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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 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Nitroxide Radical Polymer–Solvent Interactions and Solubility Parameter Determination

Redox-active polymers such as macromolecular nitroxide radicals have been studied as electrode materials for organic batteries and electronics. Polymer–solvent interactions are essential to processing and device performance, but macromolecular nitroxide radical–solvent interactions are currently not well described. In this work, the Hildebrand and Hansen solubility parameters of poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), oxidized PTMA (PTMA + ), and PTMA’s precursor (PTMPM) are determined using both experimental and group contribution methods for the first time. This work indicates that the hydrogen-bonding Hansen solubility parameter (δ h ) and the solubility sphere radii (R) provide the best prediction of the macromolecular radical’s interaction with solvents. From these solubility parameters, the group contribution values for the nitroxide and oxoammonium cation were then calculated. It is shown that this information allows for the prediction of polymer–solvent interactions for other nitroxide-based macromolecular radicals. Lastly, the discovered solubility parameters are used to predict PTMA electrode formulations for batteries that outperform controls.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Model associated with: "Thermodynamic control on the decomposition of organic matter across different electron acceptors"

This model data package is associated with the publication “Thermodynamic control on the decomposition of organic matter across different electron acceptors” submitted to Soil Biology and Biochemistry (Zheng et al., 2023; https://doi.org/10.1016/j.soilbio.2024.109364).In this research, a thermodynamic modeling framework is built to flexibly incorporate both organic matter (OM) molecules and electron acceptors for estimating potential free energy release from various redox reactions and to further predict reaction rates based on Microbial Transition State Theory. The model package includes scripts for thermodynamic modeling and postprocessing. Input Fourier-transform ion cyclotron resonance (FTICR) data are from a previous experimental study (Boye et al., 2018), and model outputs are free energy predictions and stoichiometric coefficients associated with all possible redox reactions.This data package is associated with the project GitHub repository found at MM_bioenergetic_modeling.This data package contains four folders (Input_FTICR, Model, Output, and Output_processing), a file-level metadata (FLMD) csv, and a data dictionary (dd) csv. Please see Zheng_bioenergetic_modeling_flmd.csv for a list of all files contained in this data package and descriptions for each. The Zheng_bioenergetic_modeling_dd.csv file describes the csv column headers. The “Model” folder contains scripts to run energy balance calculations for each electron acceptor. The “Output” folder contains csv files with stoichiometric information from model simulations. And the "Output_processing" folder contains scripts for reaction rate calculations and to generate plots.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

w19_OMEC Scientific Highlight [Slides]

Scientific Achievement: Revealed the effect of graphite substrate on H binding / hydrogen evolution reaction (HER) activity of organic molecular electrocatalysts (OMECs); and demonstrated the effect of molecular modification on calculated HER activity descriptor. Significance and Impact: Understanding of HER processes is important for discovering low-cost OMECs for hydrogen production and energy application; design of OMEC structures remains challenging due to the unexplored redox properties of organic molecules; and density functional theory (DFT) has been proposed to provide needed insights into HER activity for improved materials design. Research Details: DFT calculations on the binding energy of HER intermediates are used for predicting reduction potentials and and calculated H adsorption energy as activity descriptor; and LANL Institutional Computing (IC) resources are essential for successful project execution given the size of structures involved in modeling molecule-support interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Long-Term Stability of Nicotinamide Cofactors in Common Aqueous Buffers: Implications for Cell-Free Biocatalysis

The use of nicotinamide cofactors in cell-free biocatalytic systems is necessitated by the high specificity that these enzymes show for their natural redox mediators. Unfortunately, isolation and use of natural cofactors is costly, which suggests that enhancing their stability is key to enabling their use in industrial processes. This study details NAD+ and NADH stability in three buffer systems (sodium phosphate, HEPES, and Tris) at 19 °C and 25 °C and for up to 43 d. In Tris, both NADH and NAD+ were found to be highly stable. NADH degradation rates of 4 μM/d (19 °C) and 11 μM/d (25 °C) were observed in Tris buffer, corresponding to >90% and 75% remaining after 43 d, respectively. Higher degradation rates (up to 34 μM/d) were observed when sodium phosphate or HEPES buffers were used. The effect of a mild increase in temperature was determined to be significant for long-term stability, and it was shown that degradation under these conditions can be easily monitored via UV–Vis, because the degradation proceeds via the oxidation/de-aromatization of the dihydropyridine ring. Overall, this work emphasizes that the choice of buffer system is consequential for bioreactor systems employing natural nicotinamide cofactors for extended periods of time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

The origin and stability of lunar goethite, hematite and magnetite.

Extra-lunar contamination, fumarolic activity, and exposure to oxidizing gases from comet or carbonaceous meteorite impacts have been previously proposed as the causes of magnetite, hematite, and goethite in lunar materials. However, these minerals can occur in the stable low-temperature gas-solid equilibrium assemblages of lunar rocks. Below 600 C magnetite is in equilibrium with C-O-H gases with compositions compatible with high-temperature equilibrium with metallic iron; below 150 C hematite is stable in these same gases. Goethite is not stable in carbonaceous gases at low total pressure, and thus gases from impacting carbonaceous material cannot have produced it. Goethite is stable at low temperatures and pressures in almost pure H2-H2O gases. Its minimum stability against hematite is 2 bars total pressure at 130 C and 0.001 bars at 30 C for H2 to H2O ratios compatible with the high-temperature redox state of lunar materials. Thus the traces of magnetite, hematite, and goethite in lunar materials may be the result of normal low-temperature processes indigenous to the moon and not special processes.

Williams, R. J.↗
NASA NTRS2000

Metabolic Adaptation to Muscle Ischemia

Although all tissues in the body can adapt to varying physiological/pathological conditions, muscle is the most adaptable. To understand the significance of cellular events and their role in controlling metabolic adaptations in complex physiological systems, it is necessary to link cellular and system levels by means of mechanistic computational models. The main objective of this work is to improve understanding of the regulation of energy metabolism during skeletal/cardiac muscle ischemia by combining in vivo experiments and quantitative models of metabolism. Our main focus is to investigate factors affecting lactate metabolism (e.g., NADH/NAD) and the inter-regulation between carbohydrate and fatty acid metabolism during a reduction in regional blood flow. A mechanistic mathematical model of energy metabolism has been developed to link cellular metabolic processes and their control mechanisms to tissue (skeletal muscle) and organ (heart) physiological responses. We applied this model to simulate the relationship between tissue oxygenation, redox state, and lactate metabolism in skeletal muscle. The model was validated using human data from published occlusion studies. Currently, we are investigating the difference in the responses to sudden vs. gradual onset ischemia in swine by combining in vivo experimental studies with computational models of myocardial energy metabolism during normal and ischemic conditions.

Cabrera, Marco E.↗
DOE OSTI2019

Mineral Dissolution upon Alkaline Treatment and Variable Redox Conditions

Over 200.000 kg of uranium released to vadose zone from historic leaks and improper disposal of wastes from plutonium production. U highly mobile due to presence of carbonates and oxidizing conditions with partition coefficients k{sub d} of 0.11-8 mL/g at pH 8. Ammonia (NH{sub 3}) gas injection investigated as an in situ remediation technique that will not introduce additional liquid to the subsurface. Objectives: Understand the impact of remediation with base injection on geochemical process in Hanford site vadose zone. Understand effects of different base treatments on mineral dissolution. Results: - incongruent dissolution based on mineral stoichiometry: if ratio = 1 congruent dissolution occurs, if ratio <1.0 greater leaching of Si and Al and incongruent dissolution occurs. Conclusions: incongruent dissolution occurred for both alkaline treatments and redox conditions across all minerals. By 1440 hr. all normalised Al:Si ratios were <1 representing less [Al]{sub aq} and suggesting formation of secondary Al precipitates as a function of time. [Si]{sub aq} increased and [Al]{sub aq} decreased with increasing contact time with both alkaline treatments. NaOH dissolved slightly more than NH{sub 4}OH especially for [Al]{sub aq} in all investigated minerals. No clear trend for muscovite and montmorillonite for redox conditions but slightly greater Si dissolved under anaerobic conditions for illite. Ammonia gas injection increases the pH and dissolves aluminosilicate minerals in the vadose zone. U is likely to coprecipitate with secondary minerals forming at elevated pH and as the system reequilibrates at natural neutral pH. Further, U solids may be coated with low solubility, secondary precipitates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Iron Redox Chemistry and Its Environmental Impact: A Virtual Special Issue

Special Editorial Issue. Iron (Fe) is the most abundant redox-active element at the Earth’s surface. It occurs in diverse host rock lithologies, sediments, and soils as accessory oxide and oxyhydroxide minerals and nanoparticles that can dominate the reactive mineral/water interfacial area. Furthermore, designer Fe oxide nanoparticles produced to exploit the catalytic properties of specific mineral surfaces continue to undergo rapid development and deployment for a variety of purposes, including environmental remediation. The structure, charge, and chemical dynamics at these interfaces with aqueous solutions strongly impacts their interaction with other elements, organics, and contaminants. The influence of important environmental factors, especially oxygen concentration, natural organic matter, microbes, etc. remain poorly understood. Key interfacial processes can be driven by both biotic and abiotic mechanisms.

Iron redox, special issue, mechanisms, biogeochemi↗
DOE OSTI2017

Redox Controls over the Stability of U(IV) in Floodplains of the Upper Colorado River Basin

Here, aquifers in the Upper Colorado River Basin (UCRB) exhibit persistent uranium (U) groundwater contamination plumes originating from former ore processing operations. Previous observations at Rifle, Colorado, have shown that fine grained, sulfidic, organic-enriched sediments accumulate U in its reduced form, U(IV), which is less mobile than oxidized U(VI). These reduced sediment bodies can subsequently act as secondary sources, releasing U back to the aquifer. There is a need to understand if U(IV) accumulation in reduced sediments is a common process at contaminated sites basin-wide, to constrain accumulated U(IV) speciation, and to define the biogeochemical factors controlling its reactivity. We have investigated U(IV) accumulation in organic-enriched reduced sediments at three UCRB floodplains. Noncrystalline U(IV) is the dominant form of accumulated U, but crystalline U(IV) comprises up to ca. 30% of total U at some locations. Differing susceptibilities of these species to oxidative remobilization can explain this variability. Particle size, organic carbon content, and pore saturation, control the exposure of U(IV) to oxidants, moderating its oxidative release. Further, our data suggest that U(IV) can be mobilized under deeply reducing conditions, which may contribute to maintenance and seasonal variability of U in groundwater plumes in the UCRB.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Monitoring the long-term performance of organic redox flow battery by a distribution of relaxation time analysis

Organic redox flow batteries hold great promise as an energy storage technology, but their intricate chemistry makes them vulnerable to various degradation mechanisms. Monitoring this degradation is essential for identifying the limiting processes within the cells. Electrochemical impedance spectroscopy (EIS) offers a straightforward, in-situ method for measuring the total resistance of an operating cell. However, to pinpoint the limiting processes during long-term cycling, EIS data must be complemented by other techniques. Distribution of relaxation time (DRT) analysis is particularly effective for differentiating resistance components. Here, in this study, we perform a comprehensive analysis of resistance evolution and the separation of anode and cathode contributions during long-term cycling of a full cell employing 7,8-dihydroxyphenazine-2-sulfonic acid (DHPS) as the anolyte. Separate analyses of the DHPS anolyte and ferri-/ferrocyanide catholyte were conducted using a symmetric cell setup. The relaxation times derived from symmetric cells facilitate the identification of peaks in the DRT profiles from the full cell. Importantly, the DRT profiles indicate a correlation between the evolution of charge transfer resistance and the chemical degradation of DHPS. The methodologies and results outlined in this study offer significant insights for developing diagnostic tools applicable to other types of redox flow batteries.

Distribution of relaxation time↗
DOE OSTI2019

Elucidating metal and ligand redox activities of a copper-benzoquinoid coordination polymer as the cathode for lithium-ion batteries

A novel redox-active quinone-based organic building block 1,4-dicyano-2,3,5,6-tetrahydroxybenzene (LH 4 ) has been synthesized and used as a bridging ligand to form a new 1D copper-benzoquinoid coordination polymer [CuL(DMF) 2 ] n . The compound is able to deliver an initial capacity as high as 268 mA h g -1 at 30 mA g -1 (~C/2.5) when used as the cathode in Li batteries. Ex situ XPS and FT-IR reveal the involvement of both Cu and organic moieties in the multi-electron redox reaction. Cu K-edge XANES and EXAFS measurements confirm the change in the oxidation state and coordination environment of Cu during the discharge–charge process. In situ generated metallic nanoparticles have been observed by TEM. The obtained mechanistic understanding of the metal–organic electrode materials for Li-based batteries may pave the way for the design of next-generation energy-storage systems.

25 ENERGY STORAGE↗
DOE OSTI2022

Electroactive biofilms: how microbial electron transfer enables bioelectrochemical applications

Abstract Microbial biofilms are ubiquitous. In marine and freshwater ecosystems, microbe–mineral interactions sustain biogeochemical cycles, while biofilms found on plants and animals can range from pathogens to commensals. Moreover, biofouling and biocorrosion represent significant challenges to industry. Bioprocessing is an opportunity to take advantage of biofilms and harness their utility as a chassis for biocommodity production. Electrochemical bioreactors have numerous potential applications, including wastewater treatment and commodity production. The literature examining these applications has demonstrated that the cell–surface interface is vital to facilitating these processes. Therefore, it is necessary to understand the state of knowledge regarding biofilms’ role in bioprocessing. This mini-review discusses bacterial biofilm formation, cell–surface redox interactions, and the role of microbial electron transfer in bioprocesses. It also highlights some current goals and challenges with respect to microbe-mediated bioprocessing and future perspectives.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2015

Flexible Hybrid Battery/Pseudocapacitor

Batteries keep devices working by utilizing high energy density, however, they can run down and take tens of minutes to hours to recharge. For rapid power delivery and recharging, high-power density devices, i.e., supercapacitors, are used. The electrochemical processes which occur in batteries and supercapacitors give rise to different charge-storage properties. In lithium ion (Li+) batteries, the insertion of Li+, which enables redox reactions in bulk electrode materials, is diffusion controlled and can be slow. Supercapacitor devices, also known as electrical double-layer capacitors (EDLCs) store charge by adsorption of electrolyte ions onto the surface of electrode materials. No redox reactions are necessary, so the response to changes in potential without diffusion limitations is rapid and leads to high power. However, the charge in EDLCs is confined to the surface, so the energy density is lower than that of batteries.

Tucker, Dennis S.↗
DOE OSTI2018

Mesoporous nanocrystalline film architecture for capacitive storage devices

A mesoporous, nanocrystalline, metal oxide construct particularly suited for capacitive energy storage that has an architecture with short diffusion path lengths and large surface areas and a method for production are provided. Energy density is substantially increased without compromising the capacitive charge storage kinetics and electrode demonstrates long term cycling stability. Charge storage devices with electrodes using the construct can use three different charge storage mechanisms immersed in an electrolyte: (1) cations can be stored in a thin double layer at the electrode/electrolyte interface (non-faradaic mechanism); (2) cations can interact with the bulk of an electroactive material which then undergoes a redox reaction or phase change, as in conventional batteries (faradaic mechanism); or (3) cations can electrochemically adsorb onto the surface of a material through charge transfer processes (faradaic mechanism).

25 ENERGY STORAGE↗
DOE OSTI2020

Mesoporous nanocrystalline film architecture for capacitive storage devices

A mesoporous, nanocrystalline, metal oxide construct particularly suited for capacitive energy storage that has an architecture with short diffusion path lengths and large surface areas and a method for production are provided. Energy density is substantially increased without compromising the capacitive charge storage kinetics and electrode demonstrates long term cycling stability. Charge storage devices with electrodes using the construct can use three different charge storage mechanisms immersed in an electrolyte: (1) cations can be stored in a thin double layer at the electrode/electrolyte interface (non-faradaic mechanism); (2) cations can interact with the bulk of an electroactive material which then undergoes a redox reaction or phase change, as in conventional batteries (faradaic mechanism); or (3) cations can electrochemically adsorb onto the surface of a material through charge transfer processes (faradaic mechanism).

25 ENERGY STORAGE↗
DOE OSTI2024

Mesoporous nanocrystalline film architecture for capacitive storage devices

A mesoporous, nanocrystalline, metal oxide construct particularly suited for capacitive energy storage that has an architecture with short diffusion path lengths and large surface areas and a method for production are provided. Energy density is substantially increased without compromising the capacitive charge storage kinetics and electrode demonstrates long term cycling stability. Charge storage devices with electrodes using the construct can use three different charge storage mechanisms immersed in an electrolyte: (1) cations can be stored in a thin double layer at the electrode/electrolyte interface (non-faradaic mechanism); (2) cations can interact with the bulk of an electroactive material which then undergoes a redox reaction or phase change, as in conventional batteries (faradaic mechanism); or (3) cations can electrochemically adsorb onto the surface of a material through charge transfer processes (faradaic mechanism).

Dunn, Bruce S.↗
DOE OSTI2024

Clostridium autoethanogenum alters cofactor synthesis, redox metabolism, and lysine-acetylation in response to elevated H 2 :CO feedstock ratios for enhancing carbon capture efficiency

Clostridium autoethanogenum is an acetogenic bacterium that autotrophically converts carbon monoxide (CO) and carbon dioxide (CO 2 ) gases into bioproducts and fuels via the Wood–Ljungdahl pathway (WLP). To facilitate overall carbon capture efficiency, the reaction stoichiometry requires supplementation of hydrogen at an increased ratio of H 2 :CO to maximize CO 2 utilization; however, the molecular details and thus the ability to understand the mechanism of this supplementation are largely unknown. In order to elucidate the microbial physiology and fermentation where at least 75% of the carbon in ethanol comes from CO 2 , we established controlled chemostats that facilitated a novel and high (11:1) H 2 :CO uptake ratio. We compared and contrasted proteomic and metabolomics profiles to replicate continuous stirred tank reactors (CSTRs) at the same growth rate from a lower (5:1) H 2 :CO condition where ~ 50% of the carbon in ethanol is derived from CO 2 . Our hypothesis was that major changes would be observed in the hydrogenases and/or redox-related proteins and the WLP to compensate for the elevated hydrogen feed gas. Our analyses did reveal protein abundance differences between the two conditions largely related to reduction–oxidation (redox) pathways and cofactor biosynthesis, but the changes were more minor than we would have expected. While the Wood–Ljungdahl pathway proteins remained consistent across the conditions, other post-translational regulatory processes, such as lysine-acetylation, were observed and appeared to be more important for fine-tuning this carbon metabolism pathway. Metabolomic analyses showed that the increase in H 2 :CO ratio drives the organism to higher carbon dioxide utilization resulting in lower carbon storages and accumulated fatty acid metabolite levels. This research delves into the intricate dynamics of carbon fixation in C. autoethanogenum, examining the influence of highly elevated H 2 :CO ratios on metabolic processes and product outcomes. The study underscores the significance of optimizing gas feed composition for enhanced industrial efficiency, shedding light on potential mechanisms, such as post-translational modifications (PTMs), to fine-tune enzymatic activities and improve desired product yields.

09 BIOMASS FUELS↗