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Results for “oxidizing and reducing conditions”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Stability of ceramic matrix materials in molten hydroxide under oxidizing and reducing conditions

The degradation mechanism of ceramic matrix materials used as molten hydroxide electrolyte support for steam electrolysis cells, is not well documented. In this study, we have investigated the structural and chemical stability of non-oxide and oxide ceramics (SiC, YSZ, Li 2 ZrO 3, LiAlO 2 , and SrZrO 3 ) in the presence of molten hydroxide under oxidizing and reducing conditions with humidity levels of 3 and 85% at 550 °C. SiC, YSZ, Li 2 ZrO 3 and LiAlO 2 showed structural and chemical changes due to dissolution of the ceramic particles in the hydroxide melt followed by precipitation. The SrZrO 3 powder, on the other hand, remained both chemically and structurally stable during 500 h test under both oxidizing and reducing atmospheres. The findings of a stable ceramic matrix in molten hydroxide contribute to the enhancement of the durability and performance of intermediate temperature water electrolysis system.

08 HYDROGEN↗
NASA NTRS2017

Synthesis of Ti Oxides at Reducing Conditions: Implications for Beamline Standards and Cosmochemistry

These initial experiments demonstrate the great potential for synthesizing customized compounds for use as standards, or in buffering experiments at reducing conditions. We are also investigating Cr and V oxides, as well as compounds containing these elements such as FeV2O4 and FeCr2O4. Oxygen fugacity exerts a major control on mineral major element chemistry and elemental valence of minerals in any plane-tary compositional system [1]. For Earth, Fe is multivalent ranging from nearly Fe0 at low fO2 in the deep mantle to Fe2+ to Fe3+ at high low fO2. For solar nebular and meteoritic materials fO2 ranges from near IW to ~10 log fO2 units below the IW buffer [1]. Phases in CAIs, for example, contain no Fe2+, but may contain Ti4+, Ti3+, or Ti2+, and Cr3+ or Cr2+, and V3+ or V2+ [1,2,3]. De-tailed study of inclusions may reveal important differences in fO2 thus reflecting different environments in the solar nebula [4]. XANES, FEG-SEM, and TEM can reveal such variations in micro and nano samples such as Stardust and cosmic dust particles [5], but successful application to reduced conditions depends upon the availability of well characterized standards. Acquiring appropriate standards for reduced phases that contain Ti3+ or Ti2+, Cr3+ or Cr2+, and V3+ or V2+ can be a challenge. Here we report our preliminary results at synthesizing reduced Ti bearing standards, and focus on the preliminary characterization.

Righter, K.↗
DOE OSTI2024

Enhancing Stability of Surface Au under Oxidizing Conditions through Reduced Bulk Au Content

Contrary to the common assumption that a higher bulk content of precious metals facilitates the preservation of more surface noble metal by serving as a reservoir for surface enrichment, we demonstrate that a lower bulk content of Au results in a more stable arrangement of Au atoms at the surface of Cu–Au nanoparticles when exposed to an O 2 atmosphere. Using ambient pressure X-ray photoelectron spectroscopy, we investigate the surface segregation and oxidation behavior of Cu–Au nanoparticles across various compositions. Here, our results reveal that in Au-rich nanoparticles exposed to an H 2 atmosphere, surface segregation prompts the formation of a continuous Au-enriched shell, which subsequently oxidizes into a complete CuO x shell upon transitioning to an O 2 atmosphere. Conversely, in Au-poor nanoparticles during H 2 treatment, segregation results in the emergence of Au clusters embedded within the surface layer, persisting upon exposure to O 2 . This unexpected phenomenon shows that reducing the bulk content of precious metals can enhance the surface stability of noble atoms under oxidizing conditions, as further demonstrated by comparing the catalytic performance of Cu–Au nanoparticles with varying Au bulk contents in CO oxidation.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Influence of oxidizing and reducing pretreatment on the catalytic performance of CeO 2 for CO oxidation

Cerium oxide (CeO 2 ) and ceria-based materials have been extensively investigated as catalyst and support materials for various catalytic reactions, due to higher oxygen storage capacity and excellent redox properties. In the current work, we investigated the impact of pretreatment conditions (e.g., oxidation and reduction) on the physical properties of bulk CeO 2 and catalytic activity for CO oxidation as a model reaction. To understand the physical properties of pretreated CeO 2 catalysts, a suite of complementary characterization techniques, including X-ray diffraction (XRD), surface area analysis (BET), X-ray photoemission spectroscopy (XPS), and Raman spectroscopy, were applied. The results showed that a higher pretreatment temperature led to a decreased specific surface area (SSA), a decrease in oxygen vacancy/defect sites, and increased crystallite size, while surface Ce 3+ /Ce 4+ ratio did not show a specific relationship to the treatment conditions. The 700 °C treated CeO 2 samples under oxidizing and reducing conditions showed higher specific oxidation rate (μmolCO/s/m 2 ) compared to other samples at 280 and 300 °C (or < 15% CO conversion). The CO conversion per total mass of catalysts, however, decreased with increasing temperatures, especially at 700 °C under reducing condition, indicating that the catalytic performance was affected by the physical properties (SSA, oxygen vacancy/defect sites, and crystallite size).

36 MATERIALS SCIENCE↗
DOE OSTI2023

Variability in soil redox response to seasonal flooding in a vernal pond

Vernal ponds are ephemeral landscape features that experience intermittent flooding and drying, leading to variable saturation in underlying soils. Redox potential (E h ) is an important indicator of biogeochemical processes that changes in response to these hydrological shifts; however, high-resolution measurements of E h in variably inundated environments remain sparse. In this study, the responses of soil E h to ponding, drying, and rewetting of a vernal pond were investigated over a 5-month period from late spring through early autumn. Soil E h was measured at 10-min frequencies and at multiple soil depths (2–48 cm below the soil surface) in shallow and deep sections within the seasonally ponded lowland and in unsaturated soils of the surrounding upland. Over the study period, average E h in surface soils (0–8 cm) was oxidizing in the upland (753 ± 79 mV) but relatively reducing in the shallow lowland (369 ± 49 mV) and deep lowland (198 ± 37 mV). Reducing conditions (E h <300 mV) in surface soils prevailed for up to 6 days in the shallow lowland and up to 24 days in the deep lowland after surface water dried out. Intermittent reflooding resulted in multiple shifts between reducing and oxidizing conditions in the shallow lowland while the deep lowland remained reducing following reflooding. Soil E h in the uplands was consistently oxidizing over the study period with transient increases in response to rain events. Reducing conditions in the lowland resulted in greater Fe-oxide dissolution and release of dissolved Fe and P into porewater than in the surrounding uplands. We determined that change in water depth alone was not a good indicator of soil E h , and additional factors such as soil saturation and clay composition should be considered when predicting how E h responds to surface flooding and drying. These findings highlight the spatial and temporal variability of E h within ponds and have implications for how soil processes and ecosystem function are impacted by shifts in hydrology at terrestrial-aquatic interfaces.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Hydroxide melt induced corrosion of Ni at elevated temperatures under steam electrolysis conditions

Molten alkali electrolyte based high temperature water electrolysis (HTWE) process offers an efficient pathway to integrate renewable energy resources for large scale and economic hydrogen production. Long term and stable operation of these systems require an in-depth understanding of materials stability under anodic and cathodic exposure conditions of the cell and cell stacks. In the present study, we report our findings on the corrosion of Ni in the presence and absence of (LieNa) hydroxide melt at 600 °C under oxidizing and reducing conditions representative of HTWE. While the Ni electrode was found to remain thermodynamically stable in metallic form under cathodic (reducing) exposure conditions, the corrosion rate in molten hydroxide under oxidizing conditions was found to be nonparabolic in nature. A cyclic voltammetry study provides the breakdown of the passive metal-oxide surface layer at the anodic overpotential region between 0.45 V and 2 V in molten hydroxide under oxidizing conditions. As a result, a thermochemical process for accelerated corrosion based on the oxide scale fluxing in hydroxide melt has been developed.

08 HYDROGEN↗
NASA NTRS1987

Seasonal cycling of sulfur and iron in porewaters of a Delaware salt marsh

An extensive pore water data set has been gathered in the Great Marsh, Delaware over various seasons, salinities, and tides. The data all point to a complimentary redox cycle for sulfur and iron which operates seasonally and tidally. Surface oxidizing conditions prevail in summer, with more reducing conditions at depth during the winter. During the spring tides which flood the marsh, pyrite oxidation occurs releasing excess dissolved iron (II) and sulfate to the porewaters, and precipitating authigenic solid iron phases. The redox conditions in the porewaters of the upper zone during the summer is poised between mildly oxidizing and mildly reducing conditions as shown by pE calculations. This redox environment and intermediate iron-sulfur redox species may be important for the stimulation of plant growth (photosynthesis) and sustenance of a viable microbial community (heterotrophy and chemoautropy).

Luther, George W., III↗
DOE OSTI2021

Pulse Radiolysis Investigation of Radicals Derived from Water-Soluble Cyanine Dyes: Implications for Super-resolution Microscopy

Light-induced blinking, an inherent feature of many forms of super-resolution microscopy, has been linked to transient reduction of the fluorescent cyanine dye used as an imaging agent. There is, however, only scant literature information related to one-electron reduced cyanine dyes, especially in an aqueous environment. Here, we examine a small series of cyanine dyes, possessing disparate π-conjugation lengths, under selective reducing or oxidizing conditions. The experiment allows recording of both differential absorption spectra and decay kinetics of the resultant one-electron reduced or oxidized transient species in water. Relative to the ground state, absorption transitions for the various radicals are weak and somewhat broadened but do allow correlation with the π-conjugation length. In all cases, absorption maxima lie to the blue of the main ground-state transition. Under anaerobic conditions, the transient species decay on the microsecond to millisecond time scale, with the mean lifetime depending on molecular structure, radiation dose, and dye concentration. The experimental absorption spectra recorded for the one-electron reduced radicals and the presumed dimer cation radical compare well to spectra obtained from time-dependent density functional theory calculations. Furthermore, the results allow conclusions to be drawn regarding the plausibility of the reduced species being responsible for light-induced blinking in direct stochastic optical reconstruction microscopy.

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

Iron XANES measurements of carbonates and phyllosilicates in CM chondrites: A record of redox conditions during aqueous alteration

Multiple generations of calcite and dolomite precipitated in CM chondrites during ice melting events that led to episodes of liquid water. Models and laboratory analysis have suggested a long-term transition from oxidizing to reducing conditions during aqueous alteration on the CM parent body. We found that synchrotron X-ray absorption near edge spectroscopy (XANES) can detect relative differences in the oxidation state of trace iron within these carbonates. In CM chondrites, previous work interpreted Mn abundance in calcite as an indicator of relatively early or late formation, and dolomite is understood to form relatively late. In the CM1 chondrite Meteorite Hills 01070, XANES maps reveal that Mn-poor calcite contains more oxidized iron relative to Mn-rich calcite. While these measurements of carbonates support increasing iron reduction with progressive aqueous alteration in MET 01070, comparison among different CM chondrites suggests a complex picture of redox evolution. In addition to carbonates, we performed XANES measurements of the phyllosilicate-rich matrix of Allan Hills 83,100. Pre-edge centroid analysis indicates that this CM1/2 has an oxidation state similar to typical CM2 chondrites. While additional measurements are warranted to confirm the full span of redox trends in CM carbonates, our data do not support a correlation between redox state and petrologic type.

Bailey, Elizabeth [Univ. of California, Santa Cruz↗
DOE OSTI2020

Computational modeling predicts the stability of both Pd + and Pd2 + ion-exchanged into H-CHA

Passive NO x adsorbers (PNA) using Pd/zeolites have emerged as a promising solution for the reduction of cold-start emissions from vehicle exhaust. However, the nature of the active sites and the mechanisms underlying NO x adsorption in Pd/zeolites remain a subject of ongoing investigation. In this study, we employ quantum chemical simulations to investigate the structure of Pd species in cation-exchange sites at isolated Al and Al pairs in the 6-ring and 8-ring of the CHA framework before the introduction of NO x . Our calculations show that the speciation of Pd in these exchange sites strongly depends on the precise Al arrangement within the framework, as well as the operating conditions. Ionically dispersed Pd is found to be the most favorable species over a wide range of oxidizing and reducing conditions. Small oligomers of PdO and metallic Pd do not appear to be competitive at either isolated Al or Al pairs. Notably, our calculations show that ion exchange sites other than next–next–nearest neighbor Al pairs in the 6-ring will be preferentially occupied by Pd + instead of Pd 2+ . The stability of Pd + in the zeolite environment is an interesting contrast with its rareness in molecular Pd compounds. Nonetheless, a detailed analysis of the electronic structure shows that predicted Pd oxidation states are consistent with chemical intuition for all complexes investigated in this study. We also discuss the potential ambiguity in Pd characterization provided by typical experimental techniques such as XANES, EXAFS and UV-Vis, and highlight the need for additional EPR spectroscopy studies to further elucidate the initial Pd speciation in zeolites for PNA applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2019

Saponite Dissolution Experiments and Implications for Mars

Recent work suggests that the mineralogical sequence of the Murray formation at Gale crater may have resulted from diagenetic alteration after sedimentation, or deposition in a stratified lake with oxic surface and anoxic bottom waters. Fe-containing clay minerals are common both at Gale crater, and throughout the Noachian-aged terrains on Mars. These clay minerals are primarily ferric (Fe3+), and previous work suggests that these ferric clay minerals may result from alteration of ferrous (Fe2+) smectites that were oxidized after deposition. The detection of trioctahedral smectites at Gale crater by CheMin suggests Fe2+ smectite was also deposited during the early Hesperian. However, due to their sensitivity to oxygen, Fe2+ smectites are difficult to analyze on Earth and very few saponite dissolution rates exist in the literature. To the best of our knowledge, no experiments have measured the dissolution rates of ferrous saponites under oxidizing and reducing conditions. In order to better understand the characteristics of water-rock interaction at Gale crater, particularly the oxidation state, we report our results to date on ongoing syntheses of ferrous and magnesium saponites and dissolution experiments of natural saponite under ambient conditions. Future experiments will include the dissolution of synthetic ferric, ferrous, and magnesium saponites under oxidizing and anoxic conditions at a range of pH values.

Luu, N. C.↗
NASA NTRS2008

Sulfur and Iron Speciation in Gas-rich Impact-melt Glasses from Basaltic Shergottites Determined by Microxanes

Sulfur is abundantly present as sulfate near Martian surface based on chemical and mineralogical investigations on soils and rocks in Viking, Pathfinder and MER missions. Jarosite is identified by Mossbauer studies on rocks at Meridian and Gusev, whereas MgSO4 is deduced from MgO - SO3 correlations in Pathfinder MER and Viking soils. Other sulfate minerals such as gypsum and alunogen/ S-rich aluminosilicates and halides are detected only in martian meteorites such as shergottites and nakhlites using SEM/FE-SEM and EMPA techniques. Because sulfur has the capacity to occur in multiple valence states, determination of sulfur speciation (sulfide/ sulfate) in secondary mineral assemblages in soils and rocks near Mars surface may help us understand whether the fluid-rock interactions occurred under oxidizing or reducing conditions. To understand the implications of these observations for the formation of the Gas-rich Impact-melt (GRIM) glasses, we determined the oxidation state of Fe in the GRIM glasses using Fe K micro-XANES techniques.

Sutton, S. R.↗
DOE OSTI2021

Regeneration of Active Surface Alloys during Cyclic Oxidation and Reduction: Oxidation of H 2 on Pd/Ag(111)

The surface morphology and composition of a catalyst during excursions between oxidizing and reducing conditions can change substantially, especially in bimetallic alloys. Both thermodynamic and kinetic factors play a role in determining the properties of alloy surfaces where the active phase may be a metastable state. Previously, Ag oxide reduction was shown to be dramatically enhanced when Pd is on the surface; however, Pd is more stable when dissolved in Ag, raising the question as to whether a highly active Pd surface state will persist over multiple reaction cycles—a requirement for catalytic function. Experiments herein demonstrate that the enhanced chemical functionality due to the presence of Pd on the surface is retained, based on the enhanced rate of silver oxide reduction over multiple oxidation/reduction cycles for a Pd/Ag(111) model. Repeated oxidation and reduction promote PdAg alloying and reversible structural and compositional changes are detected using X-ray photoelectron spectroscopy. Furthermore, this study establishes that metastable phases can persist in reactive processes on surfaces, indicating their potential in heterogeneous catalysis.

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

Uptake of uranium by carbonate crystallization from reduced and oxidized hydrothermal fluids

This work evaluated the immobilization of uranium (U) through incorporation into calcite under reduced and oxidized conditions. We investigated how much U could be entrapped by calcite crystallizing in chloride solutions in autoclaves at temperatures from 162 to 300 °C. The oxidation state of U was set by controlling oxygen fugacity via redox buffers. Uranium was introduced into calcite growth media as a solid oxide compound or U aliquot. We found the uptake of tetravalent U by calcite is higher than that of hexavalent U by up to four orders of magnitude. Furthermore, we estimate that crystallization of a few mg of calcite immobilizes all dissolved U when 1 kg of solution is saturated with UO 2 under reduced hydrothermal conditions.

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

Thermophysical modeling of raw glaze liquidus temperature and viscosity

Raw glazes, which do not contain pre-melted glass frits, are widely used due to their low cost. The natural variability of the mineral compositions used in raw glazes affects their viscosity during firing. Molten glaze viscosity plays an important role in determining the final surface quality; therefore, it is important to determine how raw glaze composition and firing conditions affect viscosity. Thermophysical modeling provides a way to evaluate the liquidus temperature and viscosity of molten glazes as a function of composition and oxygen activity. Equilibrium phase volume fraction and composition of 242 raw glaze recipes were evaluated under oxidizing and reducing conditions. Undissolved or precipitation of solid phases explain the secondary flux transition from anti-fluxing to fluxing near the liquidus temperature. The liquidus temperature and viscosity of iron glazes decrease as a function of increasing iron content under a reducing atmosphere. The empirical probability distribution of molten glaze viscosity follows a lognormal distribution, with lead glazes having significantly lower viscosity compared with glazes without lead. Here, the peak firing temperature viscosity of lead-free glazes is near the working point of glass. Multiple linear regression analysis shows that the peak firing temperature viscosity and liquidus temperature significantly predict the viscosity factor.

36 MATERIALS SCIENCE↗
DOE OSTI2023

The NO reduction by CO over NiO x /CeO 2 catalysts with a fixed Ni surface density: pretreatment effects on the catalyst structure and catalytic activity

NiO x /CeO 2 catalysts have shown promising results in various catalytic reactions, including the NO reduction by CO. Here, in this study, we investigated the effect of oxidation and reduction treatments on the NO reduction by CO over pretreated NiO x /CeO 2 catalysts. A series of oxidized and reduced supported NiO x catalysts were synthesized in two steps: (1) the pretreatment of CeO 2 supports at different temperatures (400, 500, and 700 °C) under oxidizing and reducing conditions and (2) the synthesis of NiO x /CeO 2 catalysts by an incipient wetness impregnation method (IWI) with a fixed surface density of 5.3 Ni per nm 2 under specific conditions (oxidation/reduction) applied during the CeO 2 treatment. The prepared catalysts were characterized via BET, ICP/OES, Raman, XPS, and XRD to understand their physicochemical properties. The results showed that as the pretreatment temperature increased, the physicochemical properties of NiO x /CeO 2 catalysts were changed: a decreased specific surface area (SSA), decreased oxygen vacancy/defect sites, and an increased crystallite size. The oxidized NiO x /CeO 2 catalyst at a lower pretreatment temperature displayed a better catalytic activity, indicating that the physicochemical properties of the catalysts were key factors in enhancing the catalytic activity. To understand the intermediate species and reaction mechanism during the NO reduction by CO, an in situ DRIFTS study was performed and a possible reaction mechanism was also discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Structural insights into redox signal transduction mechanisms in the control of nitrogen fixation by the NifLA system

NifL is a conformationally dynamic flavoprotein responsible for regulating the activity of the σ 54 -dependent activator NifA to control the transcription of nitrogen fixation (nif) genes in response to intracellular oxygen, cellular energy, or nitrogen availability. The NifL-NifA two-component system is the master regulatory system for nitrogen fixation. NifL serves as a sensory protein, undergoing signal-dependent conformational changes that modulate its interaction with NifA, forming the NifL–NifA complex, which inhibits NifA activity in conditions unsuitable for nitrogen fixation. While NifL-NifA regulation is well understood, these conformationally flexible proteins have eluded previous attempts at structure determination. In work described here, we advance a structural model of the NifL dimer supported by a combination of scattering techniques and mass spectrometry (MS)-coupled structural analyses that report on the average structure in solution. Using a combination of small angle X-ray scattering-derived electron density maps and MS-coupled surface labeling, we investigate the conformational dynamics responsible for NifL oxygen and energy responses. Our results reveal conformational differences in the structure of NifL under reduced and oxidized conditions that provide the basis for a model for modulating NifLA complex formation in the regulation of nitrogen fixation in response to oxygen in the model diazotroph,Azotobacter vinelandii.

59 BASIC BIOLOGICAL SCIENCES↗