cheaper and environmentally friendly. Choline chloride-based deep eutectic solvents were studied as additives in polyethersulfone (PES)/SAPO-34 membranes to improve CO2 permeability and CO2/N2 and CO2/CH4 selectivity. SAPO-34 crystals of 150 nm with a high surface area and microporosity were synthesized using dry-gel methodology. The PES/SAPO-34 membranes were optimized following previous work and used in a defined composition, using 5 or 10 w/w% of DES during membrane preparation. All MMMs were characterized by their ideal gas permeability using N2 and CO2 pure gasses. Selected membranes were also tested using CH4 pure gas. The results presented that 5 w/w%, in polymer mass, of ChCl–glycerol presented the best result over the synthesized membranes. An increase of 200% in CO2 permeability maintains the CO2/N2 selectivity for the non-modified PES/SAPO-34 membrane. A CO2/CH4 selectivity of 89.7 was obtained in PES/SAPO-34/ChCl-glycerol membranes containing 5 w/w% of this DES, which is an outstanding ideal separation performance for MMMs when compared to other results in the literature. FTIR analysis reiterates the presence of glycerol in the membranes prepared. Dynamic Mechanical Thermal Analysis (DMTA) shows that the addition of 5 w/w% of DES does not impact the membrane flexibility or polymer structure. However, in concentrations higher than 10 w/w%, the inclusion of DES could lead to high membrane rigidification without impacting the overall thermal resistance. SEM analysis of DES-enhanced membranes presented asymmetric final membranes and reaffirmed the results obtained in DMTA about rigidified structures and lower zeolite–polymer interaction with higher concentrations of DES.

Selective Extraction of Terbium Using Functionalized Metal–Organic Framework-Based Solvent-Impregnated Mixed-Matrix Membranes

Advancements in membrane separation techniques will expand the applications and requirements for highly specialized, inventive, efficient, and resistant separation materials. The selective separation of rare earth elements (REEs) is one of the expanding applications of membrane-based techniques, as their use is becoming more widespread. Membrane techniques are becoming increasingly desired as environmentally friendly, straightforward methods for treating wastewater and separating metals. For the separation of REEs, an innovative impregnated mixed-matrix membrane (IMMM) technique was developed in this study. It provides a selective, efficient, and reusable method that is suitable for industrial applications. Terbium was selectively adsorbed from other REEs using organophosphorus IMMM with a loading capacity of 113.2 mg/g in 3 h and was reused three times without destroying the initial membrane. Solvent impregnation is thought to offer specific chelation sites that are selective for terbium separation.

Guanidinium‐Based Covalent Organic Framework Membranes for Superior Mono‐ and Divalent Cations Separation

Biological membranes exhibit extraordinary efficiency in processing ion permeability and selectivity. However, creating artificial membranes for an ideal ion separation is still challenging due to the subtle distinctions in valence and size among different ions. In the realm of biological recognition, the ultimate selectivity of ion channels is considered to stem from the specific binding interactions and appropriate charge density. Designing artificial membranes to achieve similar performance not only helps the understanding of complex ion transport in bioprocesses but also facilitates critical industrial separations. Inspiring by the remarkable performance in biological systems, a guanidinium‐based covalent organic framework membrane is designed, which exhibits an excellent capability to recognize mono‐/divalent cations, achieving K+/Mg2+ selectivity up to 202 in a mixed salt solution. Furthermore, the membrane displays rapid ion transport owing to the uniform sub‐2 nm channels. The experimental results and molecular dynamics simulations illustrate that the charge‐assisted hydrogen bonding sites and the Cl− counter ions within 1D channels play critical roles in cations sieving. Specifically, divalent ions passing through the positively charged channels need to overcome higher energy barriers than monovalent ions. These findings offer promising avenues for the development of advanced multifunctional membranes for efficient ion separation and sustainable water‐related separations.

Determination of three methylimidazole compounds in cosmetics by high performance liquid chromatography-tandem mass spectrometry

Methylimidazole compounds are byproducts formed during the caramel-coloring process and are used in various cosmetics. In addition metronidazole is an antibacterial and anti-inflammatory drug commonly used in modern medicine and is used in cosmetics to treat acne in the short-term. The illegal addition of metronidazole during cosmetics production can result in residual 2-methylimidazole (2-MEI), which, along with 4-methylimidazole (4-MEI), is a class 2B carcinogen. Therefore, establishing efficient, accurate, and sensitive analytical techniques for analyzing methylimidazole compounds in cosmetics is an urgent objective. In this study, a high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for simultaneously determining 1-methylimidazole (1-MEI), 2-MEI, and 4-MEI in cosmetics was developed. Cosmetics samples were extracted via ultrasonication in acetonitrile and purified using a mixed cation-exchange (MCX) solid-phase extraction (SPE) column, with subsequent drying under a stream of nitrogen and redissolution in acetonitrile. The resulting solution was then filtered through a 0.22 μm organic filter membrane for further testing. The analytes were separated using an XBridge® shield RP18 chromatographic column (150 mm×4.6 mm, 3.5 μm) and isocratically eluted with 20 mmol/L ammonium formate solution (containing 0.1% formic acid)-acetonitrile (98∶2, v/v). The target compounds were ionized by electrospray ionization (ESI) source, analyzed in multi-reaction monitoring (MRM) mode, and quantified using the external standard method, with the peak area of the quantitative ion and the mass concentration of the compound taken as the longitudinal and transverse coordinates, respectively. Matrix-matching working curves were also constructed. 1-MEI exhibited good linear relationships in the range of 5-200 μg/L, with correlation coefficients (r2)≥0.9994, while 2-MEI and 4-MEI showed good linearities in the range of 2-100 μg/L with r2≥0.9984. The three methylimidazole compounds exhibited limits of detection (LODs) and quantification (LOQs) of 10-30 μg/kg and 25-100 μg/kg, respectively. Under three spiked levels (LOQ, 2LOQ, 10LOQ), the recoveries of three methylimidazole compounds were 80.9%-107.9%, with relative standard deviations (RSDs, n=6) of 1.2%-12.8%. The practicability of the method was examined using 48 cosmetic samples; 4-MEI was detected in nine samples at contents of 26-1000 μg/kg, while two samples contained 240 and 267 μg/kg of 2-MEI, respectively. 1-MEI was not detected in any of the 48 samples tested. The developed method is simple, fast, and highly sensitive, and provides methodological support for assessing risks and monitoring the three methylimidazole compounds in cosmetics through screening.

Nanofiber connected metal organic frameworks adsorption membrane to enhance Li+ conduction and alleviate interfacial side reaction for solid electrolyte

Nanofiber connected metal organic frameworks adsorption membrane to enhance Li+ conduction and alleviate interfacial side reaction for solid electrolyte

Crystalline Covalent organic framework membrane with tailored chargeability for efficient pharmaceutical rejection by in-situ functionalization of polyethylene-imine

The nanofiltration (NF) membrane with better hydrophilicity, uniform pore size distribution, and dually charged properties is highly desirable to improve the pharmaceutical rejection, especially for the neutral and positively charged pharmaceuticals. Herein, a TpPa membrane was first in-situ crystallized via PTSA-mediated interfacial catalytic polymerization (ICP) strategy using 1,3,5-triformylphloroglucinol (Tp) and p-phenylenediamine (Pa), followed by post-functionalization with PEI to narrow pore size, improve hydrophilicity, and tailor membrane charges to enhance pharmaceutical rejection. PTSA was used as a catalyst to enhance the crystallinity of the TpPa membrane. The PEI introduction narrowed the pore radius from 0.382 nm to 0.272 nm, improved surface hydrophilicity from 74.8°to 37.0°, and shifted surface charge from -19.25 mV to 11.15 mV. This PEI-functionalized TpPa (TpPa-PEI) layers exhibited heterogeneous charges on both sides with a positively charged top and negatively charged bottom. MgCl2 rejection increased from 13.67% to 83.0% without sacrificing water permeance. Additionally, pharmaceutical rejection and the water permeance of the optimal TpPa-PEI membrane exceeded those of the TpPaIP-PEI membrane fabricated without PTSA by about 3.3 and 1.3 times, respectively. Furthermore, compared to the pristine TpPa membranes, the substantially enhanced electropositivity of the optimal TpPa-PEI membrane led to 3-5 times increase in positively charged pharmaceutical rejection (94.1% for propranolol, 97.2% for sulpiride, and 71.2% for metformin). The synergy of negatively charged bottom TpPa-PEI layers and reduced pore size maintained sulfadiazine rejection of 62.1%. Mechanistic study confirmed that PEI penetrated 100 nm into the TpPa layer and cross-linked with the aldehyde groups, leading to tailored chargeability, improved hydrophilicity, and reduced pore size. Via a PEI cross-linking strategy, sub-nanometer channels of crystalline COF layers can be rationally designed, featuring precisely tailored chargeability and hydrophilicity, promising functionalization of the membrane pores and remarkably robust for water reuse.

Adjustable structures and anti-fouling covalent organic networks membranes for precise organic small molecules separation

Covalent organic networks (CONs) membranes show unprecedented potential for the separation of organic small molecules owing to their adjustable structure and surface properties. Despite the variety of methodologies available for synthesizing CONs membranes, the preparation of CONs membranes by interfacial polymerization (IP) at 25 °C in a shorter period of time remains a great challenge. In this work, a highly anti-fouling EDA-TPA CONs composite nanofiltration (NF) membrane with adjustable structure was constructed by rapid IP of amine (ethylenediamine, EDA) and aldehyde (terephthalaldehyde, TPA) at 25 °C for 3 h. EDA-TPA CONs composite membranes showed good selectivity for most common organic small molecules, achieving a permeance of 35 L h−1 m−2 bar−1. Moreover, with respect to anti-fouling properties, the EDA-TPA CONs composite membranes exhibited a 96 % flux recovery ratio (FRR) during bovine serum albumin (BSA) filtration, reflecting an 81 % improvement compared to the control membranes (hydrolyzed polyacrylonitrile, HPAN). In addition, the EDA-TPA CONs composite membranes displayed robust comprehensive stability after continuous operation of 480 min, 5 times of cyclic testing, 180 min of continuous ultrasound at 16 kHZ and 24 h of mechanical agitation at 100 rpm. After these extensive evaluations, the EDA-TPA CONs composite membranes still retained their original separation efficacy. This study provides a fast and mild preparation process to fabricate the high performance CONs composite membranes with good anti-fouling performance and stability for treatment of organic small molecules in wastewater.

Hollow microporous organic network fiber membrane for efficient extraction of okadaic acid from marine organisms

Membrane-based micro-solid phase extraction (M-μSPE) has garnered great attention in sample pretreatment, suffering an inherent contradiction between permeability and adsorption capacity. In this study, a pure microporous organic network (TEB-DIB-MON) fiber membrane was prepared by combining electrostatic spinning technology, Sonogashira-Hagihara reaction and template sacrifice method. The prepared TEB-DIB-MON membrane exhibited a large specific surface area with a hollow and porous structure, thereby providing excellent solvent permeability and high adsorption capacity for okadaic acid (OA, an algal toxin). Under the optimized conditions, a sensitive analytical method was established by coupling M-μSPE with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The established method has a low detection limit (0.5 pg mL-1), a wide linear range (1.5-1000 pg mL-1, R ≥ 0.9991), and good reproducibility (RSD ≤ 9.4 %, n = 6), which was then successfully applied for OA detection in marine organisms. Trace amounts of OA (59.3-89.0 pg mL-1) was detected in the oyster and prawn samples. This work demonstrated that the excellent application potential of MON membranes in sample pretreatment, while also presents a novel synthesis strategy for MONs membranes.

Quantifying Steric, Non-Steric, and Adsorption Contributions to Solute Rejection in Covalent Organic Framework Nanofiltration Membranes

Quantifying Steric, Non-Steric, and Adsorption Contributions to Solute Rejection in Covalent Organic Framework Nanofiltration Membranes

Interfacially Fabricated Covalent Organic Framework Membranes for Film‐Based Fluorescence Humidity Sensors and Moisture Driven Actuators

AbstractRapid, on‐site measurement of ppm‐level humidity in real time remains a challenge. In this work, we fabricated a few micrometer thick, β‐ketoenamine‐linked covalent organic framework (COF) membrane via interfacially confined condensation of 1,3,5‐tris‐(4‐aminophenyl)triazine (TTA) with 1,3,5‐tri‐formylphloroglucinol (TP). Based on the super‐sensitive and reversible response of the COF membrane to water vapor, we developed a high‐performance film‐based fluorescence humidity sensor, depicting unprecedented detection limit of 0.005 ppm, fast response/recovery (2.2 s/2.0 s), and a detection range from 0.005 to 100 ppm. Remarkably, more than 7,000‐time continuous tests showed no observable change in the performance of the sensor. The applicability of the sensor was verified by on‐site and real‐time monitoring of humidity in a glovebox. The superior performance of the sensor was ascribed to the highly porous structure and unique affinity of the COF membrane to water molecules as they enable fast mass transfer and efficient utilization of the water binding sites. Moreover, based on the remarkable moisture driven deformation of the COF membrane and its composition with the known polyimide films, some conceptual actuators were created. This study brings new ideas to the design of ultra‐sensitive film‐based fluorescent sensors (FFSs) and high‐performance actuators.

Interfacially Fabricated Covalent Organic Framework Membranes for Film-Based Fluorescence Humidity Sensors and Moisture Driven Actuators.

Rapid, on-site measurement of ppm-level humidity in real time remains a challenge. In this work, we fabricated a few micrometer thick, β-ketoenamine-linked covalent organic framework (COF) membrane via interfacially confined condensation of 1,3,5-tris-(4-aminophenyl)triazine (TTA) with 1,3,5-tri-formylphloroglucinol (TP). Based on the super-sensitive and reversible response of the COF membrane to water vapor, we developed a high-performance film-based fluorescence humidity sensor, depicting unprecedented detection limit of 0.005 ppm, fast response/recovery (2.2 s/2.0 s), and a detection range from 0.005 to 100 ppm. Remarkably, more than 7,000-time continuous tests showed no observable change in the performance of the sensor. The applicability of the sensor was verified by on-site and real-time monitoring of humidity in a glovebox. The superior performance of the sensor was ascribed to the highly porous structure and unique affinity of the COF membrane to water molecules as they enable fast mass transfer and efficient utilization of the water binding sites. Moreover, based on the remarkable moisture driven deformation of the COF membrane and its composition with the known polyimide films, some conceptual actuators were created. This study brings new ideas to the design of ultra-sensitive film-based fluorescent sensors (FFSs) and high-performance actuators.

Heterogeneous Covalent Organic Framework Membranes Mediated by Polycations for Efficient Ions Separation.

Precise ions sieving at angstrom-scale is gaining tremendous attention thanks to its significant impact at the water-energy nexus. Herein, a novel polycation-modulated interfacial polymerization (IP) strategy is developed to prepare a heterogeneously charged covalent organic frameworks (COFs) membrane. Cationic poly(diallyldimethylammonium chloride) (PDDA) regulates the growth and assembly of anionic COFs nanosheets, which thus provides a negative, smooth top surface and positive, rough bottom surface, indicating the presence of heterogeneously charged angstrom-scale channels through the membrane. Experiments and simulations are conducted to understand the facilitated ions transport behavior relative to specific interactions raised by heterogeneously charged channels and angstrom-scale steric hinderance as well, rendering the membrane with robust mono-/divalent cations sieving capabilities. The selectivity (61.6) of Li+ to Mg2+ in mixed saline under the continuous cross-flow filtration mode is superior to most of the reported nanofiltration membranes. This polycation-mediated interfacial polymerization strategy offers a compelling opportunity to develop versatile heterogeneously charged COF membranes for exquisite ion sieving.

Kinetic control aspects and mechanisms in oriented membrane processes for extraction and recovery of ascorbic acid compound.

Ascorbic acid comprises four enantiomers, with only one of them, L-ascorbic acid, recognized as vitamin C. The modern industries place significant importance on obtaining this compound in its purest form. The challenge is to recover L-ascorbic acid, which requires specific processes within these industries. To satisfy this condition, purification is needed, a process that requires large quantities of solvents and high energy consumption. To overcome these limitations, we conducted a study on the facilitated extraction of L-ascorbic acid using three affinity polymer membranes, including supported liquid membrane (SLM), polymer inclusion membrane (PIM), and grafted polymer membranes (GPM) with cholic acid as the extractive agent. Following the characterization of the membranes using IR spectroscopy and SEM techniques, we investigated various parameters associated with substrate diffusion through the organic membrane phase. Regarding the biologically active L-ascorbic acid, our research findings indicated that kinetic factors drove the mechanisms of the studied processes.