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Results for “ATOMIC OXYGEN REACTIVITY”

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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Molecular Models of Atomically Dispersed Uranium at MoS 2 Surfaces Reveal Cooperative Mechanism of Water Reduction

Single atoms of uranium supported on molybdenum sulfide surfaces (U@MoS 2 ) have been recently demonstrated to facilitate the hydrogen evolution reaction (HER) through electrocatalysis. Theoretical calculations have predicted uranium hydroxide moieties bound to edge-sulfur atoms of MoS 2 as a proposed transition state involved in the HER process. However, the isolation of relevant intermediates involved in this process remains a challenge, rendering mechanistic hypotheses unverified. The present work describes the isolation and characterization of a uranium-hydroxide intermediate on molybdenum sulfide surfaces using [(Cp* 3 Mo 3 S 4 )UCp*], a molecular model of a reduced uranium center supported at MoS 2 . Mechanistic investigations highlight the metalloligand cooperativity with uranium involved in the water activation pathway. The corresponding uranium-oxo analogue, [(Cp* 3 Mo 3 S 4 )Cp*U(═O)], was also accessed from the hydroxide cluster via hydrogen atom transfer and from [(Cp* 3 Mo 3 S 4 )UCp*] through an alternative direct oxygen atom transfer. These results provide an atomistic perspective on the reactivity of low-valent uranium at molybdenum sulfide surfaces toward water, modeling key intermediates associated with the HER of U@MoS 2 catalysts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS1989

Thermal-energy reactions of O2(2+) ions with O2, N2, CO2, NO, and Ne

The paper presents results of drift-tube mass-spectrometer studies of the reactivity of doubly charged molecular oxygen ions with several molecules and neon atoms. Thermal-energ rate coefficients for the reactions with the molecular reactants were found to be large, close to the limiting Langevin rates. Charge transfer with neon atoms was observed, but the measured rate coefficient was only a small fraction of the Langevin rate. It is concluded that the measured rate constants for the reactions considereed refer to vibrationally excited ions.

Chatterjee, B. K.↗
NASA NTRS1989

Effect of reactor loading on atomic oxygen concentration as measured by NO chemiluminescence

It has previously been observed that the etch rate of polyethylene samples in the afterglow of an RF discharge in oxygen increases with reactor loading. This enhancement of the etch rate is attributed to reactive gas phase products of the polymer etching. In the present work, emission spectroscopy is employed to examine the species present in the gas phase during etching of polyethylene. In particular, the concentration of atomic oxygen downstream from the polyethylene samples is studied as a function of the reactor loading. It is found that the concentration of atomic oxygen increases as the reactor loading is increased. The increase of etch rate with increased reactor loading is attributed to the increase of atomic oxygen concentration in the vicinity of the sample.

Lerner, N. R.↗
DOE OSTI2026

Mimicking Extradiol Dioxygenase Reactivity on Iridium

Extradiol dioxygenases catalyze the cleavage of benzenediol (catechol) or vicinal aminophenols via oxygen atom insertion into the 2,3- C–C bond. These reactions are most often proposed to proceed through the migratory rearrangement of a d6 alkylperoxide, generating the corresponding d 6 ring expanded product. However, regiospecific insertion remains a rare outcome among synthetic model complexes. Here, a dioxygenated Ir complex (2) converts to (a) the paramagnetic metallatrioxolane (3) and (b) oxygen atom inserted products (4) and (5); all three complexes are third-row metal analogues of enzymatic intermediates. The conversion of 2 to 3 was triggered by an H• abstraction, generating a third-row metallatrioxolane that is one electron reduced from the canonical d 6 alkylperoxide. Alternatively, photolysis of 2 (467 nm) results in ring-expanded product 4, from which an H• can be abstracted to generate 5. This latter complex is also one electron reduced relative to the canonical ring expansion product. Because extradiol mechanisms were largely defined using Fe(II) metallocofactors, 3 and 5 may be especially relevant to the known Co(II) accepting variants. We propose these states became synthetically accessible via the incorporation of a catechol-like substrate into the larger, multidentate ligand L1. This perturbation enhances the affinity of L1 (and related intermediates) to the metal. The same perturbation may have also been key in characterizing the first κ 2 -bound, dianionic ortho ester ligand – the observed binding mode in the x-ray structure of 5. Broadly, we propose through this case study that connecting abiological dioxygen complexes to non-heme oxygenase-like intermediates might be a “roadmap” towards regiospecific aerobic oxygenations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Molecular beam epitaxy growth of IrO 2 using plasma-only oxidation

Growth of IrO 2 films via molecular beam epitaxy (MBE) using an oxygen plasma as the sole oxidant is demonstrated for the first time. We investigate the oxidizing conditions required for IrO 2 by characterizing the species present in the plasma using optical emission spectroscopy and comparing the thermodynamic equilibrium between Ir/IrO 2 under atomic and molecular oxygen. Across the pressure range accessible, monatomic oxygen was the primary reactive species present in the plasma. IrO 2 films were grown under varying Ir flux, oxygen pressure, and substrate temperature to understand growth thermodynamics and kinetics. Structural characterization assessed film phase and composition, crystallinity, strain, and surface morphology. The optimized films from this study validate plasma-only reactive growth by MBE as a successful method for growing IrO 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2024

High pressure–derived nonsymmetrical [Cu 2 O] 2+ core for room-temperature methane hydroxylation

Nonsymmetrical oxygen-bridged binuclear copper centers have been proposed and modeled as intermediates and transition states in several C–H oxidation pathways, leading to the postulation that structural dissymmetry enhances the reactivity of the bridging oxygen. However, experimentally characterizing the structure and reactivity of these transient species is remarkably challenging. Here, we report the high-pressure synthesis of a metastable nonsymmetrical dicopper-μ-oxo compound with exceptional reactivity toward the mono-oxygenation of aliphatic C–H bonds. The nonequivalent coordination environment of copper stabilizes localized mixed valency and greatly enhances the hydrogen atom abstraction activity of the bridging oxygen, enabling room-temperature hydroxylation of methane under pressure. These findings highlight the role of dissymmetry in the reactivity of binuclear copper centers and demonstrate precise control of molecular structures by mechanical means.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1995

Effects of the LDEF orbital environment on the reflectance of optical mirror materials

Specimens of eight different optical mirror materials were flown in low earth orbit as part of the Long Duration Exposure Facility (LDEF) manifest to determine their ability to withstand exposure to the residual atomic oxygen and other environmental effects at those altitudes. Optical thin films of aluminum, gold, iridium, osmium, platinum, magnesium fluoride-overcoated aluminum and reactively deposited, silicon monoxide-protected aluminum, all of which were vacuum deposited on polished fused silica substrates, were included as part of Experiment S0010, Exposure of Spacecraft Coatings. Two specimens of polished, chemical vapor deposited (CVD) silicon carbide were installed in sites available in Experiment A0114, Interaction of Atomic Oxygen with Solid Surfaces at Orbital Altitudes, which included trays in two of the spacecraft bays, one on the leading edge and the other on the trailing edge. One of the silicon carbide samples was located in each of these trays. This paper will compare specular reflectance data from the preflight and postflight measurements made on each of these samples and attempt to explain the changes in light of the specific environments to which the experiments were exposed.

Herzig, Howard↗
NASA NTRS1993

Space environmental effects on LDEF composites: A leading edge coated graphite epoxy panel

The electronics module cover for the leading edge (Row D 9) experiment M0003-8 was fabricated from T300 graphite/934 epoxy unidirectional prepreg tape in a (O(sub 2), +/- 45, O(sub 2), +/- 45, 90, 0)(sub s) layup. This 11.75 in x 16.75 in panel was covered with thermal control coatings in three of the four quadrants with the fourth quadrant uncoated. The composite panel experienced different thermal cycling extremes in each quadrant due to the different optical properties of the coatings and bare composite. The panel also experienced ultraviolet (UV) and atomic oxygen (AO) attack as well as micrometeoroid and space debris impacts. An AO reactivity of 0.99 x 10(exp -24) cm(sup 3)/atom was calculated for the bare composite based on thickness loss. The white urethane thermal control coatings (A276 and BMS 1060) prevented AO attack of the composite substrate. However, the black urethane thermal control coating (Z306) was severely eroded by AO, allowing some AO attack of the composite substrate. An interesting banding pattern on the AO eroded bare composite surface was investigated and found to match the dimensions of the graphite fiber tow widths as prepregged. Also, erosion depths were greater in the darker bands. Five micrometeoroid/space debris impacts were cross sectioned to investigate possible structural damage as well as impact/AO interactions. Local crushing and delaminations were found to some extent in all of the impacts. No signs of coating undercutting were observed despite the extensive AO erosion patterns seen in the exposed composite material at the impact sites. An extensive microcrack study was performed on the panel along with modeling of the thermal environment to estimate temperature extremes and thermal shock. The white coated composite substrate displayed almost no microcracking while the black coated and bare composite showed extensive microcracking. Significant AO erosion was seen in many of the cracks in the bare composite.

George, Pete E.↗
DOE OSTI2025

Oxygen Atom Transfer Reactions of Colloidal Metal Oxide Nanoparticles

Redox transformations at metal oxide (MO x )/solution interfaces are broadly important, and oxygen atom transfer (OAT) is one of the simplest and most fundamental examples of such reactivity. OAT is a two-electron transfer process, well-known in gas/solid reactions and catalysis. However, OAT is rarely directly observed at oxide/water interfaces, whose redox reactions are typically proposed to occur in one-electron steps. Reported here are stoichiometric OAT reactions of organic molecules with aqueous colloidal titanium dioxide and iridium oxide nanoparticles (TiO 2 and IrO x NPs). Me 2 SO (DMSO) oxidizes reduced TiO 2 NPs with the formation of Me 2 S, and IrO x NPs transfer O atoms to a water-soluble phosphine and a thioether. The reaction stoichiometries were established and the chemical mechanisms were probed using typical solution spectroscopic techniques, exploiting the high surface areas and transparency of the colloids. Furthermore, these OAT reactions, including a catalytic example, utilize the ability of the individual NPs to accumulate many electrons and/or holes. Observing OAT reactions of two different materials, in opposite directions, is a step toward harnessing oxide nanoparticles for valuable multi-electron and multi-hole transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Effects of the low Earth orbital environment on spacecraft materials

It is evident from space flights during the last three years that the low Earth orbital (LEO) environment interacts with spacecraft surfaces in significant ways. One manifestation of these interactions is recession of, in particular, organic-polymer-based surfaces presumably due to oxidation by atomic oxygen, the major component of the LEO environment. Three experiments have been conducted on Space Shuttle flights 5, 8 and 41-G to measure reaction rates and the effects of various parameters on reaction rates. Surface recession on these flights indicates reaction efficiencies approximately 3 x 10(-24) cu cm/atoms for unfilled organic polymers. Of the metals, silver and osmium are very reactive. Effects on spacecraft or experiment surfaces can be evaluated using the derived reaction efficiencies and a definition of the total exposure to atomic oxygen. This exposure is obtained using an ambient density model, solar activity data and spacecraft parameters of altitude, attitude and operational date. Oxygen flux on a given surface is obtained from the ambient density and spacecraft velocity and can then be integrated to provide the total exposure or fluence. Such information can be generated using simple computational programs and can be converted to various formats. Overall, the extent of damage is strongly dependent on the type of surface and total exposure time.

Leger, L. J.↗
NASA NTRS2012

Estimated Environmental Exposures for MISSE-7B

This paper details the 18-month environmental exposure for Materials International Space Station Experiment 7B (MISSE-7B) ram and wake sides. This includes atomic oxygen, ultraviolet radiation, particulate radiation, thermal cycling, meteoroid/space debris impacts, and observed contamination. Atomic oxygen fluence was determined by measured mass and thickness loss of polymers of known reactivity. Diodes sensitive to ultraviolet light actively measured solar radiation incident on the experiment. Comparisons to earlier MISSE flights are discussed.

Finckenor, Miria M.↗
DOE OSTI2025

Cryogenic Carbon Monoxide Oxidation on Cuprous Oxide

Performing oxidation reactions at low temperatures using earth-abundant materials is crucial for advancing solutions for sustainable chemistry. CO oxidation serves as a benchmark reaction to characterize oxidation and to advance fundamental concepts in surface chemistry. While there are several examples of CO oxidation occurring on metal oxides at low temperatures, from 300 K to ∼200 K, reactivity in the cryogenic temperature regime typically requires a metal nanoparticle on a metal oxide. Here, we show oxygen atoms on the (111) facet of Cu 2 O react with CO to form CO 2 at temperatures below 100 K. Combining spectroscopic experimental evidence with calculations, we propose a low barrier path for CO oxidation at reconstructed surface sites on Cu 2 O(111). This finding is a rare example of an earth-abundant metal oxide, in this case copper, that can provide highly reactive multifunctional sites, enabling both adsorption and reaction fundamental steps toward the efficient heterogeneous oxidation of chemicals.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Atomic Oxygen Environment, Effects and Simulation

Atomic oxygen is the most predominant constituent in the low Earth orbital environment between the altitudes of 180 and 650 km. It is also a major constituent of the Mars orbital environment. It is very chemically reactive and can oxidize materials on the outside of spacecraft. In many cases the reaction products are volatile which can lead to mechanical failure. Stable oxides can also form that change the optical or thermal properties of the material. The importance of understanding atomic oxygen reactions with materials has led to both flight experiments in low Earth orbit and ground-based testing in vacuum chambers containing atomic oxygen to study its’ effect on materials. This presentation will focus on defining atomic oxygen environments, discussing atomic oxygen effects on spacecraft materials, reviewing some methods of atomic oxygen simulation, and discussing differences in ground-based testing and space testing as well as synergistic effects.

atomic oxygen, space environment, ground-based tes↗
NASA NTRS1989

Polymer etching in the oxygen afterglow - Increased etch rates with increased reactor loading

Reactor loading has an effect on the etch rate (rate of decrease of film thickness) of films of polyvinylfluoride (Tedlar) and polyethylene exposed in the afterglow of an RF discharge in oxygen. The etch rate is found to increase with the total surface area of the polymer exposed in the reactor. The etch rates of polypyromellitimide (Kapton H) and polystyrene under these conditions are very low. However, the etch rate of these polymers is greatly enhanced by adding either Tedlar or polyethylene to the reactor. A kinetic model is proposed based on the premise that the oxygen atoms produced by the RF discharge react with Tedlar or polyethylene to produce a much more reactive species, which dominates the etching of the polymers studied.

Lerner, N. R.↗
NASA NTRS1994

Small UHV compatible hyperthermal oxygen atom generator

A high purity, hyperthermal, continuous beam atomic oxygen source capable of retrofitting to existing UHV systems has been developed. The instrument complements a general system capability, while its small size and simplicity of design permits tailoring the instrument for most experimental geometries. The flux level presently available is near 1 x 10 (exp 14) cm(exp -2)s(exp -1)(3P) but may be extended toward the theoretical limit of 3x10(exp 15 cm(exp -2)s(exp -1). The energy distribution of the emitted neutrals shows that the mean kinetic energy is about the same as observed for the ions or about 4 eV. The energy of the oxygen atoms may be substantially reduced for other applications by collision with a temperature controlled, non-reactive surface (with a concomitant spread in the energy distribution).

Outlaw, Ronald A.↗
DOE OSTI2025

Circumventing Radical Generation on Fe–V Atomic Pair Catalyst for Robust Oxygen Reduction and Zinc–Air Batteries

Iron–nitrogen–carbon (Fe–N–C) catalysts are considered the most active platinum-free alternative for oxygen reduction reaction (ORR), yet the generated reactive oxygen species (ROS) from general mechanistic pathway rapidly impair the ORR activity and stability of Fe–N–C. Herein, we establish and report an ORR pathway-switching strategy to circumvent ROS generation and fundamentally improve the activity and stability of Fe–N–C via DFT guided catalyst design. The constructed Fe–V atomic pair catalyst (Fe 1 V 1 -NC) with N 2 Fe-N 2 -VN 2 configuration enables side-on adsorption of O 2 and subsequent direct-breaking of the O═O bond to form O*, thereby avoiding the formation of ROS radicals. Importantly, there is intersite electron interaction between FeN 4 and VN 4 , which further boosts the ORR activity. Consequently, Fe 1 V 1 -NC exhibits outstanding ORR activity with onset and half-wave (E 1/2 ) potentials at 1.02 and 0.89 V versus RHE, respectively, in 0.1 M KOH. Record-high stability is achieved on Fe 1 V 1 -NC with a minimal decay in E 1/2 by 16 mV over 50000 cycles, surpassing Fe–N–C counterpart and most of the catalysts reported to date. The Fe 1 V 1 -NC-based zinc-air battery reported here demonstrates exceptional durability up to 400 h at 10 mA·cm −2 . This work identifies the intrinsic correlation between ORR pathway, activity, and stability, advancing development of stable catalytic systems.

Fe-N-C↗
NASA NTRSDate not supplied

Simulation of etch pit formation through active sites in carbon fiber micro-structures

Erosion of carbon due to oxidation does not occur uniformly but through localized etch pit formation as a result of active surface sites. In this work we demonstrate a newly developed capability to capture pitting of carbon fiber microstructures such as FiberForm, which is commonly used as the base material for NASA’s spacecraft ablative thermal protection systems (TPS). The simulations are performed at the meso-scale in order to capture the pit formation and growth using direct simulation Monte Carlo (DSMC), specifically using the Stochastic PArallel Rarefied-gas Time-accurate Analyzer (SPARTA) code. Legacy and latest models both assume uniform reactivity of carbon surface sites with oxygen even at the meso-scale level. However, in reality the carbon surface has locally different reaction rates due to the presence of defects at the atomic scale. The defective nature of these sites enhances their reactivity with atmospheric gases compared to the non-defective sites (2-3 orders of magnitude) and are termed as “active sites”. Thus, these sites tend to be the first to react and eventually get removed through the formation of gasses such as CO, CO2, and CN. Their removal results in all the neighboring atoms becoming defective, thus leading to chain reaction of localized carbon removal and formation of etch pits. Capturing the formation of pits during the ablation simulation of carbon micro-structures is critical to predicting their structural failure. Recently a detailed surface chemistry framework was developed in SPARTA, capable of incorporating various reaction mechanisms such as adsorption, desorption, Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms. We have implemented the capability of a single surface having multiple site sets with different reactivities within this framework. We have used this feature to model the presence of active sites on carbon surfaces, whose reactivity is orders of magnitude higher than that of the passive sites due to the presence of defects. The active site fraction is a property of surface elements within SPARTA and is directly proportional to the local reactivity of each surface element. By introducing an initial distribution of the active site fraction across the carbon surface and propagating it in a manner that mimics the evolution of real reacting carbon surfaces, we can capture the formation and growth of etch pits as a result of surface consumption reactions such as oxidation.

DSMC↗
NASA NTRSDate not supplied

Simulation of Etch Pit Formation in DSMC Through Active Sites in Carbon Fiber Micro-Structures

Erosion of carbon due to oxidation does not occur uniformly but through localized etch pit formation because of active surface sites. In this work we demonstrate a newly developed capability to capture pitting of carbon fiber microstructures such as FiberForm, which is commonly used as the base material for NASA’s spacecraft ablative thermal protection systems (TPS). The simulations are performed at the meso-scale in order to capture the pit formation and growth using direct simulation Monte Carlo (DSMC), specifically using the Stochastic PArallel Rarefied-gas Time-accurate Analyzer (SPARTA) code. Legacy and latest models both assume uniform reactivity of carbon surface sites with oxygen even at the meso-scale level. However, in reality the carbon surface has locally different reaction rates due to the presence of defects at the atomic scale. The defective nature of these sites enhances their reactivity with atmospheric gases compared to the non-defective sites (2-3 orders of magnitude) and are termed as “active sites”. Thus, these sites tend to be the first to react and eventually get removed through the formation of gases such as CO, CO2, and CN. Their removal results in all the neighboring atoms becoming defective, thus leading to chain reaction of localized carbon removal and formation of etch pits. Capturing the formation of pits during the ablation simulation of carbon micro-structures is critical to predicting their structural failure. Recently a detailed surface chemistry framework was developed in SPARTA, capable of incorporating various detailed surface reaction mechanisms. We have implemented the capability of a single surface having multiple site sets with different reactivities within this framework. We have used this feature to model the presence of active sites on carbon surfaces, whose reactivity is orders of magnitude higher than that of the passive sites due to the presence of defects. The active site fraction is a property of surface elements within SPARTA and is directly proportional to the local reactivity of each surface element. By introducing an initial distribution of the active site fraction across the carbon surface and propagating it in a manner that mimics the evolution of real reacting carbon surfaces, we can capture the formation and growth of etch pits as a result of surface consumption reactions such as oxidation.

DSMC↗