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At least 505 records · Page 28

Polybenzimidazole (PBI) membranes for redox flow batteries

Disclosed are redox flow battery membranes, redox flow batteries incorporating the membranes, and methods of forming the membranes. The membranes include a polybenzimidazole gel membrane that is capable of incorporating a high liquid content without loss of structure that is formed according to a process that includes in situ hydrolysis of a polyphosphoric acid solvent. The membranes are imbibed with a redox flow battery supporting electrolyte such as sulfuric acid and can operate at very high ionic conductivities of about 100 mS/cm or greater. Redox flow batteries incorporating the PBI-based membranes can operate at high current densities of about 100 mA/cm 2 or greater.

Benicewicz, Brian C.↗

Membranes in Solar-Driven Evaporation: Design Principles and Applications

In this study, solar-driven evaporation process brings exciting opportunities to recover clean water and resources in a sustainable way from diverse sources like seawater and wastewater. Separation membranes, as a vital material in many environmental and energy applications, can contribute significantly to this process owing to their structural features. However, the unique roles of membranes in solar evaporator construction and process design are seldom recognized and not summarized yet from scientific principles and application demands, which forms the motivation of this review. Herein, the roles of membranes in different processes based on solar-driven evaporation are focused and the design principles of membrane materials and devices to meet the requirements of these applications are discussed. Fabrication strategies for photothermal membranes are introduced primarily, followed by a discussion on how to design membrane materials, devices, and processes to pursue optimal performance and realize advanced functions accompanied by evaporation. Furthermore, the future of this field is forecast with both challenges and opportunities.

14 SOLAR ENERGY↗

Synergistically combining peracetic acid and reduced graphene oxide membranes to degrade trace organic contaminants

The removal of trace organic contaminants is a critical step for the reuse of municipal and industrial wastewater. Herein, we demonstrate a catalytic membrane platform synergistically integrating reduced graphene oxide (rGO) membranes and peracetic acid (PAA) oxidation, using a dye of methylene blue (MB) and a pesticide of 2,4-dichlorophenoxyacetic acid (2,4-D) as model contaminants. In a crossflow system with rGO membrane and 25 ppm PAA, the degradation rates of MB and 2,4-D were 22 and 0.12 g h −1 per g rGO, with an initial concentration of 10 and 1.1 ppm, respectively. The degradation time profile of MB and 2,4-D follows a pseudo-first-order model, and the degradation rate constant increases with increasing initial PAA doses. Here, the rGO membranes also exhibited good stability over a 1-month test for 2,4-D degradation. In addition to the nanofiltration performance of the rGO membrane, the integrated PAA-rGO membrane process shows great potential to degrade various organic contaminants without the need to separate and recover the metal-free catalyst in downstream treatment.

2,4-D↗

Scaling dynamics in low-salt-rejection reverse osmosis for high-salinity produced water desalination: Mechanistic modeling and membrane autopsy

Membrane scaling remains a critical barrier to the reliable operation of desalination systems, particularly for hypersaline produced water (PW) treatment. This study fills the knowledge gap of autopsy-based model validation for PW desalination by elucidating scaling mechanisms in a Low-Salt-Rejection Reverse Osmosis (LSRRO) system through the integration of pilot-scale experimentation and complementary modeling approaches. A semi-empirical modeling framework was developed and applied to a multistage pilot LSRRO system equipped with nanofiltration and RO membranes treating high-salinity PW from the Permian Basin. Water quality analysis showed that total dissolved solids decreased from ~130,000 mg/L to ~1900 mg/L in the permeate, then further reduced to ~300 mg/L by a second-pass RO. Two different thermodynamic modeling approaches were evaluated: the first extends the LSRRO framework by incorporating system complexity and scaling phenomena, whereas the second method explicitly captures concentration polarization in localized supersaturation. Both methods illustrate the tendency for carbonate and sulfate scaling throughout the stages. Membrane autopsies revealed a silica-dominated deposit matrix, localized CaSO 4 at Stage 2, and minor barite/celestite despite their prominence in model predictions. Quantum-chemical calculations indicated silica scaling can be rationalized by favorable adsorption of H 4 SiO 4 on Fe-oxide surfaces (ΔG ≈ −44 kJ/mol), providing a kinetic pathway for interfacial inorganic polymerization even when bulk equilibrium predictions are conservative. Overall, the thermodynamic scaling modeling and membrane autopsy revealed heterogeneous, localized deposits with limited impact on LSRRO performance, while quantum analysis rationalized the thermodynamically unfavorable precipitation formation under bulk equilibrium, reconciling model–autopsy discrepancies. These insights support targeted pretreatment and silica-specific antiscalants to extend membrane lifetime and increase recovery, providing a transferable framework for hypersaline water desalination systems. The combined experimental–computational approach provides new mechanistic insight into scaling in hypersaline membrane systems and establishes a transferable framework for predicting and mitigating scaling in next-generation desalination technologies.

Low-salt-rejection reverse osmosis↗

Deposition of an ultrathin palladium (Pd) coating on SAPO-34 membranes for enhanced H 2 /N 2 separation

Hydrogen energy has attracted great attention due to its properties of high energy transferring efficiency and zero pollution emission. Zeolite membranes are promising candidates for H 2 separation because of their uniform, molecular-sized pores and high thermal and mechanical stabilities. However, thicker membranes or modification treatments are often necessary to eliminate the defects formed during synthesis and post calcination, leading to low gas permeance. In this paper, we reported the deposition of an ultrathin palladium (Pd) coating on SAPO-34 membranes to improve H 2 separation performance. H 2 /N 2 selectivity was greatly increased by deposition of an ultrathin Pd coating on SAPO-34 membranes, while maintaining similar H 2 permeance. This might be attributed to the dissociative adsorption and associative desorption of H 2 on Pd, as well as fast diffusion of H 2 through ultrathin Pd coating. We also noticed that excessive Pd deposition would lead to the formation of cracks on SAPO-34 membranes, leading to deteriorated membrane performance.

08 HYDROGEN↗

Understanding the impact of SPMAK and PEGPEA in crosslinked PEGDA membranes: Methanol-carboxylate co-transport behavior and correlating structure-physicochemical-transport properties

Investigating multicomponent transport in dense, hydrated polymer membranes is necessary in applications such as fuel cells, electrolyzers, and desalination systems. Of particular interest are photoelectrochemical CO 2 reduction cells (PEC-CRC) which produce liquid products such as alcohols (methanol) and carboxylates (formate, acetate). Flux coupling and competitive sorption behavior of these products (solutes) have been found to affect permselectivity, thereby motivating us to investigate fundamental membrane structure-physicochemical-transport relationships. Past research has shown that systematic tuning of crosslinked cation exchange membranes (CEMs) with charge-neutral monoacrylate monomers containing alkyl and phenyl groups (i.e., poly(ethylene glycol) methacrylate (PEGMA), and poly(ethylene glycol) phenyl ether acrylate (PEGPEA)) can suppress acetate transport (permeability) in co-permeation with methanol. To further investigate this transport behavior and to enhance membrane ionic conductivities, 3-sulfopropyl methacrylate potassium (SPMAK), a sulfonated monoacrylate monomer is incorporated here. SPMAK content is varied with neutral PEGPEA and diacrylate crosslinker, poly (ethylene glycol) diacrylate (PEGDA) of two different chain lengths (n = 10 and 13) to prepare membranes of various compositions. Electrochemical and physicochemical properties including ionic conductivity, ion exchange capacity, and water uptake increase with increasing charged SPMAK content. Different states of water within hydrated membranes are probed using differential scanning calorimetry (DSC), where increasing intermediate (loosely bound) water is observed with increasing hydrophilic SPMAK content. The transport behavior of methanol and carboxylates (formate, acetate, propionate) are investigated, where permeabilities vary as methanol > formate > acetate ≈ propionate. Interestingly, permeabilities decrease with increasing PEGPEA content and are more dependent on solute diffusion than sorption. Permeabilities and diffusivities decrease while permselectivities increase with decreasing PEGDA chain length.

25 ENERGY STORAGE↗

Surface Functional Groups Affect Iron (Hydr)oxide Heterogeneous Nucleation: Implications for Membrane Scaling

Because of its favorable thermodynamics and fast kinetics, heterogeneous solid nucleation on membranes triggers early-stage mineral scaling. Iron (hydr)oxide, a typical membrane scale, initially forms as nanoparticles that interact with surface functional groups on membranes, but these nanoscale phenomena are difficult to observe in real time. In this study, we utilized in situ grazing incidence small angle X-ray scattering and ex situ atomic force microscopy to examine the heterogeneous nucleation of iron (hydr)oxide on surface functional groups commonly used in membranes, including hydroxyl (OH), carboxyl (COOH), and fluoro (F) groups. We found that, compared to nucleation on hydrophilic OH- and COOH-surfaces, the high hydrophobicity of an F-modified surface significantly reduced the extents of both heterogeneously and homogeneously formed iron (hydr)oxide nucleation. Moreover, on the OH-surface, the high functional group density of 0.76 nmol/cm 2 caused faster heterogeneous nucleation than that on a COOH-surface, with a density of 0.28 ± 0.04 nmol/cm 2 . The F-surface also had the highest heterogeneous nucleation energy barrier (26 ± 0.6 kJ/mol), followed by COOH- (23 ±0.8 kJ/mol) and OH- (20 ± 0.9 kJ/mol) surfaces. The kinetic and thermodynamic information provided here will help us better predict the rates and extents of early-stage scaling of iron (hydr)oxide nanoparticles in membrane processes. Finally, this work provides both kinetic and thermodynamic information about iron (hydr)oxide nucleation controlled by membrane-related functional groups (OH, COOH, and F).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polyvinyl Alcohol Anion Exchange Resin Composite Membrane with Co@Cu Core–Shell Particles for Direct Borohydride Fuel Cell Applications

We report a polyvinyl alcohol anion exchange resin composite membrane, functionalized with Co and Cu ions, is reported for use in direct borohydride fuel cells (DBFCs). The CoCu-functionalized membrane has a 30.5% lower fuel permeability than that of a blank membrane. Meanwhile, the cell performance of the DBFC can also be improved by employing the CoCu-functionalized membrane, reaching a maximum power density of 304 mW·cm –2 at 60 °C. High-resolution fluorescence images directly demonstrate the formation of Cu/Co core–shell structure microparticles in the CoCu membrane, which not only reduces the Co content but also increases the active surface area of Co species in CoCu-functionalized membranes, resulting in the improvement of cell performance.

36 MATERIALS SCIENCE↗

Integrated Ion-Exchange Membrane Resin Wafer Assemblies for Aromatic Organic Acid Separations Using Electrodeionization

Aromatic acids, such as p-coumaric acid, are valuable chemical intermediates that are used in the specialty chemical industries because they are precursors to phenylpropanoid compounds. The separation of p-coumaric acid from fermentation broths is a critical step in the biochemical production process and more broadly the circular carbon economy. Electrodeionization (EDI) has been applied toward separations of low-carbon chain acids, but purifying p-coumaric acid has been challenging due to fouling and irreversible binding with ion-exchange membranes and resins. Here, we report a new membrane wafer assembly (MWA) consisting of laminated ion exchange membranes to porous ionomer-binder resin wafers for EDI. The MWAs in an EDI stack showed a 7-fold increase in p-coumaric acid capture while also using 70% less specific energy consumption when benchmarked against state-of-the-art resin wafer EDI modules. The more efficient p-coumaric acid recovery was ascribed to (i) the 38% reduction in interfacial transport resistance between the membrane and resin wafer and (ii) using imidazolium anion exchange membranes and ionomer binders in the MWA. MD simulations revealed enhanced transport rates for p-coumarate in imidazolium ionomers through π–π interactions. As a result, adopting the new MWA significantly reduced the amount of ion-exchange membranes in EDI and may lead to drastic capital cost savings.

42 ENGINEERING↗

Fabrication of Polymer Membrane-Suspended Microstructures on Printed Circuit Boards

When microelectromechanical systems are manufactured in high densities, the necessary routing layer structures can become complex and thus expensive if executed in silicon technology. If, additionally, the microstructures are also to be fabricated suspended on membranes, complex thinning processes become necessary to form these often rather fragile membranes. Here, a novel fabrication concept is demonstrated that allows for the fabrication of membrane-suspended microstructures using standard microfabrication techniques directly integrated with printed circuit boards (PCB) by laminating polyimide (PI) films over cavities in the PCB. This results in cost-effective routing layer fabrication and direct compatibility with common electronic component standards such as SMT (surface-mount technology) and THT (through-hole technology). To illustrate the capabilities of the fabrication process, we fabricated an array of membrane suspended microheaters. Individual platinum microheater elements are suspended on PI membranes that are 25 μm thick and 500 μm in diameter. The fabricated PCB carries a 10x10 array of suspended microheaters on an area of 26,mm x 26,mm. Here, the characterization of the microheater array shows that a yield of 86% functional microheaters was achieved. An individual microheater shows an almost linear heating characteristic at least up to 200°C demonstrating the viability of the technique for creating functional membrane-suspended microstructures on a PCB. [2021-0226]

47 OTHER INSTRUMENTATION↗

Advanced PEM Electrolyzer Membrane for Hydrogen Crossover Mitigation

An unintended reaction in the electrochemical conversion of water to hydrogen in proton exchange membrane (PEM) electrolyzers is the crossover of hydrogen from the anode to the oxygen-containing cathode through the membrane, creating hydrogen losses and safety concerns. Efforts to date have focused on embedding platinum catalysts in perfluorosulfonic (PFSA) membranes to convert H 2 to protons. The objective of this project is to design and develop hydrocarbon (HC) proton exchange membranes (PEMs) that can help overcome the risk of high H 2 crossover in current PEM electrolyzer (ELX) stacks by designing and optimizing the gas recombination catalyst (GRC) within the membrane and membrane electrode assembly (MEA) structure.

08 HYDROGEN↗

Membrane Profiling by Free Flow Electrophoresis and SWATH-MS to Characterize Subcellular Compartment Proteomes in Mesembryanthemum crystallinum

The study of subcellular membrane structure and function facilitates investigations into how biological processes are divided within the cell. However, work in this area has been hampered by the limited techniques available to fractionate the different membranes. Free Flow Electrophoresis (FFE) allows for the fractionation of membranes based on their different surface charges, a property made up primarily of their varied lipid and protein compositions. In this study, high-resolution plant membrane fractionation by FFE, combined with mass spectrometry-based proteomics, allowed the simultaneous profiling of multiple cellular membranes from the leaf tissue of the plant Mesembryanthemum crystallinum. Comparisons of the fractionated membranes’ protein profile to that of known markers for specific cellular compartments sheds light on the functions of proteins, as well as provides new evidence for multiple subcellular localization of several proteins, including those involved in lipid metabolism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial Strong Coupling and Negative Dispersion of Propagating Polaritons in Freestanding Oxide Membranes

Membranes of complex oxides like perovskite SrTiO3 extend the multi-functional promise of oxide electronics into the nanoscale regime of 2D materials. Here, it is demonstrated that freestanding oxide membranes supply a reconfigurable platform for nano-photonics based on propagating surface phonon polaritons. Infrared near-field imaging and spectroscopy enabled by a tunable ultrafast laser are applied to study pristine nano-thick SrTiO3 membranes prepared by hybrid molecular beam epitaxy. As predicted by coupled mode theory, it is found that strong coupling of interfacial polaritons realizes symmetric and antisymmetric hybridized modes with simultaneously tunable negative and positive group velocities. By resolving reflection of these propagating modes from membrane edges, defects, and substrate structures, their dispersion is quantified with position-resolved nano-spectroscopy. Remarkably, polariton negative dispersion is found to be both robust and tunable through choice of membrane dielectric environment and thickness, and proposes a novel design for in-plane Veselago lensing harnessing this control. This work lays the foundation for tunable transformation optics at the nanoscale using polaritons in a wide range of freestanding complex oxide membranes.

freestanding oxide membranes↗

Heterogeneous Integration of Freestanding Bilayer Oxide Membrane for Multiferroicity

Transition metal oxides exhibit a plethora of electrical and magnetic properties described by their order parameters. In particular, ferroic orderings offer access to a rich spectrum of fundamental physics phenomena, in addition to a range of technological applications. The heterogeneous integration of ferroelectric and ferromagnetic materials is a fruitful way to design multiferroic oxides. The realization of freestanding heterogeneous membranes of multiferroic oxides is highly desirable. In this study, epitaxial BaTiO 3 /La 0.7 Sr 0.3 MnO 3 freestanding bilayer membranes are fabricated using pulsed laser epitaxy. The membrane displays ferroelectricity and ferromagnetism above room temperature accompanying the finite magnetoelectric coupling constant. Further, this study reveals that a freestanding heterostructure can be used to manipulate the structural and emergent properties of the membrane. In the absence of the strain caused by the substrate, the change in orbital occupancy of the magnetic layer leads to the reorientation of the magnetic easy-axis, that is, perpendicular magnetic anisotropy. These results of designing multiferroic oxide membranes open new avenues to integrate such flexible membranes for electronic applications.

36 MATERIALS SCIENCE↗

Design and operational considerations of catalytic membrane reactors for ammonia synthesis

Production of ammonia using hydrogen derived from renewable electricity instead of hydrocarbon reforming would dramatically reduce the carbon footprint of this commodity chemical. Novel technologies such as catalytic membrane reactors may potentially be more compatible with distributed ammonia production than the conventional Haber-Bosch process. Here, a reactor model is developed based on integrating a standard industrial iron catalyst into a catalytic membrane reactor (CMR) equipped with an inorganic membrane that is selective to NH 3 over N 2 /H 2 . CMR performance is studied as functions of wide ranges of membrane properties and operating conditions. Conversion and ammonia recovery are dictated principally by the ammonia permeance, and the benefits by using membranes become significant above 100 GPU = 3.4 × 10 –8 mol m –2 s –1 Pa –1 . To be effective, the CMR requires a minimum selectivity for ammonia of 10 over both nitrogen and hydrogen, and purity scales with the effective selectivity. Increasing the pressure of operation significantly improves all metrics, and at P = 30 bar with a quality membrane ammonia is almost completely recovered, enabling direct recycle of un-reacted hydrogen and nitrogen without need for recompression. Temperature drives conversion and scales monotonically without thermodynamic limitations in a CMR. Alternatively, the temperature may be reduced as low as 300°C while achieving conversion levels surpassing equilibrium limits at T = 400°C in a conventional reactor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-throughput cell-free screening of eukaryotic membrane protein expression in lipidic mimetics

Membrane proteins play essential roles in cellular function and metabolism. Nonetheless, biophysical and structural studies of membrane proteins are impeded by the difficulty of their expression in and purification from heterologous cell-based systems. As an alternative to these cell-based systems, cell-free protein synthesis has proven to be an exquisite method for screening membrane protein targets in a variety of lipidic mimetics. Here we report a high-throughput screening workflow and applied it to screen 61eukaryotic membrane protein targets. For each target, we tested its expression in lipidic mimetics: two detergents, two liposomes, and two nanodiscs. We show that 35 membrane proteins (57%) can be expressed in a soluble fraction in at least one of the mimetics with the two detergents performing significantly better than nanodiscs and liposomes, in that order. Using the established cell-free workflow, we studied the production and biophysical assays for mitochondrial pyruvate carrier (MPC) complexes. Our studies show that the complexes produced in cell-free are functional competent in complex formation and substrate binding. Our results highlight the utility of using cell-free systems for screening and production of eukaryotic membrane proteins.

59 BASIC BIOLOGICAL SCIENCES↗

Scalable Graphene Oxide Hollow Fiber Membranes for Dye Desalination Enabled by Multi‐Purpose Polyamine Functionalization

2D nanosheets such as graphene oxide (GO) can be stacked to construct membranes with fine-tuned nanochannels to achieve molecular sieving ability. These membranes are often thin to achieve high water permeance, but their fabrication with consistent nanostructures on a large scale presents an enormous challenge. Herein, GO-based hollow fiber membranes (HFMs) are developed for dye desalination by synergistically combining chemical etching to form in-plane nanopores (10–30 nm) to increase water permeance and polyamine functionalization to improve underwater stability and enable facile large-scale production using existing membrane manufacturing processes. HFM modules with areas of 88 cm 2 and GO layer thicknesses of ≈500 nm are fabricated, and they exhibited a stable dye water permeance of 75 L m −2 h −1 bar −1 , rejection of >99.5% for Direct red and Congo red, and Na 2 SO 4 /dye separation factor of 300–500, superior to state-of-the-art commercial membranes. Furthermore, the versatility of this approach is also demonstrated using different short polyamines and porous substrates. This study reveals a scalable way of designing 2D materials into high-performance robust membranes for practical applications.

amine functionalization↗

Scalable thin graphene oxide membranes enabled by polydopamine gutter layer

Two-dimensional (2D) nanosheets have been widely used to fabricate thin-film composite membranes for dye desalination. However, they often need to be thick to mitigate the defects resulting from their random stacking and rough support surface. Herein, bio-adhesive polydopamine (PDA) is used as a gutter layer to prepare graphene oxide (GO)-based membranes by improving the adhesion between the GO and porous support and providing a smooth surface to form thin, highly selective layers. For example, the PDA priming reduces the GO layer thickness by 57 %, from 447 to 190 nm, while achieving similar dye desalination properties. The effect of the dopamine concentration, exposure time, and GO layer thickness on the membrane structure and desalination performance are thoroughly investigated using various techniques, such as scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), and x-ray diffraction (XRD). The PDA gutter layer is also applied for hollow fiber membranes, achieving water permeance of 79 L m -2 h −1 bar−1 and rejection of ∼99 % for Direct red 80. The membranes were challenged by simulated dye/salt mixtures to elucidate the complicated effect of the compositions on the desalination performance. Furthermore, this study unveils a new avenue to improve separation performance and large-scale manufacturability of 2D material-based membranes.

Dye desalination↗