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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
NASA NTRS2001

Application of Fe Isotopes to the Search for Life and Habitable Planets

The relatively new field of Fe isotope geochemistry can make important contributions to tracing the geochemical cycling of Fe, which bears on issues such as metabolic processing of Fe, surface redox conditions, and development of planetary atmospheres and biospheres. It appears that Fe isotope fractionation in nature and the lab spans about 4 per mil (%) in Fe-56/Fe-54, and although this range is small, our new analytical methods produce a precision of +/- 0.05% on sample sizes as small as 100 ng (10(exp -7) g); this now provides us with a sufficient "signal-to-noise" ratio to make this isotope system useful. We review our work in three areas: 1) the terrestrial and lunar rock record, 2) experiments on inorganic fractionation, and 3) experiments involving biological processing of Fe. Additional information is contained in the original extended abstract.

Johnson, Clark M.↗
DOE OSTI2025

Metabolic Redox Coupling Controls Methane Production in Permafrost‐Affected Peatlands Through Organic Matter Quality‐Dependent Energy Allocation

ABSTRACT Permafrost thaw represents one of Earth's largest climate feedback risks, potentially releasing vast carbon (C) stores as greenhouse gases (GHG). However, our ability to predict emissions remains limited by poor understanding of how changing organic matter (OM) composition affects microbial carbon processing. We test a metabolism‐centered redox framework, which views microbial processes as coupled oxidative‐reductive reactions, to mechanistically explain how organic matter metabolite quality controls greenhouse gas production in permafrost‐affected peatland ecosystems. Rather than relying solely on geochemical redox measurements, our approach examines how microbes balance electron flow through metabolic pathways. Using active layer peat (9–19 cm) from contrasting environments (bog and fen), we employed multi‐omics approaches, including metabolomics, metagenomics, and metatranscriptomics, to link OM chemistry to microbial function. Our results reveal distinct dissolved organic matter metabolite composition, with fen systems enriched in compounds with higher substrate quality (low molecular weight (MW) sugars with high H:C ratios and low aromaticity) and bog systems dominated by compounds with lower substrate quality (high MW phenols with lower H:C ratios and higher aromaticity). In fen samples, these sugar‐like compounds correlated with higher oxidative metabolism and methanogenesis, supported by increased glycolysis gene expression. Initially, electrons from increased oxidative metabolism were balanced through nitrate and sulfate reduction, but as these electron acceptors were depleted, methanogenesis increased to maintain redox balance. Fen samples showed rapid degradation of both high‐ and low‐substrate‐quality compounds, suggesting sufficient energy for efficient C cycling. Conversely, bog samples exhibited more polyphenolic compounds, lower glycolysis activity, and higher stress‐related gene expression, suggesting energy was diverted towards cell maintenance under acidic conditions rather than C processing. This approach suggests that predicting greenhouse gas emissions requires an understanding of how organic matter quality shapes microbial energy allocation strategies, providing a mechanistic framework for improving emission predictions from permafrost‐affected peatlands and similar ecosystems.

Biodiversity & Conservation↗
DOE OSTI2022

Integrative structural and functional analysis of human malic enzyme 3: A potential therapeutic target for pancreatic cancer

Malic enzymes (ME1, ME2, and ME3) are involved in cellular energy regulation, redox homeostasis, and biosynthetic processes, through the production of pyruvate and reducing agent NAD(P)H. Recent studies have implicated the third and least well-characterized isoform, mitochondrial NADP + -dependent malic enzyme 3 (ME3), as a therapeutic target for pancreatic cancers. Here, we utilized an integrated structure approach to determine the structures of ME3 in various ligand-binding states at near-atomic resolutions. ME3 is captured in the open form existing as a stable tetramer and its dynamic Domain C is critical for activity. Catalytic assay results reveal that ME3 is a non-allosteric enzyme and does not require modulators for activity while structural analysis suggests that the inner stability of ME3 Domain A relative to ME2 disables allostery in ME3. With structural information available for all three malic enzymes, the foundation has been laid to understand the structural and biochemical differences of these enzymes and could aid in the development of specific malic enzyme small molecule drugs.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Micrometer-sized Magnetite Synthesis using Fe(OH)2(s) as a Precursor for Technetium Sequestration from Liquid Nuclear Waste Streams

Systematic batch experiments under variable adjusted physicochemical conditions were conducted to explore optimization of micrometer-sized magnetite synthesis for Tc sequestration from radionuclide waste streams using Fe(OH)2(s) as the precursor. Extensive solid characterization using x-ray diffraction and spectroscopic methods was performed to assess changes in particle morphology and size distribution, as well as Tc speciation and incorporation, in the produced mineral phases. The results show that the solution pH, temperature, and oxidation kinetics play key roles in the final mineral products. Micrometer-sized magnetite crystals (0.62-0.96 µm on average) with well-defined dodecahedral or octahedral structures were synthesized under near neutral (~pH 8) or alkaline (~pH13) conditions at 75 °C, respectively; whereas goethite dominated the end products at room temperature. An increase in pH at 75 °C improved Tc removal from 27% (near neutral pH) to 42% (alkaline pH), but the removal process remained inhibited by redox competitive Cr(VI) present in the waste streams. By adding additional Fe(II) to the system, Tc sequestration was dramatically improved to up to 87% without observable changes in the solid product. The sequestrated Tc existed as TcO2·2H2O and/or Tc(IV) incorporated into magnetite, where extended X-ray absorption fine structure (EXAFS) spectroscopy showed that more Tc was incorporated into magnetite at elevated temperatures and pH conditions, with complete Tc(IV) incorporation into magnetite occurring under 75 °C-pH 13 conditions. Our results indicate that optimal micrometer-sized magnetite can be produced for Tc sequestration by reacting Fe(OH)2(s) with a waste stream simulant under elevated pH (~13) and temperature (75 °C) conditions. The incorporation of reduced Tc(IV) into stable micrometer-sized magnetite provides a viable supplemental immobilizing technology that may be used to improve nuclear waste treatment and disposal needs.

Wang, Guohui↗
DOE OSTI2020

Highly Active Rhenium-, Ruthenium-, and Iridium-Based Dichalcogenide Electrocatalysts for Oxygen Reduction and Oxygen Evolution Reactions in Aprotic Media

Transition metal dichalcogenides (TMDCs) have garnered much attention recently due to their remarkable performance for different electrochemical systems. In this study, we report on the synthesis and catalysis of less studied TMDC nanoflakes (NFs) with a design space comprised of three transition metals (rhenium, ruthenium, and iridium) and three chalcogens (sulfur, selenium, and tellurium) for the oxygen reduction and evolution reactions (ORR and OER) in an aprotic hybrid electrolyte containing 0.1 M lithium bis(trifluoromethanesulfonypimide salt in 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid and dimethyl sulfoxide. Our results indicate that among the tested catalysts, ReS2 exhibits the highest current density for both ORR and OER, beyond those of the state-of-the-art catalysts used in aprotic media with Li salts. We performed density functional calculations to provide a mechanistic understanding of the reactions in the ReS2 NFs/ionic liquid system. These novel bifunctional catalyst results could open a way for exploiting the unique properties of these materials in Li-O-2 batteries as well as other important electrochemical systems.

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

Chemical and structural evolutions of Li–Mn-rich layered electrodes at different current densities

Although the two active redox centers in Li-rich cathodes, including the anionic and cationic contributions, can enable Li-ion batteries to achieve outstanding specific energy, their behaviors at different current densities have not been clarified. In this report we provide a comparative study of transition metals (TMs) and oxygen redox activities by directly accessing their oxidation states in Li-rich materials operated at very different current rates. Our data reveal that the oxidation of oxygen in the near-surface region is at the same level for electrodes cycled with a wide range of current rates, indicating a reaction gradient of lattice oxygen redox reactions. The oxidation process of lattice oxygen is found to be dynamically compatible with that of the TMs. Combining the results of first principles calculations and complementary experimental findings, we propose a detailed mechanism of structural distortion from octahedral Li to tetrahedral Li and the role of oxygen vacancy in Li + diffusion. It is found that fast delithiation occurring at high current densities can easily cause local structural transformation, leading to a limited Li + diffusion rate and consequently suppressing rate capability.

25 ENERGY STORAGE↗
DOE OSTI2025

Environmental Evaluation of Gas Switching Reforming for Low Carbon Hydrogen: A Power-to-X Study

Gas Switching Reforming for hydrogen production (GSR-H2) offers a promising pathway for producing low-carbon hydrogen at scale, with significant implications for Power-to-X (PtX) systems that rely on clean hydrogen as a feedstock for synthetic fuels and chemicals. GSR-H2 integrates inherent carbon capture and thermal self-sufficiency, positioning it as an efficient alternative to conventional steam methane reforming (SMR), proton exchange membrane (PEM) electrolysis, and chemical looping reforming (CLR). Unlike SMR, GSR-H2 avoids external natural gas combustion by leveraging exothermic redox cycles to generate process steam and recover electricity internally. Its innovative reactor design consolidates all reforming stages within a single reactor cluster, eliminating the need for solid circulation found in CLR, thereby reducing capital costs and improving system reliability and scalability. This presentation describes the first environmental life cycle assessment (LCA) of GSR-H2, evaluating its environmental performance across U.S. grid and renewable energy scenarios. In a renewables-powered configuration, GSR-H2 achieves a global warming potential (GWP) of 2.77 kg CO2 equivalent per kg H2, substantially lower than SMR (10.4 kg) and competitive with PEM electrolysis (1.85 kg) and CLR (1.84 kg). Results across additional impact categories, including air quality and water use, support GSR-H2’s role as a complementary hydrogen source in PtX applications. Its reduced environmental burden, thermal integration, and simplified scale-up potential make GSR-H2 a viable contributor to net-zero PtX systems, particularly where renewable energy is abundant and electricity-intensive hydrogen production faces economic or infrastructure constraints.

03 NATURAL GAS↗
DOE OSTI2023

Editorial: Hydrology, ecology, and nutrient biogeochemistry at the terrestrial-aquatic interface

Terrestrial-aquatic interfaces (TAI) play important roles in mediating the exchange of water and chemicals between land, surface and subsurface water systems, which is tightly coupled with biogeochemical transformations that influence water quality and ecosystem health (Harvey and Gooseff, 2015; Harvey et al., 2019). Understanding and predicting the interactions between the hydrologic, ecologic, and biogeochemical processes at those interfaces is crucial for the sustainable management of water resources and promotion of healthy ecosystems under different environmental stresses and disturbances, including climate change, human activities, and more frequent occurrence of extreme events. Both process-based and data-driven approaches have emerged to address critical challenges at TAIs as integral parts of the Earth system (e.g., Ward and Packman, 2019; Chen et al., 2021; Dwivedi et al., 2022). In this Research Topic, we sought research that advances the understanding of coupled hydrologic, ecologic, and biogeochemical processes along various TAIs from the summit to sea, e.g., river corridors and coastal TAI systems. We invited observational, experimental, theoretical, analytical, numerical, and data-driven research that aims to understand hydro-biogeochemical processes such as the redox dynamics and biogeochemical transformations of carbon, nutrients, and metals occurring at the TAIs and address their heterogeneity and scaling challenges.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2023

Natural sunlight-driven oxidation of Mn 2+ (aq) and heterogeneous formation of Mn oxides on hematite

The oxidation of dissolved Mn 2+ (aq) plays a critical role in driving manganese cycles and regulating the fate of essential elements and contaminants in environmental systems. Based on sluggish oxidation rate, abiotic processes have been considered less effective oxidation pathway for manganese oxidation in environmental systems. Interestingly, a recent study (Jung et al., 2021) has shown that the rapid photochemical oxidation of Mn 2+ (aq) could be a feasible scenario to uncover the potential significance of abiotic Mn 2+ (aq) oxidation. Nevertheless, the significance of photochemical oxidation of Mn 2+ (aq) under natural sunlight exposure remains unclear. Here, we demonstrate the rapid photocatalytic oxidation of Mn 2+ (aq) and the heterogeneous growth of tunnel-structured Mn oxides under simulated freshwater and seawater conditions in the presence of natural sunlight and hematite. The natural sunlight-driven photocatalytic oxidation of Mn 2+ (aq) by hematite showed kinetic constants of 1.02 h -−1 and 0.342 h −1 under freshwater and seawater conditions, respectively. The natural sunlight-driven photocatalytic oxidation rates are quite comparable to the results obtained from the previous laboratory test using artificial sunlight, which has ∼4.5 times stronger light intensity. It is likely because of ∼5.5 times larger light exposure area in the natural sunlight-driven photocatalytic oxidation than that of the laboratory test using artificial sunlight. We also elucidate the roles of cation species in controlling the oxidation rate of Mn 2+ (aq) and the crystalline structure of Mn oxide products. Specifically, in the presence of large amounts of cations, the oxidation rate of Mn 2+ (aq) was slower likely because of competitive adsorption. Furthermore, our findings highlight that Mn 2+ contributes significantly to the formation of large-tunneled Mn oxides. These results illuminate the importance of abiotic photocatalytic processes in controlling the redox chemistry of Mn in real environmental aqueous systems on the oxidation of Mn 2+ (aq), and provide an environmentally sustainable approach to effectively remediate water contaminated with Mn 2+ (aq) using natural sunlight.

Junyeong Choi↗
DOE OSTI2024

Ba₁₋ₓSrₓFeO₃₋ᵧ as an Improved Oxygen Carrier for Chemical Looping Air Separation: A Computational and Experimental Study

Chemical looping air separation (CLAS) is a promising method to generate pure carbon-dioxide from fuel combustion with a pure oxygen stream, which is produced through the capture, and targeted release, of oxygen from the atmosphere using a solid oxide carrier. The performance of this process depends on the redox characteristics of the oxide carrier. Using experimental oxygen-temperature-programmed desorption (TPD) and thermogravimetric analysis (TGA), the study shows that Ba₀․₇₅Sr₀․₂₅FeO₃ has improved oxygen storage capacity (OSC), oxidation, and reduction kinetics over pristine SrFeO₃ at temperatures ranging from 300-500 °C. The redox energetics computed by using first-principles density functional theory (DFT) calculations also depict the measured trend establishing it as an important descriptor of the measured performance. The Ba₁₋ₓSrₓFeO₃₋ᵧ depicts a Sr-substitution and oxygen stoichiometry induced structural phase transition from hexagonal at low temperatures to pseudo-cubic phase with higher OSC up to T=400 °C. Also, the mechanism leading to this structural phase transition is identified by performing electronic and vibrational structural calculations. This presentation was given on March 8, 2024 at the APS March Meeting in Minneapolis, MN.

Acharya, Shree Ram↗
DOE OSTI2022

BioGeoChemistry at Interfaces (LLNL SFA OBER FY22 Program Management and Performance Report)

The focus of the BioGeoChemistry at Interfaces SFA is to identify and quantify the biogeochemical processes and the underlying mechanisms that control actinide mobility in an effort to reliably predict and control the cycling and migration of actinides in the environment. The research approach includes: (1) Field Studies that capture actinide behavior on the timescale of decades (Research Thrust 1), and (2) Fundamental Laboratory Studies that isolate specific biogeochemical processes observed in the field (Research Thrust 2). These Research Thrusts are underpinned by the unique capabilities and staff expertise at Lawrence Livermore National Laboratory, allowing the BioGeoChemistry at Interfaces SFA to advance our understanding of actinide migration behavior in the environment, and serve as an resource for environmental radiochemistry research internationally. In the past year, our greater focus on transient redox gradients across stratified waters, sediment-water interfaces, and mineral-water interfaces extended our research beyond actinides to address processes controlling cycling of redox-sensitive metals more broadly. Nevertheless, Research Thrusts 1 and 2 are guided by the following broad central hypotheses that were developed during our last program review held at the end of FY18: Thrust 1 Hypothesis: Biogeochemical processes occurring on the timescale of years to decades lead to greater actinide recalcitrance in sediments and limits their migration in surface and groundwater. Thrust 2 Hypothesis: Long-term biogeochemical processes include mineral and surface alteration, which leads to stabilization of actinide surface associations or incorporation into mineral precipitates. Our strategic goal is to use the knowledge gained from our Science Plan to advance our understanding of the behavior of actinides and other radionuclides (e.g. Cs) and provide DOE with the scientific basis for remediation and long-term stewardship of DOE’s legacy sites. More broadly, we will enhance our understanding of transport phenomena in environmental systems sciences with a particular emphasis on environmentally relevant (long-term) timescales. While we retain our focus on actinide biogeochemistry, our increased focus on overall biogeochemical processes occurring at unique Test Bed locations associated with this SFA provides fundamental information on abiotic and biotic redox processes that control the cycling of redox sensitive metals under dynamic and transient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Competitive Oxidation and Hydration During Aqueous Alteration of Asteroids

Introduction: Studies of chondrites show that incorporation of H2O ice during formation of asteroids followed by radioactive heating caused partial oxidation and hydration of primary reduced and anhydrous rocks. Oxidation of kamacite, phosphides, troilite and organic polymers occurred through consumption of water s oxygen and release of H2. Hydration caused formation of serpentine, saponite, chlorite, talc and hydrated salts. Since H2O was the major reactant in oxidation and hydration, these processes could have been competitive. Redox reactions in asteroids should have been closely connected to hydration (dehydration) during aqueous alteration and thermal metamorphism. For example, dehydration and reduction release H2O that can be consumed in oxidation and hydration, respectively. We model asteroidal processes in order to quantify the fate of H2O and water s oxygen in major redox and hydration/dehydration reactions. Model: Equilibrium compositions in the gas-solid-liquid

Zolotov, M. Y.↗
DOE OSTI2020

High-Throughput Analysis of Materials for Chemical Looping Processes

Chemical looping is a promising approach for improving the energy efficiency of many industrial chemical processes. However, a major limitation of modern chemical looping technologies is the lack of suitable active materials to mediate the involved subreactions. Identification of suitable materials has been historically limited by the scarcity of high-temperature (>600 °C) thermochemical data to evaluate candidate materials. An accuratethermodynamic approach is demonstrated here to rapidly identify active materials which is applicable to a wide variety of chemical looping chemistries. Application of this analysis to chemical looping combustion correctly classifies 17/17 experimentally studied redox materials by their viability and identifies over 1300 promising yet previously unstudied active materials. This approach is further demonstrated by analyzing redox pairs for mediating a novel chemical looping process for producing pure SO2 from raw sulfur and air which could provide a more efficient and lower emission route to sulfuric acid. 12 promising redox materials for this process are identified, two of which are supported by previous experimental studies of their individual oxidation and reduction reactions. This approach provides the necessary foundation for connecting process design with high-throughput material discovery to accelerate the innovation and development of a wide range of chemical looping technologies.

chemical looping↗
NASA NTRS1986

Reaction of N2O5 with H2O on carbonaceous surfaces

The heterogeneous reaction of N2O5 with commercially available ground charcoal in the absence of H2O revealed a physisorption process (gamma = 0.003), together with a redox reaction generating mostly NO. Slow HNO3 formation was the result of the interaction of N2O5 with H2O that was still adsorbed after prolonged pumping at 0.0001 torr. In the presence of H2O, the same processes with gamma = 0.005 are observed. The redox reaction dominates in the early stages of the reaction, whereas the hydrolysis gains importance later at the expense of the redox reaction. The rate law for HNO3 generation was found to be d(HNO3)/dt = k(bi)(H2O)(N2O5) with k(bi), the effective bimolecular rate constants, for 10 mg of carbon being (1.6 + or - 0.3) x 10 to the -13th cu cm/s.

Brouwer, L.↗
DOE OSTI2023

Redox‐Functionalized Semiconductor Interfaces for Photoelectrochemical Separations

Redox-mediated electrosorption is a promising platform for selective electrochemical (EC) separations, due to its molecular selectivity, high uptake, and tunability for target ions. However, the electrical energy required is mainly generated by non-renewable energy sources, which limits its sustainability and overall impact to decarbonization. Here, a redox-mediated photoelectrochemical (PEC) separation process using polyvinyl ferrocene functionalized TiO 2 nanorod electrodes is proposed, which integrates direct solar energy as a driver for the selective electrosorption. The photoelectrochemically-driven oxidation and reduction with both homogeneous and heterogeneous ferrocene-systems is investigated to establish the underlying mechanism. The PEC system can separate heavy metal oxyanions at lower voltages or even without electrical energy. At 0.3 V versus SCE, a 124 mg g −1 uptake for Mo is achieved, which is comparable to the performance of EC cells at 0.75 V versus SCE. Thus, PEC systems not only can generate energy for spontaneous redox-separations, but also can reduce electrical energy consumption by 51.4% compared to EC cells for separation processes when coupled with an external electrical energy.

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

A formal Fe III/V redox couple in an intercalation electrode

Iron redox cycling between low-valent oxidation states of Fe II and Fe III drives crucial processes in nature. The Fe II/III redox couple charge compensates the cycling of lithium iron phosphate, a positive electrode (cathode) for lithium-ion batteries. High-valent iron redox couples, involving formal oxidation higher than Fe III , could deliver higher electrochemical potentials and energy densities. However, because of the instability of high-valent Fe electrodes, they have proven difficult to probe and exploit in intercalation systems. Here, in this study, we report and characterize a formal Fe III/V redox couple by revisiting the charge compensation mechanism of (de)lithiation in Li 4 FeSbO 6 . Valence-sensitive experimental and computational core-level spectroscopy reveal a direct transition from Fe III (3d 5 ) to a negative-charge-transfer FeV (3d 5 L 2 ) ground state on delithiation, without forming Fe IV , or oxygen dimers. We identify that the cation ordering in Li 4 FeSbO 6 drives a templated phase transition to stabilize the unique Fe V species and demonstrate that disrupting cation ordering suppresses the Fe III/V redox couple. Exhibiting resistance to calendar aging, high operating potential and low voltage hysteresis, the Fe III/V redox couple in Li 4 FeSbO 6 provides a framework for developing sustainable, Fe-based intercalation cathodes for high-voltage applications.

Ramachandran, Hari [Stanford Univ., CA (United Sta↗
NASA NTRS1984

An electromotive force series in a borosilicate glass-forming melt

An electromotive force series for redox couples was defined as a function of oxygen fugacity in a borosilicate melt at 1150 C. The resulting order of relative reduction potentials can be used to estimate the amounts of redox species in glass during processing. The electromotive force series in this melt is comparable to those in other silicate glass-forming melts and in aqueous systems but differs in detail because of interaction of the solvents with individual redox couples.

Schreiber, H. D.↗