Double cross-linked 3D layered PBI proton exchange membranes for stable fuel cell performance above 200 °C.

Phosphoric acid doped proton exchange membranes often experience performance degradation above 200 °C due to membrane creeping and phosphoric acid evaporation, migration, dehydration, and condensation. To address these issues, here we present gel-state polybenzimidazole membranes with double cross-linked three-dimensional layered structures via a polyphosphoric acid sol-gel process, enabling stable operation above 200 °C. These membranes, featuring proton-conducting cross-linking phosphate bridges and branched polybenzimidazole networks, effectively anchor and retain phosphoric acid molecules, prevent 96% of its dehydration and condensation, improve creep resistance, and maintain excellent proton conductivity stability. The resulting membrane, with superior through-plane proton conductivity of 0.348 S cm-1, delivers outstanding peak power densities ranging from 1.20-1.48 W cm-2 in fuel cells operated at 200-240 °C and a low voltage decay rate of only 0.27 mV h-1 over a 250-hour period at 220 °C, opening up possibilities for their direct integration with methanol steam reforming systems.

Reversibly Cross-Linked Isoporous Membranes Fabricated by the Recyclable Block Copolymer with Pendent Dithiolane Groups.

The reversible formation and cleavage of disulfide bonds under physical/chemical stimuli make it a valuable motif in constructing dynamically cross-linked materials. In the present work, the block copolymer bearing pendent dithiolanes was synthesized and fabricated into isoporous membranes by the combination of self-assembly and nonsolvent-induced phase separation strategy. The cross-linking within the membrane was realized by the thiol-initiated ring-opening cascades of cyclic disulfides. Successful formation of disulfide bond networks within the isoporous membranes was proved by the Raman spectra, UV-vis diffuse reflectance spectroscopy, differential scanning calorimetry, and rheological analysis. The cross-linking in membranes was further demonstrated by the notably improved toughness and obviously enhanced swelling resistance to acid/alkaline solution as well as organic solvents. Importantly, the cross-linked isoporous membranes were fully dissolvable in solution containing dithiothreitol, which enabled the complete cleavage of disulfide bonds and successful recovery of the block copolymer that was able to be repeatedly fabricated into isoporous membranes with pore sizes identical to membranes prepared from the freshly synthesized copolymer. Our results indicate that dynamically cross-linked isoporous membranes with improved durability and good recyclability can be custom-made by simply incorporating active dithiolane moieties into self-assembling block copolymers.

Enhancing the water permeability of composite NF membranes through the incorporation of organic ions in the aqueous phase.

Composite nanofiltration (NF) membranes prepared using interfacial polymerization (IP) have gained significant attention in the field of wastewater treatment. In this study, sodium camphor sulfonate (CSA-Na) and tetraethylammonium chloride (TEAC) were employed as aqueous phase additives to regulate the diffusion of piperazine (PIP) molecules through electrostatic interactions. The dissociated CSA-Na and TEAC in the aqueous solution formed an organic structure at a certain concentration, restricting the interfacial transport behavior of PIP monomers. The results show that when the content of CSA-Na is 2% w/v, TEAC is 3.9% w/v, that is, the material dosage ratio is 1 : 3, and the NF membrane shows the best performance, with a water flux of 55.61 L m-2 h-1 (test pressure is 0.5 MPa), and MgSO4 rejection rate of more than 98%.

Construction of PDA-PEI/ZIF-L@PE tight ultra-filtration (TUF) membranes on porous polyethylene (PE) substrates for efficient dye/salt separation.

Tight ultra-filtration (TUF) membranes were constructed by in situ growing zinc imidazole frameworks micro-crystalline leaves (ZIF-L) in polyethylene imine (PEI) and polydopamine (PDA) deposit layers on porous polyethylene (PE) substrates. The effects of preparation conditions on the surface physical and chemical structures as well as on the dye/salt separation performance of the formed TUF membranes were systematically investigated. By inserting selective water permeation channels and increasing contacting surface areas, in situ-grown ZIF-L arrays tightly cross-linked in the coating matrix greatly increased water permeation without trading off dye/salt retention selectivity. The morphology of the included ZIF-L particles could be varied by adjusting the ligand/Zn molar ratio (α) in the preparation processes. Optimized PDA-PEI/ZIF-L@PE TUF membranes containing ZIF-L of cross-cross block morphology showed very high pure water permeability of 180 ± 20 L·m-2·h-1·bar-1 (LMHB) and retention selectivity (SCR/Na2SO4 and SMB/Na2SO4) of 267 and 43, respectively, as well as excellent stability and anti-fouling properties.

Hyper-crosslinked Isoporous Block Copolymer Membranes with Robust Solvent Resistance and Customized Pore Sizes for Precise Separation.

Isoporous block copolymer membranes are viewed as the next-generation separation membranes for their unique structures and urgent application in precise separation. However, an obvious weakness for such membranes is their poor solvent-resistance which limits their applications to aqueous solution, and isoporous membranes with superior solvent-resistance and tunable pore size have been rarely prepared before. Herein, self-supporting isoporous membranes with excellent solvent resistance are prepared by the facile yet robust hyper-crosslinking approach which is able to create a rigid network in whole membranes. The hyper-crosslinking is found to be a novel and non-destructive approach that does not change pore size and isoporous structure during the reaction, and the resulting hyper-crosslinked isoporous membranes display superior structural and separation stability to a broad range of solvents with varied polarities for months to years. More importantly, hyper-crosslinking has proved to be a universal strategy that is applicable to isoporous membranes with varied pore size and pore chemistry, offering an important opportunity to prepare solvent-resistant isoporous membranes with customizable pore size and pore functionality that are important to realize their accurate separations in organic solvents. This concept is demonstrated finally by precise and on-demand separation of nanoparticles with the prepared membranes.

C-shaped porous polypropylene fibers for rapid oil absorption and effective on-line oil spillage monitoring.

Development of efficient absorbent materials for detection and treatment of offshore oil spillages remained a challenge. In this work, C-shaped polypropylene oil-absorbent fibers with sub-micron internal pores were prepared by combining spun-bonding technique and thermally induced phase separation (TIPS). The effect of drawing speed on the phase separation and the porous morphology of the shaped fiber non-woven fabric (NWF) was investigated. C-shaped NWF with porous morphology had large water contact angle, higher porosity, larger specific surface area, and increased oil absorption speed and capacity. An online oil spillage detection system was developed using porous C-shaped NWF and an oxygen sensing probe, showing shorter response time and higher signal-to-noise (STN) ratio. The response time for detecting the spillage of soybean oil and diluted crude oil (0.5 mL/0.8 L) in water were only 24 s and 10 s, respectively. The reliable oil detection low detection limit (RLDL) of the oxygen sensing probe was reduced 173 times (from 36.5 g/L to 0.21 g/L) when combined with C-shaped porous fiber NWF.

Generation of Nano-Bubbles by NaHCO3 for Improving the FO Membrane Performance.

Thin-film composite (TFC) polyamide membranes have a wide range of applications in forward osmosis, but tuning the water flux remains a significant challenge due to concentration polarization. The generation of nano-sized voids within the polyamide rejection layer can change the roughness of the membrane. In this experiment, the micro-nano structure of the PA rejection layer was adjusted by adding sodium bicarbonate to the aqueous phase to generate nano-bubbles, and the changes of its roughness with the addition of sodium bicarbonate were systematically demonstrated. With the enhanced nano-bubbles, more and more blade-like and band-like features appeared on the PA layer, which could effectively reduce the reverse solute flux of the PA layer and improve the salt rejection of the FO membrane. The increase in roughness raised the area of the membrane surface, which led to a larger area for concentration polarization and reduced the water flux. This experiment demonstrated the variation of roughness and water flux, providing an effective idea for the preparation of high-performance FO membranes.

Ligand Substitution: An Effective Way for Tuning Structures of ZIF-7 Nanoparticles (NPs) and Improving Energy Recovery Performance of ZIF/PA TFN Membranes.

It is an important initiative to reduce the building energy consumption using energy recovering ventilation (ERV) systems. The application of ERV systems is hindered by the low CO2 barrier performance of commercial total heat exchange membranes (THEMs) that lead to unsatisfactory indoor air refreshing rate, and there is an urgent need for THEMs that have improved CO2 barrier properties and effective energy recovery efficiencies. Here, we report the formation of novel ZIF/PA TFN THEMs based on ZIF-7-X nanoparticles (NPs) with "core-shell" structures and tunable particle sizes, formed from benzimidazole (BIM) ligands and BIM substituted by -NH2, -CH3, -C2H5, and -C3H7 functional groups. The NPs were mixed with pyr omellitic triformyl chloride (TMC) in the organic phase during the interface polymerization process to form ZIF/PA TFN membranes. The total heat exchange performance of ZIF/PA TFN membranes could be effectively modified by the type and quantity of ZIF-7-X NPs added. The CO2 barrier properties and water vapor permeability of ZIF/PA TFN membranes could be improved by the addition of optimal levels of ZIF-7-X NPs, showing low CO2 permeance of 7.76 GPU, high H2O permeance of 663.8 GPU, and excellent enthalpy exchange efficiency of 72.1%. This work provided an effective strategy for tuning not only the nanostructures of ZIF-7 fillers but also the CO2 barrier properties of the formed ZIF/PA TFN membranes.

Two-dimensional titanium carbide MXene produced by ternary cations intercalation via structural control with angstrom-level precision.

Highly effective decontamination of lead is a primary challenge for ecosystem protection and public health. Herein, we report a methodology of ternary cations intercalation to synthesize Ti3C2Tx MXene by structural control with angstrom-level precision through mixed fluorinated salts wet etching-alkalization approach for high-efficient lead adsorption. The successive introduction of lithium, potassium, and sodium ions continuously weakens interaction forces between Ti3C2Tx layers, resulting in achieving fine tailored interlayer distance from 9.8 to 15.9 Å. A high density of complexing groups are formed after ternary cations intercalation, which greatly improve the hydrophilicity of Ti3C2Tx to enhance the accessibility and shorten the mass transfer and provide abundant adsorption sites to exhibit strong complexing effects with lead ions. The prepared ternary cations-intercalated Ti3C2Tx nanosheets exhibited a high adsorption capacity (267.2 mg/g) toward lead ions and sharply cut down lead concentration from 10 to 0.009 mg/L, far below the drinking water standards (0.015 mg/L).

High Flux Nanofiltration Membranes with Double-Walled Carbon Nanotube (DWCNT) as the Interlayer.

Nanofiltration (NF) membranes with a high permeability and rejection are of great interest in desalination, separation and purification. However, how to improve the permeation and separation performance still poses a great challenge in the preparation of NF membranes. Herein, the novel composite NF membrane was prepared through the interfacial polymerization of M-phenylenediamine (MPD) and trimesoyl chloride (TMC) on a double-walled carbon nanotube (DWCNT) interlayer supported by PES substrate. The DWCNT interlayer had a great impact on the polyamide layer formation. With the increase of the DWCNT dosage, the XPS results revealed an increase in the number of carboxyl groups, which decreased the crosslinking degree of the polyamide layer. Additionally, the AFM results showed that the surface roughness and specific surface area increased gradually. The water flux of the prepared membrane increased from 25.4 L/(m2·h) and 26.6 L/(m2·h) to 109 L/(m2·h) and 104.3 L/(m2·h) with 2000 ppm Na2SO4 and NaCl solution, respectively, under 0.5 MPa. Meanwhile, the rejection of Na2SO4 and NaCl decreased from 99.88% and 99.38% to 96.48% and 60.47%. The proposed method provides a novel insight into the rational design of the multifunctional interlayer, which shows great potential in the preparation of high-performance membranes.

Preparation of Porous Silicate Cement Membranes via a One-Step Water-Based Hot-Dry Casting Method.

A commercial interest in the improvement in the separation performance and permeability of porous materials is driving efforts to deeply explore new preparation methods. In this study, the porous silicate cement membranes (PSCMs) were successfully prepared through an adjustable combination of hot-dry casting and a cement hydration process. The obtained membrane channel was unidirectional, and the surface layer was dense. The physical characteristics of the PSCMs including their pore morphology, porosity, and compressive strength, were diversified by adjusting the solid content and hot-dry temperature. The results indicated that with the solid content increasing from 40 wt. % to 60 wt. %, the porosity decreased by 8.07%, while the compressive strength improved by 12.46%. As the hot-dry temperature increased from 40 °C to 100 °C, the porosity improved by 23.04% and the BET specific surface area and total pore volume enlarged significantly, while the compressive strength decreased by 27.03%. The pore size distribution of the PSCMs exhibited a layered structure of macropores and mesopores, and the pore size increased with the hot-dry temperature. Overall, the PSCMs, which had typical structures and adjustable physical characteristics, exhibited excellent permeability and separation performance.

Environmental Friendly Fabrication of Porous Cement Membranes via Reusable Camphene-Based Freeze-Casting Method.

Inorganic membranes have been developed rapidly in recent years because of excellent anti-fouling performance, high mechanical strength and outstanding resistances to acid and alkali. However, the high production cost still restricts its large-scale industrial application. In this work, an environmental friendly unidirectional freezing method via introducing camphene as a reusable template was adapted to prepare porous cement membranes (PCMs). The naturally formed and highly aligned porous structures of PCMs could be divided into three parts: a dense layer, a transition layer and a supporting layer. With the solid content rising from 40 wt.% to 60 wt.%, the pore size of the PCMs decreased from 3.34 nm to 3.62 nm, the bovine serum albumin (BSA) rejection increased from 81.3% to 93.5% and water flux decreased from 346.8 L·m-2·h-1 to 167.3 L·m-2·h-1 (0.2 MPa). Significantly, the performance of PCMs was maintained; even the camphene was reused 20 times. Additionally, the recovery rate of camphene could be reached up to 97.16%. Therefore, this method is cost effective and environmental friendly, which endowed the PCMs great potential in water treatment.

Incorporating Ag@RF core-shell nanomaterials into the thin film nanocomposite membrane to improve permeability and long-term antibacterial properties for nanofiltration.

Ag@resorcinol-formaldehyde resin (Ag@RF) core-shell nanomaterials were prepared by Stöber method, and introduced into polyamide (PA) selective layer of thin-film nanocomposite (TFN) membranes through the interfacial polymerization (IP) process. Due to the abundant hydroxyl groups on the surface and suitable particle size, Ag@RF nanoparticles (Ag@RFs) could be uniformly dispersed in the piperazine aqueous solution and participate in the IP process to precisely regulate the microstructure of the PA selective layer. The resulting "crater structure" and irregular granular structure enlarged the permeable area and contributed to the surface hydrophilicity. For the nanofiltration application, the water flux of TFN membrane modified by Ag@RFs to Na2SO4 solution reached 150 L·m-2·h-1 which was 87.5% greater than TFC, and salt rejection was maintained. The antibacterial efficiency of the prepared TFN membrane on E. coli reached 99.6% in the antibacterial experiment. In addition, due to the special structure of Ag@RFs, the TFN membrane also showed an expected slow-release capability of Ag+, allowing for long-term anti-biofouling properties. This work demonstrates that Ag@RF core-shell nanoparticles with high compatibility of organic nanoparticles and antibacterial properties of Ag nanoparticles could be used as promising nanofillers for designing functional nanofiltration TFN membranes.

Ultra-low pressure PES ultrafiltration membrane with high-flux and enhanced anti-oil-fouling properties prepared via in-situ polycondensation of polyamic acid.

Polyamic acid (PAA) is a flexible polymer and has abundant valuable hydrophilic groups. Herein, we developed an ultra-low pressure ultrafiltration (UF) membrane by integrating PAA into the polyethersulfone (PES) matrix via the "in-situ polycondensation" method. PAA was well compatible with PES and distributed uniformly in the membrane. The introduction of PAA improved membrane hydrophilicity. Meanwhile, the membrane pore structures were also refined. The membrane exhibited an excellent permeability under ultra-low pressure due to its improvement of hydrophilicity and pore structures. Under 0.3 bar, compare with the water flux of PES membrane, PES/PAA membrane improved nearly 2 times (571.05 L/(m2·h)), with a high BSA rejection (≥90%). Even under a lower pressure, 0.1 bar, >300 L/(m2·h) still can be achieved. Interestingly, the membrane we developed could maintain a high performance after drying, and then is very suitable for dry preservation. PES/PAA membrane showed a high oil removal (≥92%) and could remove oil from water effectively. Besides, the membrane exhibited excellent anti-oil-fouling properties. The flux recovery rate of PES/PAA (70.0%) far exceeds that of PES (37.9%) after three filtration and cleaning cycles. The membrane we developed is very valuable in oily wastewater treatment.

Functionalized MOF-Derived Nanoporous Carbon as Compatible Nanofiller to Fabricate Defect-Free PDMS-Based Mixed Matrix Pervaporation Membranes.

Metal-organic framework (MOF)-based polydimethylsiloxane mixed matrix membranes applied for alcohol recovery with high permeability and selectivity are drawing more and more attention. However, the design and fabrication of high-quality and stable MOF-based mixed matrix membrane for pervaporation are still a big challenge. Herein, PDMS functionalized MOF-derived nanoporous carbon (P-ZNC) was first explored as compatible nanofiller to mutually blend with polydimethylsiloxane on PVDF substrate to fabricate defect-free mixed matrix membranes via dip-coating and thermal cross-linkng. Induced by UV illumination, hydrophobic modification of MOF-derived nanoporous carbon was successfully realized under mild conditions within one step, simplifying the operation step. By using this facile strategy, we can not only solve the existing problem of agglomeration, but also covalently cross-link MOF derivative with polymeric matrix and effectively eliminate the interface defect between polymer and nanoparticles without any extra steps. The method also gives a good level of generality for the synthesis of versatile stable nanoporous MOF-derived carbon-based mixed matrix membranes on various supports. The prepared PDMS/P-ZNC with commendable structures possessed excellent separation performance in low concentration n-butanol recovery and had a good balance between permeance, selectivity, and stability.

The Intrinsic Parameters of the Polyamide Nanofilm in Thin-Film Composite Reverse Osmosis (TFC-RO) Membranes: The Impact of Monomer Concentration.

The realistic resistance zone of water and salt molecules to transport across a TFC-RO membrane is the topmost polyamide nanofilm. The existence of hollow voids in the fully aromatic polyamide (PA) film gives its surface ridge-and-valley morphologies, which confuses the comprehensions of the definition of the PA thickness. The hollow voids, however, neither participate in salt-water separation nor hinder water penetrating. In this paper, the influence of intrinsic thickness (single wall thickness) of the PA layer on water permeability was studied by adjusting the concentration of reacting monomers. It confirms that the true permeation resistance of water molecules originates from the intrinsic thickness portion of the membrane. The experimental results show that the water permeability constant decreases from 3.15 ± 0.02 to 2.74 ± 0.10 L·m-2·h-1·bar-1 when the intrinsic thickness of the membrane increases by 9 nm. The defects on the film surface generate when the higher concentration of MPD is matched with the relatively low concentration of TMC. In addition, the role of MPD and TMC in the micro-structure of the PA membrane was discussed, which may provide a new way for the preparation of high permeability and high selectivity composite reverse osmosis membranes.

Antibacterial polyvinyl alcohol nanofiltration membrane incorporated with Cu(OH)2 nanowires for dye/salt wastewater treatment.

In many important industries, such as the textile printing industry, a large amount of dye/salt wastewater is often discharged, which can destroy the ecological environment of the water body. Membrane technology has a great potential in the treatment of environmental problems caused by dye/salt wastewater. Polyvinyl alcohol (PVA) nanofiltration (NF) membrane has a bright future in dye/salt wastewater treatment, however, works on this are rare. Herein, antibacterial PVA NF membrane incorporated with Cu(OH)2 nanowires for the dye/salt wastewater treatment is reported. The membrane was prepared via coating the solutions containing PVA, glutaraldehyde and Cu(OH)2 nanowires on the polyethersulfone ultrafiltration membrane. Cu(OH)2 nanowires has a diameter of 60 nm and was successfully introduced into the membrane. The introduction of nanowires improved the membrane hydrophilicity and roughness, which is conducive to the improvement of membrane flux. Membrane separation performance for one component solution and dye/salt solution were investigated. The introduction of Cu(OH)2 increases the flux of the membrane obviously (the highest increase is 178.78% (from 21.49 to 38.42 L·m-2·h-1·bar-1, for NaCl solution as the feed). Besides, the membrane doped with nanowires also possessed a high dye/salt selectivity. For one component solution, the dye removal rate was over 97.00% while the salt rejection was low (the lowest was 13.18% (NaCl)). For the dye/salt solution, the dye (Congo Red) rejection kept at a high level (98.91%) and the salt (NaCl) rejection was still low (13.71%), while the flux was also high (37.56 L·m-2·h-1·bar-1). The performance is superior to that of many membranes reported in previous works. Moreover, the Cu(OH)2 nanowires endowed the membrane with an improved and high antibacterial property. The sterilization rate of Escherichia coli and Staphylococcus aureus reached more than 99.99%.

Development of coin-shaped ZIF-7 functionalized superhydrophobic polysulfone composite foams for continuous removal of oily contaminants from water.

Development of efficient absorbent materials for oil spillage clean-up and environmental pollution remediation is highly desired but remains a challenge. In this work, superhydrophobic/superoleophilic polysulfone based ZIF-7 composite (SPZ) foams were fabricated via chemical modification of polysulfone and integrating with hydrophobic coin-shaped ZIF-7 particles. The synergistic approaches provided the SPZ foams with high porosity, low density and superhydrophobic/superoleophilic features (θwater=162.3°, θoil=0°) and outstanding self-cleaning property. The as-prepared SPZ foams exhibited highly selective absorption capacity (up to 3800 wt%) for various kinds of oils and organic solvents. Furthermore, the SPZ foams still maintained 95.2% of its pristine absorption capacity and the θwater remained at 143.6° after ten absorption/distillation cycles. The SPZ foam showed outstanding separation ability towards different types of emulsions with separation efficiency all above 97%. The high oil/water separation efficiency and robust reusability made the SPZ foams promising absorbent in dealing with practical oil spills.

Recent developments in polymeric nano-based separation membranes.

Polymeric nanomaterials, which have tuneable chemical structures, versatile functionalities, and good compatibility with polymeric matrices, have attracted increasing interest from researchers for the construction of polymeric nano-based separation membranes. With their distinctive nanofeatures, polymeric nano-based membranes show great promise in overcoming bottlenecks in polymer membranes, namely, the trade-off between permeability and selectivity, low stability, and fouling issues. Accordingly, recent studies have focused on tuning the structures and tailoring the surface properties of polymeric nano-based membranes via exploitation of membrane fabrication techniques and surface modification strategies, with the objective of pushing the performance of polymeric nano-based membranes to a new level. In this review, first, the approaches for fabricating polymeric nano-based mixed matrix membranes and homogeneous membranes are summarized, such as surface coating, phase inversion, interfacial polymerization, and self-assembly methods. Next, the manipulation strategies of membrane surface properties, namely, the hydrophilicity/hydrophobicity, charge characteristics, and surface roughness, and interior microstructural properties, namely, the pore size and content, channel construction and regulation, are comprehensively discussed. Subsequently, the separation performances of liquid ions/molecules and gas molecules through polymeric nano-based membranes are systematically reported. Finally, we conclude this review with an overview of various unsolved scientific and technical challenges that are associated with new opportunities in the development of advanced polymeric nano-based membranes.