Fabrication and Performance Evaluation of a Cation Exchange Membrane Using Graphene Oxide/Polyethersulfone Composite Nanofibers.

Ion exchange membranes, especially cation exchange membranes (CEMs), are an important component in membrane-based energy generation and storage because of their ability to transport cations via the electrochemical potential gradient while preventing electron transport. However, developing a CEM with low areal resistance, high permselectivity, and stability remains difficult. In this study, electrospun graphene oxide/polyethersulfone (GO/PES) composite nanofibers were prepared with varying concentrations of GO. To fabricate a CEM, the pores of the electrospun GO/PES nanofiber substrates were filled with a Nafion ionomer. The pore-filled PES nanofiber loaded with 1% GO revealed a noticeable improvement in hydrophilicity, structural morphology, and mechanical properties. The 1% GO/PES pore-filled CEM was compared to a Nafion membrane of a varying thickness and without a nanofiber substrate. The CEM with a nanofiber substrate showed permselectivity of 85.75%, toughness of 111 J/m3, and areal resistance of 3.7 Ω cm2, which were 12.8%, 4.3 times, and 4.0 times better, respectively, than those of the Nafion membrane at the same thickness. The development of a reinforced concrete-like GO/PES nanofiber structure containing stretchable ionomer-enhanced membrane surfaces exhibited suitable areal resistance and reduced the thickness of the composite membrane without compromising the mechanical strength, suggesting its potential application as a cation exchange membrane in electrochemical membrane-based systems.

Sulfonated graphene oxide-based pervaporation membranes inspired by a tortuous brick and mortar structure for enhanced resilience against silica scaling and organic fouling.

A novel tortuous brick-and-mortar structure utilizing intercalation of polyvinyl alcohol (PVA) on sulfonated graphene oxide (SGO) membranes was specifically tailored for brine treatment by pervaporation to ensure excessive resistance to silica scaling and organic fouling, as well as ultrafast water transport without compromising salt rejection. The synthesized SGO membrane showed a smoother surface morphology, improved zeta potential, and a higher hydration capacity than the graphene oxide (GO) membrane. Further intercalation of PVA through glutaraldehyde (GA) crosslinking, confirmed by Fourier transform infrared spectroscopy and X-ray diffraction analysis, conferred increased cohesiveness, and the SGO-PVA-GA membrane was therefore able to withstand ultrasonication tests without any erosion of the coating layer. According to a pervaporative desalination test, the SGO-PVA-GA membrane exhibited 62 kg m-2 h-1 of permeate flux, with an extraordinary salt rejection of 99.99% for a 10 wt% NaCl feed solution at 65 °C. The 72 h organic fouling, silica scaling, and combined fouling and scaling tests proved that the SGO-PVA-GA membrane sustains a stable flux with less scaling and fouling than the GO-PVA-GA membrane, attributable to dense surface negative charges and great hydration capacities caused by sulfonic acid. Thus, the SGO-PVA-GA membrane offers superlative advantages for long-term brine treatment by pervaporation, related to its ability to withstand silica scaling and organic fouling.

Open Pore Ultrafiltration Hollow Fiber Membrane Fabrication Method via Dual Pore Former with Dual Dope Solution Phase.

Hollow-fiber membranes are widely used in various fields of membrane processes because of their numerous properties, e.g., large surface area, high packing density, mass production with uniform quality, obvious end-of-life indicators, and so on. However, it is difficult to control the pores and internal properties of hollow-fiber membranes due to their inherent structure: a hollow inside surrounded by a wall membrane. Herein, we aimed to control pores and the internal structure of hollow-fiber membranes by fabricating a dual layer using a dual nozzle. Two different pore formers, polyethylene glycol (PEG) and polyvinyl pyrrolidone (PVP), were separately prepared in the dope solutions and used for spinning the dual layer. Our results show that nanoscale pores could be formed on the lumen side (26.8-33.2 nm), and the open pores continuously increased in size toward the shell side. Due to robust pore structure, our fabricated membrane exhibited a remarkable water permeability of 296.2 ± 5.7 L/m2·h·bar and an extremely low BSA loss rate of 0.06 ± 0.02%, i.e., a high BSA retention of 99.94%. In consideration of these properties, the studied membranes are well-suited for use in either water treatment or hemodialysis. Overall, our membranes could be considered for the latter application with a high urea clearance of 257.6 mL/min, which is comparable with commercial membranes.

Enhancing the Dye-Rejection Efficiencies and Stability of Graphene Oxide-Based Nanofiltration Membranes via Divalent Cation Intercalation and Mild Reduction.

Laminar graphene oxide (GO) membranes have demonstrated great potential as next-generation water-treatment membranes because of their outstanding performance and physicochemical properties. However, solute rejection and stability deterioration in aqueous solutions, which are caused by enlarged nanochannels due to hydration and swelling, are regarded as serious issues in the use of GO membranes. In this study, we attempt to use the crosslinking of divalent cations to improve resistance against swelling in partially reduced GO membranes. The partially reduced GO membranes intercalated by divalent cations (i.e., Mg2+) exhibited improved dye-rejection efficiencies of up to 98.40%, 98.88%, and 86.41% for methyl orange, methylene blue, and rhodamine B, respectively. In addition, it was confirmed that divalent cation crosslinking and partial reduction could strengthen mechanical stability during testing under harsh aqueous conditions (i.e., strong sonication).

Antiviral Nanomaterials for Designing Mixed Matrix Membranes.

Membranes are helpful tools to prevent airborne and waterborne pathogenic microorganisms, including viruses and bacteria. A membrane filter can physically separate pathogens from air or water. Moreover, incorporating antiviral and antibacterial nanoparticles into the matrix of membrane filters can render composite structures capable of killing pathogenic viruses and bacteria. Such membranes incorporated with antiviral and antibacterial nanoparticles have a great potential for being applied in various application scenarios. Therefore, in this perspective article, we attempt to explore the fundamental mechanisms and recent progress of designing antiviral membrane filters, challenges to be addressed, and outlook.

Practical Considerations of Wastewater-Seawater Integrated Reverse Osmosis: Design Constraint by Boron Removal.

The wastewater-seawater (WW-SW) integrated reverse osmosis (RO) process has gained much attention in and out of academia due to its energy saving capability, economic benefits, and sustainability. The other advantage of this process is to reduce boron concentration in the RO permeate that can exclude the post-treatment process. However, there are multiple design constraints regarding boron removal that restrict process design in the WW-SW integrated system. In this study, uncertainties in design factors of the WW-SW integrated system in consideration of boron removal have been explored. In comprehensive consideration of the blending ratio of between WW and SW, regulatory water quality standard, specific energy consumption (SEC), specific water cost, and RO recovery rate, a range of 15,000~20,000 mg/L feed turned out to be the most appropriate. Furthermore, boron rejection tests with SWRO (seawater reverse osmosis) and BWRO (brackish water reverse osmosis) membranes under actual WW-SW integration found a critical reduction in boron rejection at less than 20 bar of operating pressure. These findings emphasize the importance of caution in the use of BWRO membranes in the WW-SW integrated RO system.

Performance Evaluation and Fouling Propensity of Forward Osmosis (FO) Membrane for Reuse of Spent Dialysate.

The number of chronic renal disease patients has shown a significant increase in recent decades over the globe. Hemodialysis is the most commonly used treatment for renal replacement therapy (RRT) and dominates the global dialysis market. As one of the most water-consuming treatments in medical procedures, hemodialysis has room for improvement in reducing wastewater effluent. In this study, we investigated the technological feasibility of introducing the forward osmosis (FO) process for spent dialysate reuse. A 30 LMH of average water flux has been achieved using a commercial TFC membrane with high water permeability and salt removal. The water flux increased up to 23% with increasing flowrate from 100 mL/min to 500 mL/min. During 1 h spent dialysate treatment, the active layer facing feed solution (AL-FS) mode showed relatively higher flux stability with a 4-6 LMH of water flux reduction while the water flux decreased significantly at the active layer facing draw solution (AL-DS) mode with a 10-12 LMH reduction. In the pressure-assisted forward osmosis (PAFO) condition, high reverse salt flux was observed due to membrane deformation. During the membrane filtration process, scaling occurred due to the influence of polyvalent ions remaining on the membrane surface. Membrane fouling exacerbated the flux and was mainly caused by organic substances such as urea and creatinine. The results of this experiment provide an important basis for future research as a preliminary experiment for the introduction of the FO technique to hemodialysis.

Recent Progress in One- and Two-Dimensional Nanomaterial-Based Electro-Responsive Membranes: Versatile and Smart Applications from Fouling Mitigation to Tuning Mass Transport.

Membrane technologies are playing an ever-important role in the field of water treatment since water reuse and desalination were put in place as alternative water resources to alleviate the global water crisis. Recently, membranes are becoming more versatile and powerful with upgraded electroconductive capabilities, owing to the development of novel materials (e.g., carbon nanotubes and graphene) with dual properties for assembling into membranes and exerting electrochemical activities. Novel nanomaterial-based electrically responsive membranes have been employed with promising results for mitigating membrane fouling, enhancing membrane separation performance and self-cleaning ability, controlling membrane wettability, etc. In this article, recent progress in novel-nanomaterial-based electrically responsive membranes for application in the field of water purification are provided. Thereafter, several critical drawbacks and future outlooks are discussed.

Antibacterial rGO-CuO-Ag film with contact- and release-based inactivation properties.

To reduce the high operational costs of water treatment because of membrane biofouling, next-generation materials are being developed to counteract microbial growth. These modern anti-biofouling strategies are based on new membrane materials or membrane surface modifications. In this study, antimicrobial films comprising rGO, rGO-CuO, rGO-Ag, and rGO-CuO-Ag were synthesized, evaluated, and tested for potential biofouling control using Pseudomonas aeruginosa PAO1 as the model bacterium. The combined rGO-CuO-Ag film displayed enhanced reduction (10-log reduction) in biofouling in comparison to the rGO film (control), followed by the rGO-Ag film (8-log reduction) and rGO-CuO film (0-log reduction). This demonstrated that the use of mixed antimicrobial agents is more effective in reducing biofouling than that of a single agent. The rGO-CuO-Ag film exhibited consistent, controlled, and moderate release of silver (Ag) ions. The release of Ag ions produced a long-lasting antimicrobial effect. These results underscore the potential applications of combined antimicrobial surface-based agents in practice and further research.

Influence of hydrodynamic operating conditions on organic fouling of spiral-wound forward osmosis membranes: Fouling-induced performance deterioration in FO-RO hybrid system.

The forward osmosis-reverse osmosis (FO-RO) hybrid process has been extensively researched as part of attempts to reduce the high energy consumption of conventional seawater reverse osmosis in recent years. FO operating conditions play a substantial role in the hybrid process, dictating not only the performance of the entire system but also the propensity for fouling, which deteriorates performance in long-term field operations. Therefore, determining the optimal FO operating conditions with regard to membrane fouling may promote sustainable operation through efficient fouling control. This study thus evaluated the influence of each hydrodynamic operating condition (feed flowrate, draw flowrate, and hydraulic pressure difference) and their synergistic effects on fouling propensity in a pilot-scale FO operation under seawater and municipal wastewater conditions. Fouling-induced variation in water flux, channel pressure drop, diluted concentration, and the resulting specific energy consumption (SEC) were comparatively analyzed and utilized to project performance variation in a full-scale FO-RO system. Fouling-induced performance reduction significantly varied depending on hydrodynamic operating conditions and the resultant fouling propensity during 15 days of continuous operation. A high feed flowrate demonstrated a clear ability to mitigate fouling-induced performance deterioration in all conditions. A high draw flowrate turned out to be detrimental for fouling propensity since its high reverse solute flux accelerated fouling growth. Applying additional hydraulic pressure during FO operation caused a faster reduction of water flux, and thus feed recovery and water production; however, these drawbacks could be compensated for by a 10% reduction in the required FO membrane area and an additional reduction in RO SEC.

PIP/TMC Interfacial Polymerization with Electrospray: Novel Loose Nanofiltration Membrane for Dye Wastewater Treatment.

A loose nanofiltration (NF) membrane with excellent dye rejection and high permeation of inorganic salt is required to fractionate dye/salt mixture in dye wastewater treatment. In this study, we fabricated the loose NF membrane by using the electrospray interfacial polymerization (EIP) method. It is a novel and facile interfacial polymerization method, which controls the thickness of the poly(piperazine-amide) (PPA) layer in nanometers (1 nm/min) and changes cross-linking degree of PPA layer and pore size by varying the electrospray time; consequently, water permeance and dye/salt rejection ratio can be handled. The fabricated EIP membrane with an optimized fabrication condition (M30, electrospray time was 30 min) possessed excellent pure water permeance (20.2 LMH/bar), high dye rejection (e.g., 99.6% for congo red (CR)), and low salt rejection (e.g., 6.3% for NaCl). Moreover, the EIP membrane exhibited enhanced antifouling property than commercial NF membrane (NF90) with a high flux recovery rate (FRR) of 87.1% and low irreversible fouling (Rir) of 12.9% after fouled by bovine serum albumin (BSA) due to its great smooth surface (average roughness (Ra) is 12.2 nm), hydrophilicity property, enhanced zeta potential, and low protein adsorption. The results indicate that the EIP loose NF membrane had a high potential for dye wastewater treatment.

Influence of bore fluid composition on the physiochemical properties and performance of hollow fiber membranes for ultrafiltration.

Porous hollow fiber polysulfone (PSf) membranes were fabricated via a phase-inversion process and their performance during ultrafiltration (UF) was evaluated. The effects of the composition and concentration (0-50%) of different bore fluid mixtures, including N-methyl-2-pyrrolidone (NMP)/water, glycerol (G)/water, and ethylene glycol (EG)/water (in comparison with pure deionized water), on the structure, physicochemical properties, and performance of the fabricated membranes was investigated. Using these various bore fluid mixtures altered the thermodynamic and kinetic properties of the phase inversion system, and changed the morphology and structure of the fabricated membranes, especially on the lumen side. Increasing concentrations of NMP, G, and EG in the bore fluid resulted in increased pore size, porosity, and hydrophilicity. These bore fluid mixtures exhibited a strong influence on the perm-selectivity of the as-spun hollow fiber membranes. The membrane fabricated using 50% NMP/water as the bore fluid mixture exhibited the highest water flux of 166.98 LMH with a bovine serum albumin rejection rate of more than 97%. Overall, this study introduces an easy and effective way to control the structure of the membrane through bore fluid modification and shows how the inner skin layer properties can have a remarkable effect on water permeance, even in the out-in filtration test.

Antimicrobial mechanism of reduced graphene oxide-copper oxide (rGO-CuO) nanocomposite films: The case of Pseudomonas aeruginosa PAO1.

The antimicrobial properties of two-dimensional materials such as graphene-based surfaces are vital for environmental and biomedical applications. Here, the improvement of the antibacterial property of reduced graphene oxide by the preparation of rGO-CuO nanocomposite films was reported. The rGO-CuO nanocomposites were synthesized via a simple hydrothermal method, and the nanocomposite films were fabricated by filtering through a polytetrafluoroethylene (PTFE) filter with the assistance of a vacuum filtration unit. After characterization of the nanocomposite films, the antibacterial properties were tested against Pseudomonas aeruginosa PAO1. The fabricated rGO-CuO nanocomposite films exhibited excellent antibacterial activity, leading to complete bacterial inactivation upon contact. The antibacterial properties were closely linked to the reactive oxygen species (ROS) independent pathway rather than the ROS-dependent pathway. This work provides an insight into the antibacterial mechanisms of reduced GO and copper oxide composite film for water treatment systems and the potential application of these nanocomposites in biomedicine.

Effect of Spacer Configuration on the Characteristics of FO Membranes: Alteration of Permeation Characteristics by Membrane Deformation and Concentration Polarization.

Membrane deformation is a significant problem in osmotically driven membrane processes, as it restricts practical operating conditions and reduces overall process performance due to unfavorable alteration of membrane permeation characteristics. In this respect, a spacer plays a crucial role, as it dictates the form and extent of membrane deformation in association with concentration polarization (CP), which is also influenced by spacer-induced hydrodynamic behavior near the membrane surface. These two roles of spacers on membrane permeation characteristics are inherently inseparable with the coexistence of hydraulic and osmotic pressures. Here, we suggest a novel analytical method to differentially quantify the proportions of effective osmotic pressure drop caused by membrane deformation and CP. Furthermore, we tested two different FO membranes with three different spacer configurations to define and discuss different forms of membrane deformation and their effects on membrane permeation characteristics. The differential analysis revealed the effect of spacer configuration on effective osmotic pressure drop in membrane deformation (up to ∼201% of variation) is much greater than that in CP (up to ∼20.1% of variation). In addition, a combined configuration of a feed spacer and tricot spacer demonstrated its ability of mitigating membrane deformation with lower selectivity loss and channel pressure drop under pressurization.

Tuning the nanostructure of nitrogen-doped graphene laminates for forward osmosis desalination.

Studies have concentrated on the physicochemical properties of graphene-based membranes that can replace polymeric membranes for use in forward osmosis (FO) systems. However, recent research studies have focused on mixtures of two or more different materials (e.g., graphene oxide and polymers) due to the need to reinforce underwater stability. Alternatives include reduced forms such as reduced graphene oxide to improve the stability and size-based selectivity, which have resulted in a narrow nanochannel that restricts water permeability. Herein, we propose the use of a novel nitrogen-doped graphene (NG) membrane to solve a trade-off between permeability and selectivity, investigating the nanostructure via N-doping reaction time. In an FO process, NG membranes achieved an outstanding specific salt flux of 0.18 g L-1, compared to commercial membranes (0.55 g L-1). The pyridinic-N bonding structure improved the permeability and selectivity under a similar nanochannel size because of its negatively polarized hole defects with the moderate energy barrier enabling water passage while blocking ions. Our results confirm the possibility of fabricating novel graphene-based FO membranes by tailoring the nitrogen-bonding structure, which will significantly help develop a process for improving the scalability of membrane materials.

Low-Power Complementary Logic Circuit Using Polymer-Electrolyte-Gated Graphene Switching Devices.

The modulation of the electrical properties of graphene and its device configurations for low-power consumption are important in developing graphene-based logic electronics. Here, we demonstrate the change in the charge transport in graphene from ambipolar to unipolar using surface charge transfer doping of the polymer electrolyte. Unipolar graphene field-effect transistors (GFETs) were obtained by the surface treatment of poly(acrylic acid) (PAA) for p-type and poly(ethyleneimine) (PEI) for n-type as polymer-electrolyte gates. In addition, lithium perchlorate (LiClO4) in a polymer matrix can be used for the low-gate voltage operation of GFETs (less than ±3 V) because of its high gating efficiency. Using polymer-electrolyte-gated GFETs, complementary graphene inverters were fabricated with a voltage swing of 57% and maximum voltage gain (Vgain) of 1.1 at a low supply voltage (VDD = 1 V). This is expected to facilitate the development of graphene-based logic devices with low-cost, low-power, and flexible electronics.

Two-Dimensional Ti3C2Tx MXene Membranes as Nanofluidic Osmotic Power Generators.

Salinity-gradient is emerging as one of the promising renewable energy sources but its energy conversion is severely limited by unsatisfactory performance of available semipermeable membranes. Recently, nanoconfined channels, as osmotic conduits, have shown superior energy conversion performance to conventional technologies. Here, ion selective nanochannels in lamellar Ti3C2Tx MXene membranes are reported for efficient osmotic power harvesting. These subnanometer channels in the Ti3C2Tx membranes enable cation-selective passage, assisted with tailored surface terminal groups, under salinity gradient. A record-high output power density of 21 W·m-2 at room temperature with an energy conversion efficiency of up to 40.6% is achieved by controlled surface charges at a 1000-fold salinity gradient. In addition, due to thermal regulation of surface charges and ionic mobility, the MXene membrane produces a large thermal enhancement at 331 K, yielding a power density of up to 54 W·m-2. The MXene lamellar structure, coupled with its scalability and chemical tunability, may be an important platform for high-performance osmotic power generators.

Removal behaviors and fouling mechanisms of charged antibiotics and nanoparticles on forward osmosis membrane.

Fouling and rejection mechanisms of both charged antibiotics (ABs) and nanoparticles (NPs) were determined using a negatively-charged polyamide thin film composite forward osmosis (FO) flat sheet membrane. Two types of ABs and NPs were selected as positively and negatively charged foulants at pH 8. The ABs did not cause significant membrane fouling, but the extent of fouling and rejection changed based on the electrostatic attraction or repulsion forces. The addition of opposite charged AB and NP resulted in a decline of the membrane flux by 11.0% but a 6.5% AB average rejection efficiency improvement. On the other hand, mixing of like-charged ABs and NPs generated repulsive forces that improved average rejection efficiency about 5.5% but made no changes in the membrane flux. In addition, NPs and ABs were mixed and tested at various concentrations and pH levels to rectify the behavior of ABs. The aggregate size and removal efficiency were observed to vary with the change in the electron double layer of the mixture. It can help to make the strategy to control the ABs in the FO process and consequently it enables the FO process to produce environmentally safe effluent.

Implications of Chemical Reduction Using Hydriodic Acid on the Antimicrobial Properties of Graphene Oxide and Reduced Graphene Oxide Membranes.

The antimicrobial properties of graphene-based membranes such as single-layer graphene oxide (GO) and modified graphene oxide (rGO) on top of cellulose ester membrane are reported in this study. rGO membranes are made from GO by hydriodic acid (HI) vapor treatment. The antibacterial properties are tested after 3 h contact time with selected model bacteria. Complete bacterial cell inactivation is found only after contact with rGO membranes, while no significant bacterial inactivation is found for the control i) GO membrane, ii) the mixed cellulose ester support, and the iii) rGO membrane after additional washing that removes the remaining HI. This indicates that the antimicrobial effect is neither caused by the graphene nor the membrane support. The antimicrobial effect is found to be conclusively linked to the HI eliminating microbial growth, at concentrations from 0.005%. These findings emphasize the importance of caution in the reporting of antimicrobial properties of graphene-based surfaces.

High-flux ultrafiltration membrane with open porous hydrophilic structure using dual pore formers.

This work investigated the synergistic effect of polyvinylpyrrolidone (PVP) and hydroxypropyl-beta-cyclodextrin (HP-ß-CD) as dual pore forming agents on the properties and performance of polysulfone (PSf) ultrafiltration membranes. A fixed concentration of PVP and varying concentrations of HP-ß-CD were used to prepare the membranes using the phase inversion technique. The results showed that the inclusion of these additives in the dope solution increased its thermodynamic instability and promoted instantaneous demixing. Overall, an increase was observed in the hydrophilicity, open porous structure and mechanical strength of the membranes. Cross-flow filtration tests demonstrated that the pure water permeability of the fabricated membrane was 891 LMH bar-1, about 4.37 times higher than the pristine membrane, while bovine serum albumin (BSA) rejection was relatively constant (about 93%) for all the fabricated membranes. This work proposed that the addition of HP-ß-CD and PVP as dual pore formers can produce a viable ultrafiltration membrane with improved water permeability without a middle ground on rejection potential.