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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 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Surface Redox Pseudocapacitance of Partially Oxidized Titanium Carbide MXene in Water-in-Salt Electrolyte

Achieving pseudocapacitive intercalation in MXenes with neutral aqueous electrolytes and driving reversible redox reactions is scientifically appealing and practically useful. Here, we report that the partial oxidation of MXene intensifies pseudocapacitive Li + intercalation into Ti 3 C 2 T x MXene from neutral water-in-salt electrolytes. An in situ X-ray absorption near-edge structure analysis shows that the Ti oxidation state changes during the Li+ intercalation, indicating the presence of a surface redox reaction. The Ti oxidation/reduction is further confirmed by an in situ extended X-ray absorption fine structure analysis, which shows a reversible contraction/expansion of the Ti–C interatomic distance. The intensified Li + pseudocapacitive intercalation can be explained by the higher oxidation state of Ti at the open circuit potential. Furthermore, this work demonstrates the possibility of tuning the pseudocapacitive intercalation by adjusting the initial oxidation state of the transition metal on the MXene and offers a facile way to enhance the pseudocapacitance of various MXenes.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Optimal Linear Water Density for Proton Transport in Tunnel Oxides

Proton intercalation and transport is key to pseudocapacitive energy storage of oxide electrodes in acidic electrolytes. Although proton transport in water confined in layered or 2D materials is attracting great interest, much less is known about how the proton is transported in the 1D channels of tunnel oxides such as hexagonal WO 3 (h-WO 3 ). Here, we use first-principles molecular dynamics to reveal an optimal linear density of four water molecules per nanometer that yields the highest proton diffusivity. The volcano shape of proton diffusivity versus linear water density is a result of balancing the linear hydrogen-bond chain and the rotation of the water molecules to enable the Grotthuss mechanism. Furthermore, this insight provides a unifying view of proton transport along a single file of water molecules confined in hydrophilic 1D channels.

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

Comparison of metal oxide absorbents for regenerative carbon dioxide and water vapor removal for advanced portable life support systems

Metal-oxide absorbents (MOAs) have a demonstrated capability for removal of both metabolic CO2 and H2O from breathing atmospheres, simplifying portable life support system (PLSS) design and affording reversible operation for regeneration. Attention is presently given to the comparative performance levels obtained by silver-oxide-based and silver/zinc-oxide-based systems, which also proved to be longer-lasting than the silver oxide-absorber system. The silver/zinc system is found to substantially simplify the ventilation loop of a prospective Space Station Freedom PLSS.

Stonesifer, Greg T.↗
DOE OSTI2023

Mechanistic Insights on Permeation of Water over Iron Cations in Nanoporous Silicon Oxide Films for Selective H 2 and O 2 Evolution

Electrocatalysts encapsulated by an ultrathin and semipermeable oxide layer offer a promising avenue for efficient, selective, and cost-effective production of hydrogen through photoelectrochemical water splitting. This architecture is especially attractive for Z-scheme water splitting, for which a nanoporous oxide film can be leveraged to mitigate undesired, yet kinetically facile, reactions involving redox shuttles, such as aqueous iron cations, by limiting transport of these species to catalytically active sites. In this work, molecular dynamics simulations were combined with electrochemical measurements to provide a mechanistic understanding of permeation of water and Fe(III)/Fe(II) redox shuttles through nanoporous SiO 2 films. It is shown that even for SiO 2 pores with a width as small as 0.8 nm, water does not experience any energy barrier for permeating into the pores due to a favorable interaction with hydrophilic silanol groups on the oxide surface. In contrast, permeation of Fe(III) and Fe(II) into microporous SiO 2 pores is limited due to high energy barriers, which stem from a combination of distortion and dehydration of the second and third ion solvation shells. Furthermore, our simulations and experimental results show that SiO 2 coatings can effectively mitigate undesired Fe(III)/Fe(II) redox reactions at underlying electrodes by attenuating permeation of iron cations, while allowing water to permeate and thus participate in water splitting reactions. In a broader context, our study demonstrates that selectivity of solvated cations can be manipulated by controlling the pore size and surface chemistry of oxide films.

14 SOLAR ENERGY↗
DOE OSTI2020

Atomic layer deposition of HfO 2 films using carbon-free tetrakis(tetrahydroborato)hafnium and water

Thin hafnium oxide films were prepared by atomic layer deposition using a carbon-free precursor, tetrakis(tetrahydroborato)hafnium [Hf(BH 4 )( 4 )], and H 2 O. Film growth was studied using an in situ quartz crystal microbalance and Fourier transform infrared spectroscopy measurements. Self-limiting growth was observed between 100 and 175 degrees C, but the thermal decomposition of the Hf precursor occurred at higher temperatures. The film properties were investigated using x-ray photoelectron spectroscopy, x-ray reflectivity, x-ray diffraction, ellipsometry, time-of-flight secondary ion mass spectrometry, and x-ray absorption spectroscopy. The as-deposited films were found to consist of an amorphous mixture of HfO 2 and B 2 O 3 , and had a lower density and lower refractive index compared to pure HfO 2 thin films. Finally, annealing the films to >750 degrees C yielded crystalline monoclinic HfO 2 with a density of 9g/cm 3 and a refractive index of 2.10.

36 MATERIALS SCIENCE↗
NASA NTRS1992

Removing Solids From Supercritical Water

Apparatus removes precipitated inorganic salts and other solids in water-recycling process. Designed for use with oxidation in supercritical water which treats wastes and yields nearly pure water. Heating coils and insulation around vessel keep it hot. Locking bracket seals vessel but allows it to be easily opened for replacement of filled canisters.

Hong, Glenn T.↗
NASA NTRS2004

Oxidation of Ultra-High Temperature Ceramics in Water Vapor

Ultra High Temperature Ceramics (UHTCs) including HfB2 + 20% SiC (HS), and ZrB2 + 20% SiC (ZC), and ZrB2 + 30% C + 14% SiC (ZCS) have been investigated for use as potential aeropropolsion engine materials. These materials were oxidized in water vapor (90%) using a cyclic vertical furnace at 1 atm. The total exposure time was 10 hours at temperature of 1200, 1300, and 1400 C. CVD SiC was also evaluate as a baseline for comparison. Weight change, X-ray diffraction analysis, surface and cross-sectional SEM and EDS were performed. These results are compared with tests conducted in a stagnant air furnace at temperatures of 1327 C for 100 minutes, and with high pressure burner rig (HPBR) results at 1100 and 1300 C at 6 atm for 50 h. Total recession measurements are also reported for the two tests environments.

Nguyen, QuynGiao N.↗
DOE OSTI2022

Oxygen Isotope Fractionation in U 3 O 8 during Thermal Processing in Humid Atmospheres

The incorporation of oxygen isotopes from water into uranium oxides during industrial processing presents a pathway for determining a material’s geographical origin. This study is founded on the hypothesis that oxygen isotopes from atmospheric water vapor will exchange with isotopes of oxygen in solid uranium oxides during thermal processing or calcination. Using a commonly encountered oxide, U 3 O 8 , the exchange kinetics and equilibrium fractionation with water vapor (in a concentration range of 50–55% relative humidity) were investigated using processing temperatures of 400, 600, and 800 °C. In an atmosphere containing only water vapor diluted in N 2 , oxygen isotope equilibration in U 3 O 8 occurred within 12 h at 400 °C and within 2 h at 600 and 800 °C. Fractionation factors (1000lnα, U 3 O 8 –H 2 O) between the water and oxide were –12.1, –11.0, and –8.0 at 400, 600, and 800 °C, respectively. With both humidity and O 2 present in the calcining atmosphere, isotopic equilibration is attained within 2 h at and above 400 °C. In this mixed atmosphere, which was designed to emulate Earth’s troposphere, isotopes are incorporated preferentially from water vapor at 400 °C and from O 2 at 600 and 800 °C. Rapid and temperature/species-dependent isotope exchange also elucidated the impact of retrograde exchange in humid air, showing a shift from O 2 -dependent to H 2 O-dependent fractionation as U 3 O 8 cooled from 800 °C. These results confirm that uranium oxides inherit oxygen isotopes from humidity during thermal processing, illuminating an important mechanism in the formation of this forensic signature.

07 ISOTOPE AND RADIATION SOURCES↗
NASA NTRS1990

Characterization of metal oxide absorbents for regenerative carbon dioxide and water vapor removal for advanced portable life support systems

Characterization of the performance of a silver-oxide-based absorbent in terms of its ability to remove both gaseous CO2 and water vapor in an astronaut portable life support systems (PLSS) is discussed. Attention is focused on regeneration of the absorbent from the carbonite state of the oxide state, preconditioning of the absorbent using a humidified gas stream, and absorption breakthrough testing. Based on the results of bench-scale experiments, a test plan is carried out to further characterize the silver-oxide-based absorbent on a larger scale; it calls for examination of the absorbent in both an adiabatic packed bed and a near-isothermal cooled bed configuration. It is demonstrated that the tested absorbent can be utilized in a way that removes substantial amounts of CO2 and water vapor during an 8-hour extravehicular activity mission, and that applying the absorbent to PLSS applications can simplify the ventilation loop.

Kast, Timothy P.↗
NASA NTRS1990

Oxidation kinetics of model compounds of metabolic waste in supercritical water

In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

Webley, Paul A.↗
NASA NTRS2014

The Upside-Down Biosphere: Evidence for the Partially Oxygenated Oceans During the Archean Eon

This is a commentary on the preceding chapter by Ohmoto et al., in which it is suggested that oxygen concentrations have been high throughout Earth history. This is a contentious suggestion at odds with the prevailing view in the field, which contends that atmospheric oxygen concentrations rose from trace levels to a few percent of modern-day levels around 2.5 b.y. ago. This comment notes that many of the data sets cited by Ohmoto et al. as evidence for a relatively oxidized environment come from deep-ocean settings. This presents a possibility to reconcile some of these data and suggestions with the overwhelming evidence for an atmosphere free of oxygen at that time. Specifically, it is possible that deep-ocean waters were relatively oxidized with respect to certain redox pairs. These deep-ocean waters would have been more oxidized than surface waters, thus representing an "upside-down biosphere," as originally proposed 25 years ago by Jim Walker.

oxygenated oceans↗
DOE OSTI2025

Low-iridium stabilized ruthenium oxide anode catalyst for durable proton-exchange membrane water electrolysis

While mixing iridium (Ir) with ruthenium oxide (RuO 2 ) has proven to be an effective strategy for reducing Ir loading in anode catalysts for proton-exchange membrane (PEM) water electrolysers, achieving industrially relevant long-term stability typically requires an Ir-rich, Ru-lean combination. Here, in this study, by combining density functional theory with Metropolis Monte Carlo methods, we discovered that sufficient stabilization in the RuO 2 lattice could be achieved with less than 50 at.% of Ir, and that Ir in the first subsurface layer plays a critical role. By effectively dispersing Ir dopants within the RuO 2 lattice, we demonstrated an Ir:Ru atomic ratio of only 1:6 that exhibited exceptional stability for over 1,500 h of continuous water electrolysis at 2 A cm −2 . Our Ru 6 IrO x catalyst has the potential to reduce Ir loading by 80% compared with current commercial PEM water electrolysers, and its stability was further validated under industrial testing conditions in a 25-cm 2 PEM electrolyser.

36 MATERIALS SCIENCE↗
NASA NTRS2003

Oxidation of Ultra-High Temperature Ceramics in Water Vapor

Ultra high temperature ceramics (UHTCs) including HfB2 + SiC (20% by volume), ZrB2 + SiC (20% by volume) and ZrB2 + SiC (14% by volume) + C (30% by volume) have historically been evaluated as reusable thermal protection systems for hypersonic vehicles. This study investigates UHTCs for use as potential combustion and aeropropulsion engine materials. These materials were oxidized in water vapor (90%) using a cyclic vertical furnace at 1 atm. The total exposure time was 10 hours at temperatures of 1200, 1300, and 1400 C. CVD SiC was also evaluated as a baseline comparison. Weight change measurements, X-ray diffraction analyses, surface and cross-sectional SEM and EDS were performed. These results will be compared with tests ran in static air at temperatures of 1327, 1627, and 1927 C. Oxidation comparisons will also be made to the study by Tripp. A small number of high pressure burner rig (HPBR) results at 1100 and 1300 C will also be discussed. Specific weight changes at all three temperatures along with the SIC results are shown. SiC weight change is negligible at such short duration times. HB2 + SiC (HS) performed the best out of all the tested UHTCS for all exposure temperatures. ZrB2 + Sic (ZS) results indicate a slightly lower oxidation rate than that of ZrBl + SiC + C (ZCS) at 1200 and 1400 C, but a clear distinction can not be made based on the limited number of tested samples. Scanning electron micrographs of the cross-sections of all the UHTCs were evaluated. A representative area for HS is presented at 1400 C for 26 hours which was the composition with the least amount of oxidation. A continuous SiO2 scale is present in the outer most edge of the surface. An image of ZCS is presented at 1400 C for 10 hours, which shows the most degradation of all the compositions studied. Here, the oxide surface is a mixture of ZrSiO4, ZrO2 and SO2.

Nguyen, QuynhGiao N.↗
DOE OSTI2020

Water-promoted interfacial pathways in methane oxidation to methanol on a CeO 2 -Cu 2 O catalyst

Highly selective oxidation of methane to methanol has long been challenging in catalysis. Here, we reveal key steps for the pro­motion of this reaction by water when tuning the selectivity of a well-defined CeO 2 /Cu 2 O/Cu(111) catalyst from carbon monoxide and carbon dioxide to methanol under a reaction environment with methane, oxygen, and water. Ambient-pressure x-ray photoelectron spectroscopy showed that water added to methane and oxygen led to surface methoxy groups and accelerated methanol production. These results were consistent with density functional theory calculations and kinetic Monte Carlo simulations, which showed that water preferentially dissociates over the active cerium ions at the CeO 2 –Cu 2 O/Cu(111) interface. The adsorbed hydroxyl species blocked O-O bond cleavage that would dehydrogenate methoxy groups to carbon monoxide and carbon dioxide, and it directly converted this species to methanol, while oxygen reoxidized the reduced surface. Water adsorption also displaced the produced methanol into the gas phase.

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

Interaction of molecular nitrogen with vanadium oxide in the absence and presence of water vapor at room temperature: Near-ambient pressure XPS

Interactions of N2 at oxide surfaces are important for understanding electrocatalytic nitrogen reduction reaction (NRR) mechanisms. Interactions of N2 at the polycrystalline vanadium oxide/vapor interface were monitored at room temperature and total pressures up to 10−1 Torr using Near-Ambient Pressure X-ray Photoelectron Spectroscopy (NAP-XPS). The oxide film was predominantly V(IV), with V(III) and V(V) components. XPS spectra were acquired in environments of both pure N2 and equal pressures of N2 and H2O vapor. In pure N2, broad, partially resolved N1s features were observed at binding energies of 401.0 and 398.7 eV, with a relative intensity of ∼3:1, respectively. These features remained upon subsequent pumpdown to 10−9 Torr. The observed maximum N surface coverage was ∼1.5 × 1013 cm−2—a fraction of a monolayer. In the presence of equal pressures of H2O, the adsorbed N intensity at 10−1 Torr is ∼25% of that observed in the absence of H2O. The formation of molecularly adsorbed H2O was also observed. Density functional theory-based calculations suggest favorable absorption energies for N2 bonding to both V(IV) and V(III) cation sites but less so for V(V) sites. Hartree–Fock-based cluster calculations for N2–V end-on adsorption show that experimental XPS doublet features are consistent with the calculated shake-up and normal, final ionic configurations for N2 end-on bonding to V(III) sites but not V(IV) sites. The XPS spectra of vanadium oxide transferred in situ between electrochemical and UHV environments indicate that the oxide surfaces studied here are stable upon exposure to the electrolyte under NRR-relevant conditions.

Balogun, K.↗
DOE OSTI2023

Ion and water adsorption to graphene and graphene oxide surfaces

Graphene and graphene oxide (GO) are two particularly promising nanomaterials for a range of applications including energy storage, catalysis, and separations. Understanding the nanoscale interactions between ions and water near graphene and GO surfaces is critical for advancing our fundamental knowledge of these systems and downstream application success. Here this minireview highlights the necessity of using surface-specific experimental probes and computational techniques to fully characterize these interfaces, including the nanomaterial, surrounding water, and any adsorbed ions, if present. Key experimental and simulation studies considering water and ion structures near both graphene and GO are discussed. The major findings are: water forms 1–3 hydration layers near graphene; ions adsorb electrostatically to graphene under an applied potential; the chemical and physical properties of GO vary considerably depending on the synthesis route; and these variations influence water and ion adsorption to GO. Lastly, we offer outlooks and perspectives for these research areas.

36 MATERIALS SCIENCE↗
NASA NTRS1981

Electrophotolysis oxidation system for measurement of organic concentration in water

Methods and apparatus for determining organic carbon in aqueous solution are described. The method comprises subjecting the aqueous solution to electrolysis, for generating oxygen from water, and simultaneously to ultraviolet radiation, for oxidation of substantially all organic carbon to carbon dioxide. The carbon dioxide is measured and the value is related to the concentration of organic carbon in the aqueous solution.

Winkler, H. E.↗