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At least 1,315 records · Page 73

High-performance and cost-effective membrane electrode assemblies for advanced proton exchange membrane water electrolyzers: Long-term durability assessment

In this work, improved activity and durability performance of a two-cell (86 cm 2 ) proton exchange membrane water electrolyzer (PEMWE) stack is reported for the first time. Both membrane electrode assemblies (MEAs) contain one order of magnitude lower platinum group metal (PGM) loadings compared to the state-of-the-art PEMWEs and incorporate novel Pt recombination layers. The high-performance and cost-effective MEAs are fabricated by the unique reactive spray deposition technology (RSDT). This advanced methodology allows for one-step fabrication of MEAs and ensures precise control and distribution of the catalyst composition and loading. The RSDT-fabricated MEAs contain only 0.2 and 0.3 mg PGM cm –2 loading in the cathode and anode electrodes, respectively, and demonstrate excellent activity and durability for over 3000 h of operation at industrially-relevant operating conditions without showing significant loss in performance. This novel work shows that a significant cost reduction for PEMWEs is achieved while maintaining excellent durability, high catalysts activities, and low hydrogen cross-over.

Proton exchange membrane water electrolyzer↗

Dye Nanoaggregate Structures in MK-2, N3, and N749 Dye···TiO 2 Interfaces That Represent Dye-Sensitized Solar Cell Working Electrodes

The working electrode of a dye-sensitized solar cell (DSSC) consists of dye molecules adsorbed onto nanoparticles of a semiconductor such as TiO 2 . A reliable prediction of the DSSC photovoltaic performance of a given dye requires in-depth knowledge about the precise structure of the dye···TiO 2 interface. In this work, X-ray reflectometry (XRR) and grazing-incidence small-angle X-ray scattering (GISAXS) are employed to determine the dye···TiO 2 interfacial structure and associated dye aggregation behavior of three high-performance DSSC dyes, i.e., a metal-free organic dye, MK-2, and the two archetypal ruthenium-based organometallic dyes, N3 and N749 (Black Dye). Results show that all three dyes form nanoaggregates in dye···TiO 2 interfaces. We determine the dye nanoaggregate separations, sizes, distribution densities, and the extent of short-range order within each dye self-assembly in the longitudinal and lateral directions. Dye···TiO 2 composites fabricated using dye solutions of varying concentrations are analyzed. We find that nanoaggregates of the three dyes are separated by several hundred nanometers (158-203 nm) in dye···TiO 2 interfaces that have been fabricated using concentrated dye solutions (0.5 mM or 1.0 mM). MK-2 and N749 dyes also display smaller interparticle separations. Dye nanoparticle diameters are of the order of 156-198 nm, sizes that are comparable to the largest interparticle separations. Thus, no extraneous dye particles can be fitted into gaps between particles, so the dye self-assembly is saturated. Self-assemblies of all three dyes exhibit both lateral and longitudinal short-range order; N3 displays a particularly short coherence length along the TiO 2 surface, with extensive structured disorder along the longitudinal direction. The operation of DSSC working electrodes would therefore seem to be dependent on a dye self-assembly that may exhibit several levels of structural granularity and dye aggregation effects.

14 SOLAR ENERGY↗

Demonstration of mechanical connections between integrins, cytoskeletal filaments, and nucleoplasm that stabilize nuclear structure

We report here that living cells and nuclei are hard-wired such that a mechanical tug on cell surface receptors can immediately change the organization of molecular assemblies in the cytoplasm and nucleus. When integrins were pulled by micromanipulating bound microbeads or micropipettes, cytoskeletal filaments reoriented, nuclei distorted, and nucleoli redistributed along the axis of the applied tension field. These effects were specific for integrins, independent of cortical membrane distortion, and were mediated by direct linkages between the cytoskeleton and nucleus. Actin microfilaments mediated force transfer to the nucleus at low strain; however, tearing of the actin gel resulted with greater distortion. In contrast, intermediate filaments effectively mediated force transfer to the nucleus under both conditions. These filament systems also acted as molecular guy wires to mechanically stiffen the nucleus and anchor it in place, whereas microtubules acted to hold open the intermediate filament lattice and to stabilize the nucleus against lateral compression. Molecular connections between integrins, cytoskeletal filaments, and nuclear scaffolds may therefore provide a discrete path for mechanical signal transfer through cells as well as a mechanism for producing integrated changes in cell and nuclear structure in response to changes in extracellular matrix adhesivity or mechanics.

NASA Discipline Cell Biology↗

Nanoengineering of Complex Materials

We are primarily interested in two important biomimetic principles, namely, self-assembly based on supramolecular chemistry and the use of these structures to template in organic phases as observed in biomineralization. The projects proposed are inspired by some of our achievements in the previous funding period described above, and also by preliminary data gathered recently which we describe below. In addition to our broad objective of acquiring knowledge in supramolecular self-assembly and templating of organic–inorganic hybrid materials, we also propose here work on biomolecular structures based on DNA, peptide nucleic acids, and peptides which can serve as models for artificial materials based on biomimetic principles. The proposed work is divided into three sections, supramolecular systems, hybrid systems, and biomolecular and biological systems. In terms of functions, we are using systems that have relevance to solar cells, catalysis, dynamic/active materials, and ferroelectrics.

36 MATERIALS SCIENCE↗

Palmitoylation of caveolin-1 in endothelial cells is post-translational but irreversible

Caveolin-1 is a palmitoylated protein involved in assembly of signaling molecules in plasma membrane subdomains termed caveolae and in intracellular cholesterol transport. Three cysteine residues in the C terminus of caveolin-1 are subject to palmitoylation, which is not necessary for caveolar targeting of caveolin-1. Protein palmitoylation is a post-translational and reversible modification that may be regulated and that in turn may regulate conformation, membrane association, protein-protein interactions, and intracellular localization of the target protein. We have undertaken a detailed analysis of [(3)H]palmitate incorporation into caveolin-1 in aortic endothelial cells. The linkage of palmitate to caveolin-1 was hydroxylamine-sensitive and thus presumably a thioester bond. However, contrary to expectations, palmitate incorporation was blocked completely by the protein synthesis inhibitors cycloheximide and puromycin. In parallel experiments to show specificity, palmitoylation of aortic endothelial cell-specific nitric-oxide synthase was unaffected by these reagents. Inhibitors of protein trafficking, brefeldin A and monensin, blocked caveolin-1 palmitoylation, indicating that the modification was not cotranslational but rather required caveolin-1 transport from the endoplasmic reticulum and Golgi to the plasma membrane. In addition, immunophilin chaperones that form complexes with caveolin-1, i.e. FK506-binding protein 52, cyclophilin A, and cyclophilin 40, were not necessary for caveolin-1 palmitoylation because agents that bind immunophilins did not inhibit palmitoylation. Pulse-chase experiments showed that caveolin-1 palmitoylation is essentially irreversible because the release of [(3)H]palmitate was not significant even after 24 h. These results show that [(3)H]palmitate incorporation is limited to newly synthesized caveolin-1, not because incorporation only occurs during synthesis but because the continuous presence of palmitate on caveolin-1 prevents subsequent repalmitoylation.

Non-NASA Center↗

Dynamic Nanopeptide Assemblies for Trans-Tympanic Drug Delivery

Aim: Otitis media is a common otolaryngologic diagnosis worldwide. Invasive methods to curtail and treat frequent occurrences are undesirable, thus necessitating the identification and production of a non-invasive approach to treating the disease. Due to tympanic membrane thickness, ototopical drug delivery is challenging. In this preliminary study, formulations integrating nanopeptides and thermoresponsive polymeric hydrogels are utilized to improve the efficiency of trans-tympanic membrane drug delivery. Methods: Peptides were synthesized using standard Fmoc (fluorenylmethoxycarbonyl protecting group) based solid state peptide synthesis on an automated peptide synthesizer. Ciprofloxacin release was simulated using multiwell microplates with porous inserts. Rate of Ciprofloxacin release was measured over a 48-hour period using a 200 uL solution of peptide fibers and Ciprofloxacin at 1 wt% each, and the labeled peptide at 0.1 wt% in PBS at pH of 7.4. The cytotoxicity of the PA (peptide amphiphile, specifically c16-AHL 3 K 3 -CO 2 H) micelle and fiber with and without ciprofloxacin was investigated by examining epidermal keratinocyte viability in the presence of the material at various concentrations. Laser scanning confocal microscopy was performed with excitation of the calcein dye at 485 nm and the PA-TAMRA (rhodamine labeled peptide) at 515 nm. Results: We have demonstrated the potential viability of a self-assembled peptide amphiphile hydrogel capable of transitioning from a network of 1D nanoscale fibers to 0D micelles. This dissociative mechanism of action yields a peptide that is an effective cell penetrating peptide (CPP) while temporally controlling the release of the antibiotic ciprofloxacin. Conclusion: This work highlights the potential utility of the dynamic process of an engineered peptide hydrogel capable of dissociating into CPPs capable of facilitating drug delivery across the tympanic membrane.

cell culture↗

Self-Repair and Patterning of 2D Membrane-Like Peptoid Materials

Two-dimensional materials are of increasing interest for use in filtration, sensing, nanoelectronics, and biomedical devices. Peptoids are a class of biomimetic sequence-defined polymers for which certain amphiphillic sequences self-assemble into 2D crystalline materials with properties that mimic those of cell membranes. Using in situ AFM to both dissect these membrane-like materials and image their subsequent behavior, we explore their ability to self-repair on a range of solid substrates. We show that, in a suitable range of pH, self-repair occurs on both negatively and positively charged substrates and can even occur in the absence of an underlying surface. Following dissection of pre-assembled peptoid membranes and upon introduction of a peptoid monomer solution, peptoids repair the damage by assembling at the newly created edges. The speed of the advancing edge depends on the edge orientation, reflecting the two-fold symmetry of the underlying peptoid lattice. Moreover, because the membranes are stabilized by hydrophobic interactions, if the solution contains peptoids possessing an identical sequence in the hydrophobic block but a distinct hydrophilic block, filling of the defects creates membranes that are patterned at the nanoscale. Consequently, we can utilize this ability to create nm-sized patterns of distinct functional groups within a single coherent membrane.

Jiao, Fang↗

Engineering yeast consortia for surface-display of complex cellulosome structures

As our society marches toward a more technologically advanced future, energy and environmental sustainability are some of the most challenging problems we face today. Biomass is one of the most abundant renewable-feedstock for sustainable production of biofuels. However, the main technological obstacle to more widespread uses of this resource is the lack of low-cost technologies to overcome the recalcitrant nature of the cellulosic structure, especially the hydrolysis step on highly ordered celluloses. In this proposal, we successfully engineered several efficient and inexpensive whole-cell biocatalysts in an effort to produce economically compatible and sustainable biofuels, namely cellulosic ethanol. Our approach was to display of a highly efficient cellulolytic enzyme complex, named cellulosome, on the surface of a historical ethanol producer Saccharomyces cerevisiae for the simultaneous and synergistic saccharification and fermentation of cellulose to ethanol. We first demonstrated the feasibility of assembling a mini-cellulosome by incubating E. coli lysates expressing three different cellulases. Resting cells displaying mini-cellulosomes produced 4-fold more ethanol from phosphoric acid-swollen cellulose (PASC) than cultures with only added enzymes. The flexibility to assemble the mini-cellulosome structure was further demonstrated using a synthetic yeast consortium through intracellular complementation. Direct ethanol production from PASC was demonstrated with resting cell cultures. To create a microorganism suitable for a more cost-effective process, called consolidated bioprocessing (CBP), a synthetic consortium capable of displaying mini-cellulosomes on the cell surface via intercellular complementation was created. To further improve the efficiency, a new adaptive strategy of employing anchoring and adaptor scaffoldins to amplify the number of enzymatic subunits was developed, resulting in the creation of an artificial tetravalent cellulosome on the yeast surface and a significant improvement in cellulosic ethanol production. Although this adaptive strategy is ideal for assembling more complex cellulosome for large-scale production of cellulosic ethanol, a substantially larger number of enzymes (up to 10 to 12) is needed to better mimic the natural cellulosome structures for practical usage of the technology.

09 BIOMASS FUELS↗

Toward Qualifications of HB and LB 650 MHz Cavities for the Prototype Cryomodules for the PIP-II Project

High-beta (HB) and low-beta (LB) 650 MHz cryomodules are key components of the Proton Improvement Plan II (PIP-II) project. In this contribution we present the results of several 5-cell HB650 cavities that have been processed and tested with the purpose of qualifying them for the prototype cryomodule assembly, which will take place later this year. We also present the first results obtained in LB650 single-cell cavities process optimization. Taking advantage of their very similar geometry, we are also analyzing the effect of different surface treatments in FRIB’s 5-cell medium-beta 644MHz cavities. Cavities processed with N-doping and mid-T baking showed very promising results in term of both Q-factors and accelerating gradient for these low-beta structures.

43 PARTICLE ACCELERATORS↗

Investigation of methanol oxidation on a highly active and stable Pt–Sn electrocatalyst supported on carbon–polyaniline composite for application in a passive direct methanol fuel cell

Highlights: • PtSn/C-PANI performed superior in the MOR compared with a commercial PtRu/C. • Catalytic activity of PtRu/C was highly reduced during the accelerated durability test. • Anode of the PtSn/C-PANI in a passive DMFC lowered methanol crossover by 30%. - Abstract: Polyaniline fiber (PANI) was synthesized and utilized to fabricate a vulcan–polyaniline (C-PANI) composite. Pt/C-PANI and PtSn/C-PANI electro-catalysts with different Pt:Sn atomic ratios were prepared by the impregnation method. These electro-catalysts, along with commercial PtRu/C (Electrochem), were characterized with respect to their structural and electrochemical properties in methanol oxidation reaction (MOR). PtSn(70:30)/C-PANI showed excellent performance in MOR, the obtained maximum current density being about 40% and 50% higher than that for PtRu/C and Pt/C-PANI, respectively. It was also found that the CO tolerance and stability of PtSn(70:30)/C-PANI was considerably higher than that of PtRu/C. Finally, the performance of these two materials was compared in a passive direct methanol fuel cell (DMFC). The DMFC test results demonstrated that the membrane electrode assembly (MEA) prepared using PtSn(70:30)/C-PANI anode catalyst performed more satisfactorily in terms of maximum power density and lower methanol crossover.

36 MATERIALS SCIENCE↗

Yeast cell surface display for lipase whole cell catalyst and its applications

The cell surface display technique allows for the expression of target proteins or peptides on the microbial cell surface by fusing an appropriate protein as an anchoring motif. Yeast display systems, such as Pichia pastoris, Yarowia lipolytica and Saccharomyces cerevisiae, are ideal, alternative and extensive display systems with the advantage of simple genetic manipulation and post-translational modification of expressed heterologous proteins. Engineered yeasts show high performance characteristics and variant utilizations. Herein, we comprehensively summarize the variant factors affecting lipase whole cell catalyst activity and display efficiency, including the structure and size of target proteins, screening anchor proteins, type and chain length of linkers, and the appropriate matching rules among the above-mentioned display units. Furthermore, we also address novel approaches to enhance stability and activity of recombinant lipases, such as VHb gene co-expression, multi-enzyme co-display technique, and the micro-environmental interference and self-assembly techniques. Finally, we represent the variety of applications of whole cell surface displayed lipases on yeast cells in non-aqueous phases, including synthesis of esters, PUFA enrichment, resolution of chiral drugs, organic synthesis and biofuels. We demonstrate that the lipase surface display technique is a powerful tool for functionalizing yeasts to serve as whole cell catalysts, and increasing interest is providing an impetus for broad application of this technique.

Application↗

Lamination of >21% Efficient Perovskite Solar Cells with Independent Process Control of Transport Layers and Interfaces

Transport layer and interface optimization is critical for improving the performance and stability of perovskite solar cells (PSCs) but is restricted by the conventional fabrication approach of sequential layer deposition. While the bottom transport layer is processed with minimum constraints, the narrow thermal and chemical stability window of the halide perovskite (HP) layer severely restricts the choice of top transport layer and its processing conditions. To overcome these limitations, we demonstrate lamination of HPs—where two transport layer-perovskite half-stacks are independently processed and diffusion-bonded at the HP-HP interface—as an alternative fabrication strategy that enables self-encapsulated solar cells. Power conversion efficiencies (PCE) of >21% are realized using cells that incorporate a novel transport layer combination along with dual-interface passivation via self-assembled monolayers, both of which are uniquely enabled by the lamination approach. This is the highest reported PCE for any laminated PSC encapsulated between glass substrates. We further show that this approach expands the processing window beyond traditional fabrication processes and is adaptable for different transport layer compositions. The laminated PSCs retained >75% of their initial PCE after 1000 h of 1-sun illumination at 40 °C in air using an all-inorganic transport layer configuration without additional encapsulation. Furthermore, a laminated 1 cm 2 device maintained a V oc of 1.16 V. Finally, the scalable lamination strategy in this study enables the implementation of new transport layers and interfacial engineering approaches for improving performance and stability.

14 SOLAR ENERGY↗

Center punched solar cell module development effort

The results are given of an advanced module development program with the objective of providing a low cost solar cell mechanical interconnect design. The design approach, which avoids soldering or welding operations, lends itself to automated assembly techniques thus supporting the Low-Cost Silicon Solar Array Project goals. The first group of six modules contained aluminum contact cells and the second group of six modules contained silver-titanium-palladium contact cells. Extensive component and environmental testing at the module level showed that reliable cell mechanical interconnection can be achieved when utilizing the proper electrical contact materials and pressures. A discussion is given of the module design, manufacturing procedure, test program, significant problem areas and solutions, and conclusions and recommendations as formulated and conducted by XEOS.

Ross, R. E.↗

Nickel hydrogen common pressure vessel battery development

Our present design for a common pressure vessel (CPV) battery, a nickel hydrogen battery system to combine all of the cells into a common pressure vessel, uses an open disk which allows the cell to be set into a shallow cavity; subsequent cells are stacked on each other with the total number based on the battery voltage required. This approach not only eliminates the assembly error threat, but also more readily assures equal contact pressure to the heat fin between each cell, which further assures balanced heat transfer. These heat fin dishes with their appropriate cell stacks are held together with tie bars which in turn are connected to the pressure vessel weld rings at each end of the tube.

Jones, Kenneth R.↗

Automated aray assembly, phase 2

A manufacturing process suitable for the large-scale production of silicon solar array modules at a cost of less than $500/peak kW is described. Factors which control the efficiency of ion implanted silicon solar cells, screen-printed thick film metallization, spray-on antireflection coating process, and panel assembly are discussed. Conclusions regarding technological readiness or cost effectiveness of individual process steps are presented.

Daiello, R. V.↗

Elucidating the impact of the ionomer equivalent weight on a platinum group metal-free PEMFC cathode via oxygen limiting current

Leveraging the interactions between ionomer and catalyst can increase the performance of proton exchange membrane fuel cells. The impacts of the equivalent weight (EW) of perfluorosulfonic acid–based ionomers on the platinum group metal-free electrode structure and fuel cell performance have not been fully explored. Four membrane electrode assemblies (MEAs) were prepared by using a commercial Fe–N–C catalyst, two perfluorosulfonic acid ionomers with different EWs, that is, Aquivion 720 (A720) and Nafion 1100 (N1100), and two ionomer-to-catalyst (I/C) ratios. The four MEAs were characterized to understand the impact of the ionomer EW and content on the capacitance, proton conductivity, and mass transport on the cathode. The mass transport resistance was measured for the first time using a new oxygen reduction reaction limiting current method enabling to couple the effects of oxygen diffusion with liquid water generation. Low EW ionomer combined with a moderate I/C results in improved performance due to its enhanced proton conductivity. However, when used at high I/C, it can cause severe water flooding at high current density due to the enhanced liquid water uptake, especially at high relative humidity, resulting in lower catalyst utilization and higher mass transport resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical investigation of stainless steel corrosion in a proton exchange membrane electrolyzer cell

The lack of a fundamental understanding of the corrosion mechanisms in the electrochemical environments of proton exchange membrane (PEM) electrolyzer and/or fuel cells (ECs/FCs) has seriously hindered the improvement of performance and efficiency of PEM ECs/FCs. In this study, a stainless steel mesh was purposely used as an anode gas diffusion layer that was intentionally operated with high positive potentials under harsh oxidative environments in a PEMEC to study the corrosion mechanism of metal migration. A significant amount of iron and nickel cations were determined to transport through the anode catalyst layer, the PEM and the cathode catalyst layer during the PEMEC operation. The formation/deposition of iron oxide and nickel oxide on the carbon paper gas diffusion layer at the cathode side is first revealed by both scanning electron microscope and X-ray diffraction. The results indicate the corrosion elements of iron and nickel are transported from anode to cathode through the catalyst-coated membrane, and deposited on carbon fibers as oxides. This phenomenon could also open a new corrosion-based processing approach to potentially fabricate multifunctional oxide structures on carbon fiber devices. This study has demonstrated a new accelerated test method for investigating the corrosion and durability of metallic materials as well.

08 HYDROGEN↗