Separation Performance Of Membranes Research Articles

The Impact of Adsorption Property Modification by Crosslinkers on Graphene Oxide Membrane Separation Performance

The health risks associated with the presence of heavy metals in drinking water can be severe. To address this issue, membrane separation technology is one of the consolidated alternatives. Inorganic, porous membranes were found in applications where low energy consumption is highly desirable. The selectivity of these membranes is attained by functionalisation. Graphene oxide functionalised membrane technology is promising for removing heavy metal ions. This work summarises, discusses and presents the relationship between adsorption and overall membrane separation process performance for heavy metal ions removal from wastewater when a graphene oxide-functionalised membrane is used. The separation performance depends on the hydrophobic interactions of the membrane and the solute. The electrostatic interaction between the negatively charged membrane surface and positively charged metal ions facilitates the adsorption, leading to the rejection of these metal ions. The influences of the chemical nature of the modifiers of graphene oxide layers are highlighted.

Optimizing Membrane Performance using Various Filler Materials in Membrane Fabrication for Enhancing Gas Separation Efficiency: A Review

The membrane technology has been receiving significant interest in both research and industrial applications, particularly in the separation of CO2/CH4. These methods, as published, aim to overcome the limitations of pure polymeric membranes and offer an alternative approach in separation techniques where membrane technology can overcome the constraints of conventional methods such as Solid Phase Extraction (SPE) and Liquid-Liquid Extraction (LLE). Fabricating membranes using fillers as adsorbents can enhance membrane separation performance due to their porous nature. Hence, the selection of suitable fillers is crucial to maximize membrane efficiency in separating analytes. This paper will review 3 types of fillers-metal-organic frameworks, carbonaceous nanomaterials and mesoporous molecular sieves-from various research papers published in recent years. HIGHLIGHTS Additives introduced to polymeric membrane to increase the membrane performances in terms of selectivity and permeability. Short review of materials used for fabrication of mixed matrix membrane. Modification of selected additives used to study its effects on membrane performances. Recent advancement of hybrid additives materials, combining MOF and carbonaceous materials. GRAPHICAL ABSTRACT

Aminated ZIF‐8 to facilitate CO2 sieving through polyvinyl alcohol/ionic liquid membranes

AbstractCO2 separation technology at low pressure is most desirable in carbon capture projects to mitigate global warming. Facilitated transport membranes offer selective and effective CO2 permeation using a wide range of carbon carriers at low pressure. Porous fillers were recently included as they can carry abundant fixed carriers besides offering open channels for CO2 permeation. This study investigates the effects of amine‐modified zeolitic imidazolate framework‐8 (ZIF‐8) with well‐defined micropores and gas sieving ability in polyvinyl alcohol (PVA) membranes containing an ionic liquid that worked as mobile carriers. The effects of amine‐modified ZIF‐8 and silica nanoparticles on membrane properties and separation performance were also compared. Fourier transform infrared spectra confirmed the incorporation of ZIF‐8, secondary amine, IL anions, and silica nanoparticles in PVA membranes. Energy dispersive analysis showed the good dispersion of inorganic fillers. The amine‐modified silica nanoparticles resulted in higher thermal stability compared to the amine‐modified ZIF‐8 in PVA membranes containing [bmin][Ac] ionic liquid, as shown in the thermogravimetric analysis. However, the CO2 separation performance of PVA membranes containing [bmim][Ac] ionic liquid was improved more significantly by the amine‐modified ZIF‐8 with microporous structure. A CO2/N2 ideal selectivity of 85.65 and CO2 permeance up to 4,502.91 GPU were attained. Unlike the CO2/N2 ideal selectivity, the CO2 permeance was not significantly affected either using [bmin][Ac] or [bmin][BF4]. The humid gas greatly enhanced the CO2 permeance without much changes in the CO2/N2 ideal selectivity due to the promotion of facilitated transport. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.

Dehydration by Pervaporation of an Organic Solution for the Direct Synthesis of Diethyl Carbonate

Pervaporation has been a central subject in the research community within the scope of the further development of energy- and cost-efficient alternatives to conventional liquid–liquid separation technologies. The potential eligibility of four commercial membranes (ZEBREX ZX0, PERVAPTM 4155-80, PERVAPTM 4100, PERVAPTM 4101) for use in an integrated dehydration application of a diethyl carbonate/water/ethanol mixture by pervaporation was assessed experimentally. The impact of feed concentration, operating temperature, pressure, and sweep gas flow rate on membrane separation performance, including permeation flux, permeate quality, selectivity, and permeance, was thoroughly investigated. Applying the ZX0 membrane delivered the best qualities of all tested membranes of the permeate stream, with a water concentration of mostly >98%. In comparing the water flux, the ZX0 membrane remained reasonably competitive with the polymer membranes. Furthermore, the sweep gas volume flow rate and the operating temperature were identified as influencing the flux significantly but not the product composition. At the same time, the feed concentration of water also influenced the water purity within the permeate. The experiments were monitored with a partial least squares model, allowing a quick assessment of obtained samples while delivering accurate results.

Using zero nano-valent iron/thin film composite (ZNVI/TFC) membrane for brackish water desalination and purification

This study looked at the use of synthetic Zero Nano-valent Iron (ZNVI) particles in a unique interfacial polymerization technique on a polyamide thin film PA(TF) composite membrane for the treatment and desalination of brackish wastewater. Zero nano-valent iron (ZNVI) particles were created utilizing chemical reduction technique. ZNVI/PA(TF) NCs membrane is the outcome of advancing the PA(TF) membrane by combining with different concentration of ZNVI particles into the organic phase 1,3,5-benzenetricarbonyl trichloride (TMC). ZNVI/PA(TF) NCs membranes and ZNVI particles' surface properties were examined by the use of mechanical activity, contact angle, BET, FTIR, SEM, XRD, zeta potential, TEM analysis, and EDX studies. Using a variety of salt solutions, such as NaCl, Na2SO4, MgSO4, NaHCO3, CaSO4, CaCl2, and MgCl2, the ZNVI/PA(TF) NCs membrane performance towards salt rejection, flux (at varying pressure), anti-fouling activity, and ZNVI particles stability was assessed. This work investigated the removal efficiency of four dyes: methylene blue (MB), methyl orange (MO), Congo red (CR), and malachite green oxalate (MG). The water flux of the pristine PA(TF) membrane improved from 22 to 35 L/m2.h at 15 bar, indicating a 63% flux enhancement and the NaCl rejection was improved from 88.5 to 98.6%, indicating an 11.4% rejection improvement by incorporation of 0.3 wt.% of ZNVI particles into PA(TF) matrix. The ZNVI/PA(TF) NCs membrane's separation performances were evaluated using 5000 mg/L feed solutions of various salts at 15 bar. It was discovered that the water flux and salt rejection are, respectively, 33.4, 33, 32.7, 32, 31, 30 and 29 L/m2.h for CaSO4, MgSO4, Na2SO4, NaCl, CaCl2, MgCl2, and NaHCO3, and 97.4, 97, 96.5, 96, 94, 93.2, and 92.8%. It demonstrates that the flux recovery ratio (FRR) of the ZNVI/PA(TF) NCs membrane is greater than that of pristine PA(TF) (78%), coming in at 87%. High stability and fixing of the ZNVI particles on the modified membrane surface is indicated by the low overall ZNVI particles release rate over the course of the 10-day experiment.

Enhancing separation performance of thin film nanocomposite membranes by self-etching of polydopamine-modified calcium carbonate during interfacial polymerization process

The acid-accepting and gas-generating properties, along with the formation of extensive nanovoids, make CaCO3 nanoparticles attractive as sacrificial nanofillers for fabricating thin-film composite (TFN) nanofiltration membranes. However, challenges such as severe agglomeration and limited acid etching efficiency of the nanoparticles hinder the pursuit of superior membrane performance. In this study, the dispersion and compatibility of CaCO3 nanoparticles within the membrane matrix were improved by modifying them with a polydopamine (PDA) coating. The abundant phenolic hydroxyl groups of PDA enhanced the hydrophilicity and negative charges of membrane surface. Additionally, the PDA capsule increased the etching extent of the CaCO3 nanoparticles by improving the nanoparticle dispersion and generating additional acid, which created sufficient water channels within the polyamide layer. It was demonstrated that incorporating 45 μg/cm2 of PDA-modified CaCO3 nanoparticles doubled the water permeance to 16.7 LMH/bar, while maintaining a low molecular weight cut-off of 249 Da and achieving rejections over 90% for five types of per- and polyfluorinated substances. The PDA modification also overcame the membrane stability issue caused by the agglomerated CaCO3 nanoparticles. This study provides a novel strategy for applying properly modified self-etching nanofillers in TFN membrane development, showing great potential for water treatment applications.

Silver nanoparticle-decorated reduced graphene oxide/ nanocrystalline titanium metal-organic frameworks composite membranes with enhanced nanofiltration performance and photocatalytic ability

Nanofiltration (NF) has garnered significant attention for removing persistent dyes from industrial wastewater. However, limited membrane separation efficiency and performance deterioration due to membrane fouling are the primary challenges hindering the broader application of NF technology. Herein, we developed high-performance silver nanoparticle-coated reduced graphene oxide/nanocrystalline MIL125(Ti) composite NF membranes (nAg-rGO/n-MIL), which feature self-cleaning capabilities through photocatalytic activity. This was achieved by intercalating nanocrystalline MIL-125(Ti) (n-MIL) metal-organic frameworks between graphene oxide (GO) nanosheets, followed by reducing the GO nanosheets and decorating them with silver nanoparticles (nAg) via UV exposure. The nAg-rGO/n-MIL demonstrated high water permeability (21.7 LMH/bar) and achieved excellent removal efficiencies for targeting dyes with relatively small molecular weights ranging from 300 to 500Da. Additionally, when operated in an NF system equipped with a UV side-emitting optical fiber, the nAg-rGO/n-MIL exhibited significantly reduced water flux decline and enhanced removal efficiencies, achieving up to 97.5% for methylene blue. Moreover, the nAg-rGO/n-MIL demonstrated high durability under the tested operating conditions, indicating its potential for long-term use in industrial applications. The GO composite membrane, with nanosized MOF-intercalated nanochannels and photocatalytic activity via nAg decoration and GO reduction, offers a promising solution to performance limitations and fouling issues in current nanofiltration membranes.

Fabrication and application of highly permeable ceramic membranes: Membrane-forming mechanism, pore structure, separation performance and fouling mechanism analyses

High separation efficiency and satisfactory economic benefits are of great importance for ceramic membranes in the field of water treatment. Herein, microfiltration ceramic membrane with high permeability and selectivity was prepared in one-step (dip-coating and sintering) by sacrificial-interlayer method. The membrane-forming mechanism, effect of temperature on the morphology and pore structure, separation performance, fouling mechanism, and regeneration performance of the ceramic membranes were systematically investigated. The results show that membrane-forming mechanism of the membranes largely depends on film-coating filtration. The membrane with a mixture of nanocellulose crystals and graphene oxide as sacrificial interlayer (C1G1) and sintered at 1100–1300 °C possessed smooth surface. The open porosity and average pore size increased, and the pore size distribution became broader as the temperature increased. Moreover, the sacrificial-interlayer membrane sintered at 1300 °C (mA4S-C1G1) possessed suitable porosity (53.4%) and average pore size (200 nm), high permeance (4828 L·m−2·h−1·bar−1), which was larger than that of the membrane without sacrificial interlayer, manifesting that C1G1 could prevent the penetration of membrane-forming particles into support. The final fouling mechanism of mA4S-C1G1 was cake filtration, although complete pore blocking, standard pore blocking, intermediate pore blocking also involved in the initial stage. In addition, the oil rejection rate (∼97%) and steady-state feed flux (810–1154 L·m−2·h−1) of mA4S-C1G1 was high, and it also possessed good regeneration performance.

Enhancing the Separation Performance of Cellulose Membranes Fabricated from 1-Ethyl-3-methylimidazolium Acetate by Introducing Acetone as a Co-Solvent

Cellulose, a sustainable raw material, holds great promise as an ideal candidate for membrane materials. In this work, we focused on establishing a low-cost route for producing cellulose microfiltration membranes by adopting a co-solvent system comprising the ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc) and acetone. The introduction of acetone as a co-solvent into the casting solution allowed control over the viscosity, thereby significantly enhancing the morphologies and filtration performances of the resulting cellulose membranes. Indeed, applying this co-solvent allowed the water permeability to be significantly increased, while maintaining high rejections. Furthermore, the prepared cellulose membrane demonstrated excellent fouling resistance behavior and flux recovery behavior during a challenging oil-in-water emulsion filtration. These results highlight a promising approach to fabricate high-performance cellulose membranes.

Advanced lithium extraction nanofiltration membrane with fast transport channels via competitive diffusion and reaction of rigid electropositive phenylbiguanide molecules

The utilization of nanofiltration membranes for lithium extraction from Salt-Lake holds the potential to address lithium resource scarcity and drive energy transformation. Nevertheless, the trade-off effect between water permeability and Mg2+/Li+ separation selectivity poses a challenge in the application of these membranes. In this work, rigid-flexible interpenetration and competitive diffusion reaction strategies were proposed to regulate the pore structure and charge density of the functional layer, thus enhancing the overall separation performance of nanofiltration membrane. Phenylbiguanide (PBG) possessing rigid structure, high positive charge density, and low energy transfer barrier was embedded into flexible polyethyleneimine-based polyamide network. This integration facilitated the formation of continuous and semi-permanent microcavities with rigid-flexible coupled structure, and meanwhile, elevated the density of positive charges. Consequently, the modification extended the water molecular transport channels within the functional layer, leading to a notable enhancement in pure water flux, from 7.40 to 26.43 L m−2h−1. In addition, due to the faster diffusion of PBG than polyethyleneimine with high molecular weight (70000 Da, as aqueous monomer in this work), it could react with excess 1,3,5-trimesoyl chloride (TMC) on the surface of initial membrane to form a new polyamide layer, which repaired the defects in the functional layer and also enhanced the charge density inside pore channels. Therefore, Mg2+/Li+ separation selectivity factor increased from 3.79 of TFC membrane to 22.98 of PBG membrane, i.e., by about 6 times. This study provided an effective strategy to develop nanofiltration membranes with both good water permeability and Mg2+/Li+ selectivity.

High permeance of polyamide nanofiltration membranes with porous organic polymers interlayers based on diazo coupling reaction

Nanofiltration (NF) membranes are widely used in many fields, including food, petrochemical and brackish water desalination. One of the challenges for preparing NF membranes is to make NF membranes with high both permeability and selectivity because of the “trade-off" effect. To weaken or break through the “trade-off" effect, the thin film composite (TFC) NF membranes with high permeability and selectivity were prepared by constructing porous organic polymers (POPs) interlayers via diazo coupling reaction in the wild condition. The effects of the monomers ratio used to prepare POPs interlayers on the separation performance of the as-prepared TFC NF membranes as well as on the surface characteristics of substrate and polyamide (PA) separation layer were investigated. Due to hydrogen bonding, the POPs interlayers with hydroxyl groups slow down the diffusion rate of PIP molecules, which changes the surface structure of the polyamide (PA) separation layer from the nodular structure to the folded structure that favors increased permeability. The pure water permeance of the optimal TFC-S4 membrane (47.5 ± 0.3 L m−2 h−1 bar−1) is 3.8 times higher than that of the commercial polyamide nanofiltration membrane NF270 (12.5 L m−2 h−1 bar−1). Na2SO4 rejection of the TFC-S4 membrane is 98.7 ± 0.1 %, which is greater than that of NF270 (96 %). This study provides ideas for future applications of POPs materials in NF membranes desalination.

The role of one-dimensional materials in modulating the selective mass transport of covalent organic framework membranes for nanofiltration

Two-dimensional covalent organic frameworks (2D COFs) membranes have well-ordered nanochannels for selective molecular sieving. One-dimensional (1D) materials have been proposed to link the loosely packed COFs nanosheet for enhancing the separation performance of COFs membranes. However, it remains unclear how the enhancement arises. Herein, we demonstrate the role of 1D materials in modulating the microstructure and interlayer force of 2D COFs membranes. The optimized composite membrane, assembled from 2D COFs and chitosan exhibits a 75% enhancement in permeance without sacrificing selectivity towards different dyes. Our results show that the interaction forces between COFs and 1D materials are directly correlated to the transport nanochannels. When the interaction forces are stronger, the microstructure is more densely packed. Meanwhile, the shielding effect of 1D materials on the intrinsic channels of 2D COFs is more significant, resulting in narrow transport channels for mass transfer. In contrast, the weaker interaction forces prevent the excessive shrinkage of nanochannels, facilitating fast mass transfer and maintaining the high molecular selectivity. The work unravels the interaction forces between 2D COFs and 1D materials leading to the shaping of mass transfer nanochannels, offering a new perspective for the advancement of COFs membrane for nanofiltration.

Machine Learning‐Guided Design and Synthesis of Eco‐Friendly Poly(ethylene oxide) Membranes for High‐Efficacy CO2/N2 Separation

AbstractMachine learning (ML)‐guided polymer design and synthesis will enable the next‐generation membrane material discovery for CO2 capture. Herein, ML is leveraged to establish a structure‐performance relationship for the eco‐friendly poly(ethylene oxide) (PEO) membrane and guide its design for high‐efficacy CO2/N2 separation. Through a rational fragment representation method and knowledge sharing across membranes fabricated by different methods, the precise prediction of CO2/N2 separation performance for PEO membranes with high Pearson correlation coefficients (0.973 for permeability and 0.875 for selectivity) despite data scarcity is demonstrated. Expertise knowledge and external monomer databases are then utilized in a human‐in‐the‐loop workflow to effectively explore high‐performance PEO membranes in the design space. Several discovered thermally crosslinked PEO membranes achieve CO2/N2 separation performances close to the 2019 Robeson upper bound, which are promising for practical large‐scale carbon capture applications. Model interpretation techniques are employed to provide data‐driven insights into the design of PEO membranes for high‐efficacy CO2/N2 separation. Further life cycle assessment results reveal the outstanding advantage of discovered PEO membranes in terms of environmental friendliness. The work highlights the enormous potential of ML in expediting the discovery of high‐performance carbon capture membrane materials.

Enhanced Mg2+/Li+ separation performance of polyelectrolyte multilayers nanofiltration membranes modified by trimethylamine N-oxide zwitterions

Polyelectrolyte multilayer nanofiltration (NF) membranes have garnered attention for their potential in Mg2⁺/Li⁺ separation applications, particularly due to their positively charged nature and the versatility offered by the layer-by-layer (LbL) self-assembly technique. However, these membranes often face significant challenges in balancing high ion selectivity with adequate water permeability. Addressing these limitations, this study introduces a novel approach by grafting a zwitterionic material, trimethylamine N-oxide (TMAO), onto polyacrylamide hydrochloride (PAH), creating a new cationic polyelectrolyte (TPAH). By cyclically depositing sodium polystyrene sulfonate (PSS) and TPAH onto a polyethersulfone (PES) substrate, we have successfully fabricated a high-performance NF membrane (i.e., (PSS/TPAH)n) that demonstrates enhanced Mg2⁺/Li⁺ selectivity with high water permeability. TMAO features shorter distances between its positive and negative charge groups and smaller dipoles compared to other zwitterions. These characteristics enhance its ability to resistance to salt effects and transfer charge from amine oxide to water molecule. Furthermore, the grafting of TMAO enhanced the hydrophilicity of TPAH and regulated the charge distribution of the polyelectrolyte. Compared to the control membrane (PSS/PAH)n, the optimized membrane (PSS/TPAH)n showed reduced rejection of LiCl from 60.9 ± 2.7 % to 35.9 ± 1.5 %, while that of MgCl2 increased from 94.3 ± 1.6 % to 96.1 ± 0.7 %. Additionally, water permeability improved from 9.2 ± 0.9 LMH/bar to 16.1 ± 0.5 LMH/bar. Notably, the membranes exhibited an improved selectivity for Mg2+/Li+ ions in synthetic saline, reaching a maximum of 30.5 ± 1.5, highlighting its potential for practical separation applications. Density functional theory simulations indicate that TMAO not only enhances Donnan effect and intensify ion dehydration of polyelectrolyte multilayers NF membranes but also increases their hydrophilicity. In general, these polyelectrolyte multilayers NF membranes exhibit considerable promise for multiple applications, such as seawater pretreatment, groundwater softening and lithium extraction.

Preparation of Pebax based ternary mixed matrix membranes for enhancing CO2 transport and separation

As a type of material for membrane separation in carbon capture technology, mixed matrix membranes (MMMs) have the advantages of simple processing and excellent gas separation performance and have great research prospects. However, the affinity between organic matrix and inorganic fillers is usually poor, and microphase separation occurs at the interface. At the same time, as the filler content increases, the filler particles will aggregate, leading to non-selective defects in the homogeneous membrane and reducing the gas separation performance of MMMs. Herein, the strategy of adding a third component was adopted. Small molecule polyethylene glycol dimethyl ether (PEGDME) was introduced into the Pebax/NH2-MIL-101 membrane to prepare a ternary mixed matrix membrane Pebax/PEGDME/NH2-MIL-101. Adding small molecules as the third component optimized the membrane structure by utilizing the interaction between the third component, inorganic fillers, and polymer matrix, effectively improving the physical microenvironment of gas separation. At the same time, NH2-MIL-101 was modified to PEI-MIL-101, further improving the performance of the mixed matrix membrane. The CO2 permeability of the Pebax/PEGDME/NH2-MIL-101 ternary mixed matrix membrane reached 313 Barrer, and the CO2/N2 selectivity reached 47.7. The CO2 permeability coefficient of Pebax/PEGDME/PEI-MIL-101 membrane reached 286 Barrer, and the CO2/N2 selectivity coefficient reached 54.2. This work provides new ideas for optimizing the gas separation performance of mixed matrix membranes.

Highly selective thin B-oriented MFI zeolite membranes on scalable modified stainless steel supports

Enhancing the separation performance of molecular sieve membranes relies significantly on precise control over their membrane morphology and microstructure. This involves creating thin, closely packed, oriented, and uniform coatings of seed crystals, enabling subsequent intergrowth to establish continuous membranes. To address industrial needs, it is crucial to generate a thin and flawless membrane efficiently producible on a large-scale support. Porous stainless supports offer scalability and easy integration into membrane modules. In this study, we present a novel and straightforward process for modifying stainless-steel supports to seed zeolite membrane layers. High-performance, b-oriented MFI zeolite membranes can be synthesized on these modified stainless-steel supports through scalable filtration seeding of MFI zeolite nanosheets followed by secondary growth. By employing a carefully designed pre-treatment procedure, we achieved the growth of well-intergrown, highly b-oriented MFI zeolite membranes on the modified stainless-steel support, establishing a robust interaction with the substrate. The membranes, fabricated through gel-free secondary growth of nanosheets deposited on a scalable stainless-steel support using this technique, demonstrate ultra-selective capabilities in separating para-xylene from ortho-xylene, with a high separation factor of 388.

Low-cost, all-organic, hydrogen-bonded thin-film composite membranes for CO2 capture: Experiments and molecular dynamic simulations

Despite the excellent separation performance of organic-inorganic hybrid membranes, such as mixed-matrix membranes, their commercial application remains challenging due to difficulties in uniformly dispersing inorganic fillers and achieving good interfacial contact over large areas. In this paper, we present high-performance, thin-film composite (TFC) membranes made from low-cost, all-organic materials using a commercially attractive and straightforward process for CO2 capture. The TFC membranes were prepared on a porous polysulfone support using 2,4,6-triaminopyrimidine (TAP) dispersed in comb-shaped polymerized poly(oxyethylene methacrylate) (PPOEM), synthesized through a free radical polymerization process. The organic filler TAP functioned as a hydrogen bond inducer, controlling the free volume and reducing gas diffusivity, thereby enhancing CO2 selectivity over larger gases such as N2 and CH4. Incorporating 2 wt% TAP significantly improved separation performance by primarily reducing N2 and CH4 permeances, achieving a CO2 permeance of 1140 GPU, with CO2/N2 and CO2/CH4 selectivities of 43.3 and 15.0, respectively. The achieved performance significantly surpassed that of Pebax-based membranes and successfully met the target criteria for post-combustion CO2 capture. Variations in free volume, molecule aggregation, hydrogen bonding, and interaction energies between gases and membranes were thoroughly investigated via molecular dynamic (MD) simulations. This high-performance TFC membrane, created through simple and facile methods using entirely organic materials, achieves commercial standards for post-combustion CO2 capture.

Construction of multiple interpenetrati ng network electric field-assisted healing hydrogel composite damage-resistant membrane

Inspired by the intrinsic self-healing ability of organisms, this study proposes to incorporate healing properties into separation membranes that are susceptible to physical damage during installation, operation, maintenance, and cleaning. The polyacrylic acid (PAA) hydrogel-modified layer was first obtained by in situ cross-linking and free radical polymerization in this research. After that, the construction of multiple interpenetrating three-dimensional (3D) network hydrogel-modified layers was realized via inserting amininated carbon nanotubes (CNTs-NH2) and Fe3+. Under the external effect of the electric field, the reversible dynamic linkage bonded in the conductive network constructed by CNTs-NH2 and Fe3+ benefited the rearrangement and diffusion of PAA molecular chains at the fractured interface. The dye separation performance of the composite membrane was restored to ca. 90 % of the initial level without affecting the dynamic operation after damage. The hydrogel-modified layer can be structurally stabilized for as long as 100 days. The Fe3+/CNTs-NH2/PAA/PES hydrogel composite membrane maintained a pure water flux of as high as 124.66 L m−2 h−1∙bar−1. This coating also exhibited excellent electrical conductivity (714.33 Ω/sq), mechanical strength (4.31 Mpa), repair, and screening capabilities. It provides a theoretical basis for achieving industrial scale-up and demonstrates good application prospects and empowerment potential.

Composite organic ionic plastic crystal membranes: The effect of ether-functionalized cations on light-gas separation performance

In light of increasing concerns about climate change, there is a growing need for innovative solutions to address CO2 emissions. Addressing this urgency, this work presents a unique approach to CO2 separation utilizing composite membranes of organic ionic plastic crystals (OIPCs) with ether-functionalized cations and poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). Here we report the gas separation performance of OIPC-based membranes of 3,3-dimethyloxazolidinium [C1moxa]+, 4-ethyl-4-methylmorpholinium [C2mmor]+ and 4-isopropyl-4-methylmorpholinium [Ci3mmor]+ cations paired with the bis(fluorosulfonyl)imide [FSI]- anion. These composites demonstrated very good gas separation properties, especially [C1moxa][FSI] which produced a permeability of 63 barrer for CO2 and an overall selectivity (CO2/N2) of 205, which is the highest amongst all the OIPCs reported so far. Additionally, a large change in separation performance was observed for the [Ci3mmor][FSI] membrane upon heating above the solid-solid phase transition (II - I) at 48 °C; the CO2 permeability increased from 7 to 163 barrer and an approximately 3-fold increase in selectivity was observed. These findings advance the design of composite membranes based on OIPCs towards increased selectivity and sustained effectiveness in the separation of light gases.

Huge improved gas separation performance of carbon molecular sieve membrane by forming a double crosslinked polyimide precursor

A vital issue in searching for advanced gas separation membranes is understanding the precursor structure-gas separation properties of carbon molecular sieve (CMS) membranes. Here, we reported two crosslinked polyimides and used as CMS precursors, in which, the DCPI-4 is a double cross-linkable polyimide with 4 % triptycene triamine as a crosslinker (Type I) and COOH group that can be crosslinked at 350 °C by decarboxylation (Type II), whereas the DCPI-0 with COOH (Type II). After pyrolysis at 550 °C, the DCPI-4-CMS showed a higher SBET (812 vs 713 m2g-1), larger ultra-microporosity ratio (26.6 % vs 17.8 %), larger d-spacing (4.08 vs 3.94 Å), less graphitization (sp3/sp2 of 0.156 vs 0.118), 5.5 times higher CO2 permeability (7573 vs 1391 Barrer) and same CO2/CH4 selectivity (∼62) than DCPI-0-CMS. We consider this is due to the type I crosslinking enhances the rigidity of the polyimide backbone, and inhibits the collapse of micropores during the carbonization, which causes improved ultra-microporosity and ultra-micropore ratio that both enhances the gas diffusion and solubility coefficient as well activation energy difference of gas pairs. Conclusively, this double crosslinking method provides a good perspective for achieving CMS membranes with excellent gas separation performance.