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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 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Characterization of pitch carbon coating properties affecting the electrochemical behavior of silicon nanoparticle lithium-ion battery anodes

Silicon is an exciting material for next-generation lithium-ion battery anodes, due to its high theoretical capacity and availability, but its widespread implementation has been limited by extensive volume changes during cycling that causes mechanical damage and limits cycle life. One approach to mitigating these deleterious effects while still maintaining silicon's benefits is the addition of a pitch carbon coating to nanometer-sized silicon particles. Here, in this study, we present characterization of pitch-coated silicon electrodes without annealing and annealed at 700 °C and 1000 °C to determine the optimum temperature treatment, as well as pitch-only and silicon-only electrodes with and without annealing to elucidate the impacts of each component on early electrochemical behavior. Using Fourier transform infrared and Raman spectroscopies, atomic force and scanning spreading resistance microscopy, and electrochemical analysis, we find 700 °C to be the optimal annealing temperature, as amorphous carbon is created, which improves conductivity prior to cycling and facilitates ion storage during cycling that increases capacity. We also present in situ Raman spectroscopy data demonstrating the heterogeneous aging that occurs across the electrode surface during cycling.

25 ENERGY STORAGE↗
DOE OSTI2020

Morphology and chemical behavior of model CsO x /Cu 2 O/Cu(111) nanocatalysts for methanol synthesis: Reaction with CO 2 and H 2

Cs is a promoter of Cu-based catalysts for the synthesis of alcohols from CO 2 hydrogenation. Scanning tunneling microscopy and ambient-pressure x-ray photoelectron spectroscopy were used to study the morphology and chemical properties of surfaces generated by the deposition of cesium on Cu 2 O/Cu(111) and Cu(111) substrates. CsO x nanostructures were formed after Cs metal was deposited on Cu 2 O/Cu(111) at 300 K. The formed CsO x protrude over the surface of copper oxide by 2–4 Å, with the dimension at the base of the nanostructures being in the range of 1–3 nm. Heating to elevated temperature induced significant changes in the size and dispersion of the CsO x nanostructures, and there was a clear reconstruction of the copper oxide substrate, which then exhibited long range order with a hexagonally packed structure. The as-deposited and annealed surfaces of CsO x /Cu 2 O/Cu(111) were more reactive toward CO 2 than plain Cu 2 O/Cu(111) or clean Cu(111). Yet, none of them were stable in the presence of H 2 , which fully reduced the copper oxide at 400–450 K. In CsO x /Cu(111), the CsO x nanoclusters were dispersed all over the metallic copper in no particular order. The CsO x species had an average width of 2 nm and ~1 Å height. The CsO x /Cu(111) systems exhibited the highest activity for the binding and dissociation of CO 2 , indicating that the CsO x -copper interface plays a key role in alcohol synthesis.

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

Magnetic and electronic structures of antiferromagnetic topological material candidate EuMg 2 Bi 2

In this work, EuMg 2 Bi 2 has been investigated to understand the electronic and magnetic behaviors as an antiferromagnetic (AFM) topological semimetal candidate. High-quality single crystals of EuMg 2 Bi 2 were grown via a Bi flux and, subsequently, characterized to be consistent with the previously reported bulk magnetic and resistivity properties. A ferromagnetic interaction is indicated by the positive Curie–Weiss temperature obtained through fitting the bulk magnetic susceptibility data. The bulk resistivity measurements reveal an interesting electronic behavior that is potentially influenced by a competing antiferromagnetic and ferromagnetic interaction in and out of the ab plane. From the resulting refinement of the neutron diffraction data, EuMg 2 Bi 2 was found to exhibit an A-type magnetic structure with Eu 2+ moments ferromagnetically aligned in the plane and antiferromagnetically stacked between neighbor ferromagnetic Eu layers. The power law fitting magnetic ordering parameter below TN~8 K agrees with the 2D Heisenberg model, indicating a weak interlayer antiferromagnetic interaction. Considering the magnetic structure determined by neutron diffraction, the surface state calculation suggests that EuMg 2 Bi 2 is an AFM topological insulator candidate. Linearly dispersed Dirac surface states were also observed in our angle-resolved photoemission spectroscopy measurements, consistent with the calculation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Synergistic effects of W–Ta alloys exposed to various ELM-like fusion events

Abstract Recently tungsten alloys have shown capabilities in suppressing morphological changes when exposed to harsh fusion conditions. Morphological changes due to He + and D + ions at high temperatures (1000–2000 K) can lead to easier erosion and sputtering of tungten (W) particles towards quenching the fusion plasma. This study investigated W–3Ta alloy as potential plasma facing materials (PFMs) exposed to different edge-localized mode (ELM)-like energies and ion loadings. Performance of W–3Ta has been tested as a function of ELM-like energies (0.6–1.5 GW m −2 ) and varying He + and D + ion concentrations (100% He + , 50% He + :50% D + ,10% He + :90% D + (similar ELM-like reactor condition), and 100% D + ions). Early-stage fuzz formation and surface pores were observed during 100% He + ion irradiation and mixed ion loadings but not observed during 100% D + ion loadings. Pores decreased in quantity and increased in size with increasing transient heat loading. Grain boundaries acted as trapping sites of helium and deuterium atoms during dual beam ion irradiations, as observed through increased pore size along the grain boundary. Qualitative erosion estimates were measured using witness plates. Increased erosion was observed with increasing D + ion concentration, which is attributed to D supersaturation in the near surface region affecting thermal and mechanical properties. More erosion was observed for W–3Ta samples compared to pure W, evident through large (>10 µ m) cracks on the surface, and an increase in W metal x-ray photoelectron spectroscopy peaks under similar loading conditions. The slight enhancement in erosion is attributed to the slightly decreased thermal properties, ∼10% thermal diffusivity drop, of W–3Ta at high temperatures. The damage threshold was impacted by ion loading, where distinct cracking was observed for 100% He + at a lower heat loading. This matrix study using reactor-like loading supports the need for extensive studies on future W alloy PFMs before selecting one as an alternative.

Physics↗
DOE OSTI2020

Water-promoted interfacial pathways in methane oxidation to methanol on a CeO 2 -Cu 2 O catalyst

Highly selective oxidation of methane to methanol has long been challenging in catalysis. Here, we reveal key steps for the pro­motion of this reaction by water when tuning the selectivity of a well-defined CeO 2 /Cu 2 O/Cu(111) catalyst from carbon monoxide and carbon dioxide to methanol under a reaction environment with methane, oxygen, and water. Ambient-pressure x-ray photoelectron spectroscopy showed that water added to methane and oxygen led to surface methoxy groups and accelerated methanol production. These results were consistent with density functional theory calculations and kinetic Monte Carlo simulations, which showed that water preferentially dissociates over the active cerium ions at the CeO 2 –Cu 2 O/Cu(111) interface. The adsorbed hydroxyl species blocked O-O bond cleavage that would dehydrogenate methoxy groups to carbon monoxide and carbon dioxide, and it directly converted this species to methanol, while oxygen reoxidized the reduced surface. Water adsorption also displaced the produced methanol into the gas phase.

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

Analysis of Liquids Using the Submerged Plasma for Isotopic Detection and Elemental Resolution (SPIDER)

We developed a sensor called the Submerged Plasma for Isotopic Detection and Elemental Resolution (SPIDER) probe, which uses an atmospheric pressure glow discharge below the surface of liquids to excite species in the liquid. Through emission spectroscopy of molten salts, liquid metals, and heavy water, we demonstrated the SPIDER probe’s high resolution, accuracy, and versatility. We successfully identified trace concentrations of transition and rare-earth metals in molten salts and detected the isotopic shift of the H β → D β emission line. Our analysis revealed unconventional spectral alkali line shapes, indicating two competing excitation modes: film explosion and droplet vaporization. The film explosion mode, characterized by dense plasma, exhibited self-reversal and broadband continuum emission, while the droplet vaporization mode, associated with diffusive plasma, produced narrow-line emissions. Furthermore, by analyzing circuit transients alongside individual plasma events, we observed that film explosions generate higher currents, likely due to a shorter plasma length as the current preferentially flows through the thin liquid layer. Altogether, our results highlight the SPIDER probe’s efficacy and flexibility, making it well-suited for online material quantification of liquids in extreme environments.

AES↗
DOE OSTI2020

Long interior carrier lifetime in selective-area InAs nanowires on silicon

Catalyst-free, position-controlled indium arsenide (InAs) nanowires (NWs) of variable diameters were grown on Si (111) by selective-area epitaxy (SAE). Ultrafast pump-probe spectroscopy was conducted, from which carrier recombination mechanisms on the NW surface and interior were resolved and characterized. NWs grown using SAE demonstrated high optical quality, showing minority carrier lifetimes more than two-fold longer than that of the randomly-positioned (RP) NWs. The extracted SAE-InAs NW interior recombination lifetime was found to be as long as 7.2 ns , 13X longer than previous measurements on RP-NWs; and the surface recombination velocity 4154 cm · s - 1 . Transmission electron microscopy revealed a high density of stacking defects within the NWs, suggesting that interior recombination lifetime can be further increased by improving NW interior crystalline quality.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Neural Density Estimation and Uncertainty Quantification for ChemCam Spectra [Slides]

The ChemCam instrument of Curiosity uses laser-induced breakdown spectroscopy (LIBS). It fires a laser at target and vaporizes rock surfaces, creating a plasma. Three spectrographs divide the plasma light into wavelengths for chemical analysis: ultraviolet, violet, and visible near-infrared. Regression methods (SVR, PCR, CNN) have been employed for calibration (prediction of the elemental composition of samples); however, labeled ChemCam samples are limited. Here, we focus on unsupervised learning and employ generative models from ChemCam analysis. Further, we use labels (supervised) in combination to the generative model to compute uncertainties related to predictions. We report generative modeling can be successfully applied to model real-world data. Normalizing flow models can be efficiently constructed on latent spaces for fast downstream inference. Unsupervised and supervised learning can be combined to form an uncertainty quantification framework.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Iodine Capture Studies of Copper- and Bismuth-Based Sorbents

The release of radioiodine, one of several radionuclides of concern when recycling used nuclear fuel (UNF), is an important consideration in the fuel cycle. In this study, two sorbent materials, Cu 0 -polyacrylonitrile (PAN) and Bi 0 -PAN, were tested as solid sorbent candidates for iodine capture. Experiments using a thin bed of sorbent material were exposed to vaporized iodine for over 300 hours (~2 weeks) under varied conditions in a dynamic flow environment. The overall performance was monitored in real-time using thermogravimetric analysis, and the materials were subsequently characterized for surface and bulk analysis using scanning electron microscopy – energy-dispersive spectroscopy (SEM-EDS) and powder x-ray diffraction (pXRD), respectively. Iodine (in the form of I 2 ) is expected to be released primarily in the dissolver off-gas (DOG) stream; therefore, this study demonstrates the effects of elemental iodine (I 2 ), water vapor (H 2 O), and nitrogen dioxide (NO 2 ). When exposed to ‘ideal’ conditions (in which I 2 is carried by dry air), Cu 0 -PAN and Bi 0 -PAN behave differently, with TGA analysis indicating that Cu 0 sorption performance is higher than that of Bi 0 , as evidenced by a larger mass change. Under ‘harsh’ conditions—such as a gaseous feed containing I 2 , H 2 O, and NO 2 vapors carried by air,—iodine capture performance for both Cu 0 - and Bi 0 -PAN are affected. SEM-EDS and pXRD analysis of these materials is discussed herein.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Trends in Carbon, Oxygen, and Nitrogen Core in the X-ray Absorption Spectroscopy of Carbon Nanomaterials: A Guide for the Perplexed

Successful deployment of carbon nanomaterials in many applications, such as sensing, energy storage, and catalysis, relies on the selection, synthesis, and tailoring of the surface properties. Predictive analysis of the behavior is difficult without detailed knowledge of the differences between various carbon nanomaterials and their surface functionalization, thus leaving the selection process to traditional trial-and-error work. The present characterization fills this knowledge gap for carbon nanomaterial surface properties with respect to chemical states and functionalization. We present an overview of the chemical trends that can be extracted from soft X-ray absorption spectroscopy (XAS) spectra on an extended set of nonideal carbon nanomaterials as a function of sp 2 bonded carbon and bond ordering. In particular, the surface chemical state, the presence of long-range order in the carbon matrix, and a qualitative estimation of the amount of oxygen and nitrogen and their respective functional group formation on the material surface, together with the detailed material fabrication parameters, are reported. The results expand our understanding of carbon nanomaterial functionalization, which can support material selection in practice, provided that the specifications of the application are known.

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

Highly Active Hydrogen Evolution Reaction (HER) Catalysts Formed by Energetic Pt n Cluster Deposition: Deposition Dynamics and the HER Mechanism

Mass-selected Pt n + (n ≤ 7) were deposited at variable energies on highly oriented pyrolytic graphite (HOPG), creating highly active hydrogen evolution reaction (HER) electrocatalysts. HER mass activities were ~2 to >10 times higher than those for the surface atoms in bulk Pt and for Pt n deposited on several other supports. Thus, high activity reflects the Pt-C structures formed by energetic Pt n -HOPG impacts, in addition to high Pt surface availability. The Pt n /HOPG electrodes were probed by X-ray photoelectron spectroscopy, low energy ion scattering, and electron microscopy. Born-Oppenheimer molecular dynamics (BOMD) was used to simulate Pt n - HOPG impacts, revealing the types of structures formed at different energies, then DFT was used to probe their most important HER pathways. For low deposition energies, the Pt n deposit onto the HOPG surface with sub-unit sticking probability, aggregating at defects. With increasing deposition energy, the sticking probability initially decreases, then rises to unity as subplantation and defect creation allow formation of strongly bonded platinum-carbon structures. Barriers for HER on these structures were found to be low and weakly dependent on Pt n size, consistent with experiment. The activities were highest for small covalently-bonded Pt-C structures created at high deposition energies. The larger aggregated structures formed at low energies were less active, but still substantially better than the bulk Pt surface monolayer. The catalysts were stable in repeated potential cycling at reducing potentials, but electrodes containing subplanted Pt became more active when scanned to oxidizing potentials, due to emergence of subplanted Pt onto the surface.

08 HYDROGEN↗
DOE OSTI2022

Removable coatings: Thermal stability and decontamination of steel surfaces from 241 Am

This study presents a comparative analysis of several strippable materials for decontamination of steel surfaces from 241 Am. The strippable coatings were chosen to have a history of application, to be commercially available, easily handled and have different composition and formulation. Carbon steel and stainless steel surfaces (coupons) were utilized as the most representative industrial materials, and the experimental series were expanded to include the rusting treatment of these surfaces as it is common for decommissioned old nuclear facilities. The experiments followed the path of pre-screening of the strippable materials (easiness of application, peeling etc.), their characterization with Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA), decontamination factors (DF) or removal efficiencies for different types of steel surfaces, and enhancement of the removal efficiencies of the select strippable coatings via amendment with EDTA. As a result, DF and removal efficiencies for stainless steel (both pristine and with rusting treatment) are higher than for pristine carbon steel, and decontamination factors and removal efficiencies are higher for pristine than for rusted carbon steel across all the coatings. It is also shown that EDTA amendment can improve DF and removal efficiency for a strippable coating (i.e., CC Strip), however other factors should also be considered. Thus, the coating CC Strip exhibited easiness in handling and high DF (up to 97% when EDTA-amended), but its drying period was the longest among the rest of the materials and its thermal decomposition indicates on a risk of intense release of heat in case of a fire event.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Topological Fermi-arc surface state covered by floating electrons on a two-dimensional electride

Two-dimensional electrides can acquire topologically non-trivial phases due to intriguing interplay between the cationic atomic layers and anionic electron layers. However, experimental evidence of topological surface states has yet to be verified. Here, via angle-resolved photoemission spectroscopy (ARPES) and scanning tunnelling microscopy (STM), we probe the magnetic Weyl states of the ferromagnetic electride [Gd 2 C] 2+ ·2e - . In particular, the presence of Weyl cones and Fermi-arc states is demonstrated through photon energy-dependent ARPES measurements, agreeing with theoretical band structure calculations. Notably, the STM measurements reveal that the Fermi-arc states exist underneath a floating quantum electron liquid on the top Gd layer, forming double-stacked surface states in a heterostructure. Our work thus not only unveils the non-trivial topology of the [Gd 2 C] 2+ ·2e - electride but also realizes a surface heterostructure that can host phenomena distinct from the bulk.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Tellurite Adsorption onto Bacterial Surfaces

Tellurium (Te) is an emerging contaminant and its chemical transformation in the environment is strongly influenced by microbial processes. In this study, we investigated the adsorption of tellurite [Te(IV), TeO 3 2- ] onto the common soil bacterium Bacillus subtilis. Thiol-blocking experiments were carried out to investigate the role of cell surface sulfhydryl sites in tellurite binding, and extended X-ray absorption fine structure (EXAFS) spectroscopy was performed to determine the chemical speciation of the adsorbed tellurite. The results indicate that tellurite reacts with sulfhydryl functional groups in the extracellular polymeric substances (EPS) produced by B. subtilis. Upon binding to sulfhydryl sites in the EPS, the Te changes from Te-O bonds to Te-S coordination. Further analysis of the surface-associated molecules shows that the EPS of B. subtilis contain proteins. Removal of the proteinaceous EPS dramatically decreases tellurite adsorption and the sulfhydryl surface site concentration. These findings indicate that sulfhydryl binding in EPS plays a key role in tellurite adsorption on bacterial surfaces.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Hydroxylation and Cation Segregation in (La 0.5 Sr 0.5 )FeO 3-$δ$ Electrodes

Simultaneously achieving high activity and stability is the primary challenge when engineering (electro)catalysts. Transition metal perovskite oxides are employed as air electrodes for solid-oxide fuel cells and electrolyzers. However, degradation of oxygen exchange kinetics at the solid–gas interface, often linked to alkaline-earth cation segregation and precipitation, limits widespread commercialization. Here, we systematically investigated the surface degradation mechanism induced by gas-phase impurities in La 0.5 Sr 0.5 )FeO 3-$δ$ (LSF55) thin-film electrodes by varying the concentration of H 2 O, SO 2 , and CO 2 . Degradation of the area-specific resistance in ambient and humidified synthetic air is significantly greater than in dry ambient and dry synthetic air, pointing to the importance of water vapor. Time-resolved, in situ ambient pressure X-ray photoelectron spectroscopy performed in O 2 showed that nonbulk Sr is present on the surface before the exposure to water vapor. Upon introduction of water vapor, neither additional Sr segregation nor precipitation driven by water vapor is a necessary condition for degradation. Rather, hydroxylation of the surface induces irreversible and significant degradation. At the same time, we show that Sr migration driven by water vapor is partially reversible. These fundamental insights can be used for the rational design of electrodes with improved catalytic stability.

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

Si-based materials for lithium-ion batteries V. n-SiO powder

X-ray photoelectron spectroscopy was used to analyze Si powders that have a native oxide surface, obtained from Paraclete Energy, Inc. The spectra were obtained using incident monochromatic Al K α radiation at 1486.6 eV (0.834 01 nm). An initial survey spectrum together with O 1s, C 1s, and Si 2p are presented. A final survey spectrum was collected to ascertain the amount of beam-induced damage, which appears to be minimal. Finally, the spectra indicate the principal core level photoelectron and Auger electron signals with only minor nitrogen signal and show the expected oxidized carbon and silicon species related to atmospheric exposure.

25 ENERGY STORAGE↗
DOE OSTI2024

The Surface Chemistry of Methanol on Pd(111) and H–Pd(111) Surfaces: C–O Bond Cleavage and the Effects of Metal Hydride Formation

Palladium catalysts are frequently employed in processes where methanol is an energy vector or carrier, being useful for the synthesis of methanol from mixtures of carbon dioxide and hydrogen (CO 2 /H 2 ) or its steam reforming on demand. Results of synchrotron-based ambient pressure X-ray photoelectron spectroscopy for the adsorption of methanol on a Pd(111) model catalyst show a rich surface chemistry and complex phenomena that strongly depend on pressure and temperature. At low pressures (< 10 -6 Torr) and temperatures (< 300 K), CO is the dominant decomposition product. Further, as the pressure increases, cleavage of C-H, O-H and C-O bonds is observed, and at elevated temperatures (400-600 K) the formation of CO and CH x /C fragments compete on the surface. Thus, existing reaction networks for methanol decomposition must be modified. Furthermore, surface and subsurface hydrogen (coming from PdH x ) play a significant role in the stability and removal of CH x and C species.

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

Defect-induced displacement of topological surface state in quantum magnet MnBi2Te4

The topological magnet MnBi2⁢Te4 (MBT), with gapped topological surface state, is an attractive platform for realizing quantum anomalous Hall and axion insulator states. However, the experimentally observed surface state gaps fail to meet theoretical predictions, although the exact mechanism behind the gap suppression has been debated. Recent theoretical studies suggest that intrinsic antisite defects push the topological surface state away from the MBT surface, closing its gap and making it less accessible to scanning probe experiments. Here, we report on the local effect of defects on the MBT surface states and demonstrate that high defect concentrations lead to a displacement of the surface states well into the MBT crystal, validating the theorized mechanism. The local and global influence of antisite defects on the topological surface states are studied with samples of varying defect densities by combining scanning tunneling microscopy, angle-resolved photoemission spectroscopy, and density functional theory. Our findings identify a combination of increased defect density and reduced defect spacing as the primary factors underlying the displacement of the surface states and suppression of surface gap, guiding further development of topological quantum materials.

Lupke, Felix [Carnegie Mellon University (CMU)]↗