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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 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Stratospheric ozone depletion in the Antarctic region triggers intense changes in sea salt aerosol geochemistry

Abstract Since the early 1980s, the Antarctic environment has served as a natural field laboratory for researchers to investigate the effects of stratospheric ozone depletion, which has resulted in increased surface ultraviolet radiation levels. However, its effective threats still present gaps. We report new pieces of evidence of increased ultraviolet radiation impacting West Antarctica sea salt aerosols. Salt aerosols, particularly in the Southern Ocean Sea, play an important role in the radiative earth balance. To disclose the molecular details of sea salt aerosols, we used a synchrotron-based multi-element microscopic speciation of individual microparticles (Scanning Transmission X-ray Microscopy with Near-Edge X-ray Absorption Fine Structure Spectroscopy combined with Computer-Controlled Scanning Electron Microscopy). Here we identified substantial abundances of chlorine-enriched aerosols in sea salt generated by photolytic products, whereas ice core records revealed increased chlorine depletion from the onset of ozone depletion. Our findings reveal that modern sea salt modification has no Holocene precedent.

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

Hydration of α-UO 3 following storage under controlled conditions of temperature and relative humidity

Changes in chemical speciation of uranium oxides following storage under varied conditions of temperature and relative humidity are valuable for characterizing material provenance. In this study, subsamples of high purity α-UO 3 were stored under four sets of controlled conditions of temperature and relative humidity over several years, and then measured periodically for chemical speciation. Powder X-ray diffraction (XRD) analysis and extended X-ray absorption fine structure spectroscopy confirm hydration of α-UO 3 to a schoepite-like end product following storage under each of the varied storage conditions, but the species formed during exposure to the lower relative humidity and lower temperature condition follows different trends from those formed under the other three storage conditions (high relative humidity with high or low temperatures, and low relative humidity with a high temperature). Thermogravimetry coupled with XRD analysis was carried out to distinguish desorption pathways of water from the hydrated end products. Density functional theory calculations discern changes in the structure of α-UO 3 following incorporation of 1, 2 or 3 H 2 O molecules or 1, 2 or 3 OH groups into the orthorhombic lattice, revealing differences in lattice constants, U–O bond lengths, and U–U distances. The collective results from this analysis are in contrast to analogous studies that report that U 3 O 8 is oxidized and hydrated in air during storage under high relative humidity conditions.

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

Spectroscopic characterization of neptunium(VI), plutonium(VI), americium(VI) and neptunium(V) encapsulated in uranyl nitrate hexahydrate

The coordination of crystalline products resulting from the co-crystallization of Np(VI), Pu(VI), Am(VI), and Np(V) with uranyl nitrate hexahydrate (UNH) has been revealed through solid-state spectroscopic characterization via diffuse reflectance UV-Vis-NIR spectroscopy, SEM-EDS, and extended X-ray absorption fine structure (EXAFS) spectroscopy. Density functional and multireference wavefunction calculations were performed to analyze the An(VI/V)O 2 (NO 3 ) 2 ·2H 2 O electronic structures and to help assign the observed transitions in the absorption spectra. EXAFS show a similar coordination between the U(VI) in UNH and Np(VI) and Pu(VI); while Am resulted in a similar coordination to Am(III), as reduction of Am(VI) occurred prior to EXAFS data being obtained. Finally, the co-crystallization of the oxidized transuranic species—penta- and hexavalent—with UNH, represents a significant advance from not only a practical standpoint in providing an elegant solution for used nuclear fuel recycle, but also as an avenue to expand the fundamental understanding of the 5f electronic behavior in the solid-state.

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

Spectroscopic characterization of neptunium(VI), plutonium(VI), americium(VI) and neptunium(V) encapsulated in uranyl nitrate hexahydrate

The coordination of crystalline products resulting from the co-crystallization of Np(VI), Pu(VI), Am(VI), and Np(V) with uranyl nitrate hexahydrate (UNH) has been revealed through solid-state spectroscopic characterization via diffuse reflectance UV-Vis-NIR, SEM-EDS, and extended X-ray absorption fine structure (EXAFS). Density functional and multireference wavefunction calculations were performed to analyze the An(VI/V)O 2 (NO 3 ) 2 ·2H 2 O electronic structures and to help assign the observed transitions in the absorption spectra. EXAFS show a similar coordination between the U(VI) in UNH and Np(VI) and Pu(VI); while Am resulted in a similar coordination to Am(III), as reduction of Am(VI) occurred prior to EXAFS data being obtained. Here, the co-crystallization of the oxidized transuranic species—penta- and hexavalent—with UNH, represents a significant advance from not only a practical standpoint in providing an elegant solution for used nuclear fuel recycle, but also as an avenue to expand the fundamental understanding of the 5f electronic behavior in the solid-state.

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

Transformation of atomically dispersed platinum in SAPO-37 into platinum clusters: catalyst for ethylene hydrogenation

Atomically dispersed supported platinum catalysts were synthesized by the reaction of Pt(acac) 2 (acac = acetylacetonato) with the silicoaluminophosphate molecular sieve SAPO-37, with infrared spectra showing that the reaction involved SAPO OH groups. Extended X-ray absorption fine structure (EXAFS) spectra show that, after heating in air to 623 K, each platinum atom on average was bonded to approximately two oxygen atoms of the SAPO support, with no evidence of platinum clusters. X-ray absorption near edge spectra (XANES) indicate a platinum formal oxidation state of approximately +2. Here, these supported mononuclear species lacked catalytic activity for ethylene hydrogenation at 1 bar and room temperature, but activity arose during catalysis in a once-through flow reactor/X-ray absorption spectroscopy cell, as the XANES white line intensity decreased, indicating reduction of the platinum, and the EXAFS-determined Pt–Pt coordination number (CN) increased from essentially zero to 2.7 ± 0.5 after 2 h, indicating the formation of platinum clusters of only a few atoms each. The data indicate the almost instantaneous formation of the clusters and identify them as the catalytically active species. Subsequent exposure of the catalyst to ethylene as in situ EXAFS and XANES data were recorded led to a decrease in the Pt–Pt coordination number to 1.6 ± 0.3 and an increase in the white line intensity, indicating partial oxidative fragmentation of the clusters by ethylene. Platinum clusters in SAPO-37 formed in separate experiments by exposure to H 2 prior to catalysis were also catalytically active for ethylene hydrogenation. Here, the data thus show how to dial in the catalytic activity by forming platinum clusters by exposure of mononuclear platinum to H 2 and how to dial back the activity by oxidative fragmentation of the clusters by reaction with ethylene, all under mild conditions; the ethylene : H 2 ratio of the reactant gas determines the average platinum nuclearity and thus the catalytic activity.

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

Effects of nanoconfinement and surface charge on iron adsorption on mesoporous silica

Here, we present a combined molecular dynamics (MD) simulation and X-ray absorption fine structure (XAFS) spectroscopic investigation of aqueous iron adsorption on nanoconfined amorphous silica surfaces. The simulation models examine the effects of pore size, pH (surface charge), iron valency, and counter-ion (chloride or hydroxide). The simulation methods were validated by comparing the coordination environment of adsorbed iron with coordination numbers and bond lengths derived from XAFS. In the MD models, nanoconfinement effects on local iron coordination were investigated by comparing results for unconfined silica surfaces and in confined domains within 2 nm, 4 nm, and 8 nm pores. Experimentally, coordination environments of iron adsorbed onto mesoporous silica with 4 nm and 8 nm pores at pH 7.5 were investigated. The effect of pH in the MD models was included by simulating Fe(II) adsorption onto negatively charged SiO 2 surfaces and Fe(III) adsorption on neutral surfaces. The simulation results show that iron adsorption depends significantly on silica surface charge, as expected based on electrostatic interactions. Adsorption on a negatively charged surface is an order of magnitude greater than on the neutral surface, and simulated surface coverages are consistent with experimental results. Pore size effects from the MD simulations were most notable in the adsorption of Fe(II) at deprotonated surface sites (SiO - ), but adsorption trends varied with concentration and aqueous Fe speciation. The coordination environment of adsorbed iron varied significantly with the type of anion. Considerable ion pairing with hydroxide anions led to the formation of oligomeric surface complexes and aqueous species, resulting in larger iron hydroxide clusters at higher surface loadings.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Towards a mechanistic understanding of the sol–gel syntheses of ternary carbides

Sol–gel chemistry, while being extremely established, is to this day not fully understood, and much of the underlying chemistry and mechanisms are yet to be unraveled. Here, in this work, we elaborate on the sol–gel chemistry of Cr 2 GaC, the first layered ternary carbide belonging to the MAX phase family to ever be synthesized using this wet chemical approach. Leveraging a variety of both in- and ex situ characterization techniques, including X-ray and neutron powder diffraction, X-ray absorption fine structure analyses, total scattering analyses, and differential scanning calorimetry coupled with mass spectrometry, in-depth analyses of the local structures and reaction pathways are elucidated. While the metals first form tetrahedrally and octahedrally coordinated oxidic structures, that subsequently grow and crystallize into oxides, the carbon source citric acid sits on a separate reaction pathway, that does not merge with the metals until the very end. In fact, after decomposing it remains nanostructured and disordered graphite until the temperature allows for the reduction of the metal oxides into the layered carbide. Based on this, we hypothesize that the method is mostly applicable to systems where the needed metals are reducible by graphite around the formation temperature of the target phase.

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

Accelerating nano-XANES imaging via feature selection

We utilize feature selection to reduce experimental time by ∼80% of a nanoscale X-ray Absorption Fine Structure (XANES) spectroscopy imaging study of a sample with Fe-bearing mineral phases.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Asymmetric Rowland circle geometries for spherically bent crystal analyzers in laboratory and synchrotron applications

Spherically bent crystal analyzers (SBCAs) are the dominant high-resolution hard X-ray optic in the ongoing rebirth of laboratory-based X-ray absorption fine structure (XAFS) and X-ray emission spectroscopy (XES) as well as in synchrotron methods such as high energy resolution fluorescence detection (HERFD) and non-resonant X-ray Raman scattering (XRS). In the overwhelming majority of cases, SBCAs are implemented in a ‘symmetric’ configuration on the Rowland circle, wherein the diffracting crystal plane is nominally coincident with the analyzer surface. We report here comprehensive investigations of ‘asymmetric’ operation of SBCA on the Rowland circle, wherein the diffracting crystal plane is not coincident with the optical surface of the analyzer. First, we have developed a laboratory spectrometer for XAFS and XES that is specialized for asymmetric SBCA operation. Here we find several benefits, including the capacity to use a single SBCA over a very wide energy range via ‘hkl hopping’ and the frequent ability to eliminate Johann error, the most prevalent energy-broadening mechanism when using SBCA symmetrically on the Rowland circle. Second, we expand these ideas to synchrotron facilities with a demonstration study of HERFD and XRS where asymmetric operation also provided advantage. Our results suggest that large-array systems for HERFD augmented with an additional mechanical degree of freedom could streamline user operation and also indicate benefits to XRS in the asymmetric configuration, where larger solid angle, larger sample-to-detector distance, and decreased Johann error can be achieved simultaneously.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Formation of uranium disulfide from a uranium thioamidate single-source precursor

A single-source-precursor approach was developed to synthesize uranium-based materials outside of the typically-studied oxides. This approach allows for shorter reaction times, milder reaction conditions, and control over the chemicals present in synthesis. To this end, the first homoleptic uranium thioamidate complex was synthesized as a precursor for US 2 materials. Pyrolysis of the thioamidate results in decomposition via an alkene elimination pathway and formation of γ-US 2 , which has historically been hard to access without the need for a secondary sulfur source. Despite the oxophilicity of uranium, the method successfully forms US 2 without the inclusion of oxygen in the bulk final product. These findings are supported by simultaneous thermal analysis, elemental analysis, powder X-ray diffraction, and uranium L 3 -edge X-ray absorption fine-structure spectroscopy. This work represents the first example of a single-source precursor approach to target and synthesize actinide materials other than the oxides.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

MultiTaskDeltaNet: change detection-based image segmentation for operando ETEM with application to carbon gasification kinetics

Transforming in situ transmission electron microscopy (TEM) imaging into a tool for spatially-resolved operando characterization of solid-state reactions requires automated, high-precision semantic segmentation of dynamically evolving features. However, traditional deep learning methods for semantic segmentation often face limitations due to the scarcity of labeled data, visually ambiguous features of interest, and scenarios involving small objects. To tackle these challenges, we introduce MultiTaskDeltaNet (MTDN), a novel deep learning architecture that creatively reconceptualizes the segmentation task as a change detection problem. By implementing a unique Siamese network with a U-Net backbone and using paired images to capture feature changes, MTDN effectively leverages minimal data to produce high-quality segmentations. Furthermore, MTDN utilizes a multi-task learning strategy to exploit correlations between physical features of interest. In an evaluation using data from in situ environmental TEM (ETEM) videos of filamentous carbon gasification, MTDN demonstrated a significant advantage over conventional segmentation models, particularly in accurately delineating fine structural features. Notably, MTDN achieved a 10.22% performance improvement over conventional segmentation models in predicting small and visually ambiguous physical features. This work bridges key gaps between deep learning and practical TEM image analysis, advancing automated characterization of nanomaterials in complex experimental settings.

08 HYDROGEN↗
DOE OSTI2025

Amorphous zinc–molybdenum–sulfide chalcogel as a long-cycle, high-capacity electrode for lithium-ion batteries

The inherent limitations of intercalation-based electrodes in lithium-ion batteries have prompted the search for alternative materials with higher specific capacities and robust electrochemical stability. Sulfur-based electrodes, despite their high theoretical capacities (1672 mAh g −1 ), typically suffer from poor cycling performance. In this work, zinc molybdenum polysulfide (Zn x Mo 3 S 13 , 0.5 ≤ x), an amorphous semiconductor chalcogel, exhibits high specific capacity and excellent cycling stability. Synchrotron X-ray pair distribution function and extended X-ray absorption fine structure analyses reveal a short-range atomic structure comprising Mo–Mo, M–S (M = Mo, Zn), and S–S bonding motifs. The coordination environment of Mo and S closely resembles that of Mo 3 S 13 clusters, interconnected via S–S bridges and Zn 2+ cations. The Li/Zn x Mo 3 S 13 cell delivers an initial discharge capacity of 844 mAh g −1 at C/3, and retains 386.2 mAh g −1 after 1000 cycles with an average coulombic efficiency of 99.99%. The distribution of relaxation times analysis confirms the formation of a stable solid electrolyte interphase, which underpins the cell's long-term stability. In conclusion, this outstanding performance is attributed to the synergistic effects of the chalcogel's unique amorphous framework, semiconductive character, Zn-mediated polysulfide anchoring, and structural resilience, positioning Zn x Mo 3 S 13 chalcogel among the most durable pure metal sulfide cathodes reported for next-generation LIBs.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Elucidating Norrish type I reactive pathways by ultrafast X-ray absorption spectroscopy

Norrish type I reactions selectively cleave carbon–carbon bonds directly adjacent to carbonyl groups. Despite their broad use in combination with aromatic carbonyls for additive manufacturing and dental UV curing applications, the nature of the photochemically active state and its population mechanism remain insufficiently understood. Detailed mechanistic insight requires mapping of the photoexcited population flow involving internal conversion and intersystem crossing. We present a time-domain study of gas phase acetophenone as a prototypical aromatic carbonyl combining soft X-ray time-resolved near-edge X-ray absorption fine structure (TR-NEXAFS) spectroscopy at the oxygen K-edge with ab initio multiple spawning (AIMS) simulations. Exploiting the specific sensitivity of TR-NEXAFS spectroscopy to states with nπ* character, we observe population transfer from the initially excited 1 ππ* state to the 1 nπ* state with a time constant of (0.13 ± 0.02) ps after an initial induction period of (0.12 ± 0.02) ps without population transfer, in quantitative agreement with the AIMS simulations. The population in the 1 nπ* state subsequently decays via intersystem crossing, likely mediated by a 3 ππ* state, within (3.17 ± 0.66) ps to a long-lived 3 nπ* state, which is presumed to be active towards Norrish type I chemistry.

Graßl, Martin [SLAC National Accelerator Laborator↗
DOE OSTI2021

Ultra diffuse galaxies in the MATLAS low-to-moderate density fields

Recent advances in deep dedicated imaging surveys over the past decade have uncovered a surprisingly large number of extremely faint low surface brightness galaxies with large physical sizes called ultra diffuse galaxies (UDGs) in clusters and, more recently, in lower density environments. As part of the Mass Assembly of early-Type GaLAxies with their fine Structures (MATLAS) survey, a deep imaging large program at the Canada-France-Hawaii Telescope (CFHT), our team has identified 2210 dwarf galaxies, 59 (~3%) of which qualify as UDGs. Averaging over the survey area, we find ~0.4 UDG per square degree. They are found in a range of low to moderate density environments, although 61% of the sample fall within the virial radii of groups. Based on a detailed analysis of their photometric and structural properties, we find that the MATLAS UDGs do not show significant differences from the traditional dwarfs, except from the predefined size and surface brightness cut. Their median color is as red as the one measured in galaxy clusters, albeit with a narrower color range. The majority of the UDGs are visually classified as dwarf ellipticals with log stellar masses of ~6.5 – 8.7. The fraction of nucleated UDGs (~34%) is roughly the same as the nucleated fraction of the traditional dwarfs. Only five (~8%) UDGs show signs of tidal disruption and only two are tidal dwarf galaxy candidates. A study of globular cluster (GC) candidates selected in the CFHT images finds no evidence of a higher GC specific frequency S N for UDGs than for classical dwarfs, contrary to what is found in most clusters. The UDG halo-to-stellar mass ratio distribution, as estimated from the GC counts, peaks at roughly the same value as for the traditional dwarfs, but spans the smaller range of ~10 – 2000. Finally, we interpret these results to mean that the large majority of the field-to-group UDGs do not have a different formation scenario than traditional dwarfs.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Raman studies of hydrogen trapped in As 4 O 6 ·2H 2 at high pressure and low temperature

In this work, Raman spectroscopic measurements of the arsenolite–hydrogen inclusion compound As 4 O 6 ·2H 2 were performed in diamond anvil cells at high pressure and variable temperature down to 80 K. The experimental results were complemented by ab initio molecular dynamics simulations and phonon calculations. Observation of three hydrogen vibrons in As 4 O 6 ·2H 2 is reported in the entire temperature and pressure range studied (up to 24 GPa). While the experiments performed with protium and deuterium at variable temperatures allowed for the assignment of two vibrons as Q 1 (1) and Q 1 (0) transitions of ortho and para spin isomers of hydrogen trapped in the inclusion compound, the origin of the third vibron could not be unequivocally established. Low-temperature spectra revealed that the lowest-frequency vibron is actually composed of two overlapping bands of A g and T 2g symmetries dominated by H 2 stretching modes as predicted by our previous density functional theory calculations. We observed low-frequency modes of As 4 O 6 ·2H 2 vibrations dominated by H 2 “librations,” which were missed in a previous study. A low-temperature fine structure was observed for the J = 0 → 2 and J = 1 → 3 manifolds of hydrogen trapped in As 4 O 6 ·2H 2 , indicating the lifting of degeneracy due to an anisotropic environment. A non-spherical distribution was captured by molecular dynamics simulations, which revealed that the trajectory of H 2 molecules is skewed along the crystallographic $\langle$111$\rangle$ direction. Last but not least, low-temperature synchrotron powder x-ray diffraction measurements on As 4 O 6 ·2H 2 revealed that the bulk structure of the compound is preserved down to 5 K at 1.6 GPa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗