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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 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Enhancing T c in a composite superconductor/metal bilayer system: A dynamical cluster approximation study

It has been proposed that the superconducting transition temperature T c of an unconventional superconductor with a large pairing scale but strong phase fluctuations can be enhanced by coupling it to a metal. However, the general efficacy of this approach across different parameter regimes remains an open question. Using the dynamical cluster approximation, we study this question in a system composed of an attractive Hubbard layer in the intermediate coupling regime, where the magnitude of the attractive Coulomb interaction |U| is slightly larger than the bandwidth W, hybridized with a noninteracting metallic layer. We find that while the superconducting transition becomes more mean-field-like with increasing interlayer hopping, the superconducting transition temperature T c exhibits a nonmonotonic dependence on the strength of the hybridization t ⊥ . Furthermore, this behavior arises from a reduction of the effective pairing interaction in the correlated layer that outcompetes the growth in the intrinsic pair-field susceptibility induced by the coupling to the metallic layer. We find that the largest T c inferred here for the composite system is comparable to the maximum value currently estimated for the isolated negative-U Hubbard model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1984

IUE observations of the clusters of the Magellanic Clouds

IUE observations of 17 clusters in the Large Magellanic Cloud are presented. The derived ultraviolet colors become progressively redder as the cluster's classification in the scheme of Searle, Wilkinson, and Bagnuolo increases. With the aid of theoretical models of the integrated light of coeval clusters of varying ages, it is shown that the SWB classification is one of increasing age accompanied by decreasing metallicity toward later SWB classes. The behavior of the UV absorption line features in the integrated light of the LMC clusters supports the contention.

Cohen, J. G.↗
DOE OSTI2020

Josephson behavior in a metal-decorated topological-insulator Bi 0.91 Sb 0.09

We have fabricated W nanoscale clusters on a topological insulator Bi 0.91 Sb 0.09 . The W island arrays effectively induce two-dimensional superconductivity at the surface of Bi 0.91 Sb 0.09 via the superconducting proximity effect. We find that this heterostructure behaves as a dynamic Josephson junction, which shows a Fraunhofer-like pattern of the critical current versus the applied magnetic field. Microwave irradiation experiments reveal the existence of a 4π-periodic supercurrent carried by the topological surface state. Our results open up a route to induce topological superconductivity in a topological insulator.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Bismuth-Polyoxocation Coordination Networks: Controlling Nuclearity and Dimension-Dependent Photocatalysis

Bismuth-oxocluster nodes for metal–organic frameworks (MOFs) and coordination networks/polymers are less prolific than other families featuring zinc, zirconium, titanium, lanthanides, etc. However, Bi 3+ is non-toxic, it readily forms polyoxocations, and its oxides are exploited in photocatalysis. This family of compounds provides opportunity in medicinal and energy applications. Here, we show that Bi node nuclearity depends on solvent polarity, leading to a family of Bi x -sulfonate/carboxylate coordination networks with x = 1–38. Larger nuclearity-node networks were obtained from polar and strongly coordinating solvents, and we attribute the solvent’s ability to stabilize larger species in solution. Here, the strong role of the solvent and the lesser role of the linker in defining node topologies differ from other MOF syntheses, and this is due to the Bi 3+ intrinsic lone pair that leads to weak node–linker interactions. We describe this family by single-crystal X-ray diffraction (eleven structures), obtained in pure forms and high yields. Ditopic linkers include NDS (1,5-naphthalenedisulfonate), DDBS (2,2'-[biphenyl-4,4'-diylchethane-2,1-diyl] dibenzenesulphonate), and NH 2 -benzendicarboxylate (BDC). While the BDC and NDS linkers yield more open-framework topologies that resemble those obtained by carboxylate linkers, topologies with DDBS linkers appear to be in part driven by association between DDBS molecules. An in situ small-angle X-ray scattering study of Bi 38 -DDBS reveals stepwise formation, including Bi 38 -assembly, pre-organization in solution, followed by crystallization, confirming the less important role of the linker. We demonstrate photocatalytic hydrogen (H 2 ) generation with select members of the synthesized materials without the benefit of a co-catalyst. Band gap determination from X-ray photoelectron spectroscopy (XPS) and UV–vis data suggest the DDBS linker effectively absorbs in the visible range with ligand-to-Bi-node charge transfer. In addition, materials containing more Bi (larger Bi 38 -nodes or Bi 6 inorganic chains) exhibit strong UV absorption, also contributing to effective photocatalysis by a different mechanism. All tested materials became black with extensive UV–vis exposure, and XPS, transmission electron microscopy, and X-ray scattering of the black Bi 38 -framework suggest that Bi o is formed in situ, without phase segregation. This evolution leads to enhanced photocatalytic performance, perhaps due to increased light absorption.

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

The Kinematically Hot, Extremely Metal-poor C-19 Stellar Stream in DESI DR2

Stellar streams are the result of a host galaxy’s gravitational potential tidally disrupting satellite dwarf galaxies and globular clusters (GCs), causing them to grow leading and trailing tidal tails. The C-19 stellar stream is an extremely metal-poor stellar population, showing chemical abundance patterns characteristic of a GC. However, its large velocity dispersion is difficult to reconcile with a conventional, purely baryonic, disrupting-GC progenitor. Current techniques for stream characterization are primarily applied to Gaia DR3, relying heavily on proper-motion measurements. Using the Dark Energy Spectroscopic Instrument (DESI), which provides radial velocities and metallicities for over 10 million stars and reaches significantly fainter magnitudes than comparable surveys, we employ a mixture model approach to jointly characterize stream populations in proper motions, radial velocities, and metallicities against a Milky Way halo background. By applying this framework to the C-19 stellar stream, we identify a total of 47 spectroscopically confirmed member stars, of which 41 are newly identified and only 6 were previously reported in the literature. In this work, we measure a velocity dispersion of $7.8^{+1.5}_{-1.3}$km s −1 and a mean metallicity of [Fe/H] = $-3.36^{+0.12}_{-0.10}$. We further identify a novel “spur” feature within the stream. We conclude that our measurements are in line with previous works identifying C-19 as a “hot,” metal-poor stream. In forthcoming work, we will apply this approach to many more streams in the DESI footprint, enabling population-level comparisons with predictions from simulations.

Mohammed, Nasser [University of Toronto; Dunlap In↗
DOE OSTI2023

Exploring NaCl-PuCl 3 molten salts with machine learning interatomic potentials and graph theory

Actinide molten salts are the basis of the liquid fuels used in molten salt reactors. Due to the inherent difficulties associated with high temperature and hazardous conditions, experimental investigations of fundamental properties of these materials are usually challenging. In this work, we describe the structure and transport of NaCl-PuCl 3 mixtures using computational techniques. Three compositions were considered (16, 25, and 36 mol% PuCl 3 ) over a temperature range (730 – 1257K) using ab initio molecular dynamics, which provided the necessary data sets for training machine learned interatomic potentials. Further, molecular dynamics simulations based on these potentials were then used to determine structure and transport properties. A substantial change was noted in the structure factor when increasing the PuCl 3 content from 25 to 36 mol%. This change is linked to the aggregation of larger Pu 3+ clusters. In addition, the similarity of the atomic environments of metal cations in molten salt systems to their solid states counterparts was investigated using an unsupervised learning technique. Finally, graph theory was employed to explore the structure and size of actinide networks. Consistent with the structure factor, a dense Pu 3+ intermolecular structure is observed within the 36 mol% PuCl 3 mixture. The structure of cation-cation inter-junctions is also discussed. In all cases, the diffusion of Pu 3+ is significantly lower than that of Na + and Cl - .

36 MATERIALS SCIENCE↗
DOE OSTI2024

Catalytic, Spectroscopic, and Theoretical Studies of Fe 4 S 4 -Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Iron–sulfur clusters play essential roles in biological systems, and thus synthetic [Fe 4 S 4 ] clusters have been an area of active research. Recent studies have demonstrated that soluble [Fe 4 S 4 ] clusters can serve as net H atom transfer mediators, improving the activity and selectivity of a homogeneous Mn CO 2 reduction catalyst. Here, in this work, we demonstrate that incorporating these [Fe 4 S 4 ] clusters into a coordination polymer enables heterogeneous H atom transfer from an electrode surface to a Mn complex dissolved in solution. A previously reported solution-processable Fe 4 S 4 -based coordination polymer was successfully deposited on the surfaces of different electrodes. The coated electrodes serve as H atom transfer mediators to a soluble Mn CO 2 reduction catalyst displaying good product selectivity for formic acid. Furthermore, these electrodes are recyclable with a minimal decrease in activity after multiple catalytic cycles. The heterogenization of the mediator also enables the characterization of solution-phase and electrode surface species separately. Surface enhanced infrared absorption spectroscopy (SEIRAS) reveals spectroscopic signatures for an in situ generated active Mn–H species, providing a more complete mechanistic picture for this system. The active species, reaction mechanism, and the protonation sites on the [Fe 4 S 4 ] clusters were further confirmed by density functional theory calculations. The observed H atom transfer reactivity of these coordination polymer-coated electrodes motivates additional applications of this composite material in reductive H atom transfer electrocatalysis.

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

Ni( II )-binding affinity of Cc NikZ-II and its homologs: the role of the HH -prong and variable loop revealed by structural and mutational studies

Extracytoplasmic Ni(II)-binding proteins (NiBPs) are molecular shuttles involved in cellular nickel uptake. Here, we determined the crystal structure of apo CcNikZ-II at 2.38 Å, which revealed a Ni(II)-binding site comprised of the double His (HH-)prong (His511, His512) and a short variable (v-)loop nearby (Thr59-Thr64, TEDKYT). Mutagenesis of the site identified Glu60 and His511 as critical for high affinity Ni(II)-binding. Phylogenetic analysis showed 15 protein clusters with two groups containing the HH-prong. Metal-binding assays with 11 purified NiBPs containing this feature yielded higher Ni(II)-binding affinities. Replacement of the wild type v-loop with those from other NiBPs improved the affinity by up to an order of magnitude. This work provides molecular insights into the determinants for Ni(II) affinity and paves way for NiBP engineering.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Evidence of a Dwarf Galaxy Stream Populating the Inner Milky Way Halo

Stellar streams produced from dwarf galaxies provide direct evidence of the hierarchical formation of the Milky Way. Here, we present the first comprehensive study of the LMS-1 stellar stream, that we detect by searching for wide streams in the Gaia EDR3 data set using the STREAMFINDER algorithm. This stream was recently discovered by Yuan et al. We detect LMS-1 as a 60° long stream to the north of the galactic bulge, at a distance of ~20 kpc from the Sun, together with additional components that suggest that the overall stream is completely wrapped around the inner Galaxy. Using spectroscopic measurements from the Large Sky Area Multi-Object Fiber Spectroscopic Telescope, the Sloan Digital Sky Survey, and the Apache Point Observatory Galactic Evolution Experiment, we infer that the stream is very metal-poor (<[Fe/H]> = –2.1) with a significant metallicity dispersion (σ [Fe/H] = 0.4), and it possesses a large radial velocity dispersion (σ v = 20 ± 4 km s–1 ). These estimates together imply that LMS-1 is a dwarf galaxy stream. The orbit of LMS-1 is close to polar, with an inclination of 75° to the galactic plane. Both the orbit and metallicity of LMS-1 are remarkably similar to the globular clusters NGC 5053, NGC 5024, and the stellar stream Indus. As a result, these findings make LMS-1 an important contributor to the stellar population of the inner Milky Way halo.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Expanding the Design Space of Polymer–Metal Organic Framework (MOF) Gels by Understanding Polymer–MOF Interactions

The fabrication of polymer-MOF composite gels holds great potential to provide emergent properties for drug delivery, environmental remediation, and catalysis. To leverage the full potential of these composites, we investigated how the presence and chemistry of polymers impact MOF formation within the composites and, in turn, how MOFs impact polymer gelation. We show that polymers with a high density of strongly metal-binding carboxylic acids inhibit MOF formation; however, reducing the density of carboxylic acids or substituting them with weaker metal-binding hydroxyl groups permits both MOF formation and gelation within composites. Preparing composites with poly(ethylene glycol) (PEG), which does not bind MOF zirconium (Zr)-oxo clusters, and observing gelation suggests that MOFs can entrap polymer chains to create cross-links in addition to cross-linking them through polymer-Zr-oxo interactions. Both simulations and experiments show composite hydrogels formed with poly(vinyl alcohol) (PVA) to be more stable than those made with PEG, which can reptate through MOF pores upon heating. We demonstrate the generalizability of this composite formation process across different Zr-based MOFs (UiO-66, NU-901, UiO-67, and MOF-525) and by spin-coating gels into conformable films. PVA-UiO-66 composite hydrogels demonstrated high sorption and sustained release of methylene blue relative to the polymer alone (3× loading, 28× slower release), and PVA-MOF-525 composite hydrogels capably sorb the therapeutic peptide Angiotensin 1–7. By understanding the influence of polymer-MOF interactions on the structure and properties of composite gels, this work informs and expands the design space of this emerging class of materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The Open Cluster Chemical Abundances and Mapping Survey. VII. APOGEE DR17 [C/N]–Age Calibration

Large-scale surveys open the possibility to investigate Galactic evolution both chemically and kinematically; however, reliable stellar ages remain a major challenge. Detailed chemical information provided by high-resolution spectroscopic surveys of the stars in clusters can be used as a means to calibrate recently developed chemical tools for age-dating field stars. Using data from the Open Cluster Abundances and Mapping survey, based on the Sloan Digital Sky Survey/Apache Point Observatory Galactic Evolution Experiment 2 survey, we derive a new empirical relationship between open cluster stellar ages and the carbon-to-nitrogen ([C/N]) abundance ratios for evolved stars, primarily those on the red giant branch. With this calibration, [C/N] can be used as a chemical clock for evolved field stars to investigate the formation and evolution of different parts of our Galaxy. We explore how mixing effects at different stellar evolutionary phases, like the red clump, affect the derived calibration. We have established the [C/N]–age calibration for APOGEE Data Release 17 (DR17) giant star abundances to be $\mathrm{log}{[\mathrm{Age}(\mathrm{yr})]}_{\mathrm{DR}17}=10.14\,(\pm 0.08)+2.23(\pm 0.19)\,[{\rm{C}}/{\rm{N}}]$, usable for $8.62\leqslant \mathrm{log}(\mathrm{Age}[\mathrm{yr}])\leqslant 9.82$, derived from a uniform sample of 49 clusters observed as part of APOGEE DR17 applicable primarily to metal-rich, thin- and thick-disk giant stars. This measured [C/N]–age APOGEE DR17 calibration is also shown to be consistent with asteroseismic ages derived from Kepler photometry.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Identification and characterization of a small-molecule metallophore involved in lanthanide metabolism

Many bacteria secrete metallophores, low-molecular-weight organic compounds that bind ions with high selectivity and affinity, in order to access essential metals from the environment. Previous work has elucidated the structures and biosynthetic machinery of metallophores specific for iron, zinc, nickel, molybdenum, and copper. No physiologically relevant lanthanide-binding metallophore has been discovered despite the knowledge that lanthanide metals (Ln) have been revealed to be essential cofactors for certain alcohol dehydrogenases across a diverse range of phyla. Here, we report the biosynthetic machinery, the structure, and the physiological relevance of a lanthanophore, methylolanthanin. The structure of methylolanthanin exhibits a unique 4-hydroxybenzoate moiety which has not previously been described in other metallophores. We find that production of methylolanthanin is required for normal levels of Ln accumulation in the methylotrophic bacterium Methylobacterium extorquens AM1, while overexpression of the molecule greatly increases bioaccumulation and adsorption. Our results provide a clearer understanding of how Ln-utilizing bacteria sense, scavenge, and store Ln; essential processes in the environment where Ln are poorly bioavailable. More broadly, the identification of this lanthanophore opens doors for study of how biosynthetic gene clusters are repurposed for additional functions and the complex relationship between metal homeostasis and fitness.

Science & Technology - Other Topics↗
DOE OSTI2023

Understanding the dynamic evolution of atomically dispersed Cu catalyst for CO 2 electrochemical conversion using integrated XANES analysis and mechanistic studies

Direct electrochemical conversion of CO 2 to ethanol (CH 3 CH 2 OH) offers a promising strategy to lower CO 2 emission while storing energy from renewable electricity. Our recent study reported a carbon-supported atomically dispersed Cu catalyst that achieved the highest reported selectivity for CH 3 CH 2 OH formation (91%) at a relatively low potential (-0.6 V), however, the active site structure that is responsible for such high activity and selectivity has yet to be understood. Here, in this paper, we demonstrate a computational investigation combining X-ray absorption near edge structure (XANES) simulations and a mechanistic study via density functional theory (DFT) to understand the catalyst structures of this Cu catalyst during electrocatalysis and the corresponding reaction mechanisms of the key products. An integrated computational and experimental XANES analysis depicted the dynamic evolution of the catalytic site during electrocatalysis. The as-prepared, atomically dispersed Cu catalyst aggregates and forms metallic clusters/nanoparticles under electrochemical condition, which then break down to smaller oxidized clusters after electrocatalysis. The formed Cu clusters/nanoparticles showed distinct catalytic activity and selectivity as a function of particle size based on the mechanistic investigation using DFT, which is consistent with experimental observations for catalyst samples with different Cu loadings. This comprehensive study which combines experimental and computational XANES investigation, mechanistic study via DFT calculations, and experimental performance of the catalysts, provides unprecedented dynamic and mechanistic insights into the supported atomically dispersed metal catalysts for CO 2 reduction. Such strategy and details gained can further guide discovery of novel catalyst materials for CO 2 electrochemical reduction.

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

Averaged cluster approach to including chemical short-range order in KKR-CPA

The single-site Korringa-Kohn-Rostoker coherent potential approximation (KKR-CPA) ignores short-range ordering present in disordered metallic systems. Here in this paper, we establish a technique to fix this shortcoming by embedding an averaged cluster that displays chemical short-range order (SRO). The degree of SRO can be tuned by externally defined order parameters. This averaged cluster can be embedded in the single-site CPA medium or a self-consistently obtained effective medium that contains SRO information. The validity of this method is demonstrated by applying it to two alloy systems—the CuZn body-centered cubic (BCC) solid solution, and AlCrTiV, a four-element BCC high entropy alloy. A comparison between the non-self-consistent and self-consistent modes is also provided for the two above-mentioned systems. We make the code available on the internet. Planned extensions to this paper are discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Chandra view of Abell 407: the central compact group of galaxies and the interaction between the radio AGN and the ICM

ABSTRACT Abell 407 (A407) is a unique galaxy cluster hosting a central compact group of nine galaxies (named as ‘Zwicky’s Nonet’; G1–G9 in this work) within a 30 kpc radius region. The cluster core also hosts a luminous radio active galactic nucleus (AGN), 4C 35.06 with helically twisted jets extending over 200 kpc. With a 44 ks Chandra observation of A407, we characterize the X-ray properties of its intracluster medium and central galaxies. The mean X-ray temperature of A407 is 2.7 keV and the M200 is $1.9 \times 10^{14}\, {\mathrm{M}_{\odot }}$. We suggest that A407 has a weak cool core at r < 60 kpc scales and at its very centre, <1–2 kpc radius, a small galaxy corona associated with the strong radio AGN. We also conclude that the AGN 4C 35.06 host galaxy is most likely G3. We suggest that the central group of galaxies is undergoing a ‘slow merge’ procedure. The range of the merging time-scale is 0.3 ∼ 2.3 Gyr and the stellar mass of the future brightest cluster galaxy (BCG) will be $7.4\times 10^{11} \, \mathrm{M}_{\odot }$. We find that the regions that overlap with the radio jets have higher temperature and metallicity. This is consistent with AGN feedback activity. The central entropy is higher than that for other clusters, which may be due to the AGN feedback and/or merging activity. With all these facts, we suggest that A407 is a unique and rare system in the local universe that could help us to understand the formation of a massive BCG.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Butyltin Keggin Ion with a Rare Four-Coordinate Ca Center

Alkyltin clusters are exploited in nanolithography for the fabrication of microelectronics. The alkyltin Keggin family is unique among Keggin clusters across the periodic table; its members appear to favor the lower-symmetry β and γ isomers rather than the highly symmetrical α and ε isomers. Therefore, the alkyltin Keggin family may provide important fundamental information about the formation and isomerization of Keggin clusters. In this study, we have synthesized and structurally characterized a new butyltin Keggin cluster with a tetrahedral Ca 2+ center, fully formulated [(BuSn) 12 (CaO 4 )(OCH 3 ) 12 (O) 4 (OH) 8 ] 2+ (β-CaSn 12 ). The synthesis is a simple one-step process. Extensive solution characterization including electrospray ionization mass spectrometry, small-angle X-ray scattering, and multinuclear ( 1 H, 13 C, and 119 Sn) nuclear magnetic resonance shows β-CaSn 12 is essentially phase-pure and stable. This differs from the previously reported Na-centered analogues that always form a mixture of β and γ isomers, with facile interconversion. Therefore, this study has clarified prior confusion over complex spectroscopic and crystallographic characterization of the Na-centered analogues. Density functional theory calculations showed the following stability order: γ-CaSn 12 < γ-NaSn 12 < β-CaSn 12 < β-NaSn 12 . The β analogue is always more stable than the γ analogue, consistent with experiment. Notable outcomes of this study include a rare tetrahedral Ca coordination, a Na-free alkyltin cluster (important for microelectronics manufacturing), and a better understanding of Keggin families built of different metal cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

The effect of CO chemisorption on the metal surface CO/Ni(100)

The chemisorption of CO on Ni(100) is studied with a cluster model. The calculations suggest that chemisorption changes the nature of the Ni 3d orbitals. The open shell Ni 3d accepts charge from the Ni valence 4s4p orbitals, reducing the open shell 3d character on the Ni. The closed shell Ni 3d orbitals also mix with the Ni valence 4s4p orbitals and donate charge to the CO; thus helping to maintain the Ni 3d population near 9. These changes should affect the density of 3d states near the Fermi level and the surface magnetic moment. The variation in the bonding with the size of cluster is also discussed.

Bauschlicher, Charles, W., jr.↗