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At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Distinguishing Leptothrix and Sphaerotilus genera by an integrated genomic-phenotypic analysis supported by new Leptothrix genomes

The Sphaerotilus-Leptothrix group of bacteria includes one of the first described microorganisms, Leptothrix ochracea, an uncultured type strain, plus isolates of Leptothrix and Sphaerotilus. This group is unified by the ability to form sheaths and oxidize metals, although L. ochracea exhibits obvious ecological, morphological, and functional differences from the rest of Sphaerotilus-Leptothrix. Recently, there have been calls to combine the group into one genus, Sphaerotilus; however, these studies lacked adequate genomic representation of L. ochracea. Here, we present a comprehensive comparative genomic analysis of the Sphaerotilus-Leptothrix group, including expanded representation of L. ochracea, a closely related novel species, Leptothrix toolikensis, and two new isolates (Leptothrix mechoopdaensis). Analysis of 38 genomes resolves three phylogenetic and functional groups: the ochracea-type Leptothrix (Group 1), the mobilis-type Leptothrix (Group 2), and Sphaerotilus (Group 3). Group 1 genomes form a separate genus based on average nucleotide identity and alignment fraction. The genomes clearly diverge from the rest of Sphaerotilus-Leptothrix in phylogeny, size, and metabolic potential. Group 1 genomes are much smaller (2.59–3.04 Mb) than those of Groups 2 (4.55–6.06 Mb) and 3 (3.94–5.07 Mb), while encoding more metal oxidases and fewer carbohydrate-active enzymes. Group 2 clusters with Group 3 phylogenetically and is similar in organic carbon metabolisms but maintains more metal oxidation genes. Group 2 members lack homogeneity in phenotype and genotype, suggesting that additional isolates and genomes are needed for confident classification. However, Group 1 genomes (L. ochracea and L. toolikensis) show clear divergence, precluding their inclusion in Sphaerotilus and supporting the retention of the genus Leptothrix.

Leptothrix↗
NASA NTRS2003

Intermediate Element Abundances In Galaxy Clusters

We present the average abundances of the intermediate elements obtained by performing a stacked analysis of all the galaxy clusters in the archive of the X-ray telescope AKA. We determine the abundances of Fe, Si, S, and Ni as a function of cluster temperature (mass) from 1 - 10 keV, and place strong upper limits on the abundances of Ca and Ar. In general, Si and Ni are overabundant with respect to Fe, while Ar and Ca are very underabundant. The discrepancy between the abundances of Si, S , Ar, and Ca indicate that the alpha-elements do not behave homogeneously as a single group. We show that the abundances of the most well-determined elements Fe, Si, and S in conjunction with recent theoretical supernovae yields do not give a consistent solution for the fraction of material produced by Type Ia and Type II supernovae at any temperature or mass. The general trend is for higher temperature clusters to have more of their metals produced in Type II supernovae than in Type Ias. The inconsistency of our results with abundances in the Milky Way indicate that spiral galaxies are not the dominant metal contributors to the intracluster medium (ICM). The pattern of elemental abundances requires an additional source of metals beyond standard SNIa and SNII enrichment. The properties of this new source are well matched to those of Type II supernovae with very massive, metal-poor progenitor stars. These results are consistent with a significant fraction of the ICM metals produced by an early generation of population III stars.

White, Nicholas E.↗
DOE OSTI2021

Transformation of Highly Stable Pt Single Sites on Defect Engineered Ceria into Robust Pt Clusters for Vehicle Emission Control

Engineering surface defects on metal oxide supports could help promote the dispersion of active sites and catalytic performance of supported catalysts. Herein, a strategy of ZrO 2 doping was proposed to create rich surface defects on CeO 2 (CZO) and, with these defects, to improve Pt dispersion and enhance its affinity as single sites to the CZO support (Pt/CZO). The strongly anchored Pt single sites on CZO support were initially not efficient for catalytic oxidation of CO/C 3 H 6 . However, after a simple activation by H 2 reduction, the catalytic oxidation performance over Pt/CZO catalyst was significantly boosted and better than Pt/CeO 2 . Pt/CZO catalyst also exhibited much higher thermal stability. The structural evolution of Pt active sites by H 2 treatment was systematically investigated on aged Pt/CZO and Pt/CeO 2 catalysts. With H 2 reduction, ionic Pt single sites were transformed into active Pt clusters. Much smaller Pt clusters were created on CZO (ca. 1.2 nm) than on CeO 2 (ca. 1.8 nm) due to stronger Pt-CeO 2 interaction on aged Pt/CZO. Consequently, more exposed active Pt sites were obtained on the smaller clusters surrounded by more oxygen defects and Ce 3+ species, which directly translated to the higher catalytic oxidation performance of activated Pt/CZO catalyst in vehicle emission control applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Cycling of block copolymer composites with lithium-conducting ceramic nanoparticles

Solid polymer and perovskite-type ceramic electrolytes have both shown promise in advancing solid-state lithium metal batteries. Despite their favorable interfacial stability against lithium metal, polymer electrolytes face issues due to their low ionic conductivity and poor mechanical strength. Highly conductive and mechanically robust ceramics, on the other hand, cannot physically remain in contact with redox-active particles that expand and contract during charge-discharge cycles unless excessive pressures are used. To overcome the disadvantages of each material, polymer-ceramic composites can be formed; however, depletion interactions will always lead to aggregation of the ceramic particles if a homopolymer above its melting temperature is used. In this study, we incorporate Li 0.33 La 0.56 TiO 3 (LLTO) nanoparticles into a block copolymer, polystyrene- b -poly (ethylene oxide) (SEO), to develop a polymer-composite electrolyte (SEO-LLTO). TEMs of the same nanoparticles in polyethylene oxide (PEO) show highly aggregated particles whereas a significant fraction of the nanoparticles are dispersed within the PEO-rich lamellae of the SEO-LLTO electrolyte. We use synchrotron hard x-ray microtomography to study the cell failure and interfacial stability of SEO-LLTO in cycled lithium-lithium symmetric cells. Three-dimensional tomograms reveal the formation of large globular lithium structures in the vicinity of the LLTO aggregates. Encasing the SEO-LLTO between layers of SEO to form a “sandwich” electrolyte, we prevent direct contact of LLTO with lithium metal, which allows for the passage of seven-fold higher current densities without signatures of lithium deposition around LLTO. We posit that eliminating particle clustering and direct contact of LLTO and lithium metal through dry processing techniques is crucial to enabling composite electrolytes.

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

The APOGEE Library of Infrared SSP Templates (A-LIST): High-resolution Simple Stellar Population Spectral Models in the H Band

Integrated light spectroscopy from galaxies can be used to study the stellar populations that cannot be resolved into individual stars. This analysis relies on stellar population synthesis (SPS) techniques to study the formation history and structure of galaxies. However, the spectral templates available for SPS are limited, especially in the near-infrared (near-IR). We present A-LIST (APOGEE Library of Infrared SSP Templates), a new set of high-resolution, near-IR SSP spectral templates spanning a wide range of ages (2–12 Gyr), metallicities ( − 2.2 < [M/H] < + 0.4) and α abundances ( − 0.2 < [α/M] < + 0.4). This set of SSP templates is the highest resolution (R ∼ 22, 500) available in the near-IR, and the first such based on an empirical stellar library. Our models are generated using spectra of ∼300,000 stars spread across the Milky Way, with a wide range of metallicities and abundances, from the APOGEE survey. We show that our model spectra provide accurate fits to M31 globular cluster spectra taken with APOGEE, with best-fit metallicities agreeing with those of previous estimates to within ∼0.1 dex. We also compare these model spectra to lower-resolution E-MILES models and demonstrate that we recover the ages of these models to within ∼1.5 Gyr. This library is available in https://github.com/aishashok/ALIST-library.

47 OTHER INSTRUMENTATION↗
NASA NTRS2000

The Heavy Element Abundance in Groups of Galaxies

Over the past few years we have analyzed a sample of clusters observed by the Advanced Spacecraft for Cosmology Astrophysics (ASCA) X-ray satellite. We performed spatially resolved X-ray spectroscopy of a sample of 18 relaxed clusters of galaxies with gas temperatures below 4 keV. The spectral analysis was done using ASCA/SIS (Solid state Imaging Spectrometer) data combined with imaging data from ROSAT/PSPC (German acronym for X-ray satellite/Position Sensitive Proportional Counter) and Einstein/IPC (Imaging Proportional Counter) observations. We derived temperature profiles using single-temperature fits for all of the clusters in the sample, and also corrected for the presence of cold gas in the center of so-called 'cooling flow' clusters. For all of the clusters in the sample we derived Si and Fe abundance profiles. For a few of the clusters we also were able to derive Ne and S abundance profiles. We compared the elemental abundances derived at similar overdensities in all of the clusters in the sample. We also compared element mass-to-light ratios for the entire sample. We concluded that the preferential accretion of low entropy, low abundance gas into the potentials of groups and cold clusters can explain most of the observed trends in metallicity. In addition, we discussed the importance of preheating of the intracluster medium by Type II supernovae on the cluster scaling relations.

David, Laurence↗
NASA NTRS2013

Perspectives on Intracluster Enrichment and the Stellar Initial Mass Function in Elliptical Galaxies

The amount of metals in the Intracluster Medium (ICM) in rich galaxy clusters exceeds that expected based on the observed stellar population by a large factor. We quantify this discrepancy--which we term the "cluster elemental abundance paradox"--and investigate the required properties of the ICM-enriching population. The necessary enhancement in metal enrichment may, in principle, originate in the observed stellar population if a larger fraction of stars in the supernova-progenitor mass range form from an initial mass function (IMF) that is either bottom-light or top-heavy, with the latter in some conflict with observed ICM abundance ratios. Other alternatives that imply more modest revisions to the IMF, mass return and remnant fractions, and primordial fraction, posit an increase in the fraction of 3-8 solar mass stars that explode as SNIa or assume that there are more stars than conventionally thought--although the latter implies a high star formation efficiency. We discuss the feasibility of these various solutions and the implications for the diversity of star formation, the process of elliptical galaxy formation, and the nature of this hidden source of ICM metal enrichment in light of recent evidence of an elliptical galaxy IMF that, because it is skewed to low masses, deepens the paradox.

Lowenstein, Michael↗
DOE OSTI2025

Side-On N 2 Binding and Reduction by a Heterotetrametallic Zr 2 Co 2 Cluster

In multimetallic compounds, N 2 typically bridges late transition metals in an end-on (η 1 :η 1 ) fashion while early transition metals often bind N 2 side-on (η 2 ), with the latter resulting in more significant N–N bond elongation. In this work, N 2 fixation is accomplished by using a well-defined scaffold featuring a heterobimetallic combination of Zr and Co. We report a heterotetrametallic Zr 2 Co 2 cluster in which N 2 is bound side-on to the two Co centers and end-on to Zr in a μ 3 -η 1 :η 2 :η 2 binding mode that defies established paradigms for N 2 binding. The heterometallic approach is shown to facilitate catalytic reductive silylation of N 2 with turnover numbers far exceeding those of reported cobalt catalysts.

catalysts↗
DOE OSTI2020

Interpreting the Operando XANES of Surface-Supported Subnanometer Clusters: When Fluxionality, Oxidation State, and Size Effect Fight.

X-ray absorption near edge structure (XANES) spectroscopy is widely used for operando catalyst characterization. We show that, for highly fluxional supported nanoclusters, the customary extraction of the oxidation state of the metal from the XANES data by fitting to the bulk standards is highly questionable. The XANES signatures as well as the apparent oxidation state for such clusters arise from a complex combination of many factors, and not only from the chemical composition in reaction conditions (e.g., oxygen content in oxidizing atmosphere). The thermally accessible isomerization and population of several structurally distinct cluster forms, cluster-support interaction, and intrinsic size effects all impact the metal oxidation state and XANES signal. We demonstrate this on copper oxide clusters with different compositions, Cu4Ox(x = 2-5) and Cu5Oy (y = 3, 5), deposited on amorphous alumina and ultrananocrystalline diamond, for which we computed the XANES spectra and compare the results to the experiment. We show in addition that fitting the experimental spectrum to calculated spectra of supported clusters can, in contrast, provide good agreement and insight into the spectrum-composition-structure relation. Experimental XANES interpreted using the proposed fitting scheme shows the partial reduction of Cu oxide clusters at rising temperatures, and pinpoints the specific stoichiometries that dominate in the ensemble of cluster states as the temperature changes.

Zandkarimi, Borna↗
DOE OSTI2024

The Central Role of Oxo Clusters in Zirconium‐Based Esterification Catalysis

Oxo clusters are a unique link between oxide nanocrystals and Metal‐Organic Frameworks (MOFs), representing the limit of downscaling each of the respective crystals. Herein, the superior catalytic activity of clusters, compared to zirconium MOF UiO‐66 and nanocrystals is shown. Focus is on esterification reactions given their general importance in consumer products and the challenge of converting large substrates. Oxo clusters have a higher surface‐to‐volume ratio than nanocrystals, rendering them more active. For large substrates, for example, oleic acid, MOF UiO‐66 has negligible catalytic activity while clusters provide almost quantitative conversion, a fact we ascribe to limited diffusion of large substrates through the MOF pores. Clusters do not suffer from limited mass transfer and we also obtain high conversion in solvent‐free reactions with sterically hindered alcohols (hexanol, 2‐ethyl hexanol, benzyl alcohol, and neopentyl alcohol). The cluster catalyst can be recovered and shows identical activity when reused. The structural integrity of the cluster is confirmed using X‐ray total scattering and pair distribution function analysis. Moreover, when homogeneous zirconium alkoxides are used as catalysts, the same oxo cluster is retrieved, showing that oxo clusters are the active catalytic species, even in previously assumed homogeneously catalyzed reactions.

Pulparayil Mathew, Jikson↗
NASA NTRS2004

A MASSIF Effort To Determine The Mass-Luminosity Relation for Stars of Various Ages, Metallicities, and Evolution States

The MASSIF (Masses and Stellar Systems with Interferometry) Team will use SIM to investigate the mass content of the Galaxy - from huge stars to barely glimmering brown dwarfs, and from hot white dwarfs to exotic black holes. We will target various samples of the Galactic population to determine and relate the fundamental characteristics of mass, luminosity, age, composition, and multiplicity - attributes that together yield an extensive understanding of the stars. Our samples will include distant clusters that span a factor of 5000 in age, and commonplace stars and substellar objects that lurk near the Sun. The principal goals of the MASSIF Key Project are to (1) define the mass-luminosity relation for main sequence stars in five fundamental clusters so that effects of age and metallicity can be mapped (Trapezium, TW Hydrae, Pleiades, Hyades, and M67), and (2) determine accurate masses for representative examples of nearly every type of star, stellar descendant or brown dwarf in the Galaxy.

Henry, Todd J.↗
NASA NTRS1977

Molecular cluster theory of CO chemisorption on a nickel /100/ surface

Self-consistent Hartree-Fock-Slater molecular cluster models for the chemisorption of carbon monoxide on a (100) transition metal surface are presented. Energy levels and charge distribution for the CO:Ni5 cluster in C sub 4v symmetry are obtained, and the variation of binding energies with height of the CO molecule above the surface of nickel is studied in detail. Comparison is made with experimental binding energy spectra and with the multiple-scattering results of Batra and Bagus. The redistribution in energy of free-atom valence levels is studied by means of local-densities-of-states diagrams.

Ellis, D. E.↗
NASA NTRS2004

Chemical models for simulating single-walled nanotube production in arc vaporization and laser ablation processes

Chemical kinetic models for the nucleation and growth of clusters and single-walled carbon nanotube (SWNT) growth are developed for numerical simulations of the production of SWNTs. Two models that involve evaporation and condensation of carbon and metal catalysts, a full model involving all carbon clusters up to C80, and a reduced model are discussed. The full model is based on a fullerene model, but nickel and carbon/nickel cluster reactions are added to form SWNTs from soot and fullerenes. The full model has a large number of species--so large that to incorporate them into a flow field computation for simulating laser ablation and arc processes requires that they be simplified. The model is reduced by defining large clusters that represent many various sized clusters. Comparisons are given between these models for cases that may be applicable to arc and laser ablation production. Solutions to the system of chemical rate equations of these models for a ramped temperature profile show that production of various species, including SWNTs, agree to within about 50% for a fast ramp, and within 10% for a slower temperature decay time.

Nanotubes, Carbon/chemistry↗
DOE OSTI2022

Tuning Metal–Organic Framework (MOF) Topology by Regulating Ligand and Secondary Building Unit (SBU) Geometry: Structures Built on 8-Connected M 6 (M = Zr, Y) Clusters and a Flexible Tetracarboxylate for Propane-Selective Propane/Propylene Separation

Topology evolution originating from variations of linker and SBU (Secondary Building Unit) geometries could largely enrich the chemistry of metal–organic frameworks (MOFs). Here we report the synthesis and characterization of three MOF structures built on the same organic linker, N,N,N',N'-Tetrakis(4-carboxyphenyl)-1,4-phenylenediamine (tcppda) and similar 8-connected M 6 (M = Zr or Y) clusters. The three compounds, HIAM-402, HIAM-403, and HIAM-311, feature 4,8-connected sqc, scu, and flu topology, respectively. Detailed structural analysis revealed that different geometries of the inorganic M 6 SBUs as well as the organic linker have led to the formation of distinct MOF nets. In particular, HIAM-402 features exceptional framework stability and high porosity and acts as a propane-selective adsorbent for the discrimination of propane and propylene. Its balanced adsorption selectivity (S propane/propylene = 1.43) and capacity (Q propane = 133.3 cm 3 /g, 298 K and 1 bar) endow it with the capability of separating propane and propylene mixtures and one-step production of highly pure propylene (purity >99.9%), as validated by column breakthrough measurements, with the presence of moisture or propyne. As a result, ab initio calculations further confirm that the propane-selective behavior of HIAM-402 is a result of its higher binding energy toward propane compared to that of propylene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Back Door to the Surface Hydrated Electron

We use a Mg + metal to extend the size regime of water clusters to extrapolate to the bulk limit of the Vertical Detachment Energy (VDE) of the solvated electron to >3,200, a value between one to over two orders of magnitude for clusters previously measured experimentally or computed theoretically. We relate the VDE to the energy difference between the Mg + (H 2 O) $n$ and Mg 2+ (H 2 O) $n$ systems and the metal’s second ionization potential. The extrapolated bulk VDEs of the localized surface electron, which moves away from the metal as n increases, are 1.89 ± 0.01 eV for semiempirical ($n$ ~ 3,200; PM6-D 3 H 4 ) and 1.73 ± 0.03 eV ($n$ ~ 150; HF), 1.83 ± 0.02 eV ($n$ ~ 150; MP2) for ab-initio, in excellent agreement with the 1.6 – 1.8 eV range of experimental results. In conclusion, the VDEs converge from above (larger values) to the bulk limit, in a manner qualitatively different than previous studies and experiments, a fact justifying the “back door” approach to the solvated electron.

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

Active and Transfer Learning of High-Dimensional Neural Network Potentials for Transition Metals

Classical molecular dynamics (MD) simulations represent a very popular and powerful tool for materials modeling and design. The predictive power of MD hinges on the ability of the interatomic potential to capture the underlying physics and chemistry. There have been decades of seminal work on developing interatomic potentials, albeit with a focus predominantly on capturing the properties of bulk materials. Such physics-based models, while extensively deployed for predicting the dynamics and properties of nanoscale systems over the past two decades, tend to perform poorly in predicting nanoscale potential energy surfaces (PESs) when compared to high-fidelity first-principles calculations. These limitations stem from the lack of flexibility in such models, which rely on a predefined functional form. Machine learning (ML) models and approaches have emerged as a viable alternative to capture the diverse size-dependent cluster geometries, nanoscale dynamics, and the complex nanoscale PESs, without sacrificing the bulk properties. Here, in this study, we introduce an ML workflow that combines transfer and active learning strategies to develop high-dimensional neural networks (NNs) for capturing the cluster and bulk properties for several different transition metals with applications in catalysis, microelectronics, and energy storage, to name a few. Our NN first learns the bulk PES from the high-quality physics-based models in literature and subsequently augments this learning via retraining with a higher-fidelity first-principles training data set to concurrently capture both the nanoscale and bulk PES. Our workflow departs from status-quo in its ability to learn from a sparsely sampled data set that nonetheless covers a diverse range of cluster configurations from near-equilibrium to highly nonequilibrium as well as learning strategies that iteratively improve the fingerprinting depending on model fidelity. All the developed models are rigorously tested against an extensive first-principles data set of energies and forces of cluster configurations as well as several properties of bulk configurations for 10 different transition metals. Our approach is material agnostic and provides a methodology to transfer and build upon the learnings from decades of seminal work in molecular simulations on to a new generation of ML-trained potentials to accelerate materials discovery and design.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Study of cluster ions produced from ToF-SIMS analysis of a U-6%Nb target

Cluster ions have been previously observed during time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis of metals and metal oxides. Furthermore, we have used ToF-SIMS to investigate cluster ions formed from the hydrocarbon-containing overlayer, the mixed U and Nb surface oxide, and underlying metal of a U-6 %Nb (U6Nb) target. In the overlayer, we observe U x O y + oxides and U-species likely containing hydrocarbons. In the surface oxide, we observe UO 2 +, U 2 O 2 +, U 3 O 5 +, and U 4 O 6 + as the most intense ions for each family of oxide ions containing x U atoms. Nb oxides for NbO 1-2 - were only observed in negative polarity. In contrast to the oxide, analysis of the underlying U6Nb alloy resulted in repeating units of U n +, U n (Nb)+, and U n (Nb 2 ) + ions for n = 3–11 as the highest intensity ions for each family of ions containing n U atoms. Nb n + clusters were not observed. U n +, U n (Nb)+, and U n (Nb 2 )+ clusters containing C- and O-species were observed and were likely produced from soluble C or O species or precipitates known to be present in U6Nb.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗