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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Enhanced Ferromagnetism from Organic–Cerium Oxide Hybrid Ultrathin Nanosheets

Room-temperature ferromagnetism in two-dimensional (2D) oxide materials is an intriguing phenomenon for spintronic applications. Here, we report significantly enhanced room-temperature ferromagnetism observed from ultrathin cerium oxide nanosheets hybridized with organic surfactant molecules. The hybrid nanosheets were synthesized by ionic layer epitaxy over a large area at the water–air interface. The nanosheets exhibited a saturation magnetization of 0.149 emu/g as their thickness reduced to 0.67 nm. This value was 5 times higher than that for CeO 2 thin films and more than 20 times higher than that for CeO 2 nanoparticles. The magnetization was attributed to the high concentration (15.5%) of oxygen vacancies stabilized by surfactant hybridization as well as electron transfer between organic and oxide layers. Lastly, this work brings an effective strategy of introducing strong ferromagnetism to functional oxide materials, which leads to a promising route toward exploring new physical properties in 2D hybrid nanomaterials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Deciphering the Mechanistic Role of Individual Oxide Phases and Their Combinations in Supported Mn–Na 2 WO 4 Catalysts for Oxidative Coupling of Methane

Oxidative coupling of methane (OCM) is an attractive direct route for upgrading methane to valuable chemicals. In this study, Temporal Analysis of Products (TAP) and steady state experiments are conducted to understand the role of individual oxide phases and their combinations in supported Mn-Na 2 WO 4 /SiO 2 catalysts for OCM. The results from TAP transient kinetic studies indicate that Mn plays an important role in promoting gas phase oxygen activation, while NaO x /SiO 2 and WO x /SiO 2 are relatively inert towards gas phase oxygen and methane activation. However, the supported catalyst combining Na and W in the form Na 2 WO 4 show enhanced gas phase oxygen activation exhibiting a much lower oxygen activation energy (148 kJ/mol) and enhanced activity toward methane activation as compared to the individual supported oxide catalysts. Addition of Mn to Na 2 WO 4 /SiO 2 further decreases the oxygen activation energy by 40 kJ/mol. Moreover, methane activation is also enhanced with CH 3 as the main intermediate but, with increasing Mn content, more CH 2 intermediates are observed. Different forms of oxygen (both dioxygen and atomic) are detected on the catalyst surface using isotopic pump/probe pulsing and their distribution is found to depend on the catalyst composition. An optimal Mn content in the Na 2 WO 4 /SiO 2 catalyst system is needed to enhance the amount of dioxide surface species (e.g., superoxide 16 O 2 - or peroxide 16 O 2 2- ) associated with the Na 2 WO 4 leading to high C 2 selectivity for OCM. When the Mn content is too high, the larger MnOx domains are shown to contribute to the formation of higher concertation of monoxide surface species that lead to nonselective OCM pathways. This insight from transient kinetic characterization using TAP combined with conventional steady state studies, provides a deeper understanding of the role of individual oxide phases and their combination on supported catalysts toward the formation of intermediate surface species and their impact on the OCM reaction mechanism. This knowledge is critical toward designing superior catalyst formulations for OCM.

10 SYNTHETIC FUELS↗
DOE OSTI2017

Enhanced Hydrothermal Stability and Catalytic Activity of LaxZryOz Mixed Oxides for the Ketonization of Acetic Acid in the Aqueous Condensed Phase

Common ketonization catalysts such as ZrO2, CeO2, and TiO2-based catalysts have been reported to lose surface area, undergo phase transformation, and lose catalytic activity when utilized in the condensed aqueous phase. In this work, we synthesized a series of LaxZryOz mixed-metal oxides with different La:Zr atomic ratios with the goal of enhancing the catalytic activity and stability for the ketonization of acetic acid in condensed aqueous media at 568 K. We synthesized a hydrothermally stable LaxZryOz mixed-metal oxide catalyst with ketonization activity360 and 40 times more active than La2O3 and ZrO2, respectively. Catalyst characterization techniques suggest that the enhanced stability of the LaxZryOz catalysts is observed with the formation of a phase isomorphic with tetragonal ZrO2. DRIFT spectroscopy measurements indicated the enhanced catalytic activity of LaxZryOz catalysts correlated with greater acetic acid surface population in the presence of H2O versus pure ZrO2.

ketonization, deoxygenation, carboxylic acid, acet↗
DOE OSTI2019

Perspectives on the Development of Oxide-Based Photocathodes for Solar Fuel Production

Photoelectrochemical cells (PECs), which use semiconductor electrodes (photoelectrodes) to absorb solar energy and perform chemical reactions, constitute one of the most attractive strategies to produce chemical fuels using renewable energy sources. Oxide-based photoelectrodes specifically have been intensively investigated for the construction of PECs due to their relatively inexpensive processing costs and better stability in aqueous media compared with other types of photoelectrodes. Although there have been many advancements in the development of oxide-based photoanodes, our understanding of oxide-based photocathodes remains limited. The goal of this Perspective is to examine the recent progress made in the field of oxide-based photocathodes and discuss future research directions. The photocathode systems considered here include binary and ternary Cu-based photocathodes and ternary Fe-based photocathodes. Here, we assessed the characteristics and major advantages and drawbacks of each system and identified the most critical research gaps. The insights and discussions provided in this Perspective will serve as useful resources for the design of future studies, leading to the development of more efficient and practical PECs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Mesoporous silica-encapsulated gold core–shell nanoparticles for active solvent-free benzyl alcohol oxidation

Silica-encapsulated gold core@shell nanoparticles (Au@SiO2 CSNPs) were synthesized via a bottom-up procedure and used to catalyze the selective oxidation of benzyl alcohol. The pore size, morphology, crystallinity and composition of Au@SiO2 was evaluated using non-local density functional theory, transmission electron microscopy, high-energy x-ray diffraction and inductively coupled plasma-mass spectroscopy, respectively. The nanoparticles exhibit a mesoporous shell with an average thickness of 25.5 Å which can enhance selectivity via preferential transport of the desired product (i.e., benzaldehyde) relative to larger, undesired products (i.e, benzoic acid/benzyl benzoate). GC-FID analysis revealed the addition of potassium carbonate to the solvent-free oxidation of benzyl alcohol increased conversion from 17.3 to 60.4% while decreasing selectivity from 98.7 to 75.0%. Under equivalent conditions, a bare gold nanoparticle control catalyst deposited on a silica support with a similar gold surface area took 6 times as long to reach the same conversion, achieving only 49.4% selectivity. These results suggest that the pore size distribution within the inert silica shell of Au@SiO2 CSNPs inhibits the formation of undesired products to facilitate the selective oxidation of benzaldehyde despite a basic environment, which reduces selectivity under typical conditions. The CSNPs demonstrated a much lower activation energy than the Au-SiO2 control catalyst, 37 ± 1.9 kJ/mol and 72 ± 7.1 kJ/mol, respectively. Thiele modulus analysis indicates the CSNP pore structure does not create a mass transport limitation due to the nano-scale path of diffusion through the pore structure to the active surface. The lower activation energy and mesopore distribution together suggest the Au@SiO2 catalyst demonstrates higher activity through beneficial in-pore orientation, both reducing competitive adsorption and promoting a single, lower activation energy mechanistic pathway.

benzyl alcohol oxidation, catalysis, confinement↗
DOE OSTI2020

Direct Oxidation of Primary Alcohols to Carboxylic Acids

Oxidation of primary alcohols to carboxylic acids is a fundamental transformation in organic chemistry, yet despite its simplicity, extensive use, and relationship to pH, it remains a subject of active research for synthetic organic chemists. Since 2013, a great number of new methods have emerged that utilize transition-metal compounds as catalysts for acceptorless dehydrogenation of alcohols to carboxylates. The interest in this reaction is explained by its atom economy, which is in accord with the principles of sustainability and green chemistry. Furthermore, the methods for the direct synthesis of carboxylic acids from alcohols is ripe for a modern survey, which we provide in this review.

acceptorless dehydrogenation↗
DOE OSTI2018

MIS High-Purity Plutonium Oxide Metal Oxidation Product BLO-39-11-14-004 (SSR132 and 132A): Final Report

A high-purity, reactor-grade plutonium dioxide material from the Material Identification and Surveillance (MIS) Program inventory has been studied with regard to gas generation and corrosion in a storage environment. BLO-39-11-14-004 is a high specific power oxide that represents Hanford process plutonium oxides from oxalate process product, oxalate precipitation of impure plutonium and pure mixed uranium/plutonium nitrate solutions, PFP NDA and impure and scrap plutonium oxides 80-85% from PFP and the 300 area. It also represents plutonium oxides from oxalate precipitation at LANL and Savannah River. After calcination to 950 °C, the material contained 80% plutonium and 7% americium with no major impurities. This study followed over time the gas pressure of a sample with nominally 0.5 wt% water in a sealed container with an internal volume scaled to 1/500th of the volume of a 3013 container. A leak occurred in the original reactor (SSR132) which was terminated after 3 years. The sample was reloaded (SSR132A) and an additional set of data was collected. Results from both loadings are discussed. Gas compositions were measured periodically over three (SSR132) and four and a half (SSR132A) year periods. The maximum observed gas pressures were 93 kPa and 94 kPa, respectively. The increase over the initial pressure was primarily due to generation of nitrogen gas. For SSR132, the maximum observed gas pressure for hydrogen was 1.2 kPa and oxygen was 9.3 kPa (includes oxygen from leak). For SSR132A, the maximum observed gas pressure for hydrogen was 5.5 kPa and oxygen was 0.9 kPa. At the completion of the study, the internal components of the sealed container showed limited signs of corrosion.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Graphite Oxidation Rate Study on ET-10 and ETU-10 Grades - Task 4: QA Support and Testing for Structural Graphite Oxidation

INL performed targeted oxidation tests to measure oxidation rates for samples of ET-10 and ETU-10 graphite under CRADA No. 21CRA22 Mod. 3, Annex A, “Tritium Testing to Support Kairos Power Advanced Reactor Demonstration” (04/02/2024). All testing was conducted within INL’s Carbon Characterization Laboratory (CCL) using test standard ASTM D7542-21 "Standard Test Method for Air Oxidation of Carbon and Graphite in the Kinetic Regime" [ASTM International, 2021]. Kairos Power provided all test specimens through its graphite vendor Ibiden, Inc. to INL and ASTM specimen specified dimensions. Information within this report only provides the Arrhenius oxidation rate plots as a function of temperature for each graphite grade tested. The raw mass loss per time data will be provided on the Nuclear Data Management and Analysis System (NDMAS) portal located on the INL information system.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Synthesis of Nano-Oxide Precipitates by Implantation of Ti, Y and O Ions in Fe-10%Cr: Towards an Understanding of Precipitation in Oxide Dispersion-Strengthened (ODS) Steels

The properties of oxide dispersion-strengthened steels are highly dependent on the nature and size distribution of their constituting nano-oxide precipitates. A fine control of the processes of synthesis would enable the optimization of pertinent properties for use in various energy systems. This control, however, requires knowledge of the precise mechanisms of nucleation and growth of the nanoprecipitates, which are still a matter of debate. In the present study, nano-oxide precipitates were produced via the implantation of Y, Ti, and O ions in two different sequential orders in an Fe-10%Cr matrix that was subsequently thermally annealed. The results show that the oxides that precipitate are not necessarily favoured thermodynamically, but rather result from complex kinetics aspects related to the interaction between the implanted elements and induced defects. When Y is implanted first, the formation of nanoprecipitates with characteristics similar to those in conventionally produced ODS steels, especially with a core/shell structure, is evidenced. In contrast, when implantation starts with Ti, the precipitation of yttria during subsequent high-temperature annealing is totally suppressed, and corundum Cr 2 O 3 precipitates instead. Moreover, the systematic involvement of {110} matrix planes in orientation relationships with the precipitates, independently of the precipitate nature, suggests matrix restriction effects on the early stages of precipitation.

36 MATERIALS SCIENCE↗
NASA NTRS1991

Air oxidation of hydrazine. 1. Reaction kinetics on natural kaolinites, halloysites, and model substituent layers with varying iron and titanium oxide and O- center contents

Air oxidation of hydrazine was studied by using a group of kaolinites, halloysites, and substituent oxides as models for the tetrahedral and octahedral sheets. The rate was found to be linear with oxygen. The stoichiometry showed that oxygen was the primary oxidant and that dinitrogen was the only important nitrogen-containing product. The rates on kaolinites were strongly inhibited by water. Those on three-dimensional silica and gibbsite appeared not to be. That on a supposedly layered silica formed from a natural kaolinite by acid leaching showed transitional behavior--slowed relative to that expected from a second-order reaction relative to that on the gibbsite and silica but faster than those on the kaolinites. The most striking result of the reaction was the marked increase in the rate of reaction of a constant amount of hydrazine as the amount of clay was increased. The increase was apparent (in spite of the water inhibition at high conversions) over a 2 order of magnitude variation of the clay weight. The weight dependence was taken to indicate that the role of the clay is very important, that the number of reactive centers is very small, or that they may be deactivated over the course of the reaction. In contrast to the strong dependence on overall amount of clay, the variation of amounts of putative oxidizing centers, such as structural Fe(III), admixed TiO2 or Fe2O3, or O- centers, did not result in alteration of the rate commensurate with the degree of variation of the entity in question. Surface iron does play some role, however, as samples that were pretreated with a reducing agent were less active as catalysts than the parent material. These results were taken to indicate either that the various centers interact to such a degree that they cannot be considered independently or that the reaction might proceed by way of surface complexation, rather than single electron transfers.

NASA Discipline Number 52-20↗
NASA NTRS1996

Use-dependent loss of active sympathetic neurogenic vasodilation after nitric oxide synthase inhibition in conscious rats. Evidence for the presence of preformed stores of nitric oxide-containing factors

In this study, we examined whether air-jet stress-induced active sympathetic hindlimb vasodilation in conscious rats involves the release of preformed stores of nitric oxide-containing factors. We determined the effects of repeated episodes of air-jet stress (six episodes given 5 minutes apart) on mean arterial pressure and vascular resistances in the mesenteric bed and intact and sympathetically denervated hindlimb beds of conscious rats treated with saline or the nitric oxide synthesis inhibitor N omega-nitro-L-arginine methyl ester (L-NAME, 25 mumol/kg IV). In saline-treated rats, air-jet stress produced alerting behavior, minor changes in blood pressure, pronounced mesenteric vaso-constriction, and immediate and marked vasodilation in the sympathetically intact hindlimb but a minor vasodilation in the sympathetically denervated hindlimb. Each air-jet stress produced virtually identical responses. In L-NAME-treated rats, the first air-jet stress produced vasodilator responses in the sympathetically intact and sympathetically denervated hindlimbs that were similar to those in the saline-treated rats. However, each subsequent air-jet stress produced progressively smaller vasodilator responses in the sympathetically intact but not the sympathetically denervated hindlimb. There was no loss of air-jet stress-induced alerting behavior or mesenteric vasoconstriction, suggesting that L-NAME did not interfere with the central processing of the air-jet or the resultant changes in autonomic nerve activity. The progressive diminution of air-jet stress-induced vasodilation in the intact hindlimb of L-NAME-treated rats may be due to the use-dependent depletion of preformed stores of nitric oxide-containing factors that cannot be replenished in the absence of nitric oxide synthesis.

NASA Discipline Regulatory Physiology↗
DOE OSTI2019

Tuning the Selectivity and Activity of Electrochemical Interfaces with Defective Graphene Oxide and Reduced Graphene Oxide

Engineered solid-liquid interfaces will play an important role in the development of future energy storage and conversion (ESC) devices. In the present study, defective graphene oxide (GO) and reduced graphene oxide (rGO) structures were used as engineered interfaces to tune the selectivity and activity of Pt disk electrodes. GO was deposited on Pt electrodes via the Langmuir-Blodgett technique, which provided compact and uniform GO films, and these films were subsequently converted to rGO by thermal reduction. Electrochemical measurements revealed that both GO and rGO interfaces on Pt electrodes exhibit selectivity toward the oxygen reduction reaction (ORR), but they do not have an impact on the activity of the hydrogen oxidation reaction in acidic environments. Scanning transmission electron microscopy at atomic resolution, along with Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM), revealed possible diffusion sites for H 2 and O 2 gas molecules and functional groups relevant to the selectivity and activity of these surfaces. Based on these insights, rGO interfaces are further demonstrated to exhibit enhanced activity for the ORR in nonaqueous environments and demonstrate the power of our ex situ engineering approach for the development of next-generation ESC devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Highly Efficient Urea Oxidation via Nesting Nano-Nickel Oxide in Eggshell Membrane-Derived Carbon

Here, we reported a strategy of using an eggshell membrane to produce hierarchically porous carbon as a low-cost substrate for synthesizing a nano-nickel oxide catalyst (C@NiO), which can effectively turn biowaste—urea—into energy through an electrochemical approach. Here, the interwoven carbon networks within NiO led to highly efficient urea oxidation due to the strong synergistic effect. The as-prepared electrode only needed 1.36 V versus reversible hydrogen electrode to realize a high efficiency of 10 mA cm –2 in 1.0 M KOH with 0.33 M urea and delivered an even higher current density of 25 mA cm –2 at 1.46 V, which is smaller than that of the porous carbon and commercial Pt/C catalyst. Benefiting from theoretical calculations, Ni(III) active species and the porous carbon further enabled the electrocatalyst to effectively inhibit the “CO 2 poisoning” of electrocatalysts, as well as ensuring its superior performance for urea oxidation.

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

Investigation of long-term light stability of negative charge injected into oxide-nitride-oxide passivation stack of crystalline silicon solar cells

A negatively charged oxide-nitride-oxide stack for field-effect passivation of crystalline silicon solar cells is discussed. The negative charge was injected into the stack by a plasma charge injection technology. Charge stability was studied by exposing samples to AM1.5 simulation visible light and full-spectrum light at temperatures ranging from 55 to 78 °C for up to 300 h. Charge injection and loss were quantified based on shifts in the flatband voltage of capacitance–voltage curves measured with a mercury probe. The most probable mechanism of charge loss was found to be diffusion of negative charged hydrogen atoms through nitride and bottom oxide. The optimum recipe for each layer of the stack was investigated to minimize the loss of injected charge. The flatband voltage decay of the optimized stack was found to fit a power-law trend, suggesting the dispersive transport of hydrogen atoms with a dispersion parameter of ~0.06–0.07. The optimized stack is projected to maintain a negative charge density of about 3.6 × 10 12 cm –2 or more after 25 years of field operation in an environment such as Arizona, which would be sufficient for field-effect passivation under one-sun illumination. Furthermore, the high stability of the negative injected charge makes the plasma charging technology a safer and lower cost alternative to Al 2 O 3 -passivation technology commonly used to passivate p-type surfaces.

14 SOLAR ENERGY↗