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With recent focus on achieving carbon neutrality to tackle global warming, there is an increasing need for advanced carbon capture technology to reduce carbon emission to the atmosphere. Membrane separation is one of such technologies that can remove carbon dioxide (CO 2) in an energy-efficient and cost-effective way. In particular, the well-studied thin-film composite (TFC) membranes based on commercial polyethylene oxide (PEO)-containing materials have demonstrated strong promise for large-scale industrial post-combustion CO 2 capture. However, to realize high-performance PEO-based TFC membranes, a key challenge lies in maximizing the reduction in the thickness of the selective layer without compromising membrane integrity, which to date has achieved little progress probably due to the failure in addressing the poor selective/gutter layer interfacial compatibility issue. Here, we adopted a facile spray coating method to design a TFC membrane comprising an ultrathin Pebax-1657 selective layer, a polydimethylsiloxane (PDMS) gutter layer, and a porous polysulfone (PSF) substrate. To increase surface hydrophilicity and wettability for enhancing interfacial compatibility between the selective and gutter layers, the surface of the PDMS gutter layer was activated for a few seconds by air plasma prior to Pebax-1657 spray coating. Coupled with well-controlled spray coating manipulation, a defect-free Pebax-1657 selective layer with an ultrathin thickness as low as 30 nm could be formed. Correspondingly, the optimized TFC membrane exhibited a highest CO 2 permeance at 2022 GPU with a CO 2 /N 2 selectivity of close to 30.0, far surpassing the threshold for commercially viable post-combustion CO 2 capture (CO 2 permeance ≥1000 GPU and CO 2 /N 2 selectivity ≥20). More importantly, the use of spray coating endows the TFC design with great scalability potential, rendering our membranes, which are made solely from commercially available materials, highly relevant for industrial CO 2 separation. [Display omitted] • Pebax/PDMS/PSF TFC membranes with ultrathin selective layers were fabricated. • Air plasma was utilized to process the PDMS gutter layer to facilitate the formation of Pebax selective layer. • The best performed membrane exhibited an CO 2 permeance at 2022 GPU and a CO 2 /N 2 selectivity of 29.3. • Spray coating fabrication endows the TFC membranes with great scale-up potential. [ABSTRACT FROM AUTHOR]

Nature has contributed the best selective material, Aquaporin (AQP), for us. Herein we report on a highly permeable and selective hollow fiber composite membrane based on Aquaporin Z. The AQP-incorporated proteoliposomes were immobilized on the inner surface of a hollow fiber membrane substrate and subsequently coated by a polyamide layer formed by a non-gas assisted interfacial polymerization process. Morphological observation suggested that the introduced proteoliposomes were totally embedded in the polyamide layer with their intact spherical shape preserved. Hollow fiber composite membranes with different AQP covering densities were prepared and evaluated, and an elevated covering density of AQPs was found beneficial in improving the water flux and salt rejection of the resultant membrane. The biomimetic membrane with a high AQP covering density exhibited a 40 L m −2 h −1 permeate flux at 5 bar, almost 200% as much as the flux of a typical commercial reverse osmosis membrane (BW30). This membrane also exhibited above 97.5% rejection to a 500 ppm NaCl solution, which was superior to the commercial membrane tested under the same conditions. Moreover, a forward osmosis test of the AQP-based hollow fiber membrane also yielded a super high water flux without a notable increase in salt back diffusion. It was therefore concluded that the integration between embedded proteoliposomes and the polyamide layer was effectively defect-free, and the remarkably enhanced water permeation was contributed by the embedded AQPs. Furthermore, it was estimated that the newly developed AQP based hollow fiber membrane could reduce the power consumption significantly if applied in a water reclamation process. The AQP-based biomimetic membrane has been designed and fabricated beyond the proof-of-concept stage and is able to offer a novel means for tailoring the membrane materials to enhance membrane performance. [ABSTRACT FROM AUTHOR]

High-pressure reverse osmosis (HPRO) holds promise as a technology for the energy-efficient desalination of hypersaline brine (≥70 g/L total dissolved solids). In this work, we examined the effects of membrane compaction for four types of thin-film composite (TFC) RO membranes from DuPont Water Solutions (XLE, BW30, SW30HR, and XUS180808) using a crossflow filtration setup. The membranes were tested at a maximum applied pressure (ΔP) of 200 bar using a seawater desalination brine feed solution (70 g/L NaCl) to simulate conditions encountered in HPRO processes. Post-compaction membrane characterization revealed the densification of the support and selective layers of the TFC membranes (42–61% decrease in thicknesses and 15–22% reduction in polyamide heights, respectively) with respect to their pristine analogues. We also performed a mechanical strength analysis of the support layers that revealed the inverse relationship between the Young's modulus and magnitude of support layer compression. Our results suggest that support layers with a tensile strength ≥7 MPa and a Young's modulus ≥130 MPa are necessary to fabricate mechanically robust TFC membranes for HPRO application. In terms of desalination performance, the least compact-resistant membrane, XLE, displayed a drastic drop in water permeability and salt rejection from 1.63 L m−2 h−1 bar−1 and 97.5% in seawater RO test (ΔP: 55 bar, 35 g/L NaCl feed solution) to 0.39 L m−2 h−1 bar−1 and 95.0% in HPRO test (ΔP: 200 bar, 70 g/L NaCl feed solution). On the other hand, the most compact-resistant membrane, XUS180808, showed the least decline from 0.60 L m−2 h−1 bar−1 and 99.4% in seawater RO test to 0.35 L m−2 h−1 bar−1 and 99.2% in HPRO test. Overall, all four membranes showed irreversible decline in performance after HPRO tests whereby they could not regain their original permeability values at lower pressures (<200 bar). [Display omitted] • TFC membranes were tested in HPRO for brine desalination (ΔP: 200 bar; feed: 70 g/L NaCl). • Best-performing membrane showed a permeability of 0.35 L m−2 h−1 bar−1 (99.2 % rejection). • Compacted membranes displayed a densified support layer (42–61 % decrease in thickness). • Support layers with tensile strength ≥7 MPa and modulus ≥130 MPa are suitable for HPRO. • Nanovoids were preserved in the compacted polyamide layers (∼20 % decrease in height). [ABSTRACT FROM AUTHOR]

[Display omitted] • Reverse IP strategy was proposed to fabricate TFC PA membranes. • Defect-free PA skin layer was constructed on hydrophobic PVDF/PTFE substrates. • The membranes exhibit excellent performance in aqueous and organic solutions. • Pure water permeances are over 11 LMH/bar with MgCl 2 rejections of over 95%. • Methanol permeances are over 3.3 LMH/bar with Congo red rejections of over 98.5%. Polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE) porous membranes are ideal substrates for preparing thin-film composite (TFC) polyamide (PA) membranes with improved solvent resistance. However, it remains difficult to construct PA skin layers on PVDF and PTFE substrates via conventional interfacial polymerization (IP) due to the hydrophobic nature of these materials. To address this challenge, a reverse IP process was proposed to construct a defect-free PA skin layer on PVDF and PTFE substrates, in which the hydrophobic PVDF and PTFE substrates were soaked with the organic phase to ensure uniform coverage of reacted solution on the substrates. This novel strategy can effectively tackle the issue of uneven wetting of the aqueous phase on hydrophobic substrates in the conventional IP process. The resultant TFC membranes (i.e. M rev-PVDF and M rev-PTFE) exhibit excellent nanofiltration (NF) performance in both aqueous and organic solutions. M rev-PVDF and M rev-PTFE have MgCl 2 rejections of 96.12% and 95.17%, alongside the water permeances of 12.8 LMH/bar and 11.2 LMH/bar, respectively (M rev-PTFE was activated with DMF). It is further shown that M rev-PVDF and M rev-PTFE could also reject 99.4% and 98.5% of Congo red in methanol solution at solvent permeances of over 3.3 LMH/bar, while they also perform excellently in other polar protic solvents. Consequently, this work opens a new window for constructing high-performance TFC PA membranes on hydrophobic substrates and expands the application of the TFC PA NF membrane. [ABSTRACT FROM AUTHOR]

In recent years, novel superwetting membranes have gained popularity for oily wastewater treatments via synergy between surface chemistry and topography. However, the water fluxes of the superwetting membranes normally decrease rapidly due to pore clogging and surface fouling, especially when treating surfactant-stabilized oil-in-water emulsions. Herein, a facile strategy is proposed to develop a superwetting thin film nanofibrous composite (TFNC) membrane with remarkable antifouling and self-cleaning properties to effectively separate surfactant-stabilized oil-in-water emulsions. The membrane is composed of an ultrathin carbon nanotubes (CNTs)-polyvinyl alcohol (PVA) composite skin layer, and a highly porous electrospun nanofibrous substrate as well as a non-woven mechanical support. The robust three-dimensional (3D) CNTs composite skin layer were immobilized on the nanofibrous substrate surface by crosslinking the CNTs with PVA. This skin layer serves as a functional barrier to reject oil droplets, which exhibited excellent performance in treating surfactant-stabilized oil-in-water emulsions with a rejection of 95% and a competitive flux of ~60 Lm−2h−1 under an ultra-low pressure (20 kPa) in a cross-flow filtration process. Moreover, the CNTs composite layer also protects the membrane surface from fouling. The TFNC membrane possesses outstanding reusability, as the water flux could be recovered by 100% in a continuous cyclic operation without cleaning, which should be attributed to the underwater oil repellence of its superhydrophilic surface and self-cleaning property based on the capillary pumping effect occurred in the micron/nano-channels of the membrane surface. Image 1 • Spray coating was used to fabricate separation layer on nanofibrous substrate. • An ultrathin carbon nanotubes-polyvinyl alcohol composite layer was crosslinked. • The membrane exhibited excellent performance in treating surfactant-stabilized emulsions. • The membrane had a rejection of 95% and a competitive flux of ~60 Lm−2h−1 at 20 kPa. • The membrane showed a flux recovery rate of ~100% in a continuous cyclic operation. [ABSTRACT FROM AUTHOR]

This study focuses on enhancing the mechanical strength of aquaporin (AQP)-based biomimetic membranes for seawater desalination. AQP incorporated vesicles were embedded into the selective layer of an optimized thin film composite (TFC) membrane. The resultant membrane, denoted as ASW, exhibited a stable water flux around 20 L·m−2·h−1 and 99% NaCl rejection at a constant pressure of 55 bar using 32,000 mg·L−1 NaCl solution as feed in reverse osmosis (RO) measurement. The robustness of the ASW membranes were evaluated. The water flux of ASW membrane was almost 100% enhanced compared with that of AQP-free control TFC membranes. The filtration performance of the ASW membrane was further evaluated by a seven-day desalination test using a real seawater secondary effluent collected from a desalination plant in Singapore as feed. To our best knowledge, our study is the first report on the AQP-incorporated RO membrane applied for seawater desalination. A commercial SW30HR membrane was tested in parallel for comparison. The robust ASW membrane exhibited a nearly 80% higher water flux in comparison to the SW30HR membrane with a comparable overall solute rejection, suggesting the advantage and feasibility of Aquaporin based biomimetic membranes for seawater desalination. • The mechanical strength of aquaporin incorporated polyamide layer was characterized with AFM. • The effects of high pressure compaction and salinity on aquaporin incorporated polyamide layer were investigated. • The aquaporin based biomimetic membranes were optimized for seawater desalination (SWRO) application. • A seven-day SWRO measurement of the ASW was conducted using a real seawater secondary effluent. [ABSTRACT FROM AUTHOR]

How the membrane support affects the performance of thin-film composite (TFC) membranes has long been under debate. Our present study experimentally establishes that the support pore number density (number per unit area) as well as its surface porosity play pivotal roles in affecting the characteristics and permselectivity of TFC membranes. The structure of hollow fiber supports was finely tuned and characterized via a series of techniques, which provided a link to the physicochemical properties of the interfacially polymerized polyamide films. During the spinning process, decreasing the content of N -methyl-2-pyrrolidone in the bore fluid drastically reduced the pore size and surface porosity of the support. The resultant TFC membranes showed a lower water permeability (tested under 1 bar using 500 ppm NaCl). Adding lithium chloride to the polymer dope also led to a support with smaller pores and lower porosity, but increased surface pore number density. The resulting TFC membranes had a substantially higher water permeability and slightly higher salt rejection. In both arrays of membranes, all membranes shared similar thickness of polyamide leaf but a more crumpled film was found on a less porous support, suggesting that the surface porosity of the support affected the effective surface area of films. However, the TFC membrane with a higher effective surface area did not necessarily possess a higher permeability. Rather, a TFC membrane having a support with a higher surface porosity or a higher pore number density exhibited a higher water permeability, demonstrating that the lateral transport path of water through films had a significant impact on the water permeability of TFC membranes. Interestingly, in both cases, the selectivity of the TFC membranes was maintained when the water permeability increased. This study clarifies longstanding misunderstandings concerning the effects of the support on TFC membrane performance and provides insight into fabricating highly permeable and selective TFC membranes. • A base film embedded in the polyamide layer determines performance of TFC membranes. • Enlarging surface porosity of supports could enhance permeability of TFC membranes. • Increasing pore density of supports could enhance permeability of TFC membranes. • Supports affect lateral diffusion of water through films and thereby permeability. • Rejection was maintained while the permeability of TFC was drastically enhanced. [ABSTRACT FROM AUTHOR]

Abstract A highly efficient biocatalytic carbonic anhydrase (CA)-polydopamine (PDA)/polyethylenimine (PEI)-polyvinylidene fluoride (PVDF) (referred to as CA-m-PVDF) composite membrane was fabricated for CO 2 conversion and capture in the gas-liquid membrane contactor (GLMC) process. The co-deposition of PDA/PEI with amino functional groups was employed to amine-functionalize a PVDF substrate as support for subsequent in-situ CA immobilization by cross-linking with glutaraldehyde. This enhances the enzyme stability and prolongs its lifespan, thus facilitates CO 2 hydration efficiency in the GLMC process. In this work, different immobilization CA protocols were compared based on the CA activity and activity recovery. For biocatalytic CA-m-PVDF membranes, the best activity of 498 U m−2 (membrane) and a corresponding activity recovery of 31.5% were achieved (m(5 h)-PVDF as support, 0.67 (v/v)% GLU as cross-linking agent, 600 μg mL−1 CA solution, pH 8.0, temperature at 25 °C, and 24 h reaction time). By using water as absorbent with a liquid velocity of 0.25 m s−1 in a bench-scale GLMC setup, a high-efficiency CO 2 absorption flux of 2.5 × 10−3 mol m−2 s−1 was obtained, which was ~165% higher than that of the non-biocatalytic m-PVDF membrane. The long-term stability test showed a good enzyme activity for CO 2 hydration capacity for the CA-m-PVDF membranes during 40 days of test duration. Overall, the results achieved in this work may provide promising insights into enzyme immobilization on polymeric supports for the development of high-efficiency biocatalytic membranes for CO 2 capture in GLMC applications. Highlights • A highly efficient biocatalytic composite membrane was fabricated for CO 2 conversion and capture. • PDA/PEI with amino functional groups was co-deposited to amine-functionalize a PVDF substrate. • Subsequent in-situ carbonic anhydrase (CA) immobilization was conducted by cross-linking. • The resultant membrane shows a high CO 2 absorption flux of 2.5 × 10-3 mol m-2 s-1 in the gas-liquid membrane contactor. [ABSTRACT FROM AUTHOR]

[Display omitted] • pH-response attapulgite (p-ATP) nanofibers were prepared by surface grafting. • The compatibility between PVDF and t-ATP resulted in excellent tensile strength. • Anti-fouling performance of membrane increased due to the hydrophilic p-ATP. • Adsorption and desorption of H 2 O from p-ATP occurred with the change in pH. • The membrane is easy-cleaning due to the pH-response property of p-ATP. Membrane separation is an efficient strategy to disrupt the spread of pathogens in an aqueous solution and produce clean water, but its performance is seriously affected by fouling caused by bioadhesive. In this study, novel pH-response attapulgite (p-ATP) nanofibers were prepared and applied in the modification of poly(vinylidene fluoride) (PVDF) ultrafiltration membrane for bovine serum albumin (BSA) solution purification. Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) was grafted onto the surface of attapulgite (ATP) to offer pH-response property and to improve compatibility with PVDF. p-ATP is a hydrophilic material, which can increase the anti-biofouling performance of PVDF, and its one-dimensional structure is beneficial for enhancing the inter-entanglement with organic chains in the membrane matrix. The resultant composite membrane loaded with 7% p-ATP presented 77.2% and 108.1% increase in stationary permeance and mechanical strength, respectively, than that of the pristine PVDF membrane. Furthermore, the PDMAEMA chains in p-ATP will be shrunken or swollen with the change of pH value, resulting in adsorbing or releasing water molecules. This process is effective to mitigate the adhesion between biofoulants and membrane and can break the already formed biofouling layer. So, the composite membranes are easily to be cleaned via a simple pH-change cleaning process. The molecular dynamic simulation was also conducted to analyze the high performance of the PVDF/p-ATP membrane to provide theoretical support. [ABSTRACT FROM AUTHOR]

Internal concentration polarization (ICP) in a dense support layer is one of the main reasons holding back forward osmosis (FO) process. In this regard, a highly porous microstructured support (HPμS) featuring a quasi-sponge-free sublayer pore structure can be considered a suitable alternative to develop high-performance FO membranes. However, it has not been tested for its effects on FO. This study demonstrates that a TFC membrane prepared using the HPμS works out for FO by inducing 3.35 times higher water flux without compromising a reverse salt flux (J s) compared to a control TFC membrane prepared without support adjustment. The performance improvement could be achieved by HPμS's almost no sponge-like region and lateral walls, which were desirable to minimize ICP. Furthermore, we verified that it is possible to leverage co-solvent assisted interfacial polymerization (CAIP) to further improve FO membrane performances by creating a more permeable active layer. The in-house TFC membrane optimized by the HPμS and CAIP displayed 5.3 times higher FO water flux than the control membrane, while keeping comparable J s. We expect that this research could contribute to kicking the FO membrane performance up a notch by providing a practical example of simultaneous optimization of both support and active layers. [Display omitted] • A highly porous microstructured support (HPμS) successfully reduced ICP in FO. • Almost no sponge-like region and lateral walls of the HPμS were key in reducing ICP. • A sublayer structure of a support layer was examined by a non-destructive inspection. • Co-solvent assisted interfacial polymerization further improved FO performances. • The simultaneous optimizations of support and active layers maximized FO performances. [ABSTRACT FROM AUTHOR]

Thin film composite (TFC) polyamide (PA) membranes experience compaction at high pressure applications, resulting in the reduction in water permeability. However, the compaction mechanism is still unclear especially for different PA morphologies and substrate structures. In this work, we systematically studied the compaction of TFC PA membranes with different structures and morphologies. We first examined 2 main types of commercial reverse osmosis (RO) membranes: brackish water RO and seawater RO membranes. After that, we synthesised four types of TFC membranes with tailored PA and substrate structures to further understand the compaction behaviors. TFC membrane with a PA layer of low protuberances or nodules and dense substrate showed excellent resistance against high pressure (50 bar), with only a slight irreversible decrease of 2.1–3.5% in water permeability when retested at 5 bar. However, the PA layer of high protuberances experienced significant compaction even when it was supported by a similar dense substrate. The permeability of the TFC membrane decreased ∼10% as a result of the decrease in the effective area of the active layer. On the other hand, the TFC membrane with a PA layer of low protuberances formed atop a loose substrate showed a greater decrease (∼18.5%) in water permeability. The densified skin layer and collapsed macro-voids within the loose substrate resulted in a ∼40% decrease in the overall height of the PA layer and a 65% decline in substrate surface porosity, respectively, which are identified as the reasons for the reducing water permeability. Notably, the water-salt selectivity of this particular membrane was seriously deteriorated after compaction due to the presence of subtle defects in the PA layer caused by the drastic deformation of the loose substrate. This work deepens the understanding of the compaction behaviors of TFC PA membranes, providing a clear fundamental guidance on designing membranes applied at high operating pressures. [Display omitted] • The compaction of TFC PA membranes with different PA and substrate structures at 50-bar hydraulic pressure was investigated. • The high protuberances on the PA layer were compressed at 50 bar, resulting in an apparent decline in water permeability. • A porous substrate resulted in the decreases of water permeability and selectivity simultaneously after membrane compaction. • A TFC membrane with a low-protuberance PA layer and dense substrate is suitable for use in high-pressure processes. [ABSTRACT FROM AUTHOR]

A novel surfactant encapsulated polyoxometalate (SEP) has been synthesized by using a simple ion-exchange reaction. The prepared SEP complex was found to self-assemble into nanospherical particles whose morphology and component were characterized by TEM and XPS. The SEP was further incorporated into polyvinylidene fluoride (PVDF) to fabricate SEP incorporated composite membrane (SEP-M). Both the SEP and SEP-M exhibited excellent dye removal activities, which is for the first time reported as an intriguing property of the SEP. A regeneration scheme for SEP-M was successfully proposed without any loss of dye removal efficiency. Detailed mechanism studies were carried out to elucidate the nature of dye decolorization. Ion exchange was revealed to play a dominant role in the dye removal process. The current research not only renders a new example for the simple and direct synthesis of SEP but more importantly provides an efficient dye removal methodology. [ABSTRACT FROM AUTHOR]

A scaled-up hollow fibre thin-film composite (TFC) module was successfully developed for organic solvent forward osmosis (OSFO) application in the pharmaceutical industry. The membrane consists of cross-linked P84 polyimide substrate with a polyamide selective layer, formed via interfacial polymerisation. The performance of the lab-scale module was compared to the scaled-up module in reverse osmosis and forward osmosis modes. The results from both tests revealed that the solvent permeability of the scaled-up module decreased while its selectivity increased slightly. This might be caused by the uneven distribution of liquids during interfacial polymerisation, leading to varied membrane performance. The scaled-up module was further tested for OSFO performance using a range of PEG-400 concentrations (0.5–2 M) in acetone and isopropanol as draw solutions. At 2 M PEG-400 concentration, the module demonstrated high isopropanol and acetone permeability of 0.63 LMH and 13.9 LMH, respectively. Moreover, the reverse solute flux of PEG-400 in acetone and isopropanol were relatively low at 0.188 g/l and 0.153 g/l, respectively. The module was further tested for OSFO application in the pharmaceutical industry by concentrating levofloxacin in acetone, using 2 M PEG-400 as draw solution. The process was able to concentrate levofloxacin from 1000 ppm to 16,000 ppm with very low reverse solute flux of 0.178 g/l. Therefore, this work presents a scalable TFC membrane for OSFO application in the pharmaceutical industry. [Display omitted] • Scaled-up module (0.4 m2) of TFC hollow fibre membrane for organic solvent forward osmosis process was successfully fabricated. • High porosity (79%) and low structural parameter (217 μm) for membrane substrate was achieved. • Membrane exhibited excellent acetone and IPA solvent flux of 13.9 LMH and 0.63 LMH, respectively, using a 2 M PEG-400 draw solution. • A pharmaceutical stream was concentrated to a factor of 16 with low specific reverse solute flux [ABSTRACT FROM AUTHOR]

A scaled-up hollow fibre thin-film composite (TFC) module was successfully developed for organic solvent forward osmosis (OSFO) application in the pharmaceutical industry. The membrane consists of cross-linked P84 polyimide substrate with a polyamide selective layer, formed via interfacial polymerisation. The performance of the lab-scale module was compared to the scaled-up module in reverse osmosis and forward osmosis modes. The results from both tests revealed that the solvent permeability of the scaled-up module decreased while its selectivity increased slightly. This might be caused by the uneven distribution of liquids during interfacial polymerisation, leading to varied membrane performance. The scaled-up module was further tested for OSFO performance using a range of PEG-400 concentrations (0.5–2 M) in acetone and isopropanol as draw solutions. At 2 M PEG-400 concentration, the module demonstrated high isopropanol and acetone permeability of 0.63 LMH and 13.9 LMH, respectively. Moreover, the reverse solute flux of PEG-400 in acetone and isopropanol were relatively low at 0.188 g/l and 0.153 g/l, respectively. The module was further tested for OSFO application in the pharmaceutical industry by concentrating levofloxacin in acetone, using 2 M PEG-400 as draw solution. The process was able to concentrate levofloxacin from 1000 ppm to 16,000 ppm with very low reverse solute flux of 0.178 g/l. Therefore, this work presents a scalable TFC membrane for OSFO application in the pharmaceutical industry. [Display omitted] • Scaled-up module (0.4 m2) of TFC hollow fibre membrane for organic solvent forward osmosis process was successfully fabricated. • High porosity (79%) and low structural parameter (217 μm) for membrane substrate was achieved. • Membrane exhibited excellent acetone and IPA solvent flux of 13.9 LMH and 0.63 LMH, respectively, using a 2 M PEG-400 draw solution. • A pharmaceutical stream was concentrated to a factor of 16 with low specific reverse solute flux [ABSTRACT FROM AUTHOR]

Electrospun polymeric membranes are promising substrates for thin-film composite (TFC) membranes due to their unique interconnected pores and high porosity. However, it is still challenging to fabricate desirable electrospun substrates for organic solvent nanofiltration (OSN) owing to the relatively complex processing procedures and the organic operating environment. In this work, solvent-resistant electrospun polyimide (PI) nanofiber substrates were successfully fabricated through electrospinning followed by chemical cross-linking and heat-pressing. The cross-linking step improved the solvent tolerance of the membranes, while the heat-pressing step reduced the substrate pore size and surface roughness. However, it was found that heat-pressing at high temperatures (>140 °C) could degrade the cross-linking of PI, undermining their solvent-resistant property. A polyamide thin film layer was then synthesized on the solvent-resistant electrospun nanofibrous substrates via interfacial polymerization using reactant monomers m -phenylenediamine (MPD) and trimesoyl chloride (TMC). The TFC membranes exhibited excellent acetonitrile and acetone permeabilities of 31.28 ± 1.93 and 26.58 ± 1.13 L m−2 h−1 bar−1, respectively, with acid fuchsin (585 Da) and methyl orange (327 Da) rejections of 98.55 ± 1.24% and 92.42 ± 1.66%, respectively, in acetone. This study successfully demonstrated the potential use of electrospun PI nanofibers substrates for TFC membranes in OSN. [Display omitted] • Solvent resistant nanofibrous PI substrates were prepared by electrospinning followed by chemical cross-linking and heat-pressing. • Heat-pressing influenced the PI substrates' surface properties and solvent resistance, and the optimal point was 140 °C. • Polyamide thin film was synthesized on the PI substrates via interfacial polymerization for OSN application. • Acetone permeability was 26.58 L m−2 h−1 bar−1 with high rejection to acid fuchsin and methyl orange. [ABSTRACT FROM AUTHOR]

Nanoscale characteristics of the polyamide layer are key towards the high desalination performance of thin-film composite reverse osmosis (TFC-RO) membranes. Further advancements in the performance of TFC membranes necessitate a comprehensive understanding of the desired polyamide characteristics and its formation mechanisms. Empirical evidence has shown that the properties of the support layer is as equally important as the interfacial polymerization (IP) conditions in the fabrication of high permselectivity TFC membranes for desalination. Herein, we discuss the properties of polyamide layers formed using identical IP conditions over support membranes of different polymers and chemistries (polyethersulfone, polyetherimide and polysulfone) under fairly similar surface pore properties. The characteristics of the polyamide layers formed thereon displayed different physicochemical properties. It is postulated that the support membrane chemistry actually affects the IP reaction and polyamide formation by controlling the amine diffusion speed as well as the breadth of the IP reaction zone (i.e., the region between the interface and the furthest point in which the reaction occurs). Transmission electron microscopy analyses further revealed the nanoscale differences in the polyamide layer (heights ranging from 50 to 200 nm), including intrinsic thickness of basal layer (~10–35 nm) and leaf-like top layer (~20–85 nm), as well as the presence of nanovoids. Finally, we propose a conceptual model to underline the role of support membrane chemistry in the IP reaction, and consequently the formation mechanism of the nanoscale polyamide features. The mechanistic insights from this study are expected to provide more understanding towards a better control over the fabrication of polyamide layers for TFC membranes. The findings in this work are also expected to facilitate tailoring polyamide layers for specific osmotically driven processes. [Display omitted] • Support membrane chemistry affects MPD diffusion and partitioning extent in IP. • TEM and SEM analyses revealed changes in the polyamide (PA) nanoscale morphology. • PA layer of TFC-PES membrane was thin and smooth without any nanovoids. • PA layer of TFC-PSf membrane had thick base, thin leaves and multi-layer nanovoids. • PA layer of TFC-PEI membrane had thin basal layer with clumpy roof-like top layer. [ABSTRACT FROM AUTHOR]

High-efficient CO 2 capture using membrane separation technology is a promising approach towards environmental redemption in recent years. Thin-film composite (TFC) membrane with selective layer made of CO 2 -philic materials is the preferred membrane type for industrial-scale application, owing to its high permselectivity and good processability. Herein, we propose a facile direct spray-coating method to fabricate Pebax® 1657 thin-film on a porous polysulfone (PSF) substrate. Unlike most conventional multilayer TFC membranes, the unnecessary need for gutter layer in this work greatly simplifies the membrane fabrication process. Pebax® 1657 thin films were deposited through direct spraying of the polymer solution containing Pebax® 1657 on PSF substrate under ambient temperature. The as-prepared Pebax®1657 TFC membranes showed decent separation performances with CO 2 permeance of >200 GPU and CO 2 /N 2 selectivity of >50 for mixed gas (vol. (CO 2)/vol. (N 2) = 20/80) tests. The facile TFC membrane fabrication and good CO 2 separation performances make the direct spray coated Pebax®1657 membranes a promising strategy for large-scale CO 2 capture applications. [Display omitted] • TFC membranes are fabricated through direct spray of Pebax® 1657 solution on PSF ultrafiltration substrate. • The unnecessary need for gutter layer greatly improved the simplicity of TFC membrane preparation process. • The obtained Pebax® 1657 TFC membranes exhibit competitive CO 2 permeance (>200 GPU) and CO 2 /N 2 selectivity (>50). • The successful fabrication of A4-sized TFC membrane demonstrates the scale-up potential of the direct spray coating method. [ABSTRACT FROM AUTHOR]

Seawater reverse osmosis (SWRO) is the key technology driving an energy-efficient and cost-effective desalination process. At the center of this technology are the thin film composite (TFC) membranes, which not only promise a stable operation but also high separation performances. The objective of this review is to consolidate recent advances in SWRO membranes from the standpoint of membrane materials, fabrication methodologies and applications. First, the thermodynamic limit and energy consumption of SWRO desalination are reviewed, before we discuss the current status of SWRO membranes, highlighting the four main challenges to date – permselective tradeoff, relatively low single-pass boron rejection, membrane fouling and poor chlorine resistance. Thereafter, a comprehensive review of the membrane development is presented. We examine findings reported in research papers and patents, and various methods to achieve SWRO membranes of higher permselectivity, boron rejection, and chlorine resistance as well as lower fouling propensity. Key insights from the membrane industry are also furnished. Then, we put together an outlook, featuring our perspectives on SWRO membrane development. Empirical data in this review are collated into an upper-bound relationship, which is tailored specifically for SWRO membranes and expected to provide benchmarking for future SWRO membrane development. Since the traits of SWRO membranes are unique from those of brackish water RO (BWRO) membranes, we also distinguish the methods used for SWRO membrane fabrication to help zero in on the correct strategies, and provide insights for advancing new membrane designs. Overall, this review sums up the current state-of-the-art SWRO membranes, looking at the array of fabrication methods used thus far, and putting into perspective critical strategies to realize the next-generation TFC membranes that can address the future demands of SWRO and deliver a more competitive desalination process. [Display omitted] • Recent advances in SWRO membrane are collated from papers and industrial patents. • Current status and future outlook of SWRO membrane industry are discussed. • A permselectivity upper bound is established specifically for SWRO membranes. • The upper bound is given by A/B = 46.75 A −1.72 (A/B in bar−1 and A in Lm−2h−1 bar−1). • A roadmap for SWRO membrane fabrication is proposed (short/long-term strategies). [ABSTRACT FROM AUTHOR]

This study examined the feasibility and performance of a nanochannel-based biomimetic membrane (NBM) for brackish reverse osmosis (RO) desalination. Two types of peptide-attached synthetic nanochannels, (pR)-pillar[5]arenes (pRPH) and (pS)-pillar[5]arenes (pSPH), were incorporated into liposomes. pSPH is a diastereomer of pRPH and was used as a negative control (i.e. mutant) to pRPH in this work. The nanochannel-containing liposomes (e.g. pRPH-liposomes) were then immobilized into the active layer of the RO membranes via in situ interfacial polymerization on the top of a polysulfone support membrane to form NBM-pRPH membranes. To maximize the potential and benefits of the NBM-pRPH membrane, the physical characteristics of the polyamide layer was further tuned using some additives and the eventual membrane was named as NBM-pRPH-A. The NBM-pRPH-A membrane exhibited a water permeability of 6.09 L m−2 h−1 bar−1 and 98.2% NaCl rejection under a 15.5 bar applied pressure using 2000 mg L−1 as feed solution. The 62% flux increment with respect to the pristine control is postulated to arise from a thinner, less cross-linked (more free volume) and more hydrophilic active layer as well as the possible supplementary transport pathways of the pRPH-liposomes. The performance of the NBMs under differential feed pressures and temperatures further exemplifies the water permeation property of the pRPH nanochannels. Accordingly, the NBM-pRPH-A gave a water permeability higher than commercial RO membranes tested in this work (DuPont BW30 and Hydranautics ESPA2) as well as other RO membranes reported in the literature. This study provides a tangible foundation for the development of NBMs for brackish RO desalination. [Display omitted] • Synthetic pRPH nanochannel-based biomimetic membrane was used for BWRO application. • pRPH-liposomes were incorporated onto the PA layer via interfacial polymerization. • STEM-EDX analysis revealed the existence of liposomes in the PA layer. • High permeability of 6.09 Lm−2h−1bar−1 (98.2% NaCl rejection) was reported in BWRO. • RO tests under increasing ΔP and temperature suggested water transport across pRPH. [ABSTRACT FROM AUTHOR]

Conventional biomimetic membranes for desalination are mostly fabricated by incorporating water channels using self-assembled lipid or polymer vesicles as key platforms for protein or water channel reconstitution. Herein, we propose a thin film composite nanofiltration membrane via an unconventional liposomes-assisted fabrication without the incorporation of protein or water channels. The polyamide skin layer containing liposomes was thinner and filled with wrinkles and nanovoids. As a result, compared with the liposome-free control membrane, our optimized liposome-assisted membrane was able to achieve an increased water permeability from 11.17 to 18.21 LMH/bar, alongside an excellent MgCl 2 rejection of 95.87% and a monovalent/divalent (NaCl/MgCl 2) ion selectivity (α) of 18.2. Extensive membrane characterization showed that the liposome-assisted skin layer indeed exhibited a smaller thickness with an increased effective membrane area and a reduced surface hydrophobicity, which contribute towards a reduction in the hydrodynamic resistance of the polyamide layer. Furthermore, our approach of liposome-assisted thin film composite membrane is simpler and more scalable to fabricate without protein or water channels incorporation, rendering our design more attractive for future nanofiltration using vesicle-embedded biomimetic membranes. Image 1 • Lipid hollow vesicle was utilized to construct a thin film composite membrane. • The pathway of liposomes involved in the interfacial polymerization was confirmed via systematic characterization results. • Thinner polyamide with nanovoids and wrinkled structures was formed to facilitate water transportation. • The LE-TFC membrane exhibited better water permeability and higher divalent ion rejection. [ABSTRACT FROM AUTHOR]

Conventional mixed-matrix membranes (MMMs) possess a dense structure with a filler material uniformly dispersed within the polymer matrix to engineer the transport properties and achieve enhanced gas separation performances with respect to pure polymeric membranes. However, a dense membrane structure increases the transport resistance and undesirably requires a high filler loading to see a substantial enhancement in separation performances. To address this problem, we fabricated asymmetric MMMs that have a thin-selective layer of around 0.5 μm and a low loading (0.03–0.10 wt%) of nitrogen-doped graphene (N-G) nanosheets. The presence of the nitrogen- and oxygen-containing functional groups on the N-G nanosheets ensured good compatibility between filler and polymer matrix, which resulted in strong polymer/filler interfacial adhesions. The N-G nanosheets were also found to be capable of migrating to the top of the membranes during phase inversion. Hence, despite the low filler loadings used in this work, the capacity of the dense selective layers was greatly enhanced. Based on our experimental results, 0.07 wt% and 0.10 wt% loading of N-G nanosheets can improve both O 2 /N 2 (126.9%) and CO 2 /N 2 (45.8%) selectivities with respect to pure polymeric membranes, resulting in O 2 /N 2 separation performance surpassing the Robeson upper bound. Image 1 • Asymmetric mixed matrix membranes (MMMs) comprising nitrogen-doped graphene (N-G) were fabricated. • Asymmetric MMMs have a thin-selective layer and a very low lading of N-G (0.03–0.10 wt%). • Most N-G fillers were migrated to the dense (top) layer to reduce interface energy during the phase inversion. • The O 2 /N 2 and CO 2 /N 2 selectivities of MMMs increased by 126.9% and 45.8%, respectively. • The selectivity improvement is due to the formation of more selective tortuous pathway by N-G fillers. [ABSTRACT FROM AUTHOR]

Although a highly porous support membrane has attracted increasing attention as an alternative to enhance the water permeability of a thin-film composite (TFC) membrane without compromising salt rejection, its feasibility has not ever been tested in seawater desalination. This study explored the availability and potential of a highly porous microstructured (HPμS) support membrane as a support for a seawater reverse osmosis (SWRO) membrane. Our lab-made membranes, TFC-HPμS, exhibited a higher water permeability of 1.62 L m−2 h−1 bar−1 as compared with most of the state-of-the-art SWRO membranes recently reported in the literature, while achieving comparable NaCl rejection (99%) in SWRO test condition (55 bar, 35,000 mg L−1 of NaCl). This excellent performance is thought to stem from the HPμS support endowing a TFC membrane with comparable mechanical properties to that of existing support used for conventional SWRO membrane and shortened effective diffusion pathway of water molecules over the active layer. The robustness and enhanced mechanical strength of the TFC-HPμS membrane are attributed to its narrow and regularly arranged finger-like structure ensuring the even distribution of local stresses, thereby eliminating the presence of stress convergence points. The shortened effective diffusion pathway was estimated to be achieved mainly by less localized surface pores due to the HPμS support's highly porous surface with a larger number of even distributed surface pores. This study potentially opens up another workable pathway in the fabrication of SWRO membranes with enhanced performance without significant sacrifice of the selectivity. • Highly porous microstructured support membrane was used for seawater desalination. • The regularly arranged sublayer enhanced the mechanical strength of the support. • The effective diffusion pathway can be shortened with less localized surface pores. • The tuned TFC membrane exhibited higher permselectivity as compared to the control. • High permeability of 1.62 Lm−2h−1bar−1 (>99% NaCl rejection) was reported in SWRO. [ABSTRACT FROM AUTHOR]

Polyamide thin film membranes have shown outstanding performance in organic solvent nanofiltration (OSN). However, it is still challenging to produce polyamide hollow fibres for OSN, mainly due to limited solvent resistance of hollow fibre substrates and the difficulty to synthesize polyamide thin film on the surface of hollow fibre substrates. In this study, polyamide-based hollow fibre composite members for low pressure OSN were successfully developed. Solvent resistant polyimide hollow fibre substrates were first prepared through a non-solvent induced phase separation process, followed by chemical cross-linking with hexamethylene diamine. A polyamide thin film layer was then synthesized via interfacial polymerization, by circulating the reactant monomers including polyethyleneimine (PEI), piperazine (PIP) and trimesoyl chloride (TMC) through the hollow fibre lumen. The polyamide thin film with a thickness of ~60 nm was formed on the inner surface of the hollow fibre substrates. The membranes exhibited excellent nanofiltration (NF) performance under 2 bar operating pressure. The permeability of water, acetone and isopropanol was 6.8, 11.6 and 4.5 l m−2 h−1 bar−1, respectively. The membranes also achieved 99.9% and 91.8% rejection to rose bengal (1017 Da) and acid fuchsin (585 Da), respectively, in acetone. Furthermore, a 72-h filtration test was conducted and the membrane showed steady performance throughout the testing period. This study demonstrates the possibility of fabricating polyamide hollow fibre membranes for organic solvent nanofiltration at low pressure, which is desirable for practical applications. • Solvent resistant polyimide hollow fibre membranes were fabricated through chemical cross-linking. • Polyamide-based (PEI/PIP) layer was formed onto polyimide substrate to obtain a relatively loose selective layer. • Membranes achieved 11.6 and 4.5 l m−2 h−1 bar−1 permeability in acetone and isopropanol at 2 bar respectively. • Membranes maintained more than 90% rejection for acid fuchsin in 72-h filtration test, showing stable OSN performance. [ABSTRACT FROM AUTHOR]

Membrane compaction is commonly observed in polymeric membranes when subjected to elevated hydraulic pressure, but was rarely discussed in forward osmosis (FO) processes, since there was usually little hydraulic pressure difference across the membrane. In the current study, three TFC membranes were fabricated using hollow fiber substrates with varied water permeability to study the effect of the osmotic pressure on the TFC membranes. The TFC membranes were continuously tested in FO experiments for 24 h by using DI water as feed and NaCl solutions of different concentrations as draw solution, and their performances were checked again using fresh feed solutions. At the end of FO experiments, all TFC membranes experienced water flux and salt flux decline to different extents. The TFC membranes were characterized using SEM, TEM and AFM. Visible changes in the cross-section morphology and surface topography of the TFC membranes were observed after FO experiments. The observation suggested that the occurrence of membrane compaction could be associated with "negative pressure" build-up within the support layer of the TFC membranes. The current study could shed light on the important factors that should be considered during membrane fabrication and when establishing the testing protocols for the characterization of FO membrane. Unlabelled Image • The effect of the osmotic pressure on the TFC membrane structure during FO process was studied. • Three hollow fiber substrates with substantially different water permeability values were fabricated for the investigation. • FO tests with AL-DS configuration for 24 h continuously were conducted and membrane autopsy was performed. • All TFC membranes experienced irreversible water flux and salt flux decline in different extents. • The deformation in the polyamide layer and the support layer implied substantial internal stress build-up in the FO tests. [ABSTRACT FROM AUTHOR]

In this study, we presented a novel nanofiltration membrane fabrication strategy through rapid co-deposition of a versatile platform – metal phenolic networks (MPNs) and piperazine (PIP) on a porous substrate followed by trimesoyl chloride (TMC) crosslinking. Inspired by the catechol chemistry, tannic acid (TA) was functionalized to tether PIP monomers, and participated in the co-deposition via coordination bonds with Fe3+ ions on a substrate to form Fe3+/TA-PIP complex. A series of analyses (SEM, XPS, FT-IR, water contact angle and zeta potential) confirmed the successful synthesis Fe3+/TA-PIP deposition and polyamide (PA) layer. The resultant membrane exhibited water permeability of 13.73 LMH/bar and 89.52 % for MgSO 4 rejection. The fabrication was further improved by embedding modified graphene oxide (GO) nanosheets into the Fe3+/TA-PIP complex. The optimized nanocomposite membrane achieved a water permeability at 21.66 LMH/bar, along with a well maintained MgSO 4 rejection at 91.25 % and NaCl/MgSO 4 selectivity (α) at 10.02 under 2 bar operation pressure. The rapid co-deposition mediated by nanomaterials incorporation provides an effective approach to design high performance thin film composite (TFC) membrane. Image 1 • A novel fabrication strategy was designed for nanofiltration membrane. • Metal phenolic networks were rapidly co-deposited with piperazine followed by interfacial polymerization. • Graphene oxide was incorporated into the deposited layer without additional fabrication step. • The optimized thin film composite membrane exhibited high separation performance. [ABSTRACT FROM AUTHOR]