Search NASA⌕ Search

SEARCH · Search NASA

Results for “REDOX PROCESS”

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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Measuring Hydroxylammonium, Nitrate, and Nitrite Concentration with Raman Spectroscopy for 238 Pu Supply Program

Optical spectroscopy has great potential to improve the timeliness of important analytical measurements for the 238 Pu Supply Program by enabling real-time analysis of process solutions within radiochemical hot cells. Hydroxylammonium (H 3 NOH + ]), nitrate (NO 3 - ), and nitrite (NO 2 - ) are three important molecular species present in multiple aqueous streams throughout the program’s flow sheet. The concentration of each species normally goes uncharacterized during processing. However, rapid quantification may benefit the program because uncertainties in kinetic redox expressions describing hydroxylammonium (HA) and nitrite reactions with Np and Pu leads to uncertainty in process model predictions for solvent extraction runs. HA concentration is normally quantified using ion chromatography, a technique that requires diluted grab samples taken out of the hot cell and analyzed off-line. Here we evaluate Raman spectroscopy for determining the concentration of H 3 NOH + , NO 3 - , and NO 2 - in benchtop tests to determine limits of detection. We also consider the possibility of using Raman spectroscopy in both glove box and hot cell environments for rapid analysis and pinpoint additional development opportunities needed to make this application successful.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS2003

SNC Oxygen Fugacity Recorded in Pyroxenes and its Implications for the Oxidation State of the Martian Interior: An Experimental and Analytical Study

Knowledge of the oxidation state of a magma is critical as it is one of the parameters which controls the nature and composition of the resulting crystals. In terrestrial magmatic systems, oxygen fugacity (fo2) is known to vary by over nine orders of magnitude. With variations of this magnitude, understanding the compositional differences, phase changes, and crystallization sequence variations, caused by the magma fo2, is essential in deciphering the origin of all igneous rocks. Magmatic oxidation state is of great importance in that it reflects the degree of oxidation of the source region and can provide insight into magmatic processes, such as metasomatism, degassing, and assimilation, which may have changed them. Carmichael [1991] argues that most magmas are unlikely to have their redox states altered from those of their source region. This assumption allows for estimation of the oxidation state of planetary interiors. Conversely, it is known that the fo2 of the magma can be affected by other processes, which occur outside of the source region and therefore, the oxidation state may record those too. Processes which could overprint source region fugacities include melt dehydrogenation or other volatile loss, water or melt infiltration, or assimilation of oxidized or reduced wallrock. Understanding which of these processes is responsible for the redox state of a magma can provide crucial information regarding igneous processes and other forces active in the region. The composition of the SNC basalts and their widely varying proposed oxidation states raise some interesting questions. Do the SNC meteorites have an oxidized or reduced signature? What was the oxygen fugacity of the SNC source region at the time of melt generation? Is the fugacity calculated for the various SNC samples the fugacity of the magma source region or was it overprinted by later events? Are there different oxidation states in the Martian interior or a single one? This proposal seeks to address all of these questions.

McCanta, M. C.↗
NASA NTRS1996

Redox Disproportionation of Glucose as a Major Biosynthetic Energy Source

Previous studies have concluded that very little if any energy is required for the microbial biosynthesis of amino acids and lipids from glucose -- processes that yield almost as much ATP (adenosine triphosphate) as they consume. However, these studies did not establish the strength nor the nature of the energy source driving these biological transformations. To identify and estimate the strength of the energy source behind these processes, we calculated the free energy change due to the redox disproportionation of substrate carbon of (a) 26 redox-balanced fermentation reactions, and (b) the biosynthesis of amino acids, lipids, and nucleotides of E. coli from glucose. A plot of the negative free energy of these reactions per mmole of carbon as a function of the number of disproportionative electron transfers per mmol of carbon showed that the energy yields of these fermentations and biosyntheses were directly proportional to the degree of redox disproportionation of carbon. Since this linear relationship showed that redox disproportionation was the dominant energy source of these reactions, we were able to establish that amino acid and lipid biosynthesis obtained most of their energy from redox disproportionation (greater than 94%). In contrast nucleotide biosynthesis was not driven by redox disproportionation of carbon, and consequently depended completely on ATP for energy. This crucial and previously unrecognized role of sugars as an energy source of biosynthesis suggests that sugars were involved at the earliest stage in the origin of anabolic metabolism.

Weber, Arthur L.↗
DOE OSTI2025

Understanding Structural and Compositional Evolution during NMC Cathode Direct Recycling via Solid-State NMR

Recycling end-of-life lithium-ion batteries (LIBs) to recover high-value cathode materials such as LiNixMnyCozO2 (NMC) is driven by economical, geopolitical, and sustainability needs. There has been recent interest in direct recycling methods to improve efficiency and recovery of materials, including ionothermal, hydothermal, solid-state, or redox mediator methods. In conjunction with recycling process development, detailed structural characterization is necessary in order to understand the mechanisms and efficacy of cathode recycling steps. Solid-state nuclear magnetic resonance (NMR) spectroscopy is a unique tool that can probe Li coordination, bulk and surface environments, and transition metal ordering in recycled and upcycled NMC cathodes. Here, 6,7Li, 1H, and 19F NMR spectroscopy to probe structural and compositional changes as well as surface impurities that may form during each step in NMC direct recycling is utilized. During relithiation, Li reinsertion into the NMC lattice is observed. During upcycling, where the goal is to increase the Ni content in the NMC, incorporation of Ni-rich phases into the bulk Li environment is observed. Surface impurities formed during processing were also identified. These studies provide valuable information for optimizing recycling processes to reach targeted cathode composition and structure that can enable electrochemical performance comparable to or better than pristine materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Selective ion transport through hydrated micropores in polymer membranes

Abstract Ion-conducting polymer membranes are essential in many separation processes and electrochemical devices, including electrodialysis 1 , redox flow batteries 2 , fuel cells 3 and electrolysers 4,5 . Controlling ion transport and selectivity in these membranes largely hinges on the manipulation of pore size. Although membrane pore structures can be designed in the dry state 6 , they are redefined upon hydration owing to swelling in electrolyte solutions. Strategies to control pore hydration and a deeper understanding of pore structure evolution are vital for accurate pore size tuning. Here we report polymer membranes containing pendant groups of varying hydrophobicity, strategically positioned near charged groups to regulate their hydration capacity and pore swelling. Modulation of the hydrated micropore size (less than two nanometres) enables direct control over water and ion transport across broad length scales, as quantified by spectroscopic and computational methods. Ion selectivity improves in hydration-restrained pores created by more hydrophobic pendant groups. These highly interconnected ion transport channels, with tuned pore gate sizes, show higher ionic conductivity and orders-of-magnitude lower permeation rates of redox-active species compared with conventional membranes, enabling stable cycling of energy-dense aqueous organic redox flow batteries. This pore size tailoring approach provides a promising avenue to membranes with precisely controlled ionic and molecular transport functions.

Science & Technology - Other Topics↗
DOE OSTI2025

Heterobimetallic multi-site concerted proton electron transfer (MS-CPET) promotes coordination-induced O–H bond weakening

Coordination-induced bond weakening of X–H bonds (X = O, N, C) has been observed in a number of low-valent transition metal compounds. However, the impact of an appended electron reservoir on the bond dissociation free energy of the O–H bond (BDFE O–H ) of a substrate bound to a d 0 metal is poorly understood. To gain insight into the ability of separated deprotonation and oxidation sites to decrease the BDFE O–H during proton-coupled electron transfer (PCET) reactions, a bimetallic system in which the sites of proton and electron loss are two distinct metal sites is described. Herein, the interconversion of tris(phosphinoamide) Zr/Co complexes HO–Zr(MesNP i Pr 2 ) 3 CoCN t Bu and O$≡$Zr(MesNP i Pr 2 ) 3 CoCN t Bu via hydrogen atom addition/abstraction was studied. Since the Zr center remains in the d 0 Zr IV state throughout these transformations, the electron transfer process is mediated by the appended redox-active Co 0/I center. A series of open-circuit potential (OCP) measurements on the HO–Zr(MesNP i Pr 2 ) 3 CoCN t Bu and O$≡$Zr(MesNP i Pr 2 ) 3 CoCN t Bu complexes was performed, from which the BDFE O–H was found to be 64 ± 1 kcal mol −1 . The BDFE O–H value was further verified through a series of stoichiometric H atom transfer reactions, stoichiometric protonation/deprotonation reactions, and computational studies.

Chemistry↗
DOE OSTI2025

Old Woman Creek Wetland Sediment and Electrochemical Sensor Microbial Community, 2023

We are developing a technique to monitor microbiological activities referred to as zero resistance ammetry, which entails the deployment of graphite electrodes in sediments. Measurement of current between electrodes of contrasting redox regimes and/or predominant terminal electron accepting processes can be used as an indicator of the extents of microbiological activity. We deployed an electrode array at depths of 2 mm, 4 mm, 76 mm, 78 mm, 152 mm, 154 mm, 227 mm, and 229 mm below the wetland sediment water interface in the Old Woman Creek National Estuarine Research Center, Huron, OH, USA (Lat. = 41.380833, Long. = -82.508889). A core was collected from adjacent sediment and subsamples were collected from depth intervals of 0 – 25 mm, 25 – 127 mm, 127 – 128 mm, and below 178 mm. To determine if the microbial communities attached to the electrodes were reflective of the adjacent sediment-associated microbial community, we conducted a 16S rRNA gene-based (V4 region) survey of these respective materials. This data package contains the results of these surveys, including metadata on the depths from which samples were collected (samples.csv), DNA extraction and sequencing information (OWC_DEPTH_AMPLICON_SEQUENCING_METADATA), sequence processing information (OWC_DEPTH_BIOINFORMATIC_METADATA.csv), an operational taxonomic unit (OTU) table (OWC_DEPTH_97OTUS_TABLE.csv), and nucleotide sequences of OTUs (OWC_DEPTH_97OTUS_SEQS.fasta). All files can be opened using a text-editing application. The fasta file is compatible with bioinformatics applications.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Study of Ionic Mass Transport in Non-Conventional Electrolytes for Energy Storage and Carbon Capture Applications

In the field of energy storage, electrolytes are the materials or liquids used to transport ions or redox active chemicals to facilitate an electrochemical process. Conventional electrolytes are the most common form of electrolyte used and consist of salts dissolved in a liquid solvent medium. While conventional electrolytes are generally inexpensive and work well with lithium-ion batteries, they have many shortfalls however, such as corrosion of the cell, flammability, toxicity, price, and incompatibility with other metals. This project investigates the fundamental properties in nonconventional electrolyte systems with an initial focus on eutectics being made. Using electrochemical methods ( Cyclic Voltammetry (CV), Impedance, Conductance, etc.), we are studying the study of electrolyte systems containing ions used for thermal, chemical, or electrochemical energy storage such as Li + , Mg 2+ , Na + , K + , Al 3+ , CO 3 2- , Cl - , and O 2- . This research looks at how ion mobility effects the electrochemical characteristics and properties in green energy applications.

25 ENERGY STORAGE↗
DOE OSTI2022

Study Non-Conventional Deep Eutectic Electrolytes for Lithium Ion Batteries [Poster]

In the field of energy storage, electrolytes are the materials or liquids used to transport ions or redox active chemicals to facilitate an electrochemical process. While conventional electrolytes are generally inexpensive and work well with lithium-ion batteries, they have many shortfalls however, such as corrosion of the cell, flammability, toxicity, price, and incompatibility with other metals. Our work highlights the formation of a novel deep eutectic electrolyte (DEE) based on methyl carbamate and lithium salts. This DEE shows good cycling performance with the potential for low temperature operation. This study provides insights into a relatively unexplored field of non-conventional electrolyte systems.

25 ENERGY STORAGE↗
DOE OSTI2023

Carbon Dioxide-Free Hydrogen and Solid Carbon from Natural Gas via Metal Salt Intermediates

Production of hydrogen with low emissions and low energy input is critical for the clean energy transition, enabling all sectors of the economy to decarbonize – from electricity generation to residential heating to industrial power. In this program, Johns Hopkins University in partnership with ETCH, INC translated a novel laboratory-scale chemistry to decompose methane to hydrogen and solid carbon into a pre-commercial system. Central to the process is a closed-loop thermocatalytic redox cycle without water consumption or carbon dioxide generation that can be implemented with low capital and operating costs. Techno-economic and lifecycle analysis suggests this approach will produce the lowest cost and lowest-emissions route to hydrogen production.

03 NATURAL GAS↗
DOE OSTI2022

Enhanced physics-constrained deep neural networks for modeling vanadium redox flow battery

Numerical simulation has become indispensable in advancing cost-effective process optimization and control of flow batteries. We propose an enhanced version of the physics-constrained deep neural network (PCDNN) approach to provide high-accuracy voltage predictions in the vanadium redox flow batteries (VRFBs). The purpose of the PCDNN approach is to enforce the physics-based zero-dimensional (0D) VRFB model in a neural network to assure model generalization for various battery operation conditions. However, limited by the simplifications of the 0D model, the PCDNN cannot capture sharp voltage changes in the extreme SOC regions. To improve the accuracy of voltage prediction at extreme ranges, we introduce a second (enhanced) DNN to mitigate the prediction errors carried from the 0D model itself and call the resulting approach enhanced PCDNN (ePCDNN). By comparing with experimental data, we demonstrate that the ePCDNN approach can accurately capture the voltage response throughout the charge–discharge cycle, including the tail region of the voltage discharge curve. The loss function for training the ePCDNN is designed to be flexible by adjusting the weights of the physics-constrained DNN and the enhanced DNN. In conclusion, this allows the ePCDNN framework to be transferable to battery systems with variable physical model fidelity.

25 ENERGY STORAGE↗
DOE OSTI2021

Electronic control of redox reactions inside Escherichia coli using a genetic module

Microorganisms regulate the redox state of different biomolecules to precisely control biological processes. These processes can be modulated by electrochemically coupling intracellular biomolecules to an external electrode, but current approaches afford only limited control and specificity. Here we describe specific electrochemical control of the reduction of intracellular biomolecules in Escherichia coli through introduction of a heterologous electron transfer pathway. E . coli expressing cymAmtrCAB from Shewanella oneidensis MR-1 consumed electrons directly from a cathode when fumarate or nitrate, both intracellular electron acceptors, were present. The fumarate-triggered current consumption occurred only when fumarate reductase was present, indicating all the electrons passed through this enzyme. Moreover, CymAMtrCAB-expressing E . coli used current to stoichiometrically reduce nitrate. Thus, our work introduces a modular genetic tool to reduce a specific intracellular redox molecule with an electrode, opening the possibility of electronically controlling biological processes such as biosynthesis and growth in any microorganism.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Soluble Iron Enhances Extracellular Electron Uptake by Shewanella oneidensis MR‐1

Abstract Extracellular electron transfer (EET) is a process that microorganisms use to reduce or oxidize external insoluble electron acceptors or donors. Much of our mechanistic understanding of this process is derived from studies of transmembrane cytochrome complexes and extracellular redox shuttles that mediate outward EET to anodes and external electron acceptors. In contrast, there are knowledge gaps concerning the reverse process of inward EET from external electron donors to cells. Here, we describe a role for soluble iron (exogenous FeCl 2 ) in enhancing EET from cathodes to the model EET bacterium Shewanella oneidensis MR‐1, with fumarate serving as the intracellular electron acceptor. This iron concentration‐dependent electron uptake was eradicated upon addition of an iron chelator and occurred only in the presence of fumarate reductase, confirming an electron pathway from cathodes to this periplasmic enzyme. Moreover, S. oneidensis mutants lacking specific outer membrane and periplasmic cytochromes exhibited significantly decreased current levels relative to wild‐type. These results indicate that soluble iron can function as an electron carrier to the EET machinery of S. oneidensis .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1997

Redox Energy and Sulfur Chemistry in Prebiotic Polymer Synthesis and Replication

In the past year we have made significant progress in three research areas: (1) Most importantly, we discovered a new pathway of prebiotic amino acid synthesis in which formaldehyde and glycolaldehyde (substrates of the formose reaction) react with ammonia yielding alanine and homoserine in the presence of thiol catalysts. This thiol-dependent synthesis of amino acids undoubtedly occurs via amino acid thioester intermediates capable of forming peptides. This 'one-pot' reaction system operates under mild aqueous conditions, and like modern amino acid biosynthesis, uses sugar intermediates which are converted to amino acids by energy-yielding redox disproportionation. (2) Finally, in preparation for the analysis of Martian meteorite samples, we upgraded our HPLC system and developed an improved method capable of detecting a I femtomole of amino acid enantiomers. (3) We completed our analysis of the energetics of metabolism that revealed that life depends on biosynthetic processes driven by chemical energy made available by the redox disproportionation of carbon groups of sugars. We established that the favorable energy of redox disproportionation is based on the universal reduction potentials of carbon groups. We concluded that it is hard to imagine any other organic molecule besides sugars (formaldehyde oligomers) having the energy and reactivity needed to drive either modem biosynthesis or the chemical processes behind its origin.

Weber, Arthur L.↗
DOE OSTI2026

Reduction of Np(v) to Np(iv) using oxalic acid: rethinking decades of nuclear processing conventions

Actinide oxalate precipitation has been ubiquitous in nuclear processing since the 1950s due to its simplicity at laboratory and production scales as both a means of actinide purification and as a key intermediate solid phase towards oxide production. Historical processing information has emphasized the need to reduce actinides, including neptunium (Np), to the tetravalent or trivalent state with chemical reducing agents prior to oxalate precipitation. This work revisits the established method and reveals that oxalic acid has an unexpected role as a reducing agent for Np(v/vi). Also, the study uncovers insights into the direct precipitation of Np(iv) oxalate from neptunyl solutions, as identified by spectroscopic and X-ray diffraction analyses. These findings challenge the long-standing notion that redox adjustment of actinides is necessary for oxalate processing.

Gilson, Sara [ORNL] (ORCID:0009000706842064)↗
DOE OSTI2021

Chemical Understanding of Actinide Separations

This work provides a broad overview of the separation processes used to isolate actinides and the experimentally and computationally determined chemical characteristics that define those separations. The redox chemistry of the actinides plays a pivotal role in both aqueous and pyrochemical processing separations. The near-overlapping energies of the 6d and 5f orbitals in the light actinides allow for facile adjustment of actinide oxidation states, which is used in many established separation methods. In contrast, the stable, generally 3+ oxidation states of the mid- and heavy actinides can make it difficult to separate them from the similarly lanthanides(III). In aqueous separations, the tendency of the actinides to form anionic and neutral aqueous complexes with a variety of complexants (especially soft donors) is used to achieve high separation factors between chemically similar elements in both solid–liquid separations and liquid–liquid extraction. This selectivity can be further tuned through the use of specialized organic or solid-phase ligands. Pyroprocessing separations utilize the unique redox behavior of the actinides to adjust their distribution between a molten salt electrolyte and either a solid electrode or molten metal phase. Atomic-level insights into the mechanisms underlying actinide separation processes, with the ultimate goal of predicting separation behavior, can be provided by electronic structure and statistical mechanical-based calculation methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Understanding the Performance Gap between Polycrystalline and Single-Crystal Nickel-Rich Layered Oxide Cathodes

Singe-crystal (SC) nickel-rich layered oxide cathodes, composed of boundary-free particles with high tap density, offer significant advantages in volumetric energy density and mechanical strength compared with polycrystalline (PC) cathode materials. However, as the nickel content increases (≥80%), SC Ni-rich cathodes often suffer from faster performance degradation than PC cathodes of the same composition, and the underlying causes of this discrepancy remain poorly understood. Herein, we reveal the distinct Ni redox behaviors that govern the electrochemical performance of SC and PC Ni-rich cathodes using multiscale and operando characterization techniques. Our results indicate that the increasingly heterogeneous Ni oxidation process in SC cathodes leads to the additional irreversible oxygen redox activity that deteriorates both the mechanical and chemical structures. In contrast, PC cathodes, despite with more pronounced surface reconstruction, exhibit greater chemomechanical stability due to homogeneous redox reactions during charging. Consequently, we find that bulk degradation, more than surface reactions, ultimately leads to fast capacity decay of SC Ni-rich cathodes during cycling. In conclusion, this work offers a comprehensive view on the impact of Ni redox evolutions on the chemomechanical stability in Ni-rich layered oxide cathodes, providing new insights into the longstanding performance gap between SC and PC cathodes, and guiding the rational design of Ni-rich cathode architectures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

High‐Efficiency Ion‐Exchange Doping of Conducting Polymers

Abstract Molecular doping—the use of redox‐active small molecules as dopants for organic semiconductors—has seen a surge in research interest driven by emerging applications in sensing, bioelectronics, and thermoelectrics. However, molecular doping carries with it several intrinsic problems stemming directly from the redox‐active character of these materials. A recent breakthrough was a doping technique based on ion‐exchange, which separates the redox and charge compensation steps of the doping process. Here, the equilibrium and kinetics of ion exchange doping in a model system, poly(2,5‐bis(3‐alkylthiophen‐2‐yl)thieno(3,2‐b)thiophene) (PBTTT) doped with FeCl 3 and an ionic liquid, is studied, reaching conductivities in excess of 1000 S cm −1 and ion exchange efficiencies above 99%. Several factors that enable such high performance, including the choice of acetonitrile as the doping solvent, which largely eliminates electrolyte association effects and dramatically increases the doping strength of FeCl 3 , are demonstrated. In this high ion exchange efficiency regime, a simple connection between electrochemical doping and ion exchange is illustrated, and it is shown that the performance and stability of highly doped PBTTT is ultimately limited by intrinsically poor stability at high redox potential.

36 MATERIALS SCIENCE↗