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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Composition-Dependent Reconstructions of Titanium Oxide Clusters and Cu(111) Support via Cluster-Adatom Interactions

Mass-selected cluster deposition and scanning tunneling microscopy (STM) were used to investigate the surface structure and thermal stability of Ti 3 O y (y = 5, 6) clusters on a Cu(111) surface. STM imaging shows that the substoichiometric Ti 3 O 5 clusters aggregate into large dendritic assemblies at step edges, while the stoichiometric Ti 3 O 6 clusters are highly dispersed as single or small groupings of clusters. Cluster deposition also results in extensive reconstruction of the Cu(111) surface. The Ti 3 O 5 /Cu(111) surface exhibits one Cu-layer deep pits that are ringed by cluster assemblies that nucleate and grow at the perimeter step edges. By comparison, the Ti 3 O 6 /Cu(111) surface consists of irregular step edges and small one Cu-layer islands that are decorated with clusters. The restructuring of the Cu(111) surface is attributed to strong Cu-cluster interactions that release Cu adatoms from the step edges. This mechanism is supported by density functional theory (DFT) calculations, which predict that the Cu adatom attachment to the clusters is energetically favorable. Annealing the surfaces at elevated temperatures (400-700 K) results in higher densities of irregular steps, pits and isolated Cu islands as well as increased cluster aggregation. In conclusion, this work highlights adatom-cluster interactions as another manifestation of strong cluster-support interactions that can significantly alter the nature of the oxide-metal interface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

The R -process Alliance: Fifth Data Release from the Search for R -process-enhanced Metal-poor Stars in the Galactic Halo with the GTC

Understanding the abundance pattern of metal-poor stars and the production of heavy elements through various nucleosynthesis processes offers crucial insights into the chemical evolution of the Milky Way, revealing primary sites and major sources of rapid neutron-capture process (r-process) material in the Universe. In this fifth data release from the R-Process Alliance (RPA), we present the detailed chemical abundances of 41 faint (down to V = 15.8) and extremely metal-poor (down to [Fe/H] = -3.3) halo stars selected from the RPA. We obtained high-resolution spectra for these objects with the HORuS spectrograph on the Gran Telescopio Canarias. We measure the abundances of light, α, Fe-peak, and neutron-capture elements. We report the discovery of five carbon-enhanced metal-poor, one limited-r, three r-I, and four r-II stars, and six Mg-poor stars. We also identify one star of a possible globular cluster origin at an extremely low metallicity at [Fe/H] = -3.0. This adds to the growing evidence of a lower-limit metallicity floor for globular cluster abundances. We use the abundances of Fe-peak elements and the α-elements to investigate the contributions from different nucleosynthesis channels in the progenitor supernovae. We find the distribution of [Mg/Eu] as a function of [Fe/H] to have different enrichment levels, indicating different possible pathways and sites of their production. We also reveal differences in the trends of the neutron-capture element abundances of Sr, Ba, and Eu of various r-I and r-II stars from the RPA data releases, which provide constraints on their nucleosynthesis sites and subsequent evolution.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Heat Transfer Fluids as Co‐Diluents in Localized High‐Concentration Electrolytes for High‐Rate Lithium Metal Batteries With Enhanced Safety

Localized high-concentration electrolytes (LHCEs) have been identified as promising electrolyte formulations for lithium metal batteries, due to their effective interphase formation and promotion of compact Li deposition, yet their practical implementation is often limited by reduced ion transport kinetics. In this study, two industrially established fluorinated ethers are identified for the first time in battery research as effective co-diluents as they combine a broad electrochemical stability window with a low viscosity and intrinsic non-flammability. Incorporating these components, commonly used as heat transfer fluids, yields safer, less flammable electrolyte formulations with enhanced ion mobilities. In particular, the ternary co-diluent formulation shows improved ion mobility by reducing the electrolyte's viscosity while limiting excessive ion clustering. Based on the improved electrolyte transport kinetics, lower overvoltages and higher Coulombic efficiencies at current densities ≥ 1 mA cm −2 are achieved with the ternary co-diluent blend, resulting in markedly extended cycle life in an application-oriented zero-excess pouch cell compared with the baseline system. Complementary electrochemical and ex situ analysis of harvested electrodes at moderate current densities reveals no discernible differences in interphase morphology and composition, suggesting enhanced ion mobility as the primary cause of the improved high-rate performance.

electrolyte diluent↗
DOE OSTI2022

Phase 1 Specifications and preliminary sensitivity analyses of the OECD-NRC liquid metal fast reactor core thermal-hydraulics benchmark

The developments in wire-wrapped fuel bundle thermal-hydraulics research have become increasingly diverse and this makes comparisons across studies difficult. This paper describes an ongoing benchmark that will address this issue by directly comparing computational results with experimental data from two unique wire-wrapped thermal-hydraulic facilities. Preliminary subchannel sensitivity / uncertainty analyses show largely expected behavior for the presented cases, where rod diameter and friction factor show the greatest sensitivities to geometrical perturbations. Guidelines for computational fluid dynamics evaluations have been prepared and highlight the need for consolidated modeling strategies. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2022

A Microporous Metal–Organic Framework Incorporating Both Primary and Secondary Building Units for Splitting Alkane Isomers

We demonstrate the assembly of a mononuclear metal center, a hexanuclear cluster, and a V-shaped, trapezoidal tetracarboxylate linker into a microporous MOF featuring an unprecedented 3-nodal (4,4,8)-c lyu topology. Here, the compound, HIAM-302, represents the first example that incorporates both primary building unit (PBU) and hexanuclear secondary building unit (SBU) in one structure, which should be attributed to the desymmetrized geometry of the organic linker. HIAM-302 possesses optimal pore dimensions and can separate mono-branched and di-branched alkanes through selective molecular sieving, which is of significant value in petrochemical industry.

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

Electron Counting and High-Pressure Phase Transformations in Metal Hexaborides

Pressure-induced structural transitions of the alkaline earth hexaborides, CaB 6 , SrB 6 , and BaB 6 , are studied theoretically using electron counting rules and density functional theory calculations. Here, we demonstrate the applicability of gas-phase borane electron counting methods to solid-state metal borides under pressure and validate the assumptions of the rules by density functional theory (DFT) calculations. All three compounds share ambient-pressure and high-pressure structures, but BaB 6 differs from CaB 6 and SrB 6 at intermediate pressures. The unique BaB 6 phase is shown to break electron counting rules, while all other phases obey them. This anomaly is resolved by DFT, which reveals B–Ba covalency and unusual B–B π bonding under pressure. The relationships between structure and bonding can help us to understand the exotic behavior of lanthanide hexaborides and design new borides with desirable properties. Developing electron counting procedures for solids will enhance materials discovery efforts with chemical intuition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

In Situ Dispersion of Palladium on TiO 2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium

The application of single-atom catalysts (SACs) to high-temperature hydrogenation requires materials that thermodynamically favor metal atom isolation over cluster formation. Here, we show that Pd can be predominantly dispersed as isolated atoms onto TiO 2 during the reverse water-gas shift (rWGS) reaction at 400 °C. Achieving atomic dispersion requires an artificial increase of the absolute TiO 2 surface area by an order of magnitude and can be accomplished by physically mixing a precatalyst (Pd/TiO 2 ) with neat TiO 2 prior to the rWGS reaction. Furthermore, the in situ dispersion of Pd was reflected through a continuous increase of rWGS activity over 92 h and supported by kinetic analysis, infrared and X-ray absorption spectroscopies and scanning transmission electron microscopy. The thermodynamic stability of Pd under high-temperature rWGS conditions is associated with Pd-Ti coordination, which manifests upon O-vacancy formation and the artificial increase in TiO 2 surface area.

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

Heterointercalation in Chevrel-Phase Sulfides: A Model Periodic Solid for the Investigation of Chain Electron Transfer

Modulation of electron density localization on periodic crystal solids through electron transfer from interstitial cations can directly influence the bonding configurations of small-molecule intermediates at the catalyst binding site. This study presents the microwave-assisted solid-state synthesis of four heterointercalant Chevrel-phase (CP) sulfides with varying metal cation intercalants with compositional and electronic structure investigations of the electron density redistribution as a result of intercalation. The heterointercalant CP sulfides, with the general formula Cu x M y Mo 6 S 8 (where M = Cr, Mn, Fe, Ni; x, y = 1.5−2.5), are presented here for the probe reaction of electrochemical CO 2 reduction. A change in product selectivity is observed toward the production of methanol at low overpotentials of −0.5 V vs reversible hydrogen electrode (RHE), as a result of the intercalant combination present within the CP interstitial cavity. Structural confirmation of all materials was examined through Rietveld refinement of the powder X-ray diffraction (PXRD) data, high-resolution transmission electron microscopy (HR-TEM), and selected-area electron diffraction (SAED). Electron transfer from the intercalated metal cations to the Mo 6 S 8 cluster was investigated via X-ray photoelectron spectroscopy (XPS) of the intercalated metal cations and the chalcogenide cluster. Electron transfer was further confirmed through X-ray absorption analysis (XAS) of the K-edges of Mo and intercalants. Intermediate studies of electrochemical reduction of formaldehyde to methanol resulted in a faradaic efficiency of ∼78% methanol production on Cu x Ni y Mo 6 S 8 . The results presented herein identify distinct principles for materials design that can be utilized in other compositional spaces within the broad families of periodic crystal solids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Building [U IV 70 (OH) 36 (O) 64 ] 4– oxocluster frameworks with sulfate, transition metals, and U V

Uranium (IV) oxide clusters, colloids, and materials are designed and studied for 1) nuclear materials applications, 2) understanding environmental fate and transport of actinides, and 3) exploring the complex bonding behavior of open-shell f-elements. U IV -oxyhydroxsulfate clusters are particularly relevant in industrial processes and in nature. Recent studies have shown that counter-cations to these polynuclear anions differentiate rich structural topologies in the solid-state. Here we present nine different structures with wheel-shaped [U 70 (OH) 36 (O) 64 (SO 4 ) 60 ] 4- (U 70 ) linked into 1-dimensional and 2-dimensional frameworks with sulfate, divalent transition metals (Cr II , Fe II , Co II , Ni II ) and U V . Here, the small-angle X-ray scattering of these phases dissolved in butylamine reveals differing supramolecular assembly of U 70 clusters, controlled primarily by sulfates. However, observed trends in transition metal linking guide future design of U 70 -materials with different topologies. Finally, U 70 linking via U IV -O-U V -O-U IV bridges presents a rare example of mixed oxidation state uranium oxides without disorder.

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

Mechanistic Investigation of Enhanced Catalytic Selectivity toward Alcohol Oxidation with Ce Oxysulfate Clusters

Ceria-based materials have been highly desired in photocatalytic reactions due to their easily redox property and strong oxygen storage and transfer ability. Herein, we report the structures of one CeCe 70 oxysulfate cluster and four MCe 70 clusters (M = Cu, Ni, Co, Fe) with the same Ce 70 core. As noted, single crystal X-ray diffraction confirmed the structures of CeCe 70 and the MCe 70 series, while Raman spectroscopy indicated an increase in oxygen defects upon the introduction of Cu and Fe ions. The clusters catalyzed the oxidation of 4-methoxybenzyl alcohol under ultraviolet light. CuCe 70 and FeCe 70 exhibited enhanced reactivity compared to CeCe 70 and improved aldehyde selectivity compared to control experiments. In comparison with their homogeneous congeners, the CeCe 70 /MCe 70 clusters altered the location of radical generation from the bulk solution to the clusters’ surfaces. Mechanistic studies highlight the role of oxygen defects and specific transition metal introduction for efficient photocatalysis. Furthermore, the mechanistic pathway in this study provides insight on how to select or design a highly selective catalyst for photocatalysis.

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

Zeolite-Stabilized Di- and Tetranuclear Molybdenum Sulfide Clusters Form Stable Catalytic Hydrogenation Sites

Supercages of faujasite (FAU)-type zeolites serve as a robust scaffold for stabilizing dinuclear (Mo 2 S 4 ) and tetranuclear (Mo 4 S 4 ) molybdenum sulfide clusters. The FAU-encaged Mo 4 S 4 clusters have a distorted cubane structure similar to the FeMo-cofactor in nitrogenase. Both clusters possess one unpaired electron per Mo atom. Additionally, they show identical catalytic activity per sulfide cluster. Their catalytic activity is stable (> 150 h) for ethene hydrogenation, while layered MoS 2 structures deactivate significantly under the same reaction conditions.

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

Structural Changes during the Growth of Atomically Precise Metal Oxido Nanoclusters from Combined Pair Distribution Function and Small-Angle X-ray Scattering Analysis

The combination of in situ pair distribution function (PDF) analysis and small-angle X-ray scattering (SAXS) enables analysis of the formation mechanism of metal oxido nanoclusters and cluster–solvent interactions as they take place. Herein, we demonstrate the method for the formation of clusters with a [Bi 38 O 45 ] core. Upon dissolution of crystalline [Bi 6 O 5 (OH) 3 (NO 3 ) 5 ]∙3 H 2 O in DMSO, an intermediate rapidly forms, which slowly grows to stable [Bi 38 O 45 ] clusters. To identify the intermediate, we developed an automated modeling method, where smaller [Bi x O y ] structures based on the [Bi 38 O 45 ] framework are tested against the data. [Bi 22 O 26 ] was identified as the main intermediate species, illustrating how combined PDF and SAXS analysis is a powerful tool to gain insight into nucleation on an atomic scale. PDF also provides information on the interaction between nanoclusters and solvent, which is shown to depend on the nature of the ligands on the cluster surface.

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

Control of Permanent Porosity in Type 3 Porous Liquids via Solvent Clustering

Porous liquids (PLs) are an exciting new class of materials for carbon capture due to their high gas adsorption capacity and ease of industrial implementation. They are composed of sorbent particles suspended in a nonadsorbed solvent, forming a liquid with permanent porosity. While PLs have a vast number of potential compositions based on the number of solvents and sorbent materials available, most of the research has been focused on the selection of the sorbent rather than the solvent. Therefore, PL design criteria on the supramolecular structures of the solvent are explored to create a fundamental understanding of how the solvent enables PL formation for rapid discovery of new PL compositions. Atomistic molecular dynamics simulation of eight solvents with a range of molecular sizes, shapes, and intramolecular bonding was performed, identifying that the shape and size of molecular clusters formed in the solvent are the driving predictor of PL formation rather than the size of the individual solvent molecule. The results demonstrate a significant departure from common approaches to PL formation based on the steric exclusion of solvent molecules from the sorbent via the size of the pore aperture. A modeling and experimental validation study further supports these findings. In conclusion, through this computational material design study, a previously unexplored mechanism in PL formation, solvent–solvent clustering, is identified as a critical factor for the accelerated discovery of liquid phase carbon capture materials.

Carbon capture↗
DOE OSTI2021

Determining the three-dimensional atomic structure of an amorphous solid

Amorphous solids such as glass, plastics and amorphous thin films are ubiquitous in our daily life and have broad applications ranging from telecommunications to electronics and solar cells 1-4 . However, owing to the lack of long-range order, the three-dimensional (3D) atomic structure of amorphous solids has so far eluded direct experimental determination 5-15 . Here we develop an atomic electron tomography reconstruction method to experimentally determine the 3D atomic positions of an amorphous solid. Using a multi-component glass-forming alloy as proof of principle, we quantitatively characterize the short- and medium-range order of the 3D atomic arrangement. We observe that, although the 3D atomic packing of the short-range order is geometrically disordered, some short-range-order structures connect with each other to form crystal-like superclusters and give rise to medium-range order. We identify four types of crystal-like medium-range order-face-centred cubic, hexagonal close-packed, body-centred cubic and simple cubic-coexisting in the amorphous sample, showing translational but not orientational order. These observations provide direct experimental evidence to support the general framework of the efficient cluster packing model for metallic glasses 10,12-14,16 . Finally, we expect that this work will pave the way for the determination of the 3D structure of a wide range of amorphous solids, which could transform our fundamental understanding of non-crystalline materials and related phenomena.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Passivating Nucleobases Bring Charge Transfer Character to Optically Active Transitions in Small Silver Nanoclusters

DNA-wrapped silver nanoclusters (DNA–AgNCs) are known for their efficient luminescence. However, their emission is highly sensitive to the DNA sequence, the cluster size, and its charge state. To get better insights into photophysics of these hybrid systems, simulations based on density functional theory (DFT) are performed. Our calculations elucidate the effect of the structural conformations, charges, solvent polarity, and passivating bases on optical spectra of DNA–AgNCs containing five and six Ag atoms. It is found that inclusion of water in calculations as a polar solvent media results in stabilization of nonplanar conformations of base-passivated clusters, while their planar conformations are more stable in vacuum, similar to the bare Ag5 and Ag6 clusters. Cytosines and guanines interact with the cluster twice stronger than thymines, due to their larger dipole moments. In addition to the base–cluster interactions, hydrogen bonds between bases notably contribute to the structure stabilization. While the relative intensity, line width, and the energy of absorption peaks are slightly changing depending on the cluster charge, conformations, and base types, the overall spectral shape with five well-resolved bands at 2.5–5.5 eV is consistent for all structures. Independent of the passivating bases and the cluster size and charge, the low energy optical transitions at 2.5–3.5 eV exhibit a metal to ligand charge transfer (MLCT) character with the main contribution emerging from Ag-core to the bases. Cytosines facilitate the MLCT character to a larger degree comparing to the other bases. However, the doublet transitions in clusters with the open shell electronic structure (Ag5 and Ag6 + ) result in appearance of additional red-shifted (<2.5 eV) and optically weak band with negligible MLCT character. The passivated clusters with the closed shell electronic structure (Ag5 + and Ag6) exhibit higher optical intensity of their lowest transitions with much higher MLCT contribution, thus having better potential for emission, than their open shell counterparts.

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

Nanoscale elemental and morphological imaging of nitrogen-fixing cyanobacteria

Nitrogen-fixing cyanobacteria bind atmospheric nitrogen and carbon dioxide using sunlight. This experimental study focused on a laboratory-based model system, Anabaena sp., in nitrogen-depleted culture. When combined nitrogen is scarce, the filamentous prokaryotes reconcile photosynthesis and nitrogen fixation by cellular differentiation into heterocysts. To better understand the influence of micronutrients on cellular function, 2D and 3D synchrotron X-ray fluorescence mappings were acquired from whole biological cells in their frozen-hydrated state at the Bionanoprobe, Advanced Photon Source. To study elemental homeostasis within these chain-like organisms, biologically relevant elements were mapped using X-ray fluorescence spectroscopy and energy-dispersive X-ray microanalysis. Higher levels of cytosolic K + , Ca 2+ , and Fe 2+ were measured in the heterocyst than in adjacent vegetative cells, supporting the notion of elevated micronutrient demand. P-rich clusters, identified as polyphosphate bodies involved in nutrient storage, metal detoxification, and osmotic regulation, were consistently co-localized with K + and occasionally sequestered Mg 2+ , Ca 2+ , Fe 2+ , and Mn 2+ ions. Machine-learning-based k-mean clustering revealed that P/K clusters were associated with either Fe or Ca, with Fe and Ca clusters also occurring individually. In accordance with XRF nanotomography, distinct P/K-containing clusters close to the cellular envelope were surrounded by larger Ca-rich clusters. The transition metal Fe, which is a part of nitrogenase enzyme, was detected as irregularly shaped clusters. The elemental composition and cellular morphology of diazotrophic Anabaena sp. was visualized by multimodal imaging using atomic force microscopy, scanning electron microscopy, and fluorescence microscopy. This paper discusses the first experimental results obtained with a combined in-line optical and X-ray fluorescence microscope at the Bionanoprobe.

Anabaena sp↗