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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Permanent Nanobubbles in Water: Liquefied Hollow Carbon Spheres Break the Limiting Diffusion Current of Oxygen Reduction Reaction

Porous liquids have traditionally been designed with sterically hindered solvents. Alternatively, recent efforts rely on dispersing microporous frameworks in simpler solvents like water. Here we report a unique strategy to construct macroporous water by selectively incorporating hydrophilicity on the surfaces of hydrophobic hollow carbon spheres (HCS). Specifically, we show that the stable dispersion surface ionized HCS in water while retaining the inherent porosity. The electrocatalytic conversion of small gas molecules in aqueous electrolytes is limited by the concentration and diffusion rates of gas molecules in water. In this case, macroporous water exhibited 6 times gas uptake compared to nonporous (pure) water. Furthermore, by leveraging the high gas capacity and enhanced diffusion kinetics, the limiting diffusion current of oxygen reduction reaction (ORR) in macroporous water is 2 times that in nonporous water, offering promising prospects for sustainable energy conversion technologies.

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

Exploring the kinetics of actinyl–EDTA reduction by ferrous iron using quantum-mechanical calculations

Here, the reduction of An(VI) (An = U, Np, and Pu) to An(IV) significantly decreases its solubility and mobility. This reaction can be hindered by complexation with inorganic (e.g., carbonate) or organic ligands. Ethylenediaminetetraacetic acid (EDTA) is one such organic ligand that forms stable complexes with actinides. Therefore, it may enhance the mobility of actinides. However, the redox kinetics and mechanisms of actinyl (An(V/VI)O 2 +/2+ )–EDTA are not well characterized yet and are thus studied here using quantum-mechanical calculations. The principle is to approach the actinyl–EDTA and Fe 2+ (reductant) in small incremental steps and calculate the system energy at each distance. The overall reaction is then delineated into sub-processes (encounter frequency in bulk solution, formation of outer-sphere complex, transition from outer- to inner-sphere complex, and electron transfer), and reaction rates are determined for each sub-process. The formation of outer-sphere complexes occurs rapidly in microseconds to seconds over a wide range of actinyl concentrations (pM to μM); in contrast, the transition to the inner-sphere complex is relatively slow (milliseconds to a few seconds). Immediate electron transfer to form the pentavalent actinide is observed along the reaction path for Np(VI) and Pu(VI), but not for U(VI). Surprisingly, in acidic conditions, one of the carboxylic groups gets protonated in EDTA of [UO 2 (edta)] 2- rather than one of the amino groups. This process-based series of calculations can be applied to any redox reaction and allows the prediction of changes to the rate law and rate-limiting step in a more fundamental way for different environments

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

Defining the Mechanism of Proton Pumping in Heme-Copper Oxidases

During this award, progress was made in two distinct areas of science, one was within the context of bioinorganic chemistry and another in the context of biomimetic, small molecule chemistry. The overarching goals of this work was to understand the fundamental mechanistic drivers for biological reactions specifically, proton transfer reactions. In the biochemical sphere, this goal was investigated through investigation of the bacterial proton pump, ubiquinol oxidase (UbO). Further work in the bioinorganic space was completed in collaboration with the Bandarian group on a novel natural peptide product. While in the biomimetic space, this work was explored through a computational collaborative study with the Riordan group relating to proton coupled electron transfers in iron complexes as relating to the heme active site in proton pumping enzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1969

Simplistic analysis of reactive scattering

Angular distribution of nonreactively scattered molecules in reactive collision, analyzing relation to reaction probability using gray sphere optical model

Bernstein, R. B.↗
NASA NTRS1983

Improving Hydrocarbon Separation In Gas Chromatography

Modified solica spheres enhance chromatographic separation. Commercially available silica spheres are modified by reacting them with molecules containing isocyante and isothiocyanate groups. Applications of surface derivatized spheres that result from reaction include analysis of samples prouced by atmospheric or soil probes.

Pollock, G. E.↗
DOE OSTI2022

EUCLID Sensitivity Database

This report documents the EUCLID sensitivity database along with its several use-cases. EUCLID computed sensitivities for the following integral responses: Criticality of ICSBEP critical assemblies, LLNL pulsed-sphere neutron-leakage spectra, reaction rates in selected ICBSEP critical assemblies, delayed neutron factions of selected ICSBEP critical assemblies, reactivity coefficients in two ICSBEP critical assemblies, sub-critical assembly responses and Rossi-alpha of selected critical assemblies. It is described for each response what the reported observable constitutes, the method we used to obtain the sensitivities, and which integral experiments were studied. It is also documented briefly in what format these sensitivities are stored. These sensitivities were used for many aspects of the EUCLID project, like ML-supported large-scale nuclear-data validation, or optimization of integral experiments. But these sensitivities can also be applied for more established processes in the nuclear-data application field such as adjustment or assessing the upper sub-critical limit.

Delayed Neutron Fraction↗
DOE OSTI2022

Space-dependent calculation of the multiplicity moments for shells

In earlier work, we extended the methodology of multiplicity counting in nuclear safeguards, by elaborating the one-speed stochastic transport theory of the calculation of the so-called multiplicity moments, i.e. the factorial moments of the number of neutrons emitted from a fissile item, following a source event from an internal neutron source (spontaneous fission and (α, n) reactions). Calculations were made for spheres and cylinders of various shapes. In all our work so far, the material of the items was homogeneous, and the distribution of the internal source was assumed to be uniformly distributed within the item, with the neutron emission assumed to be isotropic. In the present work the calculations are extended to the case of a point source inside either a solid sphere or in a spherical shell. This necessitates the extension of the theory to non-homogeneous items and non-uniform and non-isotropic sources. This work describes the extension of the theory and provides some quantitative results. (authors)

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Shedding light on the 239Pu fission source term with new high-precision experiments and advanced fission modeling

In the last decade, there has been a renaissance of fission research resulting in new high-precision experiments and advanced fission modeling. For instance, the Chi-Nu and CEA teams supplied, for the first time, the 239 Pu prompt fission neutron spectrum (PFNS) for broad ranges of incident and outgoing neutron energies. The CEA team also measured 239 Pu average prompt neutron multiplicities, ν ̄ p , with lower statistical uncertainties and a technique significantly different than the one used in the past. The NIFFTE collaboration provided 239 Pu( n ,f)/ 235 U( n ,f) cross section shape ratios with uncertainties below 1% utilizing a novel detector type. Advanced fission event generators were developed, among them CGMF, FIFRELIN, FREYA, and GEF, which calculate post-scission fission observables in a correlated manner. These new experimental data and more consistent fission models change the evaluated PFNS, ν ̄ p , and ( n ,f) cross sections, some only modestly, compared to ENDF/B-VIII.0. In turn, the individual new nuclear data distinctly change simulated effective neutron multiplication factors of fast critical assemblies, but their combined impact is small, while affecting the prediction of LLNL pulsed sphere neutron leakage spectra and reaction rates only within experimental uncertainties. Also, the parameters obtained from fitting to ν ̄ p reproduce various post-scission fission observables within the uncertainties of experimental data. This indicates that new differential experiments and consistent fission modeling reduce compensating errors present in ENDF/B-VIII.0.

fission cross section↗
DOE OSTI2023

Space-Dependent Calculation of the Multiplicity Moments for Shells With the Inclusion of Scattering

In recent work, we extended the methodology of multiplicity counting in nuclear safeguards by elaborating the one-speed stochastic transport theory of the calculation of the so-called multiplicity moments, i.e., the factorial moments of the number of neutrons emitted from a fissile item, following a source event from an internal neutron source [spontaneous fission and (α; n) reactions]. Calculations were made for solid spheres and cylinders, with the source being homogeneously distributed within the item. Recent measurements of the Rocky Flats Shells during the Measurement of Uranium Subcritical and Critical (MUSIC) campaign conducted by Los Alamos National Laboratory and assisted by the University of Michigan inspired us to extend the model to spherical shell geometry with a point source in the middle of the central cavity. Comparison of the calculated results with the experimental ones indicated that accounting for fission as the only neutron reaction (the standard procedure in the point model, adapted also in our work so far) was not sufficient for reaching good agreement with measurements. The model was therefore extended to include elastic scattering into the one speed formalism, whereas the effect of inelastic scattering was accounted for in an empirical way. After these extensions, good agreement was found between the calculated and the measured values. The paper describes the extension of the theory and provides concrete quantitative results.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Influence of Polymer and Support Interactions on the Electrocatalytic Properties of Heterogenized Molecular Complexes

Heterogenized molecular catalysts have been the subject of increasing interest in the context of electrochemical small molecule activation due to the possibility of active site homogeneity and tunability, which can surpass many nanostructured materials. When molecular catalysts strongly interact with carbon supports through π–π interactions, they tend to show higher selectivity and activity during heterogeneous electrochemical reactions. Indeed, ligand modifications in the secondary sphere that allow for more π–π overlap between catalyst and carbon support often show improved performance. Interactions between catalyst and polymer binder are also a possible modulus of control in these reactions, either through coordinating moieties that interact with active sites or through control over substrate or product transport. Finally, the covalent linking of molecular complexes onto carbon materials has also been shown to result in high activity and stability. Recent advances in the use of carbon supports, both through covalent and non-covalent interactions, and polymers to alter small molecule activation by heterogenized molecular catalysts are summarized in this Perspective.

Johnson, Elizabeth K. [University of Virginia, Cha↗
DOE OSTI2022

Fast estimation of reaction rates in spherical and non-spherical porous catalysts

Here we present a methodology for modeling multi-step reaction rates in porous catalyst particles for use in CFD-DEM and two fluid models. Single-step effectiveness factors based on a Thiele modulus, while useful, cannot accurately capture the cascading reaction systems common in high temperature vapor-phase chemical reactors like fluidized catalytic cracking units and catalytic biomass fast pyrolysis systems. Instead, multi-step effectiveness vectors derived from steady-state solutions to the governing reaction-diffusion equations are needed. Solutions for various catalyst shapes are presented, including spheres, cylinders, and prisms. Computational challenges inherent in repeated evaluation of reaction rates with diffusion limitations are discussed, and an efficient implementation based on pre-computed lookup tables is proposed and demonstrated on a simulation of a fluidized bed reactor. Open-source code is provided for the compilation of reaction rate tables for use in ODE, DEM, and two-fluid models.

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

TUMME: Tsinghua University Minnesota Master Equation program

We report that TUMME is a program for assembling and solving master equations for gas-phase chemical kinetics based on chemically significant eigenmodes. TUMME has interfaces to the Gaussian, Polyrate, and/or MSTor output files that allow the master equation code to obtain the microcanonical flux coefficients needed for the coefficient matrix of the master equation. The flux coefficients for reactions with barriers can be calculated by multi-structural variational transition state theory with small-curvature tunneling (MS-VTST/SCT) or by simpler approximations to this such as conventional transition state theory without tunneling (also called RRKM theory). The flux coefficients for barrierless reactions are provided by a hard-sphere model. TUMME is written in double precision with Python 3; quadruple and octuple precision are also available for some subtasks in C++. The Python code can run in serial or parallel (MP or MPI), and the C++ code can run on a single processor or on multiple processors with OpenMP.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O 2 Reaction

The concentration of formic acid in Earth's tropo-sphere is underestimated by detailed chemical models compared to field observations. Phototautomerization of acetaldehyde to its less stable tautomer vinyl alcohol, followed by the OH-initiated oxidation of vinyl alcohol, has been proposed as a missing source of formic acid that improves the agreement between models and field measurements. Theoretical investigations of the OH + vinyl alcohol reaction in excess O 2 conclude that OH addition to the alpha carbon of vinyl alcohol produces formaldehyde + formic acid + OH, whereas OH addition to the β site leads to glycoaldehyde + HO 2 . Furthermore, these studies predict that the conformeric structure of vinyl alcohol controls the reaction pathway, with the anti-conformer of vinyl alcohol promoting α OH addition, whereas the syn-conformer promotes β addition. However, the two theoretical studies reach different conclusions regarding which set of products dominate. We studied this reaction using time-resolved multiplexed photoionization mass spectrometry to quantify the product branching fractions. Our results, supported by a detailed kinetic model, conclude that the glycoaldehyde product channel (arising mostly from syn-vinyl alcohol) dominates over formic acid production with a 3.6:1.0 branching ratio. Additionally, this result supports the conclusion of Lei et al. that conformer-dependent hydrogen bonding at the transition state for OH-addition controls the reaction outcome. As a result, tropospheric oxidation of vinyl alcohol creates less formic acid than recently thought, increasing again the discrepancy between models and field observations of Earth's formic acid budget.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Containerless high temperature property measurements by atomic fluorescence

Laser induced fluorescence techniques were developed for the containerless study of high temperature processes, material properties, levitation, and heating techniques for containerless earth-based experimentation. Experiments were performed in which fluorescence of atomic aluminum, mercury, or tungsten were studied. These experiments include measurements of: (1) Al atom evaporation from CW CO2 laser heated and aerodynamically levitated sapphire and alumina spheres, and self-supported sapphire filaments, (2) Al atom reaction with ambient oxygen in the wake of a levitated specimen, (3) Hg atom concentrations in the wake of levitated alumina and sapphire spheres, relative to the ambient Hg atom concentration, (4) Hg atom concentrations in supersonic levitation jets, and (5) metastable, electronically excited W atom concentrations produced by evaporation of an electrically heated tungsten filament.

Nordine, P. C.↗
DOE OSTI2024

Credible Criticality Safety Margin in the 30B Package with LEU+ UF 6 and Hypothetical Water Ingress

The commercial nuclear industry is pursuing advancements in fuel and reactor design that increase the uranium enrichment above 5 wt. % 235 U. These advancements will necessitate the ability to transport bulk quantities of UF 6 at increased enrichments. Currently, the 30B cylinder is the primary container used by the industry for UF 6 storage and transportation and has a long history of successful shipments. This container can support up to 2,277 kg of UF 6 at a maximum enrichment of 5 wt. % 235 U. Previous evaluations have assessed the potential impact of criticality safety for 30B transport at higher enrichments but assumed moderator intrusion would not require evaluation. Although current regulations allow for the exception of moderator intrusion for UF 6 packages through the design and quality control of the package content, this exception is limited to enrichments up to 5 wt. % 235 U. Thus, an investigation of moderator intrusion into a 30B cylinder should be performed. Moderator intrusion into a 30B cylinder is a unique condition for criticality safety evaluation in transportation because of the violent chemical reactions that occur between UF 6 and H 2 O. The resulting intrusion is strongly dependent on the breach size, breach location, breach interface solid/ullage of the UF 6 content, the UF 6 distribution (which is temperature dependent), and temperature/pressure conditions which are dynamic in accident conditions. Additionally, the complexity of the HF-UO 2 F 2 -H 2 O interface that occurs during the event can influence the potential solubility of uranium in the system, as well as influence the amount of UF 6 reaction with H 2 O. With the operating experience from Orano Federal Services LLC, the UF 6 chemical expertise from Oak Ridge National Laboratory (ORNL), and the criticality safety expertise from ORNL, this paper evaluates the neutronic conditions (i.e., k eff ) that apply the understood chemistry and experimental conditions that occur during moderator intrusion of a breached 30B cylinder under postulated accidents. This report examines the historical evaluations of UF 6 transport and expands these evaluations for the enrichments expected for nuclear industry advancement. These simulations primarily feature a homogeneous mixture of UF 6 and H 2 O as an infinite media system and as a sphere with water reflection given an impurity limit of 0.5 wt. % UF 6 . This report demonstrates that this H/U limit is valid up to 8 wt. % enrichment for both H 2 O and HF as the moderating mixture. The water-reflected homogeneous mixed spheres evaluated demonstrate the amount of safety margin applied by restricting the 30B cylinder impurity limit to 0.5 wt. %. Additionally, this report evaluates moderator ingress scenarios of a 30B cylinder. The 30B cylinder simulations vary the cylinder orientation, the mass of UF 6 in the system, the mass of H 2 O in the system, and how much H 2 O has reacted with UF 6 . The moderator ingress of a 30B cylinder was evaluated for the water-reflected homogeneous mixed spheres to demonstrate the amount of safety margin applied by restricting the 30B cylinder impurity limit to 0.5 wt. %. These simulations are standard practice and are independent of the UF 6 -H 2 O reaction. This work also explored more complex simulations that layer the H 2 O over the UF 6 , which incorporates the amount of reacted UF 6 as a separate layer and considers solubility limits of UO 2 F 2 in H 2 O as it is produced. This approach is intended to simulate the postulated event of a large hairline crack occurring on a submerged cylinder. Finally, this work considers the potential of H 2 O mixing into the UF 6 solid heterogeneously using a sponge-like model. The water ingress into the UF 6 is treated as random size spheres, and the reaction products form into a layer over the spheres.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Leveraging Triphenylphosphine-Containing Polymers to Explore Design Principles for Protein-Mimetic Catalysts

Complex interactions between noncoordinating residues are significant yet commonly overlooked components of macromolecular catalyst function. While these interactions have been demonstrated to impact binding affinities and catalytic rates in metalloenzymes, the roles of similar structural elements in synthetic polymeric catalysts remain underexplored. Using a model Suzuki–Miyuara cross-coupling reaction, we performed a series of systematic studies to probe the interconnected effects of metal–ligand cross-links, electrostatic interactions, and local rigidity in polymer catalysts. To achieve this, a novel bifunctional triphenylphosphine acrylamide (BisTPPAm) monomer was synthesized and evaluated alongside an analogous monofunctional triphenylphosphine acrylamide (TPPAm). In model copolymer catalysts, increased initial reaction rates were observed for copolymers untethered by Pd complexation (BisTPPAm-containing) compared to Pd-cross-linked catalysts (TPPAm-containing). Further, incorporating local rigidity through secondary structure-like and electrostatic interactions revealed nonmonotonic relationships between composition and the reaction rate, demonstrating the potential for tunable behavior through secondary-sphere interactions. Lastly, through rigorous cheminformatics featurization strategies and statistical modeling, we quantitated relationships between chemical descriptors of the substrate and reaction conditions on catalytic performance. Collectively, these results provide insights into relationships among the composition, structure, and function of protein-mimetic catalytic copolymers.

Catalysts↗