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.

Pretreatments of lignocellulosic and algal biomasses for sustainable biohydrogen production: Recent progress, carbon neutrality, and circular economy.

Lignocellulosic and algal biomasses are known to be vital feedstocks to establish a green hydrogen supply chain toward achieving a carbon-neutral society. However, one of the most pressing issues to be addressed is the low digestibility of these biomasses in biorefinery processes, such as dark fermentation, to produce green hydrogen. To date, various pretreatment approaches, such as physical, chemical, and biological methods, have been examined to enhance feedstock digestibility. However, neither systematic reviews of pretreatment to promote biohydrogen production in dark fermentation nor economic feasibility analyses have been conducted. Thus, this study offers a comprehensive review of current biomass pretreatment methods to promote biohydrogen production in dark fermentation. In addition, this review has provided comparative analyses of the technological and economic feasibility of existing pretreatment techniques and discussed the prospects of the pretreatments from the standpoint of carbon neutrality and circular economy.

Graphene Oxide-Based Membranes Intercalated with an Aromatic Crosslinker for Low-Pressure Nanofiltration.

Graphene oxide (GO), a carbonaceous 2D nanomaterial, has received significant interest as a next-generation membrane building block. To fabricate high-performance membranes, an effective strategy involves stacking GO nanosheets in laminated structures, thereby creating unique nanochannel galleries. One outstanding merit of laminar GO membranes is that their permselectivity is readily tunable by tailoring the size of the nanochannels. Here, a high-performance GO-based nanofiltration membrane was developed by intercalating an aromatic crosslinker, α,α/-dichloro-p-xylene (DCX), between the layers in laminated GO nanosheets. Owing to the formation of strong covalent bonds between the crosslinker and the GO, the resulting GO laminate membrane exhibited outstanding structural stability. Furthermore, due to the precisely controlled and enlarged interlayer spacing distance of the developed DCX-intercalated GO membrane, it achieved an over two-fold enhancement in water permeability (11 ± 2 LMH bar-1) without sacrificing the rejection performance for divalent ions, contrary to the case with a pristine GO membrane.

Preparation of adsorptive polyethyleneimine/polyvinyl chloride electrospun nanofiber membrane: Characterization and application.

Landfilling and burning plastic waste, especially waste polyvinyl chloride (PVC), can produce highly toxic and carcinogenic by-products that threaten the ecosystem and human health. However, there is still a lack of proper methods for waste PVC recycling. Therefore, developing feasible ways for waste PVC recovery is urgently needed. The purpose of this study is to analyze the characteristics of PVC-based adsorptive nanofiber membranes and test their ability for the treatment of wastewater containing Cibacron Brilliant Yellow 3G-P, a widely used reactive dye. The polyethylenimine/polyvinyl chloride membrane (PEI/PVCM) was characterized by FTIR, FE-SEM, TGA, tensile analysis, water contact angle measurement, and zeta-potential analysis. The FTIR analysis confirmed that the PEI has successfully crosslinked with PVC. The FE-SEM images showed that the nanofibers constituting PEI/PVCM are compact with an average fiber diameter of 181 nm. The TGA results showed that the membrane was able to remain stable in wastewater below 150 °C. The average stress and strain of the PEI/PVCM were 7.64 ± 0.32 MPa and 934.14 ± 48.12%, respectively. The water contact angle and zeta potential analysis showed that after the introduction of PEI, the membrane converted from hydrophobic to hydrophilic, and the pHpzc was increased from 3.1 to 1.08. The pure water flux of the membrane was measured at 0.1 MPa and the result was 3013 ± 60 L/m2‧h. The wastewater purification capability of PEI/PVCM was measured at an initial dye concentration of 10 ppm and pH 4-9 at 0.1 MPa. The reusability of PEI/PVCM was verified through three adsorption-desorption cycles. The results demonstrated that the PEI/PVCM is a reusable membrane for efficient purification of wastewater containing reactive dyes over a wide pH range (pH 4-8).

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).

Recent Application of Nanomaterials to Overcome Technological Challenges of Microbial Electrolysis Cells.

Microbial electrolysis cells (MECs) have attracted significant interest as sustainable green hydrogen production devices because they utilize the environmentally friendly biocatalytic oxidation of organic wastes and electrochemical proton reduction with the support of relatively lower external power compared to that used by water electrolysis. However, the commercialization of MEC technology has stagnated owing to several critical technological challenges. Recently, many attempts have been made to utilize nanomaterials in MECs owing to the unique physicochemical properties of nanomaterials originating from their extremely small size (at least <100 nm in one dimension). The extraordinary properties of nanomaterials have provided great clues to overcome the technological hurdles in MECs. Nanomaterials are believed to play a crucial role in the commercialization of MECs. Thus, understanding the technological challenges of MECs, the characteristics of nanomaterials, and the employment of nanomaterials in MECs could be helpful in realizing commercial MEC technologies. Herein, the critical challenges that need to be addressed for MECs are highlighted, and then previous studies that used nanomaterials to overcome the technological difficulties of MECs are reviewed.

Scalability of microbial electrochemical technologies: Applications and challenges.

During wastewater treatment, microbial electrochemical technologies (METs) are a promising means for in situ energy harvesting and resource recovery. The primary constraint for such systems is scaling them up from the laboratory to practical applications. Currently, most research (∼90%) has been limited to benchtop models because of bioelectrochemical, economic, and engineering design limitations. Field trials, i.e., 1.5 m3 bioelectric toilet, 1000 L microbial electrolysis cell and industrial applications of METs have been conducted, and their results serve as positive indicators of their readiness for practical applications. Multiple startup companies have invested in the pilot-scale demonstrations of METs for industrial effluent treatment. Recently, advances in membrane/electrode modification, understanding of microbe-electrode interaction, and feasibility of electrochemical redox reactions have provided new directions for realizing the practical application. This study reviews the scaling-up challenges, success stories for onsite use, and readiness level of METs for commercialization that is inexpensive and sustainable.

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.

A review on self-sustainable microbial electrolysis cells for electro-biohydrogen production via coupling with carbon-neutral renewable energy technologies.

Microbial electrolysis cell (MEC) technology is a promising bioelectrochemical hydrogen production technology that utilizes anodic bio-catalytic oxidation and cathodic reduction processes. MECs require a lower external energy input than water electrolysis; however, as they also require the application of external power sources, this inevitably renders MEC systems a less sustainable option. This issue is the main obstacle hindering the practical application of MECs. Therefore, this review aims to introduce a self-sustainable MEC technology by combining conventional MECs with advanced carbon-neutral technologies, such as solar-, microbial-, osmotic-, and thermoelectric-powers (and their combinations). Moreover, new approaches to overcome the thermodynamic barriers and attain self-sustaining MECs are discussed in detail, thereby providing a working principle, current challenges, and future perspective in the field. This review provides comprehensive insights into reliable hydrogen production as well as the latest trends towards self-sustainable MECs for practical application.

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.

MXene Materials for Designing Advanced Separation Membranes.

MXenes are emerging rapidly as a new family of multifunctional nanomaterials with prospective applications rivaling that of graphenes. Herein, a timely account of the design and performance evaluation of MXene-based membranes is provided. First, the preparation and physicochemical characteristics of MXenes are outlined, with a focus on exfoliation, dispersion stability, and processability, which are crucial factors for membrane fabrication. Then, different formats of MXene-based membranes in the literature are introduced, comprising pristine or intercalated nanolaminates and polymer-based nanocomposites. Next, the major membrane processes so far pursued by MXenes are evaluated, covering gas separation, wastewater treatment, desalination, and organic solvent purification. The potential utility of MXenes in phase inversion and interfacial polymerization, as well as layer-by-layer assembly for the preparation of nanocomposite membranes, is also critically discussed. Looking forward, exploiting the high electrical conductivity and catalytic activity of certain MXenes is put into perspective for niche applications that are not easily achievable by other nanomaterials. Furthermore, the benefits of simulation/modeling approaches for designing MXene-based membranes are exemplified. Overall, critical insights are provided for materials science and membrane communities to navigate better while exploring the potential of MXenes for developing advanced separation membranes.

Evaluation of hydrogen production and internal resistance in forward osmosis membrane integrated microbial electrolysis cells.

In order to enhance hydrogen production by facilitated proton transport through a forward osmosis (FO) membrane, the FO membrane was integrated into microbial electrolysis cells (MECs). An improved hydrogen production rate was obtained in the FO-MEC (12.5±1.84×10(-3)m(3)H2/m(3)/d) compared to that of the cation exchange membrane (CEM) - MEC (4.42±0.04×10(-3)m(3)H2/m(3)/d) during batch tests (72h). After an internal resistance analysis, it was confirmed that the enhanced hydrogen production in FO-MEC was attributed to the smaller charge transfer resistance than in the CEM-MEC (90.3Ω and 133.4Ω respectively). The calculation of partial internal resistance concluded that the transport resistance can be substantially reduced by replacing a CEM with a FO membrane; decrease of the resistance from 0.069Ωm(2) to 5.99×10(-4)Ωm(2).

Effect of initial salt concentrations on cell performance and distribution of internal resistance in microbial desalination cells.

Microbial desalination cells (MDCs) are modified microbial fuel cells (MFCs) that concurrently produce electricity and desalinate seawater, but adding a desalination compartment and an ion-exchange membrane may increase the internal resistance (Ri), which can limit the cell performance. However, the effects of a desalination chamber and initial NaCl concentrations on the internal resistances and the cell performances (i.e. Coulombic efficiency (CE), current and power density) of MDCs have yet to be thoroughly explored; thus, the cell performance and Ri distributions of MDCs having different initial concentrations and an MFC having no desalination chamber were compared. In the MDCs, the current and power density generation increased from 2.82 mA and 158.2 mW/m2 to 3.17 mA and 204.5 mW/m2 when the initial NaCl concentrations were increased from 5 to 30 g/L, as a consequence of the internal resistances decreasing from 2432.0 to 2328.4 Ω. And even though the MFC has a lower Ri than the MDCs, lower cell performances (current: 2.59 mA; power density: 141.6 mW/m2 and CE: 62.1%) were observed; there was no effect of improved junction potential in the MFC. Thus, in the MDCs, the higher internal resistances due to the addition of a desalination compartment can be offset by reducing the electrolyte resistance and improving the junction potential at higher NaCl concentrations.

Polydopamine coating effects on ultrafiltration membrane to enhance power density and mitigate biofouling of ultrafiltration microbial fuel cells (UF-MFCs).

Membrane resistance is due to the low accessibility of liquid electrolytes onto the membrane surface; resultant membrane biofouling lowers the power generation capacity of microbial fuel cells (MFCs). In this study, in order to reduce membrane resistance caused by migrative ion transport resistance and membrane biofouling, a polydopamine (PD) coating was adopted for the modification of ultrafiltration (UF) membrane surfaces in UF membrane integrated MFCs (UF-MFCs). After a PD coating was applied to a UF membrane, the contact angle measured on the support layer of a UF membrane decreased and the membrane surface charge became negative. The maximum power density of UF-MFC increased after the PD coating on a UF membrane and a remarkable reduction of charge transfer resistance was observed using electrochemical impedance spectroscopy (EIS) analysis. Lower extracellular polymeric substance (EPS) concentrations and total cell numbers were observed on the PD coated UF membrane surface after 72 h operation, although 17% of a permeate flux of UF-MFC decreased after PD coating.