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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 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Assessment of wafer scale MoS 2 atomic layers grown by metal–organic chemical vapor deposition using organo-metal, organo-sulfide, and H 2 S precursors

Transition Metal Dichalcogenides (TMDs) are a unique class of materials that exhibit attractive electrical and optical properties which have generated significant interest for applications in microelectronics, optoelectronics, energy storage, and sensing. Considering the potential of these materials to impact such applications, it is crucial to develop a reliable and scalable synthesis process that is compatible with modern industrial manufacturing methods. Metal–organic chemical vapor deposition (MOCVD) offers an ideal solution to produce TMDs, due to its compatibility with large-scale production, precise layer control, and high material purity. Optimization of MOCVD protocols is necessary for effective TMD synthesis and integration into mainstream technologies. Additionally, improvements in metrology are necessary to measure the quality of the fabricated samples more accurately. In this work, we study MOCVD of wafer-scale molybdenum disulfide (MoS 2 ) utilizing two common chalcogen precursors, H 2 S and DTBS. We then develop a metrology platform for wafer scale samples quality assessment. For this, the coalesced films were characterized using Raman spectroscopy, atomic force microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Kelvin probe force microscopy. We then correlate the structural analysis of these grown films with electrical performance by using aerosol jet printing to fabricate van der Pauw test structures and assess sheet resistance.

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

Cu site differentiation in tetracopper(I) sulfide clusters enables biomimetic N 2 O reduction

Copper clusters feature prominently in both metalloenzymes and synthetic nanoclusters that mediate catalytic redox transformations of gaseous small molecules. Such reactions are critical to biological energy conversion and are expected to be crucial parts of renewable energy economies. However, the precise roles of individual metal atoms within clusters are difficult to elucidate, particularly for cluster systems that are dynamic under operating conditions. Here, we present a metal site-specific analysis of synthetic Cu 4 (μ 4 -S) clusters that mimic the Cu Z active site of the nitrous oxide reductase enzyme. Leveraging the ability to obtain structural snapshots of both inactive and active forms of the synthetic model system, we analyzed both states using resonant X-ray diffraction anomalous fine structure (DAFS), a technique that enables X-ray absorption profiles of individual metal sites within a cluster to be extracted independently. Using DAFS, we found that a change in cluster geometry between the inactive and active states is correlated to Cu site differentiation that is presumably required for efficient activation of N 2 O gas. More precisely, we hypothesize that the Cu δ+ ∙∙∙Cu δ- pairs produced upon site differentiation are poised for N 2 O activation, as supported by computational modeling. These results provide an unprecedented level of detail on the roles of individual metal sites within the synthetic cluster system and how those roles interplay with cluster geometry to impact the reactivity function. We expect this fundamental knowledge to inform understanding of metal clusters in settings ranging from (bio)molecular to nanocluster to extended solid systems involved in energy conversion.

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

Temperature-dependent growth of hexagonal and monoclinic gallium sulfide films by pulsed-laser deposition

We demonstrate the selective, pulsed-laser deposition of hexagonal GaS and monoclinic Ga2S3 films on sapphire substrates from a single Ga 2 S 3 target in high-vacuum conditions. Growth at substrate temperatures below 550 °C causes GaS film formation, which indicates non-stoichiometric transfer from the target to the film. Surprisingly, stoichiometric transfer occurs at substrate temperatures above 650 °C with monoclinic Ga 2 S 3 as the preferred, higher S-content phase. Through a series of growth and annealing experiments, we show that GaS nucleation under S-deficient conditions leads to the preferred growth of this layered, hexagonal phase below 550 °C. Furthermore, GaS films annealed above 650 °C under high vacuum are transformed to Ga 2 S 3 , reflecting the greater stability of the monoclinic phase. By first growing Ga 2 S 3 at a higher temperature and subsequently growing GaS at a lower temperature, we can fabricate GaS/Ga 2 S 3 heterostructures in a single growth process.

36 MATERIALS SCIENCE↗
DOE OSTI2022

How transient effects can change the inferred plasma temperatures when using K-shell sulfur line ratios in a time dependent iron sulfide plasma

This paper describes how the steady state atomic kinetics approximation can underestimate the electron temperature determined from K-shell lines in ps-time-scale transient plasmas. In particular, we model the temperature determination of solid FeS targets used in opacity experiments at the Orion laser facility from the ratio of sulfur He-α to Ly-α lines. Such experiments use short-pulse lasers to heat a thin microdot of FeS buried in a plastic target to temperatures of more than 1 keV and densities of approximately 1–2 g/cm 3 . Using atomic kinetics calculations based on a temperature history from a radiation hydrodynamic simulation of the target evolution, the peak temperature inferred from the sulfur line ratios is 1.29 keV at 3.1 ps as compared with the input peak temperature of 1.41 keV at 2.0 ps. There is a time lag of 1.2 ps at the peak, and an overall 0.5 ps time lag in the temporal history of the temperature as the plasma cools over the next 10 ps.

Rilloraza, Francisco↗
DOE OSTI2021

Carotenoid biomarkers in Namibian shelf sediments: Anoxygenic photosynthesis during sulfide eruptions in the Benguela Upwelling System

Significance Anoxygenic photosynthesis by phototrophic sulfur bacteria is prevalent in microbial mat ecosystems and in restricted, highly stratified aquatic environments. This limited distribution reflects their simultaneous requirements for an anoxic habitat, reduced sulfur to supply electrons for carbon fixation, and an appropriate light regime. Although these conditions were often satisfied in ancient seas, as shown by the distinctive carotenoid and chlorophyll pigments preserved in geological samples going back as far as 1.65 billion y, we can find no record of these organisms growing in today’s generally well-ventilated oceans. An array of carotenoids in sediments from the Namibian shelf suggests that green sulfur bacteria, despite their sensitivity to oxygen, can proliferate during episodic toxic gas eruptions in the Benguela Upwelling System.

Ma, Jian↗
DOE OSTI2023

Facile and dynamic cleavage of every iron–sulfide bond in cuboidal iron–sulfur clusters

Nature employs weak-field metalloclusters to support a wide range of biological processes. The most ubiquitous metalloclusters are the cuboidal Fe–S clusters, which are comprised of Fe sites with locally high-spin electronic configurations. Such configurations enhance rates of ligand exchange and imbue the clusters with a degree of structural plasticity that is increasingly thought to be functionally relevant. Here, we examine this phenomenon using isotope tracing experiments. Specifically, we demonstrate that synthetic [Fe 4 S 4 ] and [MoFe 3 S 4 ] clusters exchange their Fe atoms with Fe 2+ ions dissolved in solution, a process that involves the reversible cleavage and reformation of every Fe–S bond in the cluster core. This exchange is facile—in most cases occurring at room temperature on the timescale of minutes—and documented over a range of cluster core oxidation states and terminal ligation patterns. In addition to suggesting a highly dynamic picture of cluster structure, these results provide a method for isotopically labeling pre-formed clusters with spin-active nuclei, such as 57 Fe. Such a protocol is demonstrated for the radical S -adenosyl- l -methionine enzyme, RlmN.

Science & Technology - Other Topics↗
DOE OSTI2016

Computational and experimental investigation for new transition metal selenides and sulfides: The importance of experimental verification for stability

Expanding the library of known inorganic materials with functional electronic or magnetic behavior is a long-standing goal in condensed matter physics and materials science. Recently, the transition metal chalcogenides including selenium and sulfur have been of interest because of their correlated-electron properties, as seen in the iron-based superconductors and the transition metal dichalcogenides. However, the chalcogenide chemical space is less explored than that of oxides, and there is an open question of whether there may be new materials heretofore undiscovered. We perform a systematic combined theoretical and experimental search over ternary phase diagrams that are empty in the Inorganic Crystal Structure Database containing cations, transition metals, and one of selenium or sulfur. In these 27 ternary systems, we use a probabilistic model to reduce the likelihood of false negative predictions, which results in a list of 24 candidate materials. We then conduct a variety of synthesis experiments to check the candidate materials for stability. While the prediction method did obtain previously unknown compositions that are predicted stable within density functional theory, none of the candidate materials formed in our experiments. Finally, we come to the conclusion that these phase diagrams are “empty” in the case of bulk synthesis, but it remains a possibility that alternate synthesis routes may produce some of these phases.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Pyrobaculum Yellowstonensis Strain WP30 Respires On Elemental Sulfur And/or Arsenate in Circumneutral Sulfidic Sediments of Yellowstone National Park

Thermoproteales populations (phylum Crenarchaeota) are abundant in high-25 temperature (>70° C) environments of Yellowstone National Park (YNP) and are important in mediating biogeochemical cycles of sulfur, arsenic and carbon. The objectives of this study were to determine specific physiological attributes of the isolate Pyrobaculum yellowstonensis strain WP30, which was obtained from an elemental sulfur sediment (Joseph’s Coat Hot Spring [JCHS]; 80 °C; pH 6.1), and relate this organism to geochemical processes occurring in situ. Strain WP30 is a chemoheterotroph that utilizes organic carbon as a source of carbon and electrons and requires elemental sulfur and/or arsenic as electron acceptors. Growth in the presence of elemental sulfur and arsenate resulted in the production of thioarsenates and polysulfides relative to sterile controls. The complete genome of this organism was sequenced (1.99 Mb, 58 % G+C) and revealed numerous metabolic pathways for the degradation of carbohydrates, amino acids and lipids, multiple dimethylsulfoxide molybdopterin (DMSO-MPT) oxidoreductase genes, which are implicated in the reduction of sulfur and arsenic, and pathways for the de novo synthesis of nearly all required cofactors and metabolites. Comparative genomics of P. yellowstonensis versus assembled metagenome sequence from JCHS showed that this organisms is highly-related (~95% average nucleotide identity) to in situ populations. The physiological attributes and metabolic capabilities of P. yellowstonensis provide importanat information towards understanding the distribution and function of these populations in YNP.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2014

Draft Genome Sequence of a Sulfide-Oxidizing, Autotrophic Filamentous Anoxygenic Phototrophic Bacterium, Chloroflexus sp. Strain MS-G (Chloroflexi)

The draft genome sequence of the thermophilic filamentous anoxygenic phototrophic bacterium Chloroflexus sp. strain MS-G (Chloroflexi), isolated from Mushroom Spring (Yellowstone National Park, WY, USA) was sequenced and comprises 4,784,183 bp in 251 contigs. The draft genome is predicted to encode 4,059 protein coding genes, 49 tRNA encoding genes, and 3 rRNA operons.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Complete genome sequence of the haloalkaliphilic, obligately chemolithoautotrophic thiosulfate and sulfide-oxidizing γ-proteobacterium Thioalkalimicrobium cyclicum type strain ALM 1 (DSM 14477T)

Abstract Thioalkalimicrobium cyclicum Sorokin et al . 2002 is a member of the family Piscirickettsiaceae in the order Thiotrichales . The γ-proteobacterium belongs to the colourless sulfur-oxidizing bacteria isolated from saline soda lakes with stable alkaline pH, such as Lake Mono (California) and Soap Lake (Washington State). Strain ALM 1 T is characterized by its adaptation to life in the oxic/anoxic interface towards the less saline aerobic waters (mixolimnion) of the stable stratified alkaline salt lakes. Strain ALM 1 T is the first representative of the genus Thioalkalimicrobium whose genome sequence has been deciphered and the fourth genome sequence of a type strain of the Piscirickettsiaceae to be published. The 1,932,455 bp long chromosome with its 1,684 protein-coding and 50 RNA genes was sequenced as part of the DOE Joint Genome Institute Community Sequencing Program (CSP) 2008.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Resolving the kinetics of individual aqueous reaction steps of actinyl (AnO 2 + and AnO 2 2+ ; An=U, Np, and Pu) tricarbonate complexes with ferrous iron and hydrogen sulfide from first principles

The solubility and mobility of actinides (An), like uranium, neptunium, and plutonium, in the environment largely depends on their oxidation states. Actinyls (An V,VI O 2 +/2+ (aq) ) form strong complexes with available ligands, like carbonate (CO 3 2- ), which may inhibit reduction to relatively insoluble An IV O 2(s) . Here we use quantum-mechanical calculations to explore the kinetics of aqueous homogeneous reaction paths of actinyl tricarbonate complexes ([AnO 2 (CO 3 ) 3 ] 5-/4- ) with two different reductants, [Fe(OH) 2 (H 2 O) 4 ] 0 and [H 2 S(H 2 O) 6 ] 0 . Energetically-favorable outer-sphere complexes (OSC) are found to form rapidly, on the order of milliseconds to seconds over a wide actinyl concentration range (pM to mM). The systems then encounter energy barriers ( E a ), some of which are prohibitively high (>100 kJ/mol for some neptunyl and plutonyl reactions with Fe 2+ and H 2 S), that define the transition from outer- to inner-sphere complex (ISC; for example, calculated E a of ISC formation between UO 2 + and UO 2 2+ with Fe 2+ are 35 and 74 kJ/mol, respectively). In some reactions, multiple OSCs are observed that represent different hydrogen bonding networks between solvent molecules and carbonate. Even when forming ISCs, electron transfer to reduce An 6+ and An 5+ is not observed (no change in atomic spin values or lengthening of An–O ax bond distances). Proton transfer from bicarbonate and water to actinyl O was tested as a mechanism for electron transfer from Fe 2+ to U 6+ and Pu 6+ . Not all proton transfer reactions yielded reduction of An 6+ to An 5+ and only a few pathways were energetically-favorable (e. g. H + transfer from H 2 O to drive Pu 6+ reduction to Pu 5+ with Δ E = -5 kJ/mol). The results suggest that the tricarbonate complex serves as an effective shield against actinide reduction in the tested reactions and will maintain actinyl solubility at elevated pH conditions. The results highlight reaction steps, such as inner-sphere complex formation and electron transfer, which may be rate-limiting. Thus, this study may serve as the basis for future research on how they can be catalyzed by a mineral surface in a heterogeneous process.

Chemistry↗