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At least 1,171 records · Page 65

Proton Selective Nanoporous Atomically Thin Graphene Membranes for Vanadium Redox Flow Batteries

Angstrom-scale proton-selective pores in atomically thin 2D materials present fundamentally new opportunities for advancing proton exchange membranes (PEMs). Vanadium Redox Flow Batteries (VRFBs) for grid-scale energy storage require PEMs with high areal proton conductance (>1 S cm −2 ) and minimal vanadium ion (VO 2+ ) crossover. However, state-of-the-art Nafion 212 membranes (N212 ≈50 µm thick), suffer from persistent VO 2+ crossover reducing performance and efficiency. Here, a layered PEM is demonstrated, comprising monolayer CVD graphene with Angstrom-scale proton-selective pores introduced via Ar plasma, integrated with an ultra-thin ≈300 nm polybenzimidazole (PBI) layer and sandwiched between two Nafion 211 (25 µm thick) layers. The layered architecture facilitates scalable membrane fabrication by mitigating defects while processing and facile stacking of graphene layers allows stochastic non-selective defect isolation enabling exceptionally low VO 2+ crossover (selectivity (H + areal conductance / VO 2+ permeability) ≈6709 × 10 6 S min cm −4 ), with proton conductance >8 S cm −2 . Systematic transport experiments supported by resistance-based transport modelling elucidate the role of defect size, defect isolation, and sealing, as well as layering/stacking, to enable orders of magnitude (>671× over N212) improvements in selectivity, along with areal proton conductance >8 S cm −2 . This work highlights the potential of atomic-scale proton-selective defect engineering in 2D materials, in conjunction with facile stacking and layering of materials as strategies for scalable, high-performance advances in PEMs for energy, electrochemical, and separation applications beyond VRFBs.

Chaturvedi, Pavan [Vanderbilt Univ., Nashville, TN↗

CO 2 in Ionene–Ionic Liquid Composite Membranes

Abstract Ionene – ionic liquid (IL) composites are promising materials for CO 2 separation, yet a molecular‐level understanding of their structure and its impact on CO 2 speciation, solubility, rotation, and diffusivity remains unclear. Herein, using multimodal nuclear magnetic resonance (NMR), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS), atomic force microscopy (AFM), and molecular dynamics (MD) simulations, we reveal that the composites contain IL‐rich domains extending across hundreds of nanometres within the ionene matrix, and these bicontinuous domains span the entire membrane depth. CO 2 also absorbs into the ionene matrix, with the distribution between two CO 2 species varying with temperature and time. The rotational correlation times of these two species are on the timescale of 0.1 and 1 ns, respectively. As IL content increases, the ionic domains expand, resulting in higher CO 2 solubility due to enhanced molecular dynamics and increased free volume in both ionene backbones and IL‐rich regions. Although CO 2 diffusion in the membranes is an order of magnitude slower than in bulk IL, the activation energy for CO 2 diffusion remains comparable. Ionene‐IL composites represent a promising platform for designing CO 2 separation membranes, offering enhanced CO 2 diffusion and selectivity through IL‐rich domains, and increased CO 2 solubility and mechanical integrity from the ionene matrix.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Self‐Consistent Model for Sorption and Transport in Polyimide‐Derived Carbon Molecular Sieve Gas Separation Membranes

Abstract Demand for energy‐efficient gas separations exists across many industrial processes, and membranes can aid in meeting this demand. Carbon molecular sieve (CMS) membranes show exceptional separation performance and scalable processing attributes attractive for important, similar‐sized gas pairs. Herein, we outline a mathematical and physical framework to understand these attributes. This framework shares features with dual‐mode transport theory for glassy polymers; however, physical connections to CMS model parameters differ from glassy polymer cases. We present evidence in CMS membranes for a large volume fraction of microporous domains characterized by Langmuir sorption in local equilibrium with a minority continuous phase described by Henry's law sorption. Using this framework, expressions are provided to relate measurable parameters for sorption and transport in CMS materials. We also outline a mechanism for formation of these environments and suggest future model refinements.

Sanyal, Oishi↗

Above‐T g Annealing Benefits in Nanoparticle‐Stabilized Carbon Molecular Sieve Membrane Pyrolysis for Improved Gas Separation

Abstract Nanoparticles can suppress asymmetric precursor support collapse during pyrolysis to create carbon molecular sieve (CMS) membranes. This advance allows elimination of standard sol‐gel support stabilization steps. Here we report a simple but surprisingly important thermal soaking step at 400 °C in the pyrolysis process to obtain high performance CMS membranes. The composite CMS membranes show CO 2 /CH 4 (50 : 50) mixed gas feed with an attractive CO 2 /CH 4 selectivity of 134.2 and CO 2 permeance of 71 GPU at 35 °C. Furthermore, a H 2 /CH 4 selectivity of 663 with H 2 permeance of 240 GPU was achieved for promising green energy resource‐H 2 separation processes.

Cao, Yuhe↗

Janus Superiority of Membranes in Chemical Engineering and Beyond

Janus configurations, characterized by their inherent asymmetry, enable directional mass transfer in membrane materials that drive novel and energy-efficient chemical processes. This Janus superiority spans applications from nanoscale molecular and ionic transport to macro-scale separation systems with asymmetric spatial architectures. This review provides an analysis of the material foundations including design principles, structure regulation, and scalability challenges underlying Janus membranes. Here, we explore the physics that governs their unique behavior and examine their diverse applications across chemical engineering, including phase transfer, and molecular or ionic transport. Through a multiscale perspective, we provide a comprehensive understanding of the impact of Janus superiority in advancing chemical engineering technologies. Finally, we discuss the hurdles in translating theoretical advances into practical applications and propose promising avenues for future research to harness the full potential of Janus membranes and systems in addressing global challenges related to energy, sustainability, and beyond.

Yang, Hao‐Cheng [Zhejiang University, Hangzhou (Ch↗

Application of Poly(ether sulfone)‐Based Membranes in Clean Energy Technology

Abstract Poly(ether sulfone) (PES) is a kind of polymer materials with excellent electrical insulation and acid/alkali stability. PES can be operated at high temperature continuously for a long time and still maintain excellent property stability in the environments with rapidly changed temperature, namely, great thermostability. Moreover, PES has low molding shrinkage, good dimensional stability and excellent film‐forming characteristics. Compared with inorganic membranes, PES‐based membranes have lower cost, which have received more attention and wide recognition in the field of clean energy technologies in recent years, such as flow batteries, fuel cells, water treatment, and gas separation. Therefore, this review summarizes the research status and prospect of the utilization of PES‐based membranes in clean energy fields, in order to further promote their development and application.

Chemistry↗

Two‐Membrane Dual Non‐Aqueous/Aqueous Electrolyte Flow Cell Operation for Electrochemical Conversion of CO 2 to Methyl Formate

Recently, tandem cathodic reactions have been demonstrated in non-aqueous solvents to couple CO 2 reduction to a secondary reaction to create novel species that are not produced in aqueous CO 2 electrolysis. One reaction that can be performed with high selectivity and durability is the electrochemical conversion of CO 2 to formic acid and in-situ esterification with methanol to produce methyl formate. However, the translation to a high-performance flow electrolyzer is far from trivial, as the non-aqueous catholyte leads to reactor challenges including flooding the gas diffusion electrode. Here, in this study, a two-membrane flow electrolyzer with both anion and cation exchange membranes was used with flowing methanol catholyte and aqueous anolyte. This design prevented methanol from flooding the cathode, which was a pervasive limiting issue for electrolyzers with a single membrane. Methyl formate production at 42.9 % faradaic efficiency was achieved with pure methanol in a flow electrolyzer with stable performance beyond 80 min. However, low-water-content catholyte compositions also led to increased cell resistance and lower operating current densities. Thus, with the present ionomer materials there is a tradeoff between methyl formate selectivity and current density depending on water concentration, highlighting a need for new ionomers tailored for desirable non-aqueous solvents such as methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mitocans induce lipid flip-flop and permeabilize the membrane to signal apoptosis

Pancratistatin (PST) and narciclasine (NRC) are natural therapeutic agents that exhibit specificity toward the mitochondria of cancerous cells and initiate apoptosis. Unlike traditional cancer therapeutic agents, PST and NRC are effective, targeted, and have limited adverse effects on neighboring healthy, noncancerous cells. Currently, the mechanistic pathway of action for PST and NRC remains elusive, which in part inhibits PST and NRC from becoming efficacious therapeutic alternatives. Herein, we use neutron and x-ray scattering in combination with calcein leakage assays to characterize the effects of PST, NRC, and tamoxifen (TAM) on a biomimetic model membrane. We report an increase in lipid flip-flop half-times (t 1/2 ) (≈12.0%, ≈35.1%, and a decrease of ≈45.7%) with 2 mol percent PST, NRC, and TAM respectively. An increase in bilayer thickness (≈6.3%, ≈7.8%, and ≈7.8%) with 2 mol percent PST, NRC, and TAM, respectively, was also observed. Lastly, increases in membrane leakage (≈31.7%, ≈37.0%, and ≈34.4%) with 2 mol percent PST, NRC, and TAM, respectively, were seen. Considering the maintenance of an asymmetric lipid composition across the outer mitochondrial membrane (OMM) is crucial to eukaryotic cellular homeostasis and survival, our results suggest PST and NRC may play a role in disrupting the native distribution of lipids within the OMM. A possible mechanism of action for PST- and NRC-induced mitochondrial apoptosis is proposed via the redistribution of the native OMM lipid organization and through OMM permeabilization.

59 BASIC BIOLOGICAL SCIENCES↗

Durability of PGM catalyst MEAs of polymer electrolyte membrane fuel cells for heavy-duty vehicles

Polymer electrolyte membrane fuel cells (PEMFCs) are promising power sources for heavy-duty vehicles (HDVs) owing to cleanliness and efficiency. However, the degradation of membrane electrode assemblies (MEAs) under HDV conditions remains a huge challenge. Here, this work investigated MEA durability under HDV conditions using a US Department of Energy standard accelerated stress test for 180,000 cycles (equivalent to 1 million miles of HDV operation). Effects of catalyst Pt content on MEA durability were examined using homemade 30% Pt/C (H-Pt/C) and commercial 46% Pt/C (C-Pt/C) catalysts. Both MEAs experienced H 2 /air and H 2 /O 2 performance loss over cycles. Analysis with scanning transmission electron microscopy, X-ray diffraction, inductively coupled plasma mass spectrometry, and mercury intrusion porosimetry revealed severe degradation of Pt nanoparticles (NPs), support structures, and the catalyst layer. Two degradation stages for NPs were proposed: Ostwald ripening dominated the initial 60,000 cycles, followed by combined Ostwald ripening and particle migration. Measurements with ion chromatography, high-frequency resistance, and oxygen-diffusion resistance revealed degradation of membrane and ionomer, respectively.

25 ENERGY STORAGE↗

Sequential membrane- and protein-bound organelles compartmentalize genomes during phage infection

Many eukaryotic viruses require membrane-bound compartments for replication, but no such organelles are known to be formed by prokaryotic viruses. Bacteriophages of the Chimalliviridae family sequester their genomes within a phage-generated organelle, the phage nucleus, which is enclosed by a lattice of the viral protein ChmA. We show that inhibiting phage nucleus formation arrests infections at an early stage in which the injected phage genome is enclosed within a membrane-bound early phage infection (EPI) vesicle. Early phage genes are expressed from the EPI vesicle, demonstrating its functionality as a prokaryotic, transcriptionally active, membrane-bound organelle. We also show that the phage nucleus is essential, with genome replication beginning after the injected DNA is transferred from the EPI vesicle to the phage nucleus. Our results show that Chimalliviridae require two sophisticated subcellular compartments of distinct compositions and functions that facilitate successive stages of the viral life cycle.

59 BASIC BIOLOGICAL SCIENCES↗

BefA, a microbiota-secreted membrane disrupter, disseminates to the pancreas and increases β cell mass

Microbiome dysbiosis is a feature of diabetes, but how microbial products influence insulin production is poorly understood. Here, we report the mechanism of BefA, a microbiome-derived protein that increases proliferation of insulin-producing β cells during development in gnotobiotic zebrafish and mice. BefA disseminates systemically by multiple anatomic routes to act directly on pancreatic islets. We detail BefA’s atomic structure, containing a lipid-binding SYLF domain, and demonstrate that it permeabilizes synthetic liposomes and bacterial membranes. A BefA mutant impaired in membrane disruption fails to expand β cells, whereas the pore-forming host defense protein, Reg3, stimulates β cell proliferation. Our work demonstrates that membrane permeabilization by microbiome-derived and host defense proteins is necessary and sufficient for β cell expansion during pancreas development, potentially connecting microbiome composition with diabetes risk.

59 BASIC BIOLOGICAL SCIENCES↗

Mathematical modeling of novel porous transport layer architectures for proton exchange membrane electrolysis cells

Thin foil based porous transport layers (PTLs) that contain highly structured pore arrays have shown promise as anode PTLs in proton exchange membrane electrolysis cells. These novel PTLs, fabricated with advanced manufacturing techniques, produce thin, tunable, multifunctional layers with reduced flow and interfacial resistances and high thermal and electric conductivities. To further optimize their design, it is important to understand their fundamental impact on the transport of protons, electrons, and liquid/vapor mixtures in the electrode. In this work, we develop a two-dimensional multiphysics model to simulate the coupled electrochemistry and multiphase transport in an electrolysis cell operated with the novel PTL architecture. The results show that larger pores improve access of water to the anode catalyst layer, which is beneficial for both the oxygen evolution reaction and membrane hydration. Larger pore sizes also improve oxygen gas transport from the catalyst layer, because generated oxygen gas is forced to travel in-plane through the anode catalyst layer until it reaches a pore opening that is connected to a channel. The discussed results confirm that the proposed thin foil based PTLs are fundamentally different from conventional PTLs, such as felts or layered meshes. The model developed in this work also provides generalizable insight into fundamental PEMEC phenomena, such as the competition between liquid and gas phase transport, membrane hydration and water management, and nonuniform electrochemical reactions, which are processes relevant to all PEMEC designs.

25 ENERGY STORAGE↗

High-performance SO 2 -depolarized electrolysis cell using advanced polymer electrolyte membranes

Three different proton conducting polymeric membrane materials (Nafion® 115, Nafion® 212, and sulfonated Diels-Alder polyphenylene [SDAPP]) were evaluated for use in SO 2 -depolarized electrolyzers for the production of hydrogen via the hybrid sulfur cycle. Their performance was measured using different water feed strategies to minimize overpotential losses while maintaining high product acid concentration. Both thin membranes (Nafion® 212 and SDAPP) showed performance superior to that of the thicker Nafion® 115. Here, the SDAPP membrane electrode assembly (MEA) performed well at higher acid concentrations, maintaining low ohmic and kinetic overpotentials. Finally, short-term (100-h) stability tests under constant current conditions showed minimal degradation for the SDAPP and Nafion® 212 MEAs. SDAPP MEA performance approached the targets needed to make the hybrid sulfur cycle a competitive process for hydrogen production (product acid concentration ≥65 wt% H 2 SO 4 at ≤ 0.6-V cell potential and ≥0.5 A-cm –2 current density).

08 HYDROGEN↗

Design and operating principles for high-performing anion exchange membrane water electrolyzers

Anion-exchange-membrane water electrolyzers (AEMWEs) provide a promising pathway to utilize low-carbon renewable electricity to produce clean hydrogen at high efficiency and purity, while maintaining low system costs compared to incumbent technologies. Though significant progress has been made in developing membranes and catalysts, AEMWEs still require better performance and durability to realize widespread deployment. Here, we overcome these challenges by decoupling anode and cathode polarization behavior via integration of a reference electrode in the membrane-electrode assembly. This measurement identified that the mass-transport losses dominate the cathode overpotential if feeding with electrolytes, while kinetic losses dominate the anode overpotential. These losses are mitigated by varying electrode properties and operating strategies, where a more hydrophobic, optimal loaded cathode, a high porosity anode, and operating with the cathode dry exhibited the best performance. These findings eventually enabled achieving a high-performing and durable complete PGM-free AEMWE operating at 1.5 Acm –2 for over 500h with negligible degradation, demonstrating significant progress for AEMWEs.

25 ENERGY STORAGE↗

Enhancing durability of polymer electrolyte membrane using cation size selective agents

Radical species generated during proton exchange membrane fuel cell operation considerably limit the achievable durability, particularly for heavy-duty vehicle applications. A promising solution to the problem is the incorporation of radical scavenger additives such as cerium which mitigates chemical attacks on the membrane. However, these additives migrate during fuel cell operation causing a loss in durability and performance due to detrimental interaction with various components of the fuel cell. Here, we study cation size selective agents as a means to immobilize cerium within perfluorosulfonic acid (PFSA) membranes. We synthesized an organometallic complex of cerium with 15-Crown-5 and investigated the effectiveness of this complex to immobilize cerium. Over 300% increase in cerium retention and an 80% increase in chemical durability were observed owing to the stabilization effect of crown ethers on cerium. Migration under a potential gradient can be eliminated while the complex also contributes to the enhancement in cerium radical scavenging activity. In conclusion, current challenges with the proposed solution are highlighted and future work is discussed.

25 ENERGY STORAGE↗

The impacts of membrane pinholes on PEM water electrolysis

Polymer electrolyte membrane (PEM) water electrolysis is a promising technology to efficiently produce green hydrogen. Irregularities in membrane electrode assembly (MEA) component materials caused by manufacturing, processing, handling, or operation can lead to performance loss and failure. One example is the presence of pinholes in the membrane, which can cause increased gas transport (crossover) and lead to electrical shorting. This work investigates the effects of intentionally introduced pinholes with various sizes up to 350μm in diameter. The presence of the pinholes resulted in minimal impacts on the cell voltage (±30 mV at 4Acm -2 ). However, the pinholes significantly increased H 2 crossover, which decreased hydrogen production efficiency and increased the minimum current density for safe operation. The impacts of the pinhole on the H 2 crossover and efficiency are more severe for open pinhole features than tear-like pinhole features. In conclusion, this research demonstrates that even small pinholes cannot be disregarded from a safety, efficiency, and operating strategy perspective.

08 HYDROGEN↗

Self-regulating behavior of hybrid membrane systems as demonstrated in an element-scale forward osmosis-reverse osmosis hybrid system

Hybrid membrane systems can be difficult to design due to the requisite flow rate matching between up- and downstream unit operations. In this work, we use a forward osmosis-reverse osmosis (FO-RO) hybrid system to demonstrate how some membrane systems can exhibit self-regulating behavior due to osmotic coupling. This can reduce the need for complex control systems for flow balancing. We show this behavior using a module-scale test bed that can mimic the behavior of larger scale operations. The system shows permeate flow rate near-convergence between the FO and RO modules after startup or when perturbed by a change in RO module pressure. The behavior of this hybrid system demonstrates that some membrane operations can exploit osmotic interdependence, rather than expensive control systems, to achieve steady state operation.

Debottlenecking↗

Water and salt transport properties of pentiptycene-containing sulfonated polysulfones for desalination membrane applications

A series of pentiptycene-containing disulfonated polysulfone copolymers (PENT-BP) were synthesized via condensation polymerization. Water and salt transport properties (solubility, diffusivity and permeability) were characterized for acid-form membranes (PENT-BP(H)) and compared with triptycene-based sulfonated polysulfones (TRP-BP(H)) and a non-iptycene-containing 4,4'-biphenol-based series (BPS(H)) of polysulfones to investigate the effect of pentiptycene on membrane performance. At comparable water content, the PENT-BP(H) exhibited increased water and salt permeability due to the additional free volume introduced by the pentiptycene units. Enhanced water/salt permeability selectivity of PENT-BP(H) series was also observed due to a significantly higher diffusivity selectivity. At comparable water permeance (P w D ~ 8 X 10 -6 cm 2 /s), the salt rejection of PENT-BP (H) copolymers obtained from dead-end filtration reached 91–93% at 400 psi, higher than that of a corresponding BPS(H) series. This study suggests that incorporation of iptycene moieties into polymer backbone is an effective strategy to enhance desalination membrane performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗