A High-Quality Mixed Matrix Membrane with Nanosheets Assembled and Uniformly Dispersed Fillers for Ethanol Recovery.

A high-quality filler within mixed matrix membranes, coupled with uniform dispersity, endows a high-efficiency transfer pathway for the significant improvement on separation performance. In this work, a zeolite-typed MCM-22 filler is reported that is doped into polydimethylsiloxane (PDMS) matrix by ultrafast photo-curing technique. The unique structure of nanosheets assembly layer by layer endows the continuous transfer channels towards penetrate molecules because of the inter-connective nanosheets within PDMS matrix. Furthermore, an ultrafast freezing effect produced by fast photo-curing is used to overcome the key issue, namely filler aggregation, and further eliminates defects. When pervaporative separating a 5 wt% ethanol aqueous solution, the resulting MCM-22/PDMS membrane exhibits an excellent membrane flux of 1486 g m-2 h-1 with an ethanol separation factor of 10.2. Considering a biobased route for ethanol production, the gas stripping and vapor permeation through this membrane also shows a great enrichment performance, and the concentrated ethanol is up to 65.6 wt%. Overall, this MCM-22/PDMS membrane shows a high separation ability for ethanol benefited from a unique structure deign of fillers and ultrafast curing speed of PDMS, and has a great potential for bioethanol separation from cellulosic ethanol fermentation.

Potassium and ammonium recovery in treated urine by zeolite based mixed matrix membranes.

Nitrogen, phosphorus and potassium are essential for crop growth, which are abundant in urine. Although numerous studies have developed techniques to recover ammonium and phosphorus from urine, limited research made efforts on the recovery of potassium, which is a non-renewable resource with uneven global distribution. In this study, we explored the possibility of zeolite based mixed matrix membranes (MMMs) to selectively recover ammonium and potassium from urine, with minimal detention of sodium. The findings demonstrated that upon the pre-treatment of zeolites with sodium chloride solution, a 70 wt% zeolite loaded MMM could achieve 69.3 % recovery of potassium and almost full recovery of ammonium. By varying the desorption temperatures and MMMs production process, it was discovered that stepwise backwash at low temperature (276 K) greatly lowered sodium recovery whilst simultaneously enhancing the recovery of potassium and ammonium. This study demonstrates the potential of recovering potassium and ammonium from urine using zeolite-loaded MMMs, coupled with achieving low-sodium recovery.

Mixed-Matrix Organo-Silica-Hydrotalcite Membrane for CO2 Separation Part 2: Permeation and Selectivity Study.

This study introduces an innovative approach to designing membranes capable of separating CO2 from industrial gas streams at higher temperatures. The novel membrane design seeks to leverage a well-researched, high-temperature CO2 adsorbent, hydrotalcite, by transforming it into a membrane. This was achieved by combining it with an amorphous organo-silica-based matrix, extending the polymer-based mixed-matrix membrane concept to inorganic compounds. Following the membrane material preparation and investigation of the individual membrane in Part 1 of this study, we examine its permeation and selectivity here. The pure 200 nm thick hydrotalcite membrane exhibits Knudsen behavior due to large intercrystalline pores. In contrast, the organo-silica membrane demonstrates an ideal selectivity of 13.5 and permeance for CO2 of 1.3 × 10-7 mol m-2 s-1 Pa-1 at 25 °C, and at 150 °C, the selectivity is reduced to 4.3. Combining both components results in a hybrid microstructure, featuring selective surface diffusion in the microporous regions and unselective Knudsen diffusion in the mesoporous regions. Further attempts to bridge both components to form a purely microporous microstructure are outlined.

Advances in mixed-matrix membranes for biorefining of biogas from anaerobic digestion.

This article provides a comprehensive review of the state-of-the-art technology of polymeric mixed-matrix membranes for CO2/CH4 separation that can be applied in medium, small, and domestic biogas systems operating at low pressures (0.2-6 kPa). Critical data from the latest publications of CO2/CH4 separation membranes were analyzed, considering the ratio of CO2/CH4 permeabilities, the CO2 selectivity, the operating pressures at which the membranes were tested, the chemistry of the polymers studied and their gas separation mechanisms. And the different nanomaterials as fillers. The intrinsic microporous polymers (PIMs) were identified as potential candidates for biomethane purification due to their high permeability and selectivity, which are compatible with operation pressures below 1 bar, and as low as 0.2 bar. This scenario contrasts with other polymers that require pressures above 1 bar for operation, with some reaching 20 bar. Furthermore, the combination of PIM with GO in MMMs was found to not influence the permeability significantly, but to contribute to the membrane stability over time, by preventing the structural collapse of the membrane caused by aging. The systematic analysis here presented is a valuable resource for defining the future technological development of CO2/CH4 separation membranes for biogas biorefining.

Mixed Matrix Pt-Carbon Nanofiber Polyethersulfone Catalytic Membranes for Glucose Dehydrogenation.

The advancement of technologies for producing chemicals and materials from non-fossil resources is of critical importance. An illustrative example is the dehydrogenation of glucose, to yield gluconic acid, a specialty chemical. In this study, we propose an innovative production route for gluconic acid while generating H2 as a co-product. Our concept involves a dual-function membrane, serving both as a catalyst for glucose dehydrogenation into gluconic acid and as a means to efficiently remove the produced H2 from the reaction mixture. To achieve this two membranes were developed, one catalytically active and one dense aimed at H2 removal. The catalytic membrane showed significant activity, yielding 16 % gluconic acid (t=120 min) with a catalyst selectivity of 93 % and stable performance over five consecutive cycles. Incorporating the H2 separating membrane showed the significance of H2 removal in driving the reaction forward. Its inclusion led to a twofold increase in gluconic acid yield, aligning with Le Chatelier's principles. As a future prospect the two layers can be combined into a dual-layer membrane which opens the way for a new production route to simultaneously produce gluconic acid and H2, using high-throughput reactors such as hollow-fiber systems.

Defect-Engineered Metal-Organic Framework/Polyimide Mixed Matrix Membrane for CO2 Separation.

Defect-engineered metal-organic frameworks (MOFs) with outstanding structural and chemical features have become excellent candidates for specific separation applications. The introduction of structural defects in MOFs as an efficient approach to manipulate their functionality provides excellent opportunities for the preparation of MOF-based mixed matrix membranes (MMMs). However, the use of this strategy to adjust the properties and develop the separation performance of gas separation membranes is still in its early stages. Here, a novel defect-engineered MOF (quasi ZrFum or Q-ZrFum) was synthesized via a controlled thermal deligandation process and incorporated into a CO2-philic 6FDA-durene polyimide (PI) matrix to form Q-ZrFum loaded MMMs. Defect-engineered MOFs and fabricated MMMs were investigated regarding their characteristic properties and separation performance. The incorporation of defects into the MOF structure increases the pore size and provides unsaturated active metal sites that positively affect CO2 molecule transport. The interfacial compatibility between the Q-ZrFum particles and the PI matrix increases via the deligandation process, which improves the mechanical strength of Q-ZrFum loaded membranes. MMM containing 5 wt.% of defect-engineered Q-ZrFum exhibits excellent CO2 permeability of 1308 Barrer, which increased by 99 % compared to the pure PI membrane (656 Barrer) at a feed pressure of 2 bar. CO2/CH4 and CO2/N2 selectivity reached 44 and 26.6 which increased by about 70 and 16 %, respectively. This study emphasizes that defect-engineered MOFs can be promising candidates for use as fillers in the preparation of MMMs for the future development of membrane-based gas separation applications.

Synergistic enhancement of CO2/N2 separation performance via Ce-MOF-infused chitosan mixed matrix membrane.

Reticular chemistry, exemplified by metal-organic frameworks (MOFs), has proven invaluable in creating porous materials with finely tuned structures to address critical global energy and environmental challenges. In this context, the need for efficient carbon dioxide (CO2) capture and utilization has taken center stage. One promising approach involves the integration of MOFs into polymer matrix to develop mixed matrix membranes (MMMs). In this work, cerium-based MOFs (Ce-MOF) were selected due to their robust CO2 capture capabilities, while chitosan (CS) was chosen as the polymer matrix due to its reasonably good selectivity and balanced CO2 permeance for the development of MMMs for CO2/N2 (20/80 vol%) separation. A comprehensive suite of analytical techniques, including FTIR, XRD, FESEM, XPS, TGA, EDX, FETEM, and BET, was applied for precise characterization of both the MOF and MMMs. Various operational parameters, such as Ce-MOF content and temperature, were systematically explored to investigate the CO2 capture efficiency of the synthesized MMMs. The results revealed that the optimized Ce-MOF-embedded CS MMMs consistently outperformed the bare CS membranes.

Ionic Cross-Linked MOF-Polymer Mixed-Matrix Membranes for Suppressing Interfacial Defects and Plasticization Behavior.

To address the plasticization phenomenon and MOF-polymer interfacial defects, we report the synthesis of ionic cross-linked MOF MMMs from a dual brominated polymer and MOF components by using N,N'-dimethylpiperazine as the cross-linker. We synthesized brominated MIL-101(Cr) nanoparticles by using mixed linkers and prepared brominated polyimide (6FDA-DAM-Br) to form ionic cross-linked MMMs. The gas permeation properties of the polyimide, ionic cross-linked MOF-polymer MMMs, and non-cross-linked MOF-polymer MMMs with various MOF weight loadings were investigated systematically to effectively understand the effects of MOF weight loading and ionic cross-linking. The ionic cross-linked 40 wt % MOF-polymer MMM exhibited significantly enhanced gas permeability with an H2 permeability of 1640 Barrer and CO2 permeability of 1981 Barrer and slightly decreased H2/CH4, H2/N2, CO2/CH4 and CO2/N2 selectivities of 16.9, 15.4, 20.5, and 18.6, respectively. The H2 and CO2 permeabilities are approximately 2-3 fold higher than those of the pure polyimide (6FDA-DAM) membrane. Moreover, the ionic cross-linked 40 wt % MOF-polymer MMM exhibited significantly increased resistance to plasticization. This is because the brominated MOF incorporation boosted molecular transport and polymer chain rigidity, and ionic cross-linking further reduced the number of interfacial defects and polymer chain mobility.

Self-Sorting of Interfacial Compatibility in MOF-Based Mixed Matrix Membranes.

Metal-organic framework (MOF)-based mixed matrix membranes (MMMs) have shown great promises to overcome the performance upper limit of polymeric membranes for various gas separation processes. However, the gas separation properties of the MMMs largely depend on the MOF-polymer interfacial compatibility which is a metric difficult to quantify. In most cases, whether a MOF filler and a polymer matrix make a good pair is not revealed until the gas transport experiments are performed. This is because there is a lack of characterization techniques to directly probe the MOF-polymer interfacial compatibility. In this work, we demonstrate a self-sorting method to rank the interface compatibility among several MOF-polymer pairs. By mixing one MOF with two polymers in an MMM, the demixing of two polymers will form two polymer domains. The MOF particles will preferably partition into the "preferred" polymer domain due to their higher interfacial affinity. By scanning different polymer pairs, a rank of MOF-polymer interfacial compatibility from high to low can be obtained. Moreover, based on this ranking, it was also found that a highly compatible MOF-polymer pair suggested by this method also corresponds to a more predictable MMM gas separation performance.

Synthesis of MOF-5/polyethersulfone (PES) mixed matrix membranes for enhancing membrane filtration performance in polyphenol purification.

The various apple products industries produce a large amount of apple residue, which is easily fermented, causes environmental pollution, and its disposal cost is high, but is rich in nutrients, such as polyphenols. Polyphenols can be purified to realize high-value deep processing of apple pomace and to promote energy reuse of food waste. In this study, the highly selective purification of polyphenols was achieved by membrane filtration using prepared Metal-organic framework (MOF)-5/PES mixed matrix membranes with apple peels as raw material. The polyethersulfone mixed matrix membrane was loaded with MOF-5 by the phase inversion method, and their structural and physicochemical properties were characterized by scanning electron microscopy (SEM), and X-ray diffraction (XRD). Zeta potential and specific surface area of MOF-5 particles were measured, as well as the water contact angle and anti-fouling properties of the mixed matrix membrane were analyzed. It was confirmed that the membrane loaded with MOF-5 showed better hydrophilicity and mechanical properties compared with the pristine polyether sulfone membrane. Under practical conditions, the increased hydrophilicity could enhance the anti-fouling properties of membranes, which would improve the flux recovery ratio of membranes. In addition, the prepared MOF-5/PES mixed matrix membrane was applied to the purification of polyphenols, showing excellent purification performance of polyphenols. In particular, the purity of polyphenol after membrane filtration could reach 70.45% when the additional amount of MOF-5 was 10%. This research provides a method to prepare MOF-5/PES mixed matrix membranes, which effectively solves the problem of unstable and unsatisfactory purification effect of commercially available membranes, promotes the development of new materials in membrane science, and realizes high-value deep processing and comprehensive resource development of food waste using membrane filtration.

Augmenting the Efficacy of a Polyvinyl Alcohol Selective Layer Coated on Polyvinylidene Fluoride Support Membranes with Kaolinite Introduction for Improved Pervaporation Dehydration of Epichlorohydrin/Isopropanol/Water Ternary Systems.

Composite membranes with a polyvinyl alcohol (PVA) selective layer composed of well-dispersed hydrophilic kaolinite particles coated on a polyvinylidene fluoride (PVDF) support were developed. They were applied to the pervaporation dehydration of the industrially important epichlorohydrin (ECH)/isopropanol (IPA)/water ternary mixture. In comparison with raw kaolinite (RK), hydrophilic kaolinite (HK) enhanced the mechanical properties, hydrophilicity, and thermal stability of the PVA selective layer, as confirmed by universal testing, the contact angle, and TGA analyses, respectively. The pervaporation results revealed that the addition of HK particles significantly enhanced the separation factor (3-fold). Only a marginal reduction in flux was observed with ECH/IPA/water, 50/30/20 (w/w %) at 40 °C. An HK particle concentration of 4 wt.% with respect to PVA delivered the highest flux performance of 0.86 kg/m2h and achieved a separation factor of 116. The PVA-kaolinite composite membrane exhibited pronounced resistance to the ECH-containing feed, demonstrating a sustained flux and separation factor throughout an extended pervaporation stability test lasting 250 h.

Graphene-modified MIL-125-NH2 mixed matrix membranes for efficient H2 and CH4 purification.

This study investigates the performance of the mixed matrix membranes (MMMs) incorporating hybrid fillers of metal-organic framework (MIL-125-NH2) and graphene nanosheets (GNs) for enhanced methane (CH4) and hydrogen (H2) separation in the purification sector. The physico-chemical properties of the MMMs were evaluated by SEM, XRD, FTIR, AFM, TGA, DTG, and Brunauer-Emmett-Teller. The permeability and selectivity of the MMMs were determined using different single gases (CO2, N2, H2, and CH4) at various temperatures (20-60 °C). Optimization of fabrication parameters resulted in a significant improvement in porosity and roughness of the fabricated MMMs. The permeabilities of the MOF/PES membrane are 20.3 (CO2), 23.9 (N2), 32.2 (CH4), and 24.1 (H2) x 104 Barrer, while incorporating 0.05 wt% of GNs into the MOF/PES membrane improved the permeability by 36 % (CO2), 41 % (N2), 31 % (CH4), and 370 % (H2). In addition, the H2/CO2 and H2/N2 selectivities of the MMMs significantly increased up to 4 and 3.3, with an improvements of 236 % and 230 %, respectively, compared to the MOF/PES membrane. Furthermore, the CH4/CO2 and CH4/N2 selectivities of the MMMs decreased by 4 %. Therefore, a hybrid filler (10 wt % of MIL-125-NH2 and 0.05 wt % of GNs is highly recommended to improve the permeability and selectivity of the PES membrane, expanding its potential applications in CH4 and H2 purification.

How 2D Nanoflakes Improve Transport in Mixed Matrix Membranes: Insights from a Simple Lattice Model and Dynamic Mean Field Theory.

Mixed matrix membranes (MMMs), incorporating graphene and graphene oxide structural fragments, have emerged as promising materials for challenging gas separation processes. What remains unclear is the actual molecular mechanism responsible for the enhanced permeability and perm-selectivity of these materials. With the fully atomistic models still unable to handle the required time and length scales, here, we employ a simple qualitative model based on the lattice representation of the physical system and dynamic mean field theory. We demonstrate that the performance enhancement results from the flux-regularization impact of the 2D nanoflakes and that this effect sensitively depends on the orientation of the nanoflakes and the properties of the interface between the nanoflakes and the polymer.

MOF-Based Membranes for Remediated Application of Water Pollution.

Membrane separation plays a crucial role in the current increasingly complex energy environment. Membranes prepared by metal-organic framework (MOF) materials usually possess unique advantages in common, such as uniform pore size, ultra-high porosity, enhanced selectivity and throughput, and excellent adsorption property, which have been contributed to the separation fields. In this comprehensive review, we summarize various designs and synthesized strategies of free-standing MOF and composite MOF-based membranes for water treatment. Special emphases are given not only on the effects of MOF on membrane performance, removal efficiencies, and elimination mechanisms, but also on the importance of MOF-based membranes for the applications of oily and micro-pollutant removal, adsorption, separation, and catalysis. The challenges and opportunities in the future for the industrial implementation of MOF-based membranes are also discussed.

Removal of phosphorus by modified bentonite:polyvinylidene fluoride membrane-study of adsorption performance and mechanism.

Enhanced phosphorus management, geared towards sustainability, is imperative due to its indispensability for all life forms and its close association with water bodies' eutrophication, primarily stemming from anthropogenic activities. In response to this concern, innovative technologies rooted in the circular economy are emerging, to remove and recover this vital nutrient to global food production. This research undertakes an evaluation of the dead-end filtration performance of a mixed matrix membrane composed of modified bentonite (MB) and polyvinylidene fluoride (PVDF) for efficient phosphorus removal from water media. The MB:PVDF membrane exhibited higher permeability and surface roughness compared to the pristine membrane, showcasing an adsorption capacity (Q) of 23.2 mgP·m-2. Increasing the adsorbent concentration resulted in a higher removal capacity (from 16.9 to 23.2 mgP·m-2) and increased solution flux (from 0.5 to 16.5 L·m-2·h-1) through the membrane. The initial phosphorus concentration demonstrates a positive correlation with the adsorption capacity of the material, while the system pressure positively influences the observed flux. Conversely, the presence of humic acid exerts an adverse impact on both factors. Additionally, the primary mechanism involved in the adsorption process is identified as the formation of inner-sphere complexes.

Fabrication of Oriented MOF-Based Mixed Matrix Membrane via Ion-Induced Synchronous Synthesis.

Developing a facile strategy for constructing oriented mixed matrix membranes (MMMs) with uniformly dispersed and high-loading metal-organic frameworks (MOFs) is a crucial scientific challenge in probing the enhanced capability and potential applications of MOF-polymer MMMs. Herein, a novel synchronous synthetic method for constructing oriented CuBDC/poly(m-phenylenediamine) (CuBDC/PmPD) MMM with uniform MOF dispersion at high loading at the air-solution interface via the dual function of metal ions is reported. The resulting MMM exhibits excellent separation performance in ion sieving and seawater desalination due to the structural integrity of the proposed membrane and the highly interconnected channels created through the oriented distribution of MOF in a polymer matrix. Such a cutting-edge approach may provide promising insights into the development of advanced MMMs with optimized structure and superior performances.

Removing polyfluoroalkyl substances (PFAS) from wastewater with mixed matrix membranes.

Polyfluoroalkyl and perfluoroalkyl (PFAS) chemicals are fluorinated and exhibit complicated behavior. They are determined and highly resistant to ecological modifications that render plants ecologically robust. Thermal stability and water and oil resistance are examples of material qualities. Their adverse consequences are causing increasing worry due to their bioaccumulative nature in humans and other creatures. Direct data indicates that PFAS exposure in humans causes endocrine system disruption, immune system suppression, obesity, increased cholesterol, and cancer. Several PFASs are present in drinking water at low doses and may harm people. These cancer-causing PFAS have caused concern for water bodies all around the globe. Analytical techniques are used to identify and measure PFAS in an aqueous medium (membrane). Furthermore, a deeper explanation is provided for PFAS removal methods, including mixed matrix membrane (MMM) technology. By removing over 99 % of the PFAS from wastewater, MMMs may effectively remove PFAS from sewage when the support matrix contains adsorbing components. Furthermore, we consider several factors affecting the removal of PFAS and practical sorption methods for PFAS onto various adsorbents.

ZIF-8 decorated cellulose acetate mixed matrix membrane: An efficient approach for textile effluent treatment.

The textile industry is the second largest water-intensive industry and generates enormous wastewater. The dyes and heavy metals present in the textile effluent, even at their lower concentrations, can cause an adverse effect on the environment and human health. Recently, mixed matrix membranes have gained massive attention due to membrane property enhancement caused by incorporating nanofillers/additives in the polymer matrix. This current study examines the efficacy of ZIF-8/CA membrane on dye removal and treatment of real-time textile industry effluent. Initially, ZIF-8 nanoparticles were synthesized using a probe sonicator. The XRD, FT-IR, and SEM analysis confirmed the formation of crystalline and hexagonal facet ZIF-8 nanoparticles. The ZIF-8 nanoparticles were dispersed into a cellulose acetate matrix, and a membrane was prepared using the "phase inversion method." The membrane was characterized using FT-IR and SEM analysis, which endorse incorporating ZIF-8 into the polymer matrix. Later, the efficacy of the ZIF-8/CA membrane was verified by dye removal studies. The dye removal studies on crystal violet, acid red 13, and reactive black 5 reveal that the membrane is ∼85% efficient in dye removal, and the studies were further extended to real-time textile effluent treatment. The studies on textile effluent prevail that ZIF-8/CA membrane is also proficient in removing chemical oxygen demand (COD) ∼70%, total organic carbon (TOC) ∼80%, and heavy metals such as lead, chromium, and cadmium from textile wastewater and proved to be efficient in treating the textile effluent.

Highly Sensitive Ratiometric Fluorescent Flexible Sensor Based on the RhB@ZIF-8@PVDF Mixed-Matrix Membrane for Broad-Spectrum Antibiotic Detection.

Antibiotics play an essential role in the treatment of various diseases. However, the overuse of antibiotics has led to the pollution of water bodies and food safety, affecting human health. Herein, we report a dual-emission MOF-based flexible sensor for the detection of antibiotics in water, which was prepared by first encapsulating rhodamine B (RhB) by a zeolite imidazolium ester skeleton (ZIF-8) and then blending it with polyvinylidene difluoride (PVDF). The luminescent properties, structural tunability, and flexible porosity of the MOF-based composites were combined with the processability and flexibility of polymers to prepare luminescent membranes. The sensor is capable of dual-emission ratiometric fluorescence sensing of nitrofurantoin (NFT) and oxytetracycline (OTC), exhibiting sensitive detection of fluorescence burst and fluorescence enhancement, respectively, with detection limits of 0.012 µM and 8.9 nM. With the advantages of visual detection, high sensitivity, short detection time, and simplicity, the highly sensitive ratiometric fluorescent flexible sensor has great potential for detecting antibiotics in an aqueous environment. It will further stimulate interest in luminescent MOF-based mixed matrix membranes and their sensing applications.

Developing Mixed Matrix Membranes with Good CO2 Separation Performance Based on PEG-Modified UiO-66 MOF and 6FDA-Durene Polyimide.

The use of mixed matrix membranes (MMMs) comprising metal-organic frameworks (MOFs) for the separation of CO2 from flue gas has gained recognition as an effective strategy for enhancing gas separation efficiency. When incorporating porous materials like MOFs into a polymeric matrix to create MMMs, the combined characteristics of each constituent typically manifest. Nevertheless, the inadequate dispersion of an inorganic MOF filler within an organic polymer matrix can compromise the compatibility between the filler and matrix. In this context, the aspiration is to develop an MMM that not only exhibits optimal interfacial compatibility between the polymer and filler but also delivers superior gas separation performance, specifically in the efficient extraction of CO2 from flue gas. In this study, we introduce a modification technique involving the grafting of poly(ethylene glycol) diglycidyl ether (PEGDE) onto a UiO-66-NH2 MOF filler (referred to as PEG-MOF), aimed at enhancing its compatibility with the 6FDA-durene matrix. Moreover, the inherent CO2-philic nature of PEGDE is anticipated to enhance the selectivity of CO2 over N2 and CH4. The resultant MMM, incorporating 10 wt% of PEG-MOF loading, exhibits a CO2 permeability of 1671.00 Barrer and a CO2/CH4 selectivity of 22.40. Notably, these values surpass the upper bound reported by Robeson in 2008.