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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5

Tailoring catalyst layer structures for anion exchange membrane fuel cells by controlling the size of ionomer aggreates in dispersion

The development of anion exchange membranes and ionomers plays a critical role in performance of anion exchange membrane fuel cells. However, the optimal design of catalyst layer structures still remains unexplored despite its significance. Herein, the rational design guide is presented for cathode and anode catalyst layers using m-TPN1 ionomer by controlling the size of ionomer aggregates in dispersion and comparing various catalyst layer structures. The size of m-TPN1 aggregates decreases, creating a more uniform ionomer distribution and a larger triple-phase-boundary. As ionomer distribution of the cathode catalyst layer becomes more uniform, the power density of membrane-electrode-assembly is enhanced. Also, the power density at fully humidified condition strongly correlates with the porosity of anode catalyst layer due to the limitation of hydrogen transport at anode by water flooding.

42 ENGINEERING↗

Structure and dynamics of lipid membranes interacting with antivirulence end-phosphorylated polyethylene glycol block copolymers

The structure and dynamics of lipid membranes in the presence of extracellular macromolecules are critical for cell membrane functions and many pharmaceutical applications. The pathogen virulence-suppressing end-phosphorylated polyethylene glycol (PEG) triblock copolymer (Pi-ABAPEG) markedly changes the interactions with lipid vesicle membranes and prevents PEG-induced vesicle phase separation in contrast to the unphosphorylated copolymer (ABAPEG). Pi-ABAPEG weakly absorbs on the surface of lipid vesicle membranes and slightly changes the structure of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) unilamellar vesicles at 37 °C, as evidenced by small angle neutron scattering. X-ray reflectivity measurements confirm the weak adsorption of Pi-ABAPEG on DMPC monolayer, resulting in a more compact DMPC monolayer structure. Neutron spin-echo results show that the adsorption of Pi-ABAPEG on DMPC vesicle membranes increases the membrane bending modulus $κ$.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improved chemical and isotopic labeling of biomembranes in Bacillus subtilis by leveraging CRISPRi inhibition of beta-ketoacyl-ACP synthase (fabF)

Assessing the structure of living microbial cell membranes is a challenging analytical goal. The cell membrane is defined by its transverse structure, an approximately 5 nm-thick selectively permeable bilayer that serves many important cellular functions. Compositionally complex, dynamic, and organized in both the transverse and lateral dimensions, understanding the cell membrane structure—and the role that structure plays in cellular function, communication, and environmental sensing is an active scientific effort. Previously, we have devised a novel isotopic labeling approach for membrane lipids to enable direct in vivo structural studies of the cell membrane in the Gram-positive bacterium, Bacillus subtilis , using small-angle neutron scattering. This was accomplished through a genetic inhibition of fatty acid (FA) degradation (Δ fadN ) and a chemical inhibition of FA biosynthesis using cerulenin, an irreversible inhibitor of type II fatty acid synthases. Here, we improve upon the previous system by introducing a dCas9/sgRNA- fabF complex that blocks transcription of the essential fabF gene when under xylose induction. This leads to greater sensitivity to cerulenin in the mutant strain (JEBS102) and more robust cell growth when supplementary FAs are introduced to the culture medium. A subtle change in FA uptake is noted when compared to the prior labeling strategy. This is seen in the gas chromatography/mass spectrometry (GC/MS) data as a higher ratio of n 16:0 to a 15:0, and manifests in an apparent increase in the membrane thickness determined via neutron scattering. This represents an improved method of isotopic labeling for the cell membrane of Bacillus subtilis; enabling improved investigations of cellular uptake and utilization of FAs, cell membrane structure and organization as a phenotypic response to metabolic and environmental changes.

59 BASIC BIOLOGICAL SCIENCES↗

Open-top microfluidic devices and methods for simulating a function of a tissue

A device for simulating a function of a tissue includes a first structure, a second structure, and a membrane. The first structure defines a first chamber. The first chamber includes a matrix disposed therein and an opened region. The second structure defines a second chamber. The membrane is located at an interface region between the first chamber and the second chamber. The membrane includes a first side facing toward the first chamber and a second side facing toward the second chamber. The membrane separates the first chamber from the second chamber.

Varone, Antonio↗

Structures of the mycobacterial membrane protein MmpL3 reveal its mechanism of lipid transport

The mycobacterial membrane protein large 3 (MmpL3) transporter is essential and required for shuttling the lipid trehalose monomycolate (TMM), a precursor of mycolic acid (MA)-containing trehalose dimycolate (TDM) and mycolyl arabinogalactan peptidoglycan (mAGP), in Mycobacterium species, including Mycobacterium tuberculosis and Mycobacterium smegmatis. However, the mechanism that MmpL3 uses to facilitate the transport of fatty acids and lipidic elements to the mycobacterial cell wall remains elusive. Here, we report 7 structures of the M. smegmatis MmpL3 transporter in its unbound state and in complex with trehalose 6-decanoate (T6D) or TMM using single-particle cryo-electron microscopy (cryo-EM) and X-ray crystallography. Combined with calculated results from molecular dynamics (MD) and target MD simulations, we reveal a lipid transport mechanism that involves a coupled movement of the periplasmic domain and transmembrane helices of the MmpL3 transporter that facilitates the shuttling of lipids to the mycobacterial cell wall.

60 APPLIED LIFE SCIENCES↗

Creation of Self-Semi-Interpenetrating Network Structures in PIM-1 Membranes for Enhanced Physical Aging Resistance

A series of self-semi-interpenetrating network (ssIPN) thin films based on PIM-1 structure were developed by end-cross-linking telechelic PIM-1 oligomers end-capped with curable carboxylic acid groups to form model networks, which are penetrated by linear high-molecular-weight PIM-1 chains. ssIPN films with systematically varied network content ranging from 10 to 30 wt % were comprehensively examined on their microstructure and gas permeation properties. Fresh PIM-1 ssIPN films exhibited gas separation performances close to those of as-cast linear PIM-1, where the films closely followed the upper bound trade-off line, gaining as much selectivity as they lose gas permeability as the network content increases. This indicates that gas permeability is largely preserved despite cross-linking. Wide-angle X-ray scattering supported this observation, with peaks shifting toward lower d-spacing as oligomer content increased, suggesting tighter chain packing with higher cross-linkable oligomer loading. In physical aging studies over two months, all ssIPN films outperform linear PIM-1 for H 2 /CH 4 and O 2 /N 2 separations. Notably, the PIM-1 ssIPN with 10 wt % network content showed the best physical aging resistance, with negligible permeability loss even after one month. Finally, these findings highlight a promising macromolecular strategy for enhancing the physical aging resistance of microporous polymer membranes for gas separation.

PIM-1↗

Advanced Electrode Structures for Proton Exchange Membrane Fuel Cells: Current Status and Path Forward

Abstract Proton exchange membrane fuel cells (PEMFCs) have demonstrated their viability as a promising candidate for clean energy applications. However, performance of conventional PEMFC electrodes, especially the cathode electrode, suffers from low catalyst utilization and sluggish mass transport due to the randomly distributed components and tortuous transport pathways. Development of alternative architectures in which the electrode structure is controlled across a range of length scales provides a promising path toward overcoming these limitations. Here, we provide a comprehensive review of recent research and development of advanced electrode structures, organized by decreasing length-scale from the millimeter-scale to the nanometer-scale. Specifically, advanced electrode structures are categorized into five unique architectures for specific functions: (1) macro-patterned electrodes for enhanced macro-scale mass transport, (2) micro-patterned electrodes for enhanced micro-scale mass transport, (3) electrospun electrodes with fiber-based morphology for enhanced in-plane proton transport and through-plane O 2 transport, (4) enhanced-porosity electrodes for improved oxygen transport through selective inclusion of void space, and (5) catalyst film electrodes for elimination of carbon corrosion and ionomer poisoning. The PEMFC performance results achieved from each alternative electrode structure are presented and tabulated for comparison with conventional electrode architectures. Moreover, analysis of mechanisms by which new electrode structures can improve performance is presented and discussed. Finally, an overview of current limitations and future research needs is presented to guide the development of electrode structures for next generation PEMFCs. Graphical Abstract Development of improved electrode architectures with the control of structure on length scales ranging from millimeters to nanometers could enable a new generation of fuel cells with increased performance and reduced cost. This paper presents an in-depth review and critical analysis of recent developments and future outlook on the design of advanced electrode structures.

25 ENERGY STORAGE↗

The physical basis for solvent flow in organic solvent nanofiltration

Organic solvent nanofiltration (OSN) is an emerging membrane technology that could revolutionize chemical separations in numerous vital industries. Despite its significance, there remains a lack of fundamental understanding of solvent transport mechanisms in OSN membranes. Here, we use an extended Flory-Rehner theory, nonequilibrium molecular dynamic simulations, and organic solvent transport experiments to demonstrate that solvent flow in OSN membranes is driven by a pressure gradient. We show that solvent molecules migrate as clusters through interconnected pathways within the membrane pore structure, challenging the widely accepted diffusion-based view of solvent transport in OSN. We further reveal that solvent permeance is dependent on solvent affinity to the OSN membrane, which, in turn, controls the membrane pore structure. Our fundamental insights lay the scientific groundwork for the development of next-generation OSN membranes.

42 ENGINEERING↗

Rapid macrovoid characterization in membranes prepared via nonsolvent-induced phase separation: A comparison between 2D and 3D techniques

Optimizing the performance of asymmetric membranes prepared via nonsolvent-induced phase separation (NIPS) requires a quantitative understanding of how processing variables influence membrane morphology. Presently, the most useful structural quantification techniques require 3D visualization of the membrane structure and are best suited for studies seeking detailed information on small datasets. This study proposes and validates a rapid and accurate technique for quantifying macroporosity (i.e., D m ), a simple descriptor of sublayer macrovoid content in asymmetric membranes D m . values measured from segmented cross-sectional imaging performed via X-ray computed tomography (XCT) and scanning electron microscopy (SEM) are presented and compared for three asymmetric membranes prepared from commercial polymers. Importantly, analyses of 3D XCT membrane reconstructions reveal that D m is described by a single, centralized mean, which demonstrates that macrovoid content is spatially homogenous. Thus, D m can be approximated from limited sampling of the 2D cross-sectional membrane structure via SEM. A proposed 2D SEM sampling method provides D m estimates within ±6% of corresponding 3D XCT values with 30 independent measurements for the three membranes. Further sensitivity is achieved using complementary descriptors such as macrovoid count density (i.e., C m ). This technique is thus a useful tool for characterizing macroporosity from a broad selection of membrane samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication and analysis of hydroxide/ceramic dual-phase (HCDP) membranes

Ceramic materials show potential to serve as support structures for membranes that can be used to uptake carbon dioxide from high temperature environments, like those found in nuclear flue plants. The porosity of ceramic materials allows for the infilling of those pores with molten hydroxides, that show a natural affinity for absorbing CO 2 from its surroundings. The membranes are easy to produce and were made with thickness of 0.5mm, 1.0mm, and 2.0mm. The membranes were exposed to various conditions after the infilling process and their responses were measured. The percent of hydroxides were measured after the infilled membranes had been in a tube furnace at 400°C, followed by exposure to 30 minutes of CO 2 , and lastly 4 hours of steam. Those tests yielded mole percent hydroxide results of 88.4% ± 4.6%, 68.6% ± 5.1%, and 80.7% ± 4.6%, respectively.

36 MATERIALS SCIENCE↗

Highly tunable structure-by-design polymer brush membranes for organic solvent nanofiltration

Synthetic polymeric nanofiltration membrane processes offer an alternate low-energy option to energy-intensive distillation to fractionate similar size organic solvents for chemical, petroleum, food and biotechnology industries. Here, in this study, we synthesize and test a new class of structure-by-design hydrophilic polymeric brush membranes, that address the limitations of commercial polymer membranes, are tunable and exhibit commercially relevant filtration performance. Because these brush membranes are grafted by Single Electron Transfer-Living Radical Polymerization (SET-LRP) and replace statistically random phase inversion or interfacial polymerization used for synthesizing commercial polymer membranes, their porous structure can be remodeled by varying their morphology and chemistry. We graft hydroxyethyl methacrylate (HEMA) brush structures with short and long crosslinkers, demonstrate two competing phenomena - pore stiffening and opening - and obtain high selectivity at reasonable permeability for commercially relevant methanol/toluene separation. This new class of stable, tunable, and scalable membranes offers exciting opportunities to reduce energy for separation of organic solvents.

42 ENGINEERING↗

Relating Geometric Nanoconfinement and Local Molecular Environment to Diffusion in Ionic Polymer Membranes

Understanding structure-diffusion relationships in ionic polymer membranes not only illuminates fundamental mechanisms for membrane transport, but also informs further membrane development. In this study, we employ NMR diffusometry and molecular dynamics (MD) simulations to investigate diffusion coefficients and activation energies of diffusion (Ea) for both a lithium-form perfluorosulfonic acid membrane and aqueous solutions of lithium triflate. NMR shows that, at high water/ion molar ratio (?), Ea for water diffusion is slightly lower in the membrane than in solution. Conversely, membrane transport exhibits much higher Ea at low hydration as compared to solutions. MD simulations of a model system consisting of carbon nanotubes with varying diameter reveal that Ea of diffusion clearly relates to both the geometric nanoconfinement of the hydrophilic pathways in the membrane as well as the local molecular environment. These results demonstrate that Ea of diffusion can serve as a revelatory tool for the study of molecular transport processes and the coupling of morphology with transport at the nanoscale. This study thus provides new insights and new experimental and computational models for understanding transport in a wide range of polymer membranes, such as those used in molecular separations applications.

Zhang, Rui↗

Effect of cell compression on the performance and the structure of proton exchange membrane water electrolyzer (PEMWE) assembly

Here, in the field of water electrolysis, the proton exchange membrane water electrolyzer (PEMWE) is currently the most advanced technology for producing hydrogen without emitting CO 2 . Although PEMWE plants are already in operation, further research is needed to improve cell efficiency and reduce the use of rare materials, such as iridium oxide catalysts for the oxygen evolution reaction (OER). One of the main causes of performance loss in PEMWE is the relatively low electric conductivity of the porous transport layer (PTL) and of the anode catalyst layer, which results in ohmic losses and low catalyst utilization during high current density operation. The objective of this study is to investigate how optimization of the PTL and electrode interface can increase the cell performance. To this end, we tested different cell assemblies using fibrous and sintered PTLs, decreasing membrane thickness, reducing iridium loading, and inserting a microporous layer to increase contact surface area. Electrochemical characterization of each cell configuration was systematically performed at various compression levels as the pressure is a crucial parameter influencing the electrode/PTL contact area. In parallel, X-ray microcomputed tomography (micro-CT) was employed to investigate the effects of cell hydration and compression on the structure of PEMWE components. This study combining electrochemistry and micro-CT imaging presents how optimizing the electrode/PTL contact surface area, minimizes ohmic losses, and enables PEMWE operation with low iridium loading at high current densities.

Catalyst - PTL interface↗

Solvent Transport in Disordered and Dynamic Membrane Pores: Implications for Reverse Osmosis and Nanofiltration Membranes

Pressure-driven separations with nanoporous membranes, such as reverse osmosis and nanofiltration, play a vital role in addressing water scarcity and enabling resource recovery. Understanding water or solvent transport in membrane pores is essential for advancing membrane separation technologies. A key question in transport modeling is to establish a relationship between solvent permeability and membrane porous structure properties, such as porosity or pore size. The nano- and subnanometer pores in polymeric membranes such as reverse osmosis and nanofiltration membranes are highly tortuous and dynamically connected, which challenges the conventional methods of transport modeling. This study addresses this challenge by developing a theoretical framework to describe solvent transport through membranes with dynamic and disordered porous structure. Specifically, we propose a lattice model to describe the pore network, while preserving the viscous nature of solvent permeation. We further establish a relationship between solvent permeability and membrane porosity or pore size, which is validated by molecular dynamics simulations and experimental data. By integrating this relationship into the solution-friction model, we define pore connectivity and local friction coefficient to quantify the impact of pore structure on solvent permeability. Our analysis highlights the dominant influence of pore connectivity on the permeability of reverse osmosis and nanofiltration membranes, particularly when the pore size approaches the dimensions of solvent molecules. Overall, this study provides critical insights into water and solvent transport mechanisms in nanoporous membranes, opening the door for strategies to substantially enhance membrane performance.

membranes↗