Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “oxide activation”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Oxygen-Plasma-Induced Hetero-Interface NiFe2O4/NiMoO4 Catalyst for Enhanced Electrochemical Oxygen Evolution

The electrolysis of water to produce hydrogen is an effective method for solving the rapid consumption of fossil fuel resources and the problem of global warming. The key to its success is to design an oxygen evolution reaction (OER) electrocatalyst with efficient conversion and reliable stability. Interface engineering is one of the most effective approaches for adjusting local electronic configurations. Adding other metal elements is also an effective way to enrich active sites and improve catalytic activity. Herein, high-valence iron in a heterogeneous interface of NiFe 2 O 4 /NiMoO 4 composite was obtained through oxygen plasma to achieve excellent electrocatalytic activity and stability. In particular, 270 mV of overpotential is required to reach a current density of 50 mA cm -2 , and the overpotential required to reach 500 mA cm -2 is only 309 mV. The electron transfer effect for high-valence iron was determined by X-ray photoelectron spectroscopy (XPS). The fast and irreversible reconstruction and the true active species in the catalytic process were identified by in situ Raman, ex situ XPS, and ex situ transmission electron microscopy (TEM) measurements. This work provides a feasible design guideline to modify electronic structures, promote a metal to an active oxidation state, and thus develop an electrocatalyst with enhanced OER performance.

36 MATERIALS SCIENCE↗
NASA NTRS1986

Friction-Testing Machine

Testing machine evaluates wear and ignition characteristics of materials in rubbing contact. Offers advantages over other laboratory methods of measuring wear because it simulates operating conditions under which material will actually be used. Machine used to determine wear characteristics, rank and select materials for service with such active oxidizers as oxygen, halogens, and oxides of nitrogen, measure wear characteristics, and determine coefficients of friction.

Benz, F. J.↗
NASA NTRS1990

Alternative catalysts for low-temperature CO-oxidation

MnO sub x, Ag/MnO sub x, Cu/MnO sub x, Pt/MnO sub x, Ru/MnO sub x, Au/CeO sub x, and Au/Fe2O3 were synthesized and tested for CO oxidation activity in low concentrations of stoichiometric CO and O2 at 30 to 75 C. Catalytic activity was measured for periods as long as 18000 minutes. At 75 deg Au/MnO sub x is most active sustaining nearly 100 percent CO conversion for 10000 minutes. It also retains high activity at 50 and 30 C with negligible decay in activity. A direct comparison between an unpretreated 10 percent Au/MnO sub x catalyst and an optimized 19.5 percent Pt/SnO sub 2 (pretreated) catalyst shows that the Au/MnO sub x catalyst exhibits much higher catalytic activity and far superior decay characteristics. Other catalysts including Au/CeO sub x and Au/Fe2O3 also perform well. The Cu/MnO sub x exhibits a high initial activity which decays rapidly. After the decay period the activity remains very stable making Cu/MnO sub x a potential candidate for long-term applications such as CO2 lasers in space.

Gardner, Steven D.↗
NASA NTRS1990

Platinized tin oxide catalysts for CO2 lasers: Effects of pretreatment

Platinized tin oxide surfaces used for low-temperature CO oxidation in CO2 lasers have been characterized before and after reduction in CO at 125 and 250 C using ion scattering spectroscopy (ISS) and X ray photoelectron spectroscopy (XPS). XPS indicates that the Pt is present initially as PtO2. Reduction at 125 C converts the PtO2 to Pt(OH)2 while reduction at 250 C converts the PtO2 to metallic Pt. ISS shows that the Pt in the outermost atomic layer of the catalyst is mostly covered by substrate species during the 250 C reduction. Both the ISS and XPS results are consistent with Pt/Sn alloy formation. The surface dehydration and migration of substrate species over surface Pt and Sn appear to explain why a CO pretreatment at 250 C produces inferior CO oxidation activities compared to a 125 C pretreatment.

Gardner, Steven D.↗
NASA NTRS1989

Platinized tin oxide catalysts for CO2 lasers - Effects of pretreatment

Platinized tin oxide surfaces used for low-temperature CO oxidation in CO2 lasers have been characterized before and after reduction in CO at 125 and 250 C using ion scattering spectroscopy (ISS) and X-ray photoelectron spectroscopy (XPS). XPS indicates that the Pt is present initially as Pto2. Reduction at 125 C converts the PtO2 to Pt(OH)2 while reduction at 250 C converts the PtO2 to metallic Pt. ISS shows that the Pt in the outermost atomic layer of the catalyst is mostly covered by substrate species during the 250 C reduction. Both the ISS and XPS results are consistent with Pt/Sn alloy formation. The surface dehydration and migration of substrate species over surface Pt and Sn appear to explain why a CO pretreatment at 250 C produces inferior CO oxidation activities compared to a 125 C pretreatment.

Gardner, Steven D.↗
NASA NTRS2021

Development and Characterization of Lightweight Durable Composite Conductor for Cables

Sustainable aviation in the form of electrified propulsion is likely to lead to an increase in the electrical assets contained within a single aircraft. As a result, it is desirable to design light weight conductor materials, thus reducing the payload of components like motor windings, low voltage signal cables, and transmission cables for data and power. One approach involves replacing pure Cu wiring with metalized CNT composites. This paper evaluates a framework for modeling overall conductivity and current sharing within such composites. Processing methods and parameters were refined. Select electroplated samples outperformed pure Cu in conductivity and had comparable ultimate tensile strengths. Tensile strengths are expected to improve with an additional densification step during processing. Acoustic emission data was used to predict the failure mechanism of the composite. Theories explaining improved intrinsic conductivity are discussed, with a focus on chemical and mechanical interactions at the Cu-CNT interface. These include Cu infiltration of CNT crevices, CNT oxidation, activity at defects in CNT walls, and the release of carbide-forming metals from CNT walls. Validating any or all these theories will require further work replicating data, collecting electron micrographs and conducting chemical analyses.

Metalized CNT↗
NASA NTRSDate not supplied

Thermochemical Instabilities at High Temperature Ceramic Surfaces

The surface of silicon-based high temperature ceramics exhibits thermochemical instabilities when exposed to oxygen-rich high enthalpy flows. These instabilities manifest as sudden temperature jumps of several hundred degrees and rapid material failure, when temperatures exceed 2000 K. Understanding and predicting these phenomena is critical to the design of thermal protection systems for sustained high speed flight vehicles. In this talk we review a series of test cases where surface temperature jumps were observed during plasmatron wind tunnel testing of ceramic materials, including ZrB2-SiC ultra-high temperature ceramics, C/SiC ceramic matrix composites, and silicone-based coatings for low-density carbon phenolic ablators. The underlying physical processes occurring when Si-containing ceramics are exposed to high enthalpy air flow include formation of passivating scales at low temperatures, passive to active oxidation transition, melting of oxide scales, changes in surface radiative properties, formation of porosity and changes in effective conductivity, surface catalytic recombination and transitions in catalytic properties, as well as high-temperature phase changes. The role of these processes in promoting thermochemical instabilities for the different material systems is discussed.

Ultra High Temperature Ceramics, UHTC↗
NASA NTRS2001

Effects of Potassium Permanganate Oxidation on Subsurface Microbial Activity

In situ chemical oxidation has the potential for degrading large quantities of organic contaminants and can be more effective and timely than traditional ex situ treatment methods. However, there is a need to better characterize the potential effects of this treatment on natural processes. This study focuses on potential inhibition to anaerobic dechlorination of trichloroethene (TCE) in soils from a large manufacturing facility as a result of in situ oxidation using potassium permanganate (KMn04)Previous microcosm studies established that natural attenuation occurs on-site and that it is enhanced by the addition of ethanol to the system. A potential remediation scheme for the site involves the use of potassium permanganate to reduce levels of TCE in heavily contaminated areas, then to inject ethanol into the system to "neutralize" excess oxidant and enhance microbial degradation. However, it is currently unknown whether the exposure of indigenous microbial populations to potassium permanganate may adversely affect biological reductive dechlorination by these microorganisms. Consequently, additional microcosm studies were conducted to evaluate this remediation scheme and assess the effect of potassium permanganate addition on biological reductive dechlorination of TCE. Samples of subsurface soil and groundwater were collected from a TCE-impacted area of the site. A portion of the soil was pretreated with nutrients and ethanol to stimulate microbial activity, while the remainder of the soil was left unamended. Soil/groundwater microcosms were prepared in sealed vials using the nutrient-amended and unamended soils, and the effects of potassium permanganate addition were evaluated using two permanganate concentrations (0.8 and 2.4 percent) and two contact times (1 and 3 weeks). TCE was then re-added to each microcosm and TCE and dichloroethene (DCE) concentrations were monitored to determine the degree to which microbial dechlorination occurred following chemical oxidation. Evidence of microbial degradation was generally detected within four weeks after TCE addition. Increases in DCE concentrations were consistent with decreases in TCE. The concentration of TCE in the nutrient-amended samples exposed to 2.4% KMnO4 for one week degraded somewhat more slowly than the samples exposed to the 0.8% KMnO4. The rates of degradation did not correlate with the length of KMn04 exposure for the nutrient-amended microcosms. Microbial degradation of TCE in the unamended microcosms was generally similar to that observed in the nutrient-amended microcosms. One treatment condition (unamended, one week exposure, 2.4% KMnO4) was exposed to elevated levels of ethanol and showed little evidence of degradation. It is suspected that the high levels of ethanol were toxic to the microorganisms. The results of the study indicate that exposure of indigenous soil and groundwater microbial populations to KMnO4 at concentrations of 0.8 to 2.4% do not impair the ability of the microbial populations to dechlorinate TCE. Consequently, the combination of chemical oxidation followed by enhanced biological reductive dechlorination appears to be a viable remedial strategy for highly-impacted subsurface areas of the site.

Rowland, Martin A.↗
DOE OSTI2022

Molybdenum oxide and sulfide active sites for isobutane dehydrogenation with methanol as a probe molecule

Molybdenum oxides and sulfides are alternative catalysts for several reactions, including alkane dehydrogenation. Correlations have been developed between reactivity and structure, but it is difficult to compare different catalysts without determining numbers of active sites. Here, methanol temperature programmed surface reaction (TPSR) is applied to bulk MoS 2 and a series of supported molybdenum oxides and sulfides used for isobutane dehydrogenation. Rates and deactivation behavior are similar between supported molybdenum oxides and sulfides. Coking increases with loading and correlates well with the fraction of Mo-based CO 2 -forming sites from methanol TPSR. Normalizing isobutane dehydrogenation rates by formaldehyde-forming sites unifies rates over oxide and sulfide materials. Further, these measurements confirm earlier hypotheses that MoS 2 and higher loadings of oxides and sulfides are intrinsically fast catalysts, but they have few active sites and are prone to coking. In general, methanol TPSR is proposed as an accessible route to count sites on both supported oxides and sulfides.

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

Active anaerobic methane oxidation and sulfur disproportionation in the deep terrestrial subsurface

Abstract Microbial life is widespread in the terrestrial subsurface and present down to several kilometers depth, but the energy sources that fuel metabolism in deep oligotrophic and anoxic environments remain unclear. In the deep crystalline bedrock of the Fennoscandian Shield at Olkiluoto, Finland, opposing gradients of abiotic methane and ancient seawater-derived sulfate create a terrestrial sulfate-methane transition zone (SMTZ). We used chemical and isotopic data coupled to genome-resolved metaproteogenomics to demonstrate active life and, for the first time, provide direct evidence of active anaerobic oxidation of methane (AOM) in a deep terrestrial bedrock. Proteins from Methanoperedens (formerly ANME-2d) are readily identifiable despite the low abundance (≤1%) of this genus and confirm the occurrence of AOM. This finding is supported by 13C-depleted dissolved inorganic carbon. Proteins from Desulfocapsaceae and Desulfurivibrionaceae, in addition to 34S-enriched sulfate, suggest that these organisms use inorganic sulfur compounds as both electron donor and acceptor. Zerovalent sulfur in the groundwater may derive from abiotic rock interactions, or from a non-obligate syntrophy with Methanoperedens, potentially linking methane and sulfur cycles in Olkiluoto groundwater. Finally, putative episymbionts from the candidate phyla radiation (CPR) and DPANN archaea represented a significant diversity in the groundwater (26/84 genomes) with roles in sulfur and carbon cycling. Our results highlight AOM and sulfur disproportionation as active metabolisms and show that methane and sulfur fuel microbial activity in the deep terrestrial subsurface.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Enhancing Acidic Oxygen Evolution Activity by Controlling Oxidation State of Iridium

Iridium oxides with high oxidation states have been reported to be effective in enhancing the acidic oxygen evolution reaction (OER) performance. Herein, we develop ultrasmall IrO x nanoparticles (NPs) over titanium nitride (TiN), which undergoes surface oxidation under oxidative conditions to form oxygen-modified TiN (oxi-TiN), enabling the formation of highly oxidized Ir δ+ (δ > 4). This IrO x /oxi-TiN catalyst delivers higher Ir mass activity than commercial IrO 2 , while comparable stability is maintained. The superior OER activity of IrO x /oxi-TiN is further demonstrated in a proton exchange membrane water electrolyzer (PEMWE), requiring only 1.88 V to reach 3 A cm −2 , achieving the U.S. Department of Energy 2025 target (1.90 V at 3 A cm −2 ). In situ X-ray absorption spectroscopy (XAS) confirms that the superior OER activity of IrO x /oxi-TiN originates from highly oxidized Ir δ+ under OER conditions. Further, density functional theory (DFT) calculations reveal a general correlation between the oxidation state of Ir and OER overpotential. Specifically, the introduction of interfacial oxygen at the Ir/TiN interface increases the oxidation state of deposited Ir δ+ from δ < 4 to δ > 4, decreasing the OER overpotential. This study highlights the critical role of high oxidation states of Ir δ+ in enhancing OER activity, providing guidance for the development of advanced acidic OER catalysts.

In situ measurements↗
DOE OSTI2024

Benchmarking nitrous oxide adsorption and activation in metal–organic frameworks bearing coordinatively unsaturated metal centers

Anthropogenic emissions of N 2 O, the third most abundant greenhouse gas after CO 2 and CH 4 , are contributing to global climate change. Although metal–organic frameworks (MOFs) have been widely studied as adsorbents for CO 2 and CH 4 , less effort has focused on the use of MOFs to remove N 2 O from emission streams or from air. Further, N 2 O activation would enable its use as an inexpensive oxidant for fine chemical synthesis. Here, in this paper, we identify features that contribute to strong binding and high uptake of N 2 O at coordinatively unsaturated metal sites in the M 2 Cl 2 (btdd) (M = Mn, Co, Ni, Cu; btdd 2– = bis(1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin) and M 2 (dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn; dobdc 4– = 2,5-dioxido-1,4-benzenedicarboxylate) series of MOFs. Combined experimental and computational studies suggest that N 2 O adsorption at open-metal-sites is primarily based on electrostatic interactions, rather than π-backbonding, causing MOFs with more Lewis acidic metal centers to be superior N 2 O adsorbents. As a result, Mg 2 (dobdc) demonstrates strong binding and record-setting N 2 O uptake (8.75 mmol g –1 at 1 bar and 298 K). Using density functional theory (DFT) to characterize reactive intermediates and transition states, we demonstrate that N 2 O activation to form a M(IV)–oxo species and N 2 is thermodynamically favorable in Mn 2 (dobdc) and Fe 2 (dobdc) but appears to be kinetically limited in Mn 2 (dobdc). Our work lays a foundation for understanding N 2 O adsorption and activation in MOFs, paving the way for the design of promising next-generation materials for N 2 O capture and utilization.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Enhancing Acidic Oxygen Evolution Activity by Controlling Oxidation State of Iridium

Iridium oxides with high oxidation states have been reported to be effective in enhancing the acidic oxygen evolution reaction (OER) performance. In this work, we develop ultrasmall IrO x nanoparticles (NPs) over titanium nitride (TiN), which undergoes surface oxidation under oxidative conditions to form oxygen‐modified TiN (oxi‐TiN), enabling the formation of highly oxidized Ir δ+ (δ > 4). This IrO x /oxi‐TiN catalyst delivers higher Ir mass activity than commercial IrO 2 , while comparable stability is maintained. The superior OER activity of IrO x /oxi‐TiN is further demonstrated in a proton exchange membrane water electrolyzer (PEMWE), requiring only 1.88 V to reach 3 A cm −2 , achieving the U.S. Department of Energy 2025 target (1.90 V at 3 A cm −2 ). In situ X‐ray absorption spectroscopy (XAS) confirms that the superior OER activity of IrO x /oxi‐TiN originates from highly oxidized Ir δ+ under OER conditions. Density functional theory (DFT) calculations reveal a general correlation between the oxidation state of Ir and OER overpotential. Specifically, the introduction of interfacial oxygen at the Ir/TiN interface increases the oxidation state of deposited Ir δ+ from δ < 4 to δ > 4, decreasing the OER overpotential. This study highlights the critical role of high oxidation states of Ir δ+ in enhancing OER activity, providing guidance for the development of advanced acidic OER catalysts.

58 GEOSCIENCES↗