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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Surface Charge and Electrostatic Spin Crossover Effects in CoN 4 Electrocatalysts

Carbon materials doped with nitrogen and 3d transition metals have attracted a great deal of interest for catalyzing electrochemical reactions such as water splitting, oxygen reduction, and carbon dioxide reduction. Here, we employed density functional theory to study Co–N-doped carbon as electrocatalysts for the oxygen reduction and oxygen evolution reactions. Specifically, we investigated the interplay among adsorption energies, the spin state of the CoN 4 active center, and the applied potential. We found that adsorption energies strongly depend on both the applied potential and the spin state of the Co center. Furthermore, spin state transitions induced by the applied potential also play an important role in determining the adsorption energies. Here, this effect originates from a different potential of zero charge and capacitance of each spin state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1987

The evolution of glutathione metabolism in phototrophic microorganisms

Of the many roles ascribed to glutathione (GSH) the one most clearly established is its role in the protection of higher eucaryotes against oxygen toxicity through destruction of thiol-reactive oxygen byproducts. If this is the primary function of GSH then GSH metabolism should have evolved during or after the evolution of oxygenic photosynthesis. That many bacteria do not produce GSH is consistent with this view. In the present study we have examined the low-molecular-weight thiol composition of a variety of phototrophic microorganisms to ascertain how evolution of GSH production is related to evolution of oxygenic photosynthesis. Cells were extracted in the presence of monobromobimane (mBBr) to convert thiols to fluorescent derivatives, which were analyzed by high-pressure liquid chromatography. Significant levels of GSH were not found in the green bacteria (Chlorobium thiosulfatophilum and Chloroflexus aurantiacus). Substantial levels of GSH were present in the purple bacteria (Chromatium vinosum, Rhodospirillum rubrum, Rhodobacter sphaeroides, and Rhodocyclus gelatinosa), the cyanobacteria [Anacystis nidulans, Microcoleus chthonoplastes S.G., Nostoc muscorum, Oscillatoria amphigranulata, Oscillatoria limnetica, Oscillatoria sp. (Stinky Spring, Utah), Oscillatoria terebriformis, Plectonema boryanum, and Synechococcus lividus], and eucaryotic algae (Chlorella pyrenoidsa, Chlorella vulgaris, Euglena gracilis, Scenedesmus obliquus, and Chlamydomonas reinhardtii). Other thiols measured included cysteine, gamma-glutamylcysteine, thiosulfate, coenzyme A, and sulfide; several unidentified thiols were also detected. Many of the organisms examined also exhibited a marked ability to reduce mBBr to syn-(methyl,methyl)bimane, an ability that was quenched by treatment with 2-pyridyl disulfide or 5,5'-bisdithio-(2-nitrobenzoic acid) prior to reaction with mBBr. These observations indicate the presence of a reducing system capable of electron transfer to mBBr and reduction of reactive disulfides. The distribution of GSH in phototrophic eubacteria indicates that GSH synthesis evolved at or around the time that oxygenic photosynthesis evolved.

NASA Discipline Exobiology↗
DOE OSTI2020

Catalytic Porphyrin Framework Compounds

Porphyrins are frequently observed in nature and play a vital role in many biological functions, including light-harvesting, oxygen transport, and catalytic transformations. The rigid, robust, and multifunctional features of porphyrins enable the construction of framework compounds such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) for use in several important applications. This short review here summarizes the types of porphyrin building blocks with varying connectivity, their assembly into framework compounds, and key structural factors governing porphyrin ligand design. Furthermore, we highlight emerging catalytic applications of these porphyrin framework compounds as Lewis acid catalysts, oxidation catalysts, photocatalysts, and electrocatalysts. Together, this review supplies a timely update on porphyrin ligand design and framework compound synthesis and guides the future development of porphyrin framework compounds with diverse functionalities for efficient catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1973

Handbook on thermophysical properties of oxygen

Handbook has been compiled by Cryogenic Data Center of National Bureau of Standards. It covers thermodynamic functions, physical properties, and heat transfer data for oxygen. Handbook addresses primarily low temperature regime, but also includes some data above room temperature.

Roder, H. M.↗
DOE OSTI2020

The histone H3-H4 tetramer is a copper reductase enzyme

Eukaryotic histone H3-H4 tetramers contain a putative copper (Cu 2+ ) binding site at the H3-H3′ dimerization interface with unknown function. The coincident emergence of eukaryotes with global oxygenation, which challenged cellular copper utilization, raised the possibility that histones may function in cellular copper homeostasis. We report that the recombinant Xenopus laevis H3-H4 tetramer is an oxidoreductase enzyme that binds Cu 2+ and catalyzes its reduction to Cu 1+ in vitro. Loss- and gain-of-function mutations of the putative active site residues correspondingly altered copper binding and the enzymatic activity, as well as intracellular Cu 1+ abundance and copper-dependent mitochondrial respiration and Sod1 function in the yeast Saccharomyces cerevisiae . The histone H3-H4 tetramer, therefore, has a role other than chromatin compaction or epigenetic regulation and generates biousable Cu 1+ ions in eukaryotes.

Attar, Narsis↗
DOE OSTI2024

Preparation of ultrathin sputtered gold films on palladium as efficient oxygen reduction electro-catalysts

Herein, we present the preparation of ultrathin gold (Au) films on different M (M = Pd, Pt, Rh, Ir, and Ru) electrodes (Au/M) using magnetron sputtering deposition for oxygen reduction reaction (ORR). The ORR electro-catalytic activities of prepared Au/M catalysts increase as follows: Au/Ru < Au/Ir < Au/Rh < Au/Pt < Au/Pd. Accordingly, the oxygen reduction catalytic behaviors of the Au-modified palladium (Au/Pd) thin films with various Au thicknesses (0.16, 0.24, 0.5, and 1 nm) are investigated in acidic environments. It is found that Au modifications can promote oxygen reduction performances due to the development of more catalytic active sites on the Pd catalyst through the existence of Au atoms. Noticeably, Au/Pd samples exhibit a connection in oxygen reduction ability as a function of Au thickness, with the ultrathin 0.16 nm Au/Pd being the most active ORR catalyst. Significantly, the 0.16 nm Au/Pd material demonstrates superior stability after 1000 potential cycles compared with the 0.16 nm Pt/Pd owing to the influence of Au coating and structurally stable surfaces. Therefore, surface modification with the deposition of Au films on Pd represents a favorable technique to boost both the ORR capability and stability of the electro-catalysts.

Magnetron sputtering↗
NASA NTRS2007

Biomedical Support of U.S. Extravehicular Activity

The world's first extravehicular activity (EVA) was performed by A. A. Leonov on March 18, 1965 during the Russian Voskhod-2 mission. The first US EVA was executed by Gemini IV astronaut Ed White on June 3, 1965, with an umbilical tether that included communications and an oxygen supply. A hand-held maneuvering unit (HHMU) also was used to test maneuverability during the brief EVA; however the somewhat stiff umbilical limited controlled movement. That constraint, plus difficulty returning through the vehicle hatch, highlighted the need for increased thermal control and improved EVA ergonomics. Clearly, requirements for a useful EVA were interrelated with the vehicle design. The early Gemini EVAs generated requirements for suits providing micro-meteor protection, adequate visual field and eye protection from solar visual and infrared radiation, gloves optimized for dexterity while pressurized, and thermal systems capable of protecting the astronaut while rejecting metabolic heat during high workloads. Subsequent Gemini EVAs built upon this early experience and included development of a portable environmental control and life support systems (ECLSS) and an astronaut maneuvering unit. The ECLSS provided a pressure vessel and controller with functional control over suit pressure, oxygen flow, carbon dioxide removal, humidity, and temperature control. Gemini EVA experience also identified the usefulness of underwater neutral buoyancy and altitude chamber task training, and the importance of developing reliable task timelines. Improved thermal management and carbon dioxide control also were required for high workload tasks. With the Apollo project, EVA activity was primarily on the lunar surface; and suit durability, integrated liquid cooling garments, and low suit operating pressures (3.75 pounds per square inch absolute [psia] or 25.8 kilopascal [kPa],) were required to facilitate longer EVAs with ambulation and significant physical workloads with average metabolic rates of 1000 BTU/hr and peaks of up to 2200 BTU/hr. Mobility was further augmented with the Lunar Roving Vehicle. The Apollo extravehicular mobility unit (EMU) was made up of over 15 components, ranging from a biomedical belt for capturing and transmitting biomedical data, urine and fecal containment systems, a liquid cooling garment, communications cap, a modular portable life support system (PLSS), a boot system, thermal overgloves, and a bubble helmet with eye protection. Apollo lunar astronauts performed successful EVAs on the lunar surface from a 5 psia (34.4 kPa) 100% oxygen environment in the Lunar Lander. A maximum of three EVAs were performed on any mission. For Skylab a modified A7LB suit, used for Apollo 15, was selected. The Skylab astronaut life support assembly (ALSA) provided umbilical support through the life support umbilical (LSU) and used open loop oxygen flow, rather than closed-loop as in Apollo missions. Thermal control was provided by liquid water circulated by spacecraft pumps and electrical power also was provided from the spacecraft via the umbilical. The cabin atmosphere of 5 psia (34.4 kPa), 70% oxygen, provided a normoxic atmosphere and because of the very low nitrogen partial pressures, no special protocols were required to protect against decompression sickness (DCS) as was the case with the Apollo spacecraft with a 5 psi, 100% oxygen environment.

Gernhardt, Michael L.↗
DOE OSTI2026

The ionomer as an oxygen evolution reaction promoter: piperidinium’s impact on mechanistic pathways on NiO, IrO 2 , and Fe–NiO

The commercial viability of anion exchange membrane (AEM) electrolysis requires optimization of various stack components, with specific catalyst-ionomer combinations often yielding higher current densities, lowered Tafel slopes, and improved mass activity. In this joint theoretical-experimental study, theoretical calculations detail the impact of Versogen’s piperidinium functional group on the complex, kinetically limiting oxygen evolution reaction, finding that the functional group can act as a promoter of specific steps (O*/O 2 * formation; H 2 O/O 2 desorption with reaction enthalpies ranging between 0.2–0.6 eV at higher coverages of O x H y intermediates) on NiO and NiFeO x catalysts. In particular, Fe sites on the NiFeO x catalyst facilitate concerted mechanisms of O*/O 2 * formation and H 2 O desorption with a low enthalpy of 0.5 eV; O 2 desorption alone requires only 0.3 eV. In contrast, Versogen-IrO 2 results in stronger Ir–O bonds, where the enthalpies for bond breaking (Ir–OH 2 and Ir–O 2 ) are considerably higher (1.4 eV and 1.6 eV, respectively). Rotating disk electrode studies utilized commercially available NiO and IrO 2 and synthesized 7.5 wt % Fe in NiFeO x catalysts in combination with Versogen, a common AEM ionomer, and Nafion, an alternative binder. Electrochemical testing validated the impact of these mechanistic changes on ionomer-catalyst combinations, finding that Versogen particularly activates NiO and NiFeO x compared to IrO 2 . Following a 13.5 h hold at 1.8 V, mass activities and Tafel slopes improved to 34 ± 13 A g −1 and 79 ± 2 mV dec −1 (NiO) and 82 ± 4.9 A g −1 and 72 ± 2 mV dec −1 (NiFeO x ). In contrast, Versogen-IrO 2 only reached 17 ± 2.9 A g −1 and 81 ± 3 mV dec −1 . Optimization of the ionomer-catalyst can yield significant increases in performance from initial activity and after an electrochemical conditioning procedure: this enhancement to the mass activity resulted in a 200.9 ± 106.1% improvement for Versogen-NiFeO x and 1284.2 ± 260.5% for Versogen-NiO. In contrast, Nafion-NiFeO x and -NiO offered moderate improvements of 39.1 ± 30.5% and 120.9 ± 59.1%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

MPCVD-Grown Nanodiamond Microelectrodes with Oxygen Plasma Activation for Neurochemical Applications

Nanodiamonds (NDs) are a carbon nanomaterial that has a diamond core with heteroatoms and defects at the surface. The large surface area, defect sites, and functional groups on NDs make them a promising material for electrochemical sensing. Previously, we dip-coated ND onto carbon-fiber microelectrodes (CFMEs) and found increases in sensitivity, but the coating was sparse. Here, for this work, we directly grew thin films of ND on niobium wires using microwave plasma chemical vapor deposition (MP-CVD) to provide full surface coverage. ND microelectrodes show a reliable performance in neurotransmitter detection with good antifouling properties. To improve sensitivity, we oxygen plasma etched ND films to activate the surface and intentionally add defects and oxygen surface functional groups. For fast-scan cyclic voltammetry detection of dopamine, oxygen plasma-etching increases the sensitivity from 21 nA/μM to 90 nA/μM after treatment. Fouling was tested by repeated injections of serotonin or tyramine, and both ND and plasma oxidized nanodiamond (NDO) microelectrodes maintain their currents better compared to CFMEs and therefore are more antifouling. Furthermore, a biofouling test in brain slices shows that ND microelectrodes barely have any current drop, while the more hydrophilic NDO microelectrodes decrease more, but still not as much as CFMEs. Overall, grown ND microelectrodes are promising in neurotransmitter detection with excellent fouling resistance, whereas oxygen plasma etching slightly lowers the fouling resistance but dramatically increases sensitivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Oxygen plasma ashing effects on aluminum and titanium space protective coatings

Using variable angle spectroscopic ellipsometry and atomic force microscopy (AFM), the surface roughness and oxidation of aluminum and titanium thin films have been studied as a function of substrate deposition temperature and oxygen plasma exposure. Increasing substrate deposition temperatures affect film microstructure by greatly increasing grain size. Short exposures to an oxygen plasma environment produce sharp spikes rising rapidly above the surface as seen by AFM. Ellipsometric measurements were made over a wide range of plasma exposure times, and results at longer exposure times suggest that the surface is greater than 30% void. This is qualitatively verified by the AFM images.

Synowicki, R.↗
DOE OSTI2023

Covalent Triazine Framework-Derived Membranes: Engineered Sol–Gel Construction and Gas Separation Application

Covalent triazine frameworks (CTFs) represent one of the most extensively studied organic networks characterized by graphitic π-conjugated structures linked by aza-fused rings, possessing unique features such as compositions of light elements (e.g., C, H, and N), porous architectures abundant heteroatom involvement, and extensively conjugated structures. In addition, the textural and chemical structures of CTFs could be engineered via synthesis control to accommodate diverse applications. CTF materials with notable characteristics, including plentiful (ultra-)micropores, high surface areas, and the presence of CO 2 -philic functional groups involving nitrogen (N), oxygen (O), and fluorine (F), hold great promise as potential candidates for anthropogenic CO 2 capture and sequestration (CCS) applications. However, the conventional high-temperature involved ionothermal procedures and the solution-based coupling pathway only afforded CTF materials in powder form, which is difficult to be processed toward membrane formation. Successful fabrication of CTF-derived membranes will rely on the development of alternative polymerization approaches as well as structural engineering to afford membrane architectures with controllable porosity distribution and active interaction sites with CO 2 benefiting the CO 2 separation procedure. In this Account, a demonstration of the latest progress in the development of CTF-derived membranes was provided. The CTF membranes were mainly synthesized via a superacid (e.g., CF 3 SO 3 H)-promoted sol–gel approach involving the polymerization of aromatic nitrile monomers. The formation of the triazine unit through the trimerization of cyano groups served as the cross-linkers, resulting in the creation of π-conjugated networks alongside the arenes present in the starting materials. The aromatic nitrile monomers with rigid and sterically hindered structures were required to afford CTF membranes with nanoporous architectures. The acidity of the superacid and reactivity of the aromatic monomers played critical roles in the polymerization efficiency. The monomer diversity and synthesis tunability endowed the introduction of CO 2 -philic functionalities (e.g., pyrazole and fluorine) within the CTF skeletons, and integration of ionic moieties was achieved by adopting FSO 3 H with stronger acidity as the catalyst and aromatic nitrile monomers with pyrazine structures. To ensure the successful construction of fluorinated CTF membranes, it is important to avoid any fluorines on the ortho-position of the cyano groups on the benzene ring. Through control over the monomers and reaction conditions, flexible, transparent, and insoluble CTF membranes could be fabricated. The sol–gel method could be further expanded to membrane fabrication through acetyl-to-benzene transformation through synthesis control. The mild oxidation-exfoliation-filtration method was also demonstrated to fabricate substrate-supported CTF membranes. The as-afforded membranes are well characterized to determine the structural features and provide information to study the structure-performance relationship. Here, the application of CTF membranes in CO 2 separation was summarized, focusing on the approaches being developed to enhance CO 2 uptake and separation performance. In addition to utilizing the pristine CTF membranes for gas separation, functionalized carbon molecular sieve membranes could be obtained from the pyrolysis of thermally stable CTF membrane precursors toward efficient CO 2 separation, benefiting from the abundant ultramicropores being created during the pyrolysis/decomposition procedure and involvement of CO 2 -philic functionalities such as fluorine and nitrogen-containing moieties. Based on these achievements, unsolved issues in CTF membrane-related fabrication and applications, including the potential solution approaches, have been proposed to advance the application of CTF membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Three-Dimensional Integration of Functional Oxides and Crystalline Silicon for Optical Neuromorphic Computing Using Nanometer-Scale Oxygen Scavenging Barriers

Dating to the first reports of epitaxial oxide deposition on Si(001), the integration of complex oxides on silicon has been a fast-moving area of research, where fundamental materials physics is intimately connected to tremendous technological promise in such areas as integrated electronics, optical neuromorphic and quantum computing, and sensing, to name a few. Despite their great promise, devices relying on the co-integration of silicon and epitaxial perovskites are typically limited to basic, planar geometries due to practical issues with their fabrication. In this paper, we overcome these long-standing challenges by developing a method to produce high-quality Si(001)/TMO/Si(001)/TMO heterostructures without wafer bonding, resulting in the straightforward three-dimensional integration of functional complex oxides and active Si(001) layers into a technologically relevant platform that is needed for on-chip hardware implementations of neuromorphic computing based on optical signals. We present detailed structural and chemical characterization of our heterostructures and discuss generalized design rules for their fabrication. Our results exponentially expand the universe of practically achievable TMO-based integrated devices and push this promising class of materials closer to realizing their full technological potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1980

The adsorption of cesium on lanthanum hexaboride surfaces

The adsorption/desorption characteristics of cesium on clean and oxygen-covered LaB6 (100) surfaces were studied using various surface analysis techniques. On the initially clean surface (phi = 2.77 eV), adsorption produces a minimum work function of 1.96 eV and a saturation work function of 2.07 eV. For the oxygen-saturated surface, the cesium adsorption curve shows no minimum, the lowest work function (1.35 eV) occurring at cesium saturation. The utility of LaB6 (100) as an emitter or collector in thermionic converter applications (particularly for space nuclear electric propulsion) is evaluated.

Davis, P. R.↗
NASA NTRS2004

Manipulation of Microenvironment with a Built-in Electrochemical Actuator in Proximity of a Dissolved Oxygen Microsensor

Abstract - Biochemical sensors for continuous monitoring require dependable periodic self- diagnosis with acceptable simplicity to check its functionality during operation. An in situ self- diagnostic technique for a dissolved oxygen microsensor is proposed in an effort to devise an intelligent microsensor system with an integrated electrochemical actuation electrode. With a built- in platinum microelectrode that surrounds the microsensor, two kinds of microenvironments, called the oxygen-saturated or oxygen-depleted phases, can be created by water electrolysis depending on the polarity. The functionality of the microsensor can be checked during these microenvironment phases. The polarographic oxygen microsensor is fabricated on a flexible polyimide substrate (Kapton) and the feasibility of the proposed concept is demonstrated in a physiological solution. The sensor responds properly during the oxygen-generating and oxygen- depleting phases. The use of these microenvironments for in situ self-calibration is discussed to achieve functional integration as well as structural integration of the microsensor system.

Kim, Chang-Soo↗
DOE OSTI2021

Polymeric membranes for CO 2 separation and capture

Over the past decade, CO 2 separation and capture have become the new bandwagon for polymer science and membrane research. This review presents the fundamentals of CO 2 /gas separation in polymeric membranes and discusses how these principles underpin opportunities and challenges for post-combustion carbon capture (CO 2 /N 2 ), hydrogen purification (CO 2 /H 2 ), and natural gas and biogas sweetening (CO 2 /CH 4 ). Emerging polymeric membrane materials are discussed, including a few polymers containing a high content of polar functional groups (i.e., ether oxygen-rich polymers and polymeric ionic liquids), shape-persisting glassy polymers (i.e., perfluoropolymers, thermally rearranged polymers, iptycene-containing polymers), and reactive polymers featuring facilitated transport. Moreover, the promising candidates for each CO 2 separation application are highlighted. Lastly, the permeability-selectivity data reviewed were plotted against their 2008 and 2019 upper bounds.

08 HYDROGEN↗
DOE OSTI2025

Graphene Oxide Nanoribbons for High Early-Strength Cement Concrete

Longitudinal oxidative unzipping of the outer walls of multiwalled carbon nanotubes (MWCNTs) yields graphene oxide nanoribbons (GONRs), which exhibit greater open surface area and functional edge content than MWCNTs. This paper presents a study of the nano-amendment of Portland cement concrete with GONRs in concentrations between 0.05% (in weight of cement, wt%) and 0.0005 wt%, thus up to two orders of magnitude lower than that reported as lower-bound in the archival literature. The dispersibility in aqueous solution as a function of GONR concentration and oxygen weight content (O%) was assessed through dynamic light scattering (DLS) and zeta potential analysis. The results indicated that less effective suspensions were obtained for 0.05 wt% of GONRs and 22.7 O%. Therefore, GONR water suspensions with 30-40% O% were used to manufacture 50 mm × 100 mm cylindrical concrete specimens. After 7 days of curing, results from uniaxial compression tests using four specimens per configuration (MWCNT concentration and O%) showed that the incorporation of GONRs resulted in an average increase in compressive strength up to 45%. Consistent with the DLS and compression test results, SEM micrographs showed well-dispersed GONRs together with accelerated and preferential formation of calcium silicate hydrates (C-S-H) for all GONR concentrations. The results indicate, for the first time, that the incorporation of very small concentrations (as low as 0.0005 wt%) of well-dispersed GONR amendments can significantly enhance the early-age concrete strength. However, such enhancement became insignificant after 28 days of curing.

cement↗