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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution

We present a study of the lithium nickel manganese cobalt oxide (LiNi 0.6 Mn 0.2 Co 0.2 O 2 , NMC622) cathode-electrolyte interphase (CEI) during galvanostatic charging and discharging using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) methods to investigate the voltage dependent electrolyte solution structure changes at the interface, transition metal (TM) redox chemistry, and cathode/electrolyte interfacial layer evolution. Furthermore, our in situ cell design provides both reliable electrochemical device testing and strong FTIR vibrational absorption signals near the cathode surface. Specifically, advanced spectral analysis elucidates changes of near-surface Li+ ion (de)solvation by solvent molecules during galvanostatic cycling. Moreover, cathode metal-oxygen vibrational absorptions, sensitive to TM redox behaviors and subsequent local structural variations, were correlated to cathode de-lithiation (and lithiation) and electrolyte solution structure changes. In addition, we have detected the formation and evolution of a CEI surface layer on the NMC622 cathode that contributes to the cell's capacity fade.

25 ENERGY STORAGE↗
DOE OSTI2021

Regulators’ Energy Transition Primer: Economic Impacts of the Energy Transition on Energy Communities, Environmental Justice Considerations, and Implications on Clean Energy Jobs

Applications of new technology, such as horizontal drilling and hydraulic fracturing, enabled the United States to significantly increase its production of oil and natural gas during the last decade—the “Shale Gas Revolution.” As natural gas began to dominate the market with abundant supply and low prices, coal production and consumption have declined. Concurrently, the competitiveness of renewable energy and energy storage has climbed sharply, and analysts expect to see continued reductions in fossil fuel use in the coming decades. Many of these changes have been driven by market forces (i.e., low-cost natural gas and renewables), but current and future policy decisions aimed at tackling climate change concerns and reducing greenhouse gas emissions will also shape the future of the energy sector. This transition to low-carbon fuels has created both opportunities for clean energy technologies and challenges for communities traditionally dependent on fossil fuel-related industries. The power sector’s ongoing shift away from coal has left many coal miners and coal-fired power plant employees unemployed and often unprepared for jobs in other industries, including growing clean energy fields. This primer focuses on the declining coal industry, impacts on communities and workers, opportunities to transition workers who have lost their jobs to clean energy and other related sectors (including hydrogen-oriented jobs), recruitment and training strategies, and available programs and actions to make the shift to a low-carbon economy in a fair, just, and equitable manner by engaging the resources of federal and state governments, as well as the private sector.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Phase Transitions in Metal–Organic Frameworks Directly Monitored through In Situ Variable Temperature Liquid-Cell Transmission Electron Microscopy and In Situ X-ray Diffraction

Zr 6 -based metal–organic frameworks (MOFs) with tetratopic organic linkers have been extensively investigated owing to their versatile structural tunability. While diverse topologies and polymorphism in the resulting MOFs are often encountered with tetratopic linkers and Zr 6 nodes, reports on phase transitions within these systems are rare. Thus, we have a limited understanding of polymorph transformations, hindering the rational development of pure phase materials. In this study, a phase transition from a microporous MOF, scu-NU-906, to a mesoporous MOF, csq-NU-1008, was discovered and monitored through in situ variable temperature liquid-cell transmission electron microscopy (VT-LCTEM), high-resolution transmission electron microscopy (HRTEM), and in situ variable temperature powder X-ray diffraction (VT-PXRD). Furthermore, it was found that the microporous- to-mesoporous transformation in the presence of formic acid occurs via a concomitant dissolution–reprecipitation process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

High pressure structural phase transitions in Dysprosium to 202 GPa

High pressure structural phase transitions in heavy lanthanide metal Dysprosium (Dy) have been studied to 202 GPa (Volume Compression V/V 0 = 0.36) in a diamond anvil cell employing copper as an internal x-ray pressure standard. The previously assigned monoclinic (C2/m) phase above 72 GPa has been reexamined and assigned to an orthorhombic phase with sixteen atoms per cell (oF16) based on structural refinements. The equation of state is presented to 202 GPa and indicates a volume change of 2.3% during the structural phase transition from distorted face-centered cubic (hR24) phase to oF16 phase at 72 GPa. The oF16 phase can be regarded as a pseudo-orthorhombic eight-layered structure with (b/c) ratio decreasing from an ideal value of $\sqrt{3}$ with increasing pressure to 202 GPa. The ultrahigh pressure structural phases of Dy are compared with other members of the lanthanide series.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Observing the effects of numbers of valence nucleons on 0$^{+}_{𝑔⁡𝑠}$ → 2$^{+}_{1}$ transitions in deformed nuclei by comparing proton and neutron transition matrix elements

We examined the ratios of neutron and proton transition matrix elements, 𝑀 𝑛 /𝑀 𝑝 , for the 0$^{+}_{𝑔⁡𝑠}$ → 2$^{+}_{1}$ transitions in 48 even-even stable nuclei with 𝑁 > 20 for which electromagnetic matrix elements were compiled by Pritychenko et al. and for which high-quality inelastic proton-scattering data were available. Several deformed rare-earth nuclei have (𝑀 𝑛 /𝑀 𝑝 )/(𝑁/𝑍) values significantly below 1.0, which is not consistent with a simple liquid-drop picture. However, this phenomenon can be explained using a schematic picture in which 𝑀 𝑝 reaches a maximum at proton midshell (𝑍 = 66) and 𝑀𝑛 reaches its maximum at neutron midshell (𝑁 = 104). Several midmass vibrational nuclei have 𝑀 𝑛 /𝑀 𝑝 values significantly below 𝑁/𝑍, which is not consistent with the expectation that 𝑀 𝑛 /𝑀 𝑝 = 𝑁/𝑍 in such nuclei. As a result, a shell-model investigation of these observations might yield insights about this behavior.

Collective levels↗
DOE OSTI2023

Fort Erie Case Study - Transition from Fixed-Route to On-Demand Transit

Rural and smaller-sized communities in North America face unique mobility challenges due to their low population density, lower public transit spending per capita compared to major cities, and a high reliance on private vehicles. In recent years, communities such as Fort Erie, Ontario, have restructured or advanced their public transit systems using on-demand services. Fort Erie is a relatively sparsely populated region of 32,901 residents, spread across a land area of 166 square kilometers (64 square miles), for an average population density of 193 residents per square kilometer (500 per square mile). In October 2021, the town implemented a mobility-on-demand system integrated with smartphone software to replace its fixed-route community bus system, which consisted of four buses with three routes, each with a roughly 1-hour, one-way loop. The new service utilizes a fleet of six minivans, two of which are retrofitted with wheelchair-accessible ramps. The system may require that a passenger requesting a standard van walk up to 400 meters (a quarter mile) to their pickup location to optimize vehicle routing while providing origin-to-destination service. The on-demand system proved effective in providing service, eclipsing pre-pandemic ridership by 40%, decreasing greenhouse gas emissions per ride by 63%, and decreasing the cost to the town per ride by 29%. This report documents both the previous system and the new system in terms of routes, ridership, costs, fuel, and other notable system parameters. This work is part of an ongoing series of case studies on providing small communities with on-demand, right-sized vehicle service coupled with a smartphone application.

ADVANCED PROPULSION SYSTEMS,ENERGY PLANNING, POLIC↗
DOE OSTI2021

Predicting the onset of metal-insulator transitions in transition metal oxides-A first step in designing neuromorphic devices.

Several transition metal oxides, including La1-xSrxCoO3, are promising materials to realize resistive switching devices for neuromorphic applications, as they can undergo a metal-to-insulator transition (MIT) upon small perturbations to their electronic structure. Here, we focus on the MIT induced by varying the oxygen vacancy concentration, and we propose a model to predict the required electrical bias, based on three fundamental quantities: the vacancy formation energy, the permanent polarization in the material, and its dielectric constant. We obtain these quantities using first-principles electronic structure calculations, and we discuss strategies to minimize the electrical bias which may be adopted experimentally to design and optimize neuromorphic devices.

Zhang, Shenli↗
DOE OSTI2021

Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

The merger of photoredox catalysis with transition metal catalysis, termed metallaphotoredox catalysis, has become a mainstay in synthetic methodology over the past decade. Metallaphotoredox catalysis has combined the unparalleled capacity of transition metal catalysis for bond formation with the broad utility of photoinduced electron- and energy-transfer processes. Photocatalytic substrate activation has allowed the engagement of simple starting materials in metal-mediated bond-forming processes. Moreover, electron or energy transfer directly with key organometallic intermediates has provided novel activation modes entirely complementary to traditional catalytic platforms. Finally, this Review details and contextualizes the advancements in molecule construction brought forth by metallaphotocatalysis.

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

Pronounced Pressure Dependence of Electronic Transitions for Americium Compared to Isomorphous Neodymium and Samarium Mellitates

The mellitate ion is relevant in spent nuclear fuel processing and is utilized as a surrogate for studying the interactions of f elements with humic acids. A wealth of different coordination modes gives the potential for diverse structural chemistry across the actinide series. In this study, an americium mellitate, 243 Am 2 [(C 6 (COO – ) 6 ](H 2 O) 8 ·2H 2 O (1-Am), has been synthesized and characterized using structural analysis and spectroscopy at ambient and elevated pressures. 1-Am was then compared to isomorphous neodymium (1-Nd) and samarium (1-Sm) mellitates via bond-length analysis and pressure dependence of their Laporte-forbidden f → f transitions. Results show that the pressure dependence of the f → f transitions of 1-Am is significantly greater than that observed in 1-Nd and 1-Sm, with average shifts of 21.4, 4.7, and 3.6 cm –1 /GPa, respectively. Finally, this greater shift found in 1-Am shows further evidence that the 5f orbitals are more affected than the 4f orbitals when pressure is applied to isostructural compounds.

Actinides↗
DOE OSTI2021

Two Polymorphs of BaZn 2 P 2 : Crystal Structures, Phase Transition, and Transport Properties

Here, the novel α-BaZn 2 P 2 structural polymorph has been synthesized and structurally characterized for the first time. Its structure, elu-cidated from single crystal X-ray diffraction, indicates that the compound crystallizes in the orthorhombic α-BaCu 2 S 2 structure type, with unit cell parameters a = 9.7567(14) Å, b = 4.1266(6) Å, and c = 10.6000(15) Å. With β-BaZn 2 P 2 being previously iden-tified as belonging to the ThCr 2 Si 2 family, and with the precedent of structural phase transitions between the α-BaCu 2 S 2 type and the ThCr 2 Si 2 type, the potential for the pattern to be extended to the two different structural forms of BaZn 2 P 2 was explored. Thermal analysis suggest that a first order phase transition occurs at ~1123 K, whereby the low-temperature orthorhombic α-phase transforms to a high-temperature tetragonal β-BaZn 2 P 2 ; the structure of which was also studied and confirmed by single-crystal X-ray diffraction. Preliminary transport properties and band structure calculations indicate that α-BaZn 2 P 2 is a p-type, narrow-gap semiconductor with a direct bandgap (Eg) of 0.5 eV. The Seebeck coefficient, S(T), for the material increases steadily from the room temperature value of 119 µV/K to 184 µV/K at 600 K. The electrical resistivity of α-BaZn 2 P 2 is relatively high, on the order of 40 mΩ·cm, and the ρ(T) dependence shows gradual decrease upon heating. Such behavior is comparable to those of the typical semimetals or degenerate semiconductors. Although the observed values of the as-synthesized samples are not optimal, the carrier concentration can apparently be tuned to fall between the values of metals and semiconductors, thus providing an open window for optimizing this phase towards achieving an enhanced thermoelectric figure of merit zT. The calculated indirect band gap for the β-BaZn 2 P 2 phase is Eg = 0.03 eV which is about an order of magnitude lower than that of α-BaZn 2 P 2 . It is expected that the cage-like structural motif and layered structure possessed by α-BaZn 2 P 2 and β-BaZn 2 P 2 phases, respectively, would promote the realiza-tion of a low thermal conductivity in both compounds.

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

Plastic recognition and electrogenic uniport translocation of 1 st -, 2 nd -, and 3 rd -row transition and post-transition metals by primary-active transmembrane P 1B-2 -type ATPase pumps

Transmembrane P 1B -type ATPase pumps catalyze the extrusion of transition metal ions across cellular lipid membranes to maintain essential cellular metal homeostasis and detoxify toxic metals. Zn(II)-pumps of the P 1B-2 -type subclass, in addition to Zn 2+ , select diverse metals (Pb 2+ , Cd 2+ and Hg 2+ ) at their transmembrane binding site and feature promiscuous metal-dependent ATP hydrolysis in the presence of these metals. Yet, a comprehensive understanding of the transport of these metals, their relative translocation rates, and transport mechanism remain elusive. We developed a platform for the characterization of primary-active Zn(II)-pumps in proteoliposomes to study metal selectivity, translocation events and transport mechanism in real-time, employing a “multi-probe” approach with fluorescent sensors responsive to diverse stimuli (metals, pH and membrane potential). Together with atomic-resolution investigation of cargo selection by X-ray absorption spectroscopy (XAS), we demonstrate that Zn(II)-pumps are electrogenic uniporters that preserve the transport mechanism with 1 st -, 2 nd - and 3 rd -row transition metal substrates. Promiscuous coordination plasticity, guarantees diverse, yet defined, cargo selectivity coupled to their translocation.

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

Structure and phase transitions in niobium and tantalum derived nanoscale transition metal perovskites, Ba(Ti,MV)O3, M=Nb,Ta

The prospect of creating ferroelectric or high permittivity nanomaterials provides motivation for investigating complex transition metal oxides of the form Ba(Ti, MV)O3, where M = Nb or Ta. Solid state processing typically produces mixtures of crystalline phases, rarely beyond minimally doped Nb/Ta. Using a modified sol-gel method, we prepared single phase nanocrystals of Ba(Ti, M)O3. Compositional and elemental analysis puts the empirical formulas close to BaTi0.5Nb0.5O3−δ and BaTi0.5Ta0.5O3−δ. For both materials, a reversible temperature dependent phase transition (non-centrosymmetric to symmetric) is observed in the Raman spectrum in the region 533–583 K (260–310 °C); for Ba(Ti, Nb)O3, the onset is at 543 K (270 °C); and for Ba(Ti, Ta)O3, the onset is at 533 K (260 °C), which are comparable with 390–393 K (117–120 °C) for bulk BaTiO3. The crystal structure was resolved by examination of the powder x-ray diffraction and atomic pair distribution function (PDF) analysis of synchrotron total scattering data. It was postulated whether the structure adopted at the nanoscale was single or double perovskite. Double perovskites (A2B′B″O6) are characterized by the type and extent of cation ordering, which gives rise to higher symmetry crystal structures. PDF analysis was used to examine all likely candidate structures and to look for evidence of higher symmetry. The feasible phase space that evolves includes the ordered double perovskite structure Ba2(Ti, MV)O6 (M = Nb, Ta) Fm-3m, a disordered cubic structure, as a suitable high temperature analog, Ba(Ti, MV)O3Pm-3m, and an orthorhombic Ba(Ti, MV)O3Amm2, a room temperature structure that presents an unusually high level of lattice displacement, possibly due to octahedral tilting, and indication of a highly polarized crystal.

Chemistry↗
DOE OSTI2021

Enhancing the formation of ionic defects to study the ice Ih/XI transition with molecular dynamics simulations

Ice Ih, the common form of ice in the biosphere, contains proton disorder. Its proton-ordered counterpart, ice XI, is thermodynamically stable below 72 K. However, the formation of ice XI is kinetically hindered, and experimentally it is obtained by doping with KOH. Doping creates ionic defects that promote the migration of protons and the associated change in proton configuration. In this article, we mimic the effect of doping with a bias potential that enhances the formation of ionic defects in molecular dynamics simulations. The recombination of the ions thus formed proceeds through fast migration of the hydroxide along hydrogen bond loops, providing a physical and expedite way to change the proton configuration. Here, a key ingredient of this approach is a machine learning potential trained with density functional theory data and capable of modelling molecular dissociation. We exemplify the usefulness of this idea by studying the order-disorder transition using an appropriate order parameter that distinguishes the proton environments in ice Ih and XI. We calculate the changes in free energy, enthalpy, and entropy associated with the transition. Our estimated entropy agrees with experiment within the error bars of the calculation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Reaching the prolate-oblate boundary at 𝑁=116 via first fragmentation of a 198 Pt beam: Sharp transition to triaxiality in 189 Ta

High-spin isomers in very-neutron-rich 𝐴≈190 Hf-Ta-W nuclei were populated via the pioneering fragmentation of a 198 Pt primary beam at the National Superconducting Cyclotron Laboratory. The nuclei were implanted in a Si detector stack surrounded by the Gamma-Ray Energy Tracking In-beam Nuclear Array (GRETINA) to detect delayed 𝛾 rays, providing first level schemes using 𝛾−𝛾 coincidence data from isomeric decays in this previously inaccessible region of the nuclear chart. Here, a sudden transition to a strong triaxial shape is observed in the very-neutron-rich 189 Ta (𝑁 = 116) nucleus from axially prolate shapes in lighter Ta isotopes, providing a critical experimental benchmark for competing theoretical predictions of nuclear-shape evolution.

150 ≤ A ≤ 189↗