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At least 883 records · Page 49

Multi-functional anodes boost the transient power and durability of proton exchange membrane fuel cells

Abstract Proton exchange membrane fuel cells have been regarded as the most promising candidate for fuel cell vehicles and tools. Their broader adaption, however, has been impeded by cost and lifetime. By integrating a thin layer of tungsten oxide within the anode, which serves as a rapid-response hydrogen reservoir, oxygen scavenger, sensor for power demand, and regulator for hydrogen-disassociation reaction, we herein report proton exchange membrane fuel cells with significantly enhanced power performance for transient operation and low humidified conditions, as well as improved durability against adverse operating conditions. Meanwhile, the enhanced power performance minimizes the use of auxiliary energy-storage systems and reduces costs. Scale fabrication of such devices can be readily achieved based on the current fabrication techniques with negligible extra expense. This work provides proton exchange membrane fuel cells with enhanced power performance, improved durability, prolonged lifetime, and reduced cost for automotive and other applications.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Halogenation-Dependent Effects of the Chlorosulfolipids of Ochromonas danica on Lipid Bilayers

The chlorosulfolipids are amphiphilic natural products with stereochemically complex patterns of chlorination and sulfation. Despite their role in toxic shellfish poisoning, potential pharmacological activities, and unknown biological roles, they remain understudied due to the difficulties in purifying them from natural sources. The structure of these molecules, with a charged sulfate group in the middle of the hydrophobic chain, appears incompatible with the conventional lipid bilayer structure. Questions about chlorosulfolipids remain unanswered partly due to the unavailability of structural analogues with which to conduct structure–function studies. Here, we approach this problem by combining enantioselective total synthesis and membrane biophysics. Using a combination of Langmuir pressure–area isotherms of lipid monolayers, fluorescence imaging of vesicles, mass spectrometry imaging, natural product isolation, small-angle X-ray scattering, and cryogenic electron microscopy, we show that danicalipin A (1) likely inserts into lipid bilayers in the headgroup region and alters their structure and phase behavior. Specifically, danicalipin A (1) thins the bilayer and fluidizes it, allowing even saturated lipid to form fluid bilayers. Lipid monolayers show similar fluidizing upon insertion of danicalipin A (1). Furthermore, we show that the halogenation of the molecule is critical for its membrane activity, likely due to sterically controlled conformational changes. Synthetic unchlorinated and monochlorinated analogues do not thin and fluidize lipid bilayers to the same extent as the natural product. Overall, this study sheds light on how amphiphilic small molecules interact with lipid bilayers and the importance of stereochemistry and halogenation for this interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hippocampal thinning linked to longer TOMM40 poly‐T variant lengths in the absence of the APOE ε4 variant

Abstract Introduction The translocase of outer mitochondrial membrane 40 ( TOMM40 ), which lies in linkage disequilibrium with apolipoprotein E ( APOE ), has received attention more recently as a promising gene in Alzheimer's disease (AD) risk. TOMM40 influences AD pathology through mitochondrial neurotoxicity, and the medial temporal lobe (MTL) is the most likely brain region for identifying early manifestations of AD‐related morphology changes. Methods In this study, we examined the effects of TOMM40 using high‐resolution magnetic resonance imaging in 65 healthy, older subjects with and without the APOE ε4 AD‐risk variant. Results Examining individual subregions within the MTL, we found a significant relationship between increasing poly‐T lengths of the TOMM40 variant and thickness of the entorhinal cortex only in subjects who did not carry the APOE ε4 allele. Discussion Our data provide support for TOMM40 variant repeat length as an important contributor to AD‐like MTL pathology in the absence of APOE ε4.

Burggren, Alison C.↗

Morphology of the Vestibular Utricule in Toadfish, Opsanus Tau

The uticle is an otolith organ in the vertebrate inner ear that provides gravitoinertial acceleration information into the vestibular reflex pathways. The aim of the present study was to provide an anatomical description of this structure in the adult oyster toadfish, and establish a morphological basis for interpretation of subsequent functional studies. Light, scanning electron and transmission electron microscopy were applied to visualize the sensory epithelium and its neural innervation. Electrophysiological techniques were used to identify utricular afferents by their response to translation stimuli. Similar to nerve afferents supplying the semicircular canals and lagena, utricular afferents commonly exhibit a short-latency increase of firing rate in response to electrical activation of the central efferent pathway. Afferents were labeled with biocytin either intraaxonally or with extracellular bulk deposits. Light microscope images of serial thick sections were used to make three-dimensional reconstructions of individual labeled afferents to identify the dendritic morphology with respect to epithelial location. Scanning electron microscopy was used to visualize the surface of the otolith mass facing the otolith membrane, and the hair cell polarization patterns of strioler and extrastriolar regions. Transmission electron micrographs of serial thin sections were compiled to create a three-dimensional reconstruction of the labeled afferent over a segment of its dendritic field and to examine the hair cell-afferent synaptic contacts.

Bass, L.↗

Molecular Based Temperature and Strain Rate Dependent Yield Criterion for Anisotropic Elastomeric Thin Films

A molecular formulation of the onset of plasticity is proposed to assess temperature and strain rate effects in anisotropic semi-crystalline rubbery films. The presented plane stress criterion is based on the strain rate-temperature superposition principle and the cooperative theory of yielding, where some parameters are assumed to be material constants, while others are considered to depend on specific modes of deformation. An orthotropic yield function is developed for a linear low density polyethylene thin film. Uniaxial and biaxial inflation experiments were carried out to determine the yield stress of the membrane via a strain recovery method. It is shown that the 3% offset method predicts the uniaxial elastoplastic transition with good accuracy. Both the tensile yield points along the two principal directions of the film and the biaxial yield stresses are found to obey the superposition principle. The proposed yield criterion is compared against experimental measurements, showing excellent agreement over a wide range of deformation rates and temperatures.

Bosi, F.↗

Ultrathin gas permeable oxide membranes for chemical sensing: Nanoporous Ta 2 O 5 test study

Conductometric gas sensors made of gas permeable metal oxide ultrathin membranes can combine the functions of a selective filter, preconcentrator, and sensing element and thus can be particularly promising for the active sampling of diluted analytes. Here we report a case study of the electron transport and gas sensing properties of such a membrane made of nanoporous Ta 2 O 5 . These membranes demonstrated a noticeable chemical sensitivity toward ammonia, ethanol, and acetone at high temperatures above 400 °C. Furthermore, different from traditional thin films, such gas permeable, ultrathin gas sensing elements can be made suspended enabling advanced architectures of ultrasensitive analytical systems operating at high temperatures and in harsh environments.

36 MATERIALS SCIENCE↗

Porous condensers can double the efficiency of membrane distillation

Among membrane distillation (MD) configurations, air gap MD (AGMD) has superior energy efficiency at high salinity. However, flooding of the gap prevents optimal thin gap depths as water removal is a challenge. To address these challenges, this work provides the first analysis of efficiency enhancement via porous wicking conductive condensers in MD. To do so, we examined performance with experiments and comprehensive thermo-fluid numerical models; we find that the porous wick condenser significantly improves thermal efficiency, gain output ratio (GOR), and flux. MD experiments show that the porous copper foam improves the thermal efficiency of air gap membrane distillation up to 40 % and water flux up to 144 %. Numerical modeling shows the porous copper foam improves the GOR of membrane distillation in high salinity by 98.7 %, outperforming air gap MD, permeate gap MD, and conductive gap MD. Furthermore, the optimized thickness and permeability of porous condensers significantly help eliminate the risk of flooding in AGMD.

42 ENGINEERING↗

Operational constraints and strategies for systems to effect the sustainable, solar-driven reduction of atmospheric CO 2

The operational constraints for a 6-electron/6-proton CO 2 reduction system that operates at the concentration of CO 2 in the current atmosphere (p CO 2 = 400 ppm) have been evaluated on a variety of scale lengths that span from laboratory scale to global scale. Due to the low concentration of CO 2 in the atmosphere, limitations due to mass transport of CO 2 from the tropopause have been evaluated through five different regions, each with different characteristic length scales: the troposphere; the atmospheric boundary layer (ABL); the canopy layer; a membrane layer; and an aqueous electrolyte layer. The resulting CO 2 conductances, and associated physical transport limitations, will set the ultimate limit on the efficiency and areal requirements of a sustainable solar-driven CO 2 reduction system regardless of the activity or selectivity of catalysts for reduction of CO 2 at the molecular level. At the electrolyte/electrode interface, the steady-state limiting current density and the concomitant voltage loss associated with the CO 2 concentration overpotential in a one-dimensional solar-driven CO 2 reduction cell have been assessed quantitatively using a mathematical model that accounts for diffusion, migration and convective transport, as well as for bulk electrochemical reactions in the electrolyte. At p CO 2 = 400 ppm, the low diffusion coefficient combined with the low solubility of CO 2 in aqueous solutions constrains the steady-state limiting current density to <0.1 mA cm -2 in a typical electrochemical cell with natural convection and employing electrolytes with a range of pH values. Hence, in such a system, the CO 2 capture area must be 100- to 1000-fold larger than the solar photon collection area to enable a >10% efficient solar-driven CO 2 reduction system (based on the solar collection area). This flux limitation is consistent with estimates of oceanic CO 2 uptake fluxes that have been developed in conjunction with carbon-cycle analyses for use in coupled atmosphere/ocean general circulation models. Two strategies to improve the feasibility of obtaining efficient and sustainable CO 2 transport to a cathode surface at p CO 2 = 400 ppm are described and modeled quantitatively. The first strategy employs yet unknown catalysts, analogous to carbonic anhydrases, that dramatically accelerate the chemically enhanced CO 2 transport in the aqueous electrolyte layer by enhancing the acid–base reactions in a bicarbonate buffer system. The rapid interconversion from bicarbonate to CO 2 in the presence of such catalysts near the cathode surface would in principle yield significant increases in the steady-state limiting current density and allow for >10% solar-fuel operation at the cell level. The second strategy employs a thin-layer cell architecture to improve the diffusive transport of CO 2 by use of an ultrathin polymeric membrane electrolyte. Rapid equilibration of CO 2 at the gas/electrolyte interface, and significantly enhanced diffusive fluxes of CO 2 in electrolytes, are required to increase the steady-state limiting current density of such a system. This latter approach however only is feasible for gaseous products, because liquid products would coat the electrode and therefore thicken the hydrodynamic boundary layer and accordingly reduce the diffusive CO 2 flux to the electrode surface. Regardless of whether the limitations due to mass transport to the electrode surface are overcome on the laboratory scale, at global scales the ultimate CO 2 flux limitations will be dictated by mass transport considerations related to transport of atmospheric CO 2 to the boundary plane of the solar-driven reactor system. The transport of CO 2 across the troposphere/ABL interface, the ABL/canopy layer interface, and the canopy layer/electrolyte interface have therefore been assessed in this work, to provide upper bounds on the ultimate limits for the solar-to-fuel (STF) conversion efficiency for systems that are intended to effect the reduction of atmospheric CO 2 in a sustainable fashion at global scale.

54 ENVIRONMENTAL SCIENCES↗

Hydrogen permeability and stability of palladium films in a high pressure reactor

Palladium (Pd) thin films were fabricated by colloidal spray deposition (CSD) on substrates of porous yttrium stabilized zirconium oxide (YSZ). The films were sintered at 1140–1160 °C for 2–3 h in argon and had thickness of 5–11 μm. The hydrogen (H 2 ) permeation flux for the Pd film was measured with simulated feed gases (90% H 2 /He, syn-gas/steam, or syn-gas/steam with H 2 S) flowing on the film side and sweep gas (Ar) flowing on the substrate side. Here, the hydrogen flux with the Pd film was obtained by adjusting the flow rate and pressure of the gas. Hydrogen flux values of 121–173 cm 3 min -1 cm -2 were measured at 388–596 °C (feed: 90% H 2 /He at 200 mL min -1 ; sweep: Ar at 1400 mL min -1 ; and ΔP = ~170 psi), and the permeability was calculated and compared with literature values. Because Pd is known to be sensitive to some gases, the stability of Pd films was evaluated by examining the microstructures of samples after their exposure to gas mixtures containing CO, CO 2 , H 2 O, and H 2 S. From the results of stability tests in H 2 S-containing atmospheres, the Pd/Pd 4 S phase boundary was determined, and this measured boundary was compared to the Pd/Pd 4 S boundary calculated from the thermodynamic data in the literature.

36 MATERIALS SCIENCE↗

Antimony nanobelt asymmetric membranes for sodium ion battery

In this study, composite asymmetric membranes containing antimony (Sb) nanobelts are prepared via a straightforward phase inversion method in combination with post-pyrolysis treatment. Sb nanobelt asymmetric membranes demonstrate improved cyclability and specific capacity as the alloy anode of sodium ion battery compared to Sb nanobelt thin films without asymmetric porous structure. The unique structure can effectively accommodate the large volume expansion of Sb-based alloy anodes, prohibit the loss of fractured active materials, and aid in the formation of stable artificial solid electrolyte interphases as evidenced by an outstanding capacity retention of ~98% in 130 cycles at 60 mA g -1 . A specific capacity of ~600 mAh g -1 is obtained at 15 mA g -1 (1/40C). When the current density is increased to 240 mA g -1 , ~80% capacity can be maintained (~480 mAh g -1 ). The relations among phase inversion conditions, structures, compositions, and resultant electrochemical properties are revealed through comprehensive characterization.

25 ENERGY STORAGE↗

Acid Exfoliation of Imine‐linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films

Abstract Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge‐storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large‐scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two‐dimensional imine‐linked COF powders by temporarily protonating their linkages. The resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 μm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates.

Burke, David W.↗

Proton Conduction and Oxygen Diffusion in Ultra-Thin Nafion Films in PEM Fuel Cell: How Thin?

The success of PEM fuel cells lies in the design of the cathode where C-supported Pt catalyst is covered by a thin layer of ionomer, allowing easy access of oxygen and protons. The high current densities (1-2 A/cm 2 ) are achieved by the optimization of the thickness of the ionomer between two opposing trends: thinner ionomer allows high oxygen through-plane diffusion, while the in-plane conduction of the protons requires reasonable thickness. Anisotropy is likely to develop in such thin films. The purpose of this work was to investigate the effect of a thinner ionomer layer on the diffusion and conductivity and to establish how thin the ionomer layer can be. Oxygen permeability (DH) and proton conductivity in ultra-thin Nafion films (100-1000nm) were respectively characterized on SiO 2 substrate via limiting current measurement and electrochemical impedance spectroscopy for a range of temperature and relative humidity conditions. The transport behavior of these films is comparable to the electrode membrane layer of PEM fuel cells. Values of oxygen permeability were shown to increase with decreasing film thickness. The oxygen diffusion through the gas boundary layer becomes significant only at ultra-thin film thickness. The proton conductivity decreases with decreasing thickness and was disproportional to bulk Nafion behavior. Post-test SEM imaging shows buckling of the thin layer on the silicon wafer between the Pt sites, partially explaining the opposing trends in diffusivity and conductivity as film thickness decreases. Anisotropy exists as the thickness becomes comparable to the size of the aqueous regions of the Nafion ionomer. Measurements of thinner layers (<100nm) were experimentally limited, yet the trends indicate that the thinness of the ionomer in the cathode is limited by its ability to allow proton conductance.

25 ENERGY STORAGE↗

IR Scattering by Optically Inhomogeneous Nanoporous Anodic Alumina Films

This paper presents results of thermographic studies of nanoporous alumina films having different geometric parameters of their porous layer (thickness and average pore diameter), which were exposed to thermal radiation. The films have been shown to shield thermal radiation. The present results suggest that nanoporous alumina membranes can be used as heat shields for reducing the thermal contrast of an object and the surrounding background in the IR spectral region.

36 MATERIALS SCIENCE↗

An Experimental Study of Fatigue Crack Growth in Aluminum Sheet Subjected to Combined Bending and Membrane Stresses

An experimental study was conducted to determine the effects of combined bending and membrane cyclic stresses on the fatigue crack growth behavior of aluminum sheet material. The materials used in the tests were 0.040-in.- thick 2024-T3 alclad and 0.090-in.-thick 2024-T3 bare sheet. In the tests, the membrane stresses were applied as a constant amplitude loading at a stress ratio (minimum to maximum stress) of 0.02, and the bending stresses were applied as a constant amplitude deflection in phase with the membrane stresses. Tests were conducted at ratios of bending to membrane stresses (B/M) of 0, 0.75, and 1.50. The general trends of the results were for larger effects of bending for the higher B/M ratios, the lower membrane stresses, and the thicker material. The addition of cyclic bending stresses to a test with cyclic membrane stresses had only a small effect on the growth rates of through-thickness cracks in the thin material, but had a significant effect on the crack growth rates of through-thickness cracks in the thick material. Adding bending stresses to a test had the most effect on the initiation and early growth of cracks and had less effect on the growth of long through-thickness cracks.

Phillips, Edward P.↗

Progress in Development of Improved Ion-Channel Biosensors

Further improvements have recently been made in the development of the devices described in Improved Ion-Channel Biosensors (NPO-30710), NASA Tech Briefs, Vol. 28, No. 10 (October 2004), page 30. As discussed in more detail in that article, these sensors offer advantages of greater stability, greater lifetime, and individual electrical addressability, relative to prior ion-channel biosensors. In order to give meaning to a brief description of the recent improvements, it is necessary to recapitulate a substantial portion of the text of the cited previous article. The figure depicts one sensor that incorporates the recent improvements, and can be helpful in understanding the recapitulated text, which follows: These sensors are microfabricated from silicon and other materials compatible with silicon. Typically, the sensors are fabricated in arrays in silicon wafers on glass plates. Each sensor in the array can be individually electrically addressed, without interference with its neighbors. Each sensor includes a well covered by a thin layer of silicon nitride, in which is made a pinhole for the formation of a lipid bilayer membrane. In one stage of fabrication, the lower half of the well is filled with agarose, which is allowed to harden. Then the upper half of the well is filled with a liquid electrolyte (which thereafter remains liquid) and a lipid bilayer is painted over the pinhole. The liquid contains a protein that forms an ion channel on top of the hardened agarose. The combination of enclosure in the well and support by the hardened agarose provides the stability needed to keep the membrane functional for times as long as days or even weeks. An electrode above the well, another electrode below the well, and all the materials between the electrodes together constitute a capacitor. What is measured is the capacitive transient current in response to an applied voltage pulse. One notable feature of this sensor, in comparison with prior such sensors, is a relatively thick dielectric layer between the top of the well and the top electrode. This layer greatly reduces the capacitance of an aperture across which the ion channels are formed, thereby increasing the signal-to-noise ratio. The use of a relatively large aperture with agarose support makes it possible to form many ion channels instead of only one, thereby further increasing the signal-to-noise ratio and effectively increasing the size of the available ionic reservoir. The relatively large reservoir makes it possible to measure AC rather than DC. This concludes the recapitulation from the cited previous article.

Nadeau, Jay L.↗

Ultra-thin microporous/hybrid materials

Ultra-thin hybrid and/or microporous materials and methods for their fabrication are provided. In one embodiment, the exemplary hybrid membranes can be formed including successive surface activation and reaction steps on a porous support that is patterned or non-patterned. The surface activation can be performed using remote plasma exposure to locally activate the exterior surfaces of porous support. Organic/inorganic hybrid precursors such as organometallic silane precursors can be condensed on the locally activated exterior surfaces, whereby ALD reactions can then take place between the condensed hybrid precursors and a reactant. Various embodiments can also include an intermittent replacement of ALD precursors during the membrane formation so as to enhance the hybrid molecular network of the membranes.

36 MATERIALS SCIENCE↗

Mechanism-Informed Breakdown: Understanding Degradation by Controlling Voltage-Hold Patterns in Proton Exchange Membrane Water Electrolyzers

Low catalyst loadings pose challenges to performance stability in proton exchange membrane (PEM) water electrolysis over extended operation. To study the impact of degradation mechanisms and voltage loss rates, different stress tests are applied to membrane electrode assemblies. Potential cycling conditions were observed to induce higher degrees of iridium (Ir) oxide crystallization, ionomer degradation, and catalyst layer (CL) thinning, which likely contributed to higher kinetic loss rates. On the other hand, while Ir migrating into the PEM (Ir band) generally impairs performance, the interconnected and more uniform Ir band formed under a constant 2 V hold may allow for Ir at the catalyst/membrane interface to remain electronically connected and kinetically accessible, as well as indicate greater Ir site access during the applied stressor. The 2 V hold also demonstrates improved kinetic durability through a lower Tafel slope, faster polarization kinetics, and reduced charge transfer resistance. In contrast, potential cycling caused the migration of disconnected Ir agglomerates into the membrane bulk and created a steady increase in charge transfer resistance, a more dramatic decrease in capacitance (46.7% loss), and significant damage to the surrounding ionomer, indicating a decline in both the quality and quantity of active sites in the anode CL. This work underscores the distinct degradation pathways associated with load holds versus cycling, highlighting the role of catalyst-ionomer interactions in kinetic performance and long-term stability. These insights can inform operational strategies for PEM electrolyzers powered by intermittent energy sources, aiming to minimize efficiency losses over extended operation.

36 MATERIALS SCIENCE↗