Membrane Separation Research Articles

Development and evaluation of environmentally sustainable cenosphere ceramic membrane for the efficient separation of methylene blue dye

Development and evaluation of environmentally sustainable cenosphere ceramic membrane for the efficient separation of methylene blue dye

Membrane Budding Inspired Biomimetic Nanocarrier Delivers Brain‐derived Neurotrophic Factor to Improve AD Cognition

AbstractNeurotropic factors, crucial for neural cell maturation and proliferation, hold great therapeutic potential for treating neurodegenerative diseases but face challenges in brain delivery. This study introduces a novel membrane budding‐inspired lipoprotein biomimetic nanocarrier for efficient packaging and precise brain delivery of brain‐derived neurotrophic factor (BDNF). The nanocarrier is created by mixing protein‐loaded biomimetic gel with liposomes composed of lipids prone to forming liquid‐disordered and liquid‐ordered phases. This interaction triggers phase separation and lipid membrane rearrangement, enabling effective protein encapsulation. To enhance blood‐brain barrier permeability and target damaged cerebral vasculature in Alzheimer's Disease, the nanocarrier (RAP‐BHP‐rHDL) is functionalized with Apolipoprotein E3 and αRAP peptides. The obtained RAP‐BHP‐rHDL alleviates neuronal damage, promotes neurogenesis, normalizes the cerebral microvasculature, improves the function of neurovascular units, and restores memory function in 5 × FAD mice. This innovative packaging approach and biomimetic nanocarrier design offer a promising strategy for delivering neurotropic factors to the central nervous system, potentially advancing the management of neurodegenerative diseases.

Macrocyclic Chiral Two‐Dimensional Membranes for Enantiomers Separation

AbstractChiral enantiomers, while typically exhibiting similar physical and chemical properties, often have distinct therapeutic effects. The preparation of pure enantiomers is therefore of significant interest in the food, chemical, and pharmaceutical industries, making the separation of enantiomers highly sought after. Membrane separation technology has garnered widespread attention for its environmental friendliness and scalability. Recently, chiral two‐dimensional (2D) membranes have demonstrated superior separation performance due to their ultrathin nature and orderly transmission channels. Macrocyclic chiral 2D membranes, in particular, combine the inherent cavity structure of macrocyclic molecules with the host‐guest interaction capabilities that specifically recognize chiral molecules. Additionally, they benefit from the excellent chemical stability and adjustable interlayer spacing of 2D materials. This combination allows these membranes to achieve high enantioselectivity while improving flux. By optimizing the trade‐off between flux and enantioselectivity, this strategy offers a promising new approach for developing advanced chiral membranes.

Precision Macroporous Monoliths Made Using High‐Throughput Microfluidic Emulsification

Materials with pore sizes ranging from micrometers to millimeters find use in thermal insulation, acoustics, separation, and energy‐related applications. While several routes have been developed to manufacture such macroporous materials, current fabrication technologies remain limited in either scalability or pore size control. Herein, a scalable microfluidic approach is reported to create macroporous materials with precisely controlled pore sizes from monodisperse emulsion templates. Emulsion droplets produced in a parallelized step emulsification device are assembled by gravity and converted into macroporous monoliths by polymerization and drying. Microstructural analysis and model filtration experiments show that the pore windows of the bulk macroporous material can be tightly controlled and used for the size‐selective separation of particles from suspensions. By heat treating macroporous structures of selected compositions, one can also create bulk carbon and silica glass monoliths with unique cellular architectures for potential applications as filters, separation membranes, or catalyst supports.

Constructing polyolefin-based lithium-ion battery separators membrane for energy storage and conversion

Owing to the escalating demand for environmentally friendly commodities, lithium-ion batteries (LIBs) are gaining extensive recognition as a viable means of energy storage and conversion. LIBs comprise cathode and anode electrodes, electrolytes, and separators. Notably, the separator, a crucial and indispensable element in LIBs that mainly comprises a porous membrane material, necessitates substantial research focus. Scholars have consequently strived to devise novel systems that augment separator efficiency, bolster safety measures, and surmount existing constraints. This review endeavors to equip researchers with comprehensive information on polyolefin-based separator membranes, encompassing performance prerequisites, functional attributes, scientific advancements, and so on. Specifically, it scrutinizes the latest innovations in porous membrane configuration, fabrication, and enhancement that utilize the most prevalent polyolefin materials today. Consequently, robust and enduring membranes fabricated have demonstrated superior effectiveness across diverse applications, facilitating a circular economy that curbs waste materials, reduces operational expenses, and mitigates environmental impact.

Phase-transformable metal-organic polyhedra for membrane processing and switchable gas separation.

The capability of materials to interconvert between different phases provides more possibilities for controlling materials' properties without additional chemical modification. The study of state-changing microporous materials just emerged and mainly involves the liquefication or amorphization of solid adsorbents into liquid or glass phases by adding non-porous components or sacrificing their porosity. The material featuring reversible phases with maintained porosity is, however, still challenging. Here, we synthesize metal-organic polyhedra (MOPs) that interconvert between the liquid-glass-crystal phases. The modular synthetic approach is applied to integrate the core MOP cavity that provides permanent microporosity with tethered polymers that dictate the phase transition. We showcase the processability of this material by fabricating a gas separation membrane featuring tunable permeability and selectivity by switching the state. Compared to most conventional porous membranes, the liquid MOP membrane particularly shows theselectivity for CO2 over H2 with enhanced permeability.

High detail resolution cellulose structures through electroprinting.

Electrospinning is a technique used to fabricate polymer fibers in micro- and nanoscales. Due to the large distance between the nozzle and collector, there is a limited positioning accuracy of electrospun fibers. To enhance the possibility of fabricating structures with micrometer placement, an electroprinting technique has been developed. By reducing the distance between the nozzle and the collector it is demonstrated that it is possible to get an improved control over fiber positioning which gives a possibility to fabricate designed 3D structures at the micron scale. In this study, cellulose acetate (CA) has been selected as a biomaterial to advance the 3D printing of membranes with possible use in separation applications. Various parameters, such as CA concentration and molecular weight, printing speed, printing pattern, applied voltage, etc. are evaluated with respect to printing control. Results indicate that by optimizing the printing parameters it is possible to print structures with inter- fiber distances down to 3µm and fiber diameters at a sub-µm scale. This electroprinting development is promising for the fabrication of customized separation membranes. However, printing speed still remains a challenge.

Highly Enantioselective Transportation Across Liquid Membranes Mediated by Porous Covalent Organic Frameworks.

Chiral liquid membrane separation is crucial in pharmaceuticals and chemical synthesis for its simplicity and stability, yet designing membrane carriers that enable efficient enantioseparation remains a challenge. Here, we demonstrated for the first time that chiral porous materials can act as mobile carriers of bulk liquid membranes (BLMs) to enhance enantioselective transport and separation. We design and prepare three 2D chiral covalent organic frameworks (CCOFs) by imine condensations of a chiral dialdehyde with triamines containing ethyl, fluorine and/or isopropyl groups. These isostructural CCOFs feature ABC stacking, excellent water, acid and base tolerance, and chiral amine groups in 1D porous channels, promoting efficient enantioselective transportation of amino acid enantiomers. Among them, the CCOF with both -F and -iPr groups showing superior transport performance. Exfoliating the CCOF into chiral nanosheets creates flexible layers with accessible active sites, enabling nanosheet-mediated liquid membranes to separate chiral drug enantiomers, a feat unattainable with the pristine CCOF. This work establishes CCOFs as a promising platform for chiral BLM separations and will guide the design of high-performance BLMs using porous materials for enantioselective separation.

Highly Enantioselective Transportation Across Liquid Membranes Mediated by Porous Covalent Organic Frameworks

Chiral liquid membrane separation is crucial in pharmaceuticals and chemical synthesis for its simplicity and stability, yet designing membrane carriers that enable efficient enantioseparation remains a challenge. Here, we demonstrated for the first time that chiral porous materials can act as mobile carriers of bulk liquid membranes (BLMs) to enhance enantioselective transport and separation. We design and prepare three 2D chiral covalent organic frameworks (CCOFs) by imine condensations of a chiral dialdehyde with triamines containing ethyl, fluorine and/or isopropyl groups. These isostructural CCOFs feature ABC stacking, excellent water, acid and base tolerance, and chiral amine groups in 1D porous channels, promoting efficient enantioselective transportation of amino acid enantiomers. Among them, the CCOF with both ‐F and ‐iPr groups showing superior transport performance. Exfoliating the CCOF into chiral nanosheets creates flexible layers with accessible active sites, enabling nanosheet‐mediated liquid membranes to separate chiral drug enantiomers, a feat unattainable with the pristine CCOF. This work establishes CCOFs as a promising platform for chiral BLM separations and will guide the design of high‐performance BLMs using porous materials for enantioselective separation.

Nanofoamed Polyamide Membranes: Mechanisms, Developments, and Environmental Implications.

Thin film composite (TFC) polyamide membranes have been widely applied for environmental applications, such as desalination and water reuse. The separation performance of TFC polyamide membranes strongly depends on their nanovoid-containing roughness morphology. These nanovoids not only influence the effective filtration area of the polyamide film but also regulate the water transport pathways through the film. Although there have been ongoing debates on the formation mechanisms of nanovoids, a nanofoaming theory─stipulating the shaping of polyamide roughness morphology by nanobubbles of degassed CO2 and the vapor of volatile solvents─has gained much attention in recent years. In this review, we provide a comprehensive summary of the nanofoaming mechanism, including related fundamental principles and strategies to tailor nanovoid formation for improved membrane separation performance. The effects of nanovoids on the fouling behaviors of TFC membranes are also discussed. In addition, numerical models on the role of nanovoids in regulating the water transport pathways toward improved water permeance and antifouling ability are highlighted. The comprehensive summary on the nanofoaming mechanism in this review provides insightful guidelines for the future design and optimization of TFC polyamide membranes toward various environmental applications.

Microwave‐Assisted Fabrication of Highly Crystalline, Robust COF Membrane for Organic Solvent Nanofiltration

AbstractFabrication of crystalline, robust covalent organic framework (COF) membranes based on disorder‐to‐order strategy is promising yet highly challenging. Herein, a microwave‐assisted method for fabricating COF membranes is proposed. Initially, monomers polymerize rapidly on the surface of porous Al2O3 substrate at room temperature to form an amorphous pristine membrane. Subsequently, a microwave field is exerted to trigger fast crystallization, acquiring a crystalline COF membrane within 60 min. The amorphous pristine membrane exhibits a high dissipation factor, indicating excellent microwave absorption capability, which accelerates the dynamic reversible reactions during the microwave treatment and thus ensures a rapid transition from the amorphous to the crystalline state. Owing to the high‐crystallinity and robust structure, the COF membranes exhibit high rejection rates for solute molecules with molecular weights exceeding 700 Da (e.g., Evans blue: 98.7%) and high solvent permeance for organic solvents (e.g., ethanol: 87.8 Lm−2h−1 bar−1, n‐hexane: 222.3 Lm−2h−1 bar−1). Surprisingly, the COF membranes exhibit superior mechanical properties, with Young's modulus of 33.91 ± 3.94 GPa, outperforming previously reported polycrystalline COF membranes and are close to those for inorganic zeolite membranes. The microwave‐assisted COF crystallization method opens a new avenue to fabricating a variety of crystalline membranes for advanced separations.

Engineering Ion Affinity of Zr-MOF Hybrid PDMS Membranes for the Selective Separation of Na+/Ca2+

Ion-selective separation, especially Na+/Ca2+ separation, is of significant importance in the realms of biomimetic research and the fabrication of biomimetic devices, underscoring the pivotal role that sodium and calcium ions play in cellular metabolism. However, the analogous ionic radii and charge densities shared by sodium and calcium ions significantly impede their effective discrimination, presenting formidable challenges for the precise engineering of ion separation materials, such as separation membranes. In this study, a polydimethylsiloxane (PDMS) separation membrane hybridized with zirconium-based metal–organic frameworks (UiO-66, UiO-66-NO2 and UiO-66-NH2) was constructed. Through the meticulous design of the MOF functional groups, the material’s affinity for specific ions was modulated, thereby achieving efficient Na+/Ca2+ separation. Notably, the PDMS integrated with amino-modified Zr-MOF exhibited an efficacious selective separation of Na+ and Ca2+ ions. The interaction between the amino group of UiO-66-NH2 and Ca2+ gave rise to the observed superior selectivity toward Ca2+ cations and enhanced separation efficiencies of up to 64% compared to pristine PDMS for UiO-66-NH2-embedded membranes.

Twinned Metal-Organic Framework Nanoplates for Hydrocarbon Separation Membranes.

Filler morphology control is critical for enhancing the gas separation performance of mixed matrix membranes (MMMs). A vertical transport channel using the crystal twinning phenomenon is designed on the zeolitic imidazolate framework (ZIF) nanoplate. Twinned ZIF-8 (TZIF-8) nanoplate is prepared by controlling the shape of ZIF-L from nanosheet to twinned flake, followed by conversion into the ZIF-8 phase. With the addition of TZIF-8 in 6FDA-DAM polymer, propylene/propane selectivity is dramatically enhanced, showing propylene permeability of 40 Barrer and propylene/propane selectivity of 82. The separation performance surpasses the performance of MMMs reported so far, and the selectivity is comparable to that of polycrystalline ZIF-8 membranes. A transport mechanism study using mathematical models implies that the percolated twin fillers create rapid and selective gas channels for desired molecules and substantial tortuous pathways for undesired molecules.

Pathways to Carbon Neutrality in Civil Engineering

Abstract. With the development of the global economy and trade exchanges worldwide, urban infrastructure and industrial development have become part of the competition among countries. However, the construction industry and the production of chemical materials emit a large amount of carbon dioxide, leading to the continuous deterioration of the environment, so it is necessary to effectively reduce emissions. As a synonym for global emission reduction, carbon neutrality plays an important role in different industries, especially in civil engineering. In this paper, we start with building materials and green construction to explore the realization of carbon neutrality at the source and center of carbon emission in civil engineering. Firstly, we introduce the low-carbon production technologies of cement and steel, including calcium recycling and membrane separation technology in the cement industry, high-temperature combustion technology and carbon capture technology in steel industry. Then, we take renewable concrete as an example to discuss the emission reduction path of green building materials. Finally, it outlines how to carry out green construction, introduces assembly carbon reduction technology and energy integration system, and demonstrates the possibility of this green construction program in the case of "T&A House".

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.

Utilizing metal-organic framework porosity for efficient antibiotic separation and sustained release

Metal-organic frameworks (MOFs) have emerged as a revolutionary class of nanoporous materials due to their highly tunable porosity and functionality. With the vast number of MOFs being discovered, traditional experimental techniques to identify the best candidates for various applications, including water treatment and drug delivery become time-consuming and expensive. This is where computational screening offers a powerful solution. We present a computational screening strategy using Monte Carlo (MC) simulation to identify the promising MOFs among over 14,000 MOFs for efficient absorption, membrane separation, and sustained delivery of antibiotics (e.g., azithromycin, AZ). The MC simulation was used to calculate the loading capacity and isosteric heat of the AZ absorption. These absorption properties were correlated with several structural characteristics of the MOF, including the largest cavity diameter, pore limiting diameter, accessible volume, helium void fraction, etc. Critical evaluation of the correlation results identified the best MOFs for AZ absorption, separation, and delivery. The results recommended a total of 578 MOFs, with 126 identified as suitable for use as AZ adsorbents or drug carriers, and 452 for use as membranes to separate AZ from water. Furthermore, the adsorption mechanism of the top MOF was analyzed using molecular dynamics simulation and non-covalent interactions. The solvation-free energy of AZ was evaluated in various solvents to identify the most effective solvent for extracting AZ from MOFs, thereby facilitating the regeneration of the MOF.

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.

Poly(bis(1‐methylpiperazin‐1‐ium‐amide) Nanofilm Composite Membrane with Nanochannel‑Enabled Microporous Structure and Enhanced Steric Hindrance for Magnesium/Lithium Separation

AbstractEfficient lithium/magnesium (Li+/Mg2+) separation attainment is fundamental to the extraction of lithium from brine by nanofiltration membrane separation process, which is essential for resource recovery and a circular water economy. However, for poly(piperazine‐amide) nanofilm composite membranes, the higher electronegativity affects the Mg2+ rejection and consequently Li+/Mg2+ separation performance. Manipulating the positive charge density and pore size regulation of the nanofiltration membranes are determinative of the Li+/Mg2+ separation performance improvement. Here, a new monomer 1,1′‐(hexane‐1,6‐diyl)bis(1‐methylpiperazin‐1‐ium) bromide containing bis‐quaternary ammonium cations is employed as a molecular building block to fabricate polyamide nanofilms via interfacial polymerization. The dual quaternary ammoniums and the rod‐shaped conformation of the monomer confer enhanced electropositivity, steric hindrance, loosely packed microporous network structure (pore diameter∼0.8–1.35 nm), and high free volume. The resultant membrane exhibits high water permeance of 28.34 L m−2 h−1 bar−1 with good Li+/Mg2+ selectivity of up to 76.9. In addition, the membrane also exhibits chlorine stability performance owing to the lack of the chlorine sensitive −NH groups in the formed tertiary amide structures. Computational insights on the structural properties, nanofilm formation, and transmembrane water and ion transport behaviors are provided. This study offers insightful theoretical and technological concepts to design and construct membrane materials for energy‐efficient separations.

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.