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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Tunable Spectral Ordering of Magnetic Plasmon Resonances in Noble Metal Nanoclusters

Experimental characterization of the optical and magnetic properties of noble metal nanoclusters has exposed a size regime in between single-ring and extended two-dimensional nanocluster networks where the behavior of magnetic plasmon resonances is not well understood. In this intermediate size regime, individual electric dipole plasmons on each nanoparticle within the cluster can hybridize into delocalized magnetic modes that couple to either the electric or magnetic field of light with seemingly arbitrary energy ordering. In this work, using a coupled-dipole model that includes fully retarded interactions between electric dipole plasmons, we show that magnetic plasmon resonance energies can be controllably tuned and even made to cross as a function of nanocluster size. Experimental confirmation of this prediction is challenging because optical selection rules dictate the simultaneous excitation of many spectrally overlapping magnetic plasmon modes. However, based on analytic modeling and numerical simulation, we show that angle-resolved cathodoluminescence offers an approach to cleanly isolate these magnetic modes and observe the size-dependence of their spectrum. Not only does our work clarify the rich optical and magnetic behavior of noble metal nanoclusters in the intermediate-size regime, but it also suggests strategies to design negative-index plasmonic metamaterials with multiple tunable resonances in the visible spectrum.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory Study

We present a first-principles, self-consistent periodic density functional theory (PW91-GGA) study of formic acid (HCOOH) decomposition on model (111) and (100) facets of eight fcc metals (Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh) and (0001) facets of four hcp (Co, Os, Ru, and Re) metals. The calculated binding energies of key formic acid decomposition intermediates including formate (HCOO), carboxyl (COOH), carbon monoxide (CO), water (H2O), carbon dioxide (CO2), hydroxyl (OH), carbon (C), oxygen (O), and hydrogen (H; H2) are presented. Using these energetics, we develop thermochemical potential energy diagrams for both the carboxyl-mediated and the formate-mediated dehydrogenation mechanisms on each surface. We evaluate the relative stability of COOH, HCOO, and other isomeric intermediates (i.e., CO + OH, CO2 + H, CO + O + H) on these surfaces. These results provide insights into formic acid decomposition selectivity (dehydrogenation versus dehydration), and in conjunction with calculated vibrational frequency modes, the results can assist with the experimental search for the elusive carboxyl (COOH) surface intermediate. Results are compared against experimental reports in the literature.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

Conversion Reaction Mechanisms in Lithium Ion Batteries: Study of the Binary Metal Fluoride Electrodes

Materials that undergo a conversion reaction with lithium (e.g., metal fluorides MF{sub 2}: M = Fe, Cu, ...) often accommodate more than one Li atom per transition-metal cation, and are promising candidates for high-capacity cathodes for lithium ion batteries. However, little is known about the mechanisms involved in the conversion process, the origins of the large polarization during electrochemical cycling, and why some materials are reversible (e.g., FeF{sub 2}) while others are not (e.g., CuF{sub 2}). In this study, we investigated the conversion reaction of binary metal fluorides, FeF{sub 2} and CuF{sub 2}, using a series of local and bulk probes to better understand the mechanisms underlying their contrasting electrochemical behavior. X-ray pair-distribution-function and magnetization measurements were used to determine changes in short-range ordering, particle size and microstructure, while high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) were used to measure the atomic-level structure of individual particles and map the phase distribution in the initial and fully lithiated electrodes. Both FeF{sub 2} and CuF{sub 2} react with lithium via a direct conversion process with no intercalation step, but there are differences in the conversion process and final phase distribution. During the reaction of Li{sup +} with FeF{sub 2}, small metallic iron nanoparticles (<5 nm in diameter) nucleate in close proximity to the converted LiF phase, as a result of the low diffusivity of iron. The iron nanoparticles are interconnected and form a bicontinuous network, which provides a pathway for local electron transport through the insulating LiF phase. In addition, the massive interface formed between nanoscale solid phases provides a pathway for ionic transport during the conversion process. These results offer the first experimental evidence explaining the origins of the high lithium reversibility in FeF{sub 2}. In contrast to FeF{sub 2}, no continuous Cu network was observed in the lithiated CuF{sub 2}; rather, the converted Cu segregates to large particles (5-12 nm in diameter) during the first discharge, which may be partially responsible for the lack of reversibility in the CuF{sub 2} electrode.

Wang, Feng↗
DOE OSTI2014

Oxidation of ethane to ethanol by N 2 O in a metal-organic framework with coordinatively unsaturated iron(II) sites

Enzymatic haem and non-haem high-valent iron–oxo species are known to activate strong C–H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron–oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)–oxo compounds. In particular, although nature's non-haem iron(IV)–oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal–organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal–organic framework Fe 2 (dobdc) (dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe 0.1 Mg 1.9 (dobdc), are able to activate the C–H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)–oxo species.

Xiao, Dianne J.↗
DOE OSTI2015

Probing the mechanism of CO 2 capture in diamine-appended metal–organic frameworks using measured and simulated X-ray spectroscopy

Diamine-appended metal–organic frameworks display great promise for carbon capture applications, due to unusual step-shaped adsorption behavior that was recently attributed to a cooperative mechanism in which the adsorbed CO 2 molecules insert into the metal–nitrogen bonds to form ordered ammonium carbamate chains. We present a detailed study of this mechanism by in situ X-ray absorption spectroscopy and density functional theory calculations. Distinct spectral changes at the N and O K-edges are apparent upon CO 2 adsorption in both mmen-Mg 2 (dobpdc) and mmen-Mn 2 (dobpdc), and these are evaluated based upon computed spectra from three potential adsorption structures. The computations reveal that the observed spectral changes arise from specific electronic states that are signatures of a quasi-trigonal planar carbamate species that is hydrogen bonded to an ammonium cation. This eliminates two of the three structures studied, and confirms the insertion mechanism. Here, we note the particular sensitivity of X-ray absorption spectra to the insertion step of this mechanism, underpinning the strength of the technique for examining subtle chemical changes upon gas adsorption.

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

Predicting metal–metal interactions. I. The influence of strain on nanoparticle and metal adlayer stabilities

Strain-engineering of bimetallic nanomaterials is an important design strategy for developing new catalysts. In this paper, we introduce an approach for including strain effects into a recently introduced, density functional theory (DFT)-based alloy stability model. The model predicts adsorption site stabilities in nanoparticles and connects these site stabilities with catalytic reactivity and selectivity. Strain-based dependencies will increase the model’s accuracy for nanoparticles affected by finite-size effects. In addition to the stability of small nanoparticles, strain also influences the heat of adsorption of epitaxially grown metal-on-metal adlayers. In this respect, we successfully benchmark the strain-including alloy stability model with previous experimentally determined trends in the heats of adsorption of Au and Cu adlayers on Pt (111). For these systems, our model predicts stronger bimetallic interactions in the first monolayer than monometallic interactions in the second monolayer. We explicitly quantify the interplay between destabilizing strain effects and the energy gained by forming new metal–metal bonds. While tensile strain in the first Cu monolayer significantly destabilizes the adsorption strength, compressive strain in the first Au monolayer has a minimal impact on the heat of adsorption. Hence, this study introduces and, by comparison with previous experiments, validates an efficient DFT-based approach for strain-engineering the stability, and, in turn, the catalytic performance, of active sites in bimetallic alloys with atomic level resolution.

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

Methods of producing metal sulfides, metal selenides, and metal sulfides/selenides having controlled architectures using kinetic control

The present invention is directed to methods of preparing metal sulfide, metal selenide, or metal sulfide/selenide nanoparticles and the products derived therefrom. In various embodiments, the nanoparticles are derived from the reaction between precursor metal salts and certain sulfur- and/or selenium-containing precursors each independently having a structure of Formula (I), (II), or (III), or an isomer, salt, or tautomer thereof, where Q1, Q2, Q3, R1, R2, R3, R5, and X are defined within the specification.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Method embodiments for making lanthanide metal complexes from lanthanide metal oxides and separating the same from heavy lanthanide metal oxides, actinide oxides, and non-lanthanide rare earth element oxides

The present disclosure is directed to method embodiments for making anhydrous lanthanide halide complexes. At least some embodiments comprise making a lanthanide halide complex by reacting a lanthanide metal oxide with an oxygen scavenger and catalyst in the presence of a donor solvent. The method is selective toward light lanthanide metal oxides and thus further provides a method for separating light lanthanide metal oxides from heavy lanthanide metal oxides, actinide oxides, and non-lanthanide rare earth element oxides.

Kiplinger, Jaqueline Loetsch↗
DOE OSTI2022

Mode I tensile fracture behavior of adhesively-bonded metal–metal, metal–CFRP, and CFRP–CFRP bi-material combinations analyzed by size effect method

Understanding the adhesive and interfacial fracture is important for developing and achieving better adhesive jointing in bi-materials, the location which becomes less vulnerable in engineered structure components. Still, to characterize the fracturing behavior of various adhesively-bonded materials, it was shown in this work that the Mode I fracture energies estimated from conventional methods (e.g., work-of-fracture, (modified) compliance calibration method, (modified) beam theory, etc.) can be strongly affected by adherent thickness, adhesive bond length, and material type. Consequently, this hindered the proper understanding of fracturing in adhesive jointing of bi-materials since the estimated fracture energies can exhibit unreasonable difference among various material combinations, thus leading to the confusion in the literature due to the unfair comparison on these non-objective results estimated by leveraging conventional methods on the specimens with different geometries. This work compared size effect method with conventional methods on the calculation of the Mode I fracture energies of metal-metal, metal-CFRP, and CFRP-CFRP material combinations via Double Cantilever Beam (DCB) tests. The results showed that the estimated fracture energies of various material combinations are not dependent on the specimen geometries. This aspect allowed the fair comparison particularly on the interfacial fracturing between metal/adhesive and CFRP/adhesive, and the difference was further explained and correlated with the damage morphology on the material surface after failure identified through three-dimensional profilometer.

36 MATERIALS SCIENCE↗
DOE OSTI2023

A study of adhesive bonding in metal–metal, metal–CFRP, and CFRP–CFRP material combinations under shear deformation: Fracture morphologies and damage mechanisms

Safe design of adhesive joining in multi-materials in engineered structures requires the accumulation of numerous experimental data on the failure behavior of various adhesively-bonded material combinations under different loading conditions. The deep understanding of mechanical performance, fracturing morphologies, and main damage mechanisms is also quintessential for accelerating the development of proper physics-based and multi-scale models for assisting the design. Towards this goal, this work presents a comprehensive characterization of the failure behavior of adhesively-bonded metal–metal, metal–CFRP, and CFRP–CFRP material combinations under global shear deformation via single lap shear testing. Thanks to a synergistic combination of measurement methods by using Digital Imaging Correlation (DIC) and 3D optical profilometry, adhesive features on the adherend after failure were quantified and the main progressive damage mechanisms were identified. The characterization performed in this work provides quantitative data that contributes to a better understanding of shear failure in adhesive bonding across different bi-material combinations. Finally, the obtained results have practical implications, including the potential to enhance adhesive bonding design, identify failure causes in adhesive joints, and develop or validate computational models capable of capturing the observed behavior in various adhesively-bonded materials under global shear deformation.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Unraveling the convoluted and dynamic interphasial mechanisms on Li metal anode

Accurate understanding of the chemistry of solid-electrolyte interphase (SEI) is key to developing new electrolytes for high-energy batteries using lithium metal (Li-0) anodes(1). SEI is generally believed to be formed by the reactions between Li-0 and electrolyte(2,3). However, our new study shows this is not the whole story. Through synchrotron-based X-ray diffraction and pair distribution function analysis, we reveal a much more convoluted formation mechanism of SEI, which receives considerable contributions from electrolyte, cathode, moisture and native surface species on Li-0, with highly dynamic nature during cycling. Using isotope labelling, we traced the origin of LiH to electrolyte solvent, moisture and a new source: the native surface species (LiOH) on pristine Li-0. When lithium accessibility is very limited as in the case of anode-free cells, LiOH develops into plate-shaped large crystals during cycling. Alternatively, when the lithium source is abundant, as in the case of Li||NMC811 cells, LiOH reacts with Li-0 to form LiH and Li2O. While the desired anion-derived LiF-rich SEI is typically found in the concentrated electrolytes or their derivatives, we found it can also be formed in low-concentration electrolyte via the crosstalk effect, emphasizing the importance of formation cycle protocol and opening up opportunities for low-cost electrolyte development.

Polzin, Bryant J.↗
DOE OSTI2016

A unified relation for the solid-liquid interface free energy of pure FCC, BCC, and HCP metals

We study correlations between the solid-liquid interface (SLI) free energy and bulk material properties (melting temperature, latent heat, and liquid structure) through the determination of SLI free energies for bcc and hcp metals from molecular dynamics (MD) simulation. Values obtained for the bcc metals in this study were compared to values predicted by the Turnbull, Laird, and Ewing relations on the basis of previously published MD simulation data. We found that of these three empirical relations, the Ewing relation better describes the MD simulation data. Moreover, whereas the original Ewing relation contains two constants for a particular crystal structure, we found that the first coefficient in the Ewing relation does not depend on crystal structure, taking a common value for all three phases, at least for the class of the systems described by embedded-atom method potentials (which are considered to provide a reasonable approximation for metals).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Metal-poor stars observed with the Magellan Telescope. III. New extremely and ultra metal-poor stars from SDSS/SEGUE and insights on the formation of ultra metal-poor stars

We report the discovery of one extremely metal-poor (EMP; [Fe/H] < −3) and one ultra metal-poor (UMP; [Fe/H] < −4) star selected from the Sloan Digital Sky Survey/Sloan Extension for Galactic Understanding and Exploration survey. These stars were identified as EMP candidates based on their medium-resolution (R ∼2000) spectra, and were followed up with high-resolution (R ∼ 35,000) spectroscopy with the Magellan/Clay Telescope. Their derived chemical abundances exhibit good agreement with those of stars with similar metallicities. We also provide new insights on the formation of the UMP stars, based on comparisons with a new set of theoretical models of supernovae (SNe) nucleosynthesis. The models were matched with 20 UMP stars found in the literature, together with one of the program stars (SDSS J1204+1201), with [Fe/H]=−4.34. From fitting their abundances, we find that the SNe progenitors, for stars where carbon and nitrogen are measured, had masses ranging from 20.5 M{sub ⊙} to 28 M{sub ⊙} and explosion energies from 0.3 to 0.9×10{sup 51} erg. These results are highly sensitive to the carbon and nitrogen abundance determinations, which is one of the main drivers for a future high-resolution follow-up of UMP candidates. In addition, we are able to reproduce the different CNO abundance patterns found in UMP stars with a single progenitor type by varying its mass and explosion energy.

79 ASTRONOMY AND ASTROPHYSICS↗