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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Insulating band gaps both below and above the Néel temperature in d -electron LaTi O 3 , LaV O 3 , SrMn O 3 , and LaMn O 3 perovskites as a symmetry-breaking event

Metal d-electron oxides having an odd number of electrons per cell should exhibit band degeneracy at the Fermi energy, making them, in band theory, formally metallic. In many cases, however, these are “false metals”, as evidenced by the observation that many ABO 3 oxide perovskites with a magnetic 3d B-atom are observed to be insulators both below and above the Néel temperature. These inconsistencies between experimental observation and expectation have historically been resolved by invoking degeneracy-breaking physics, based largely on -pure electron effects, such as strong interelectronic correlation for d-electron compounds (the Mott mechanism). Such explanations generally consider microscopic lattice or magnetic degrees of freedom (m-DOF) as largely passive spectators, not a cause of the formally metallic being an insulator. Yet, it has long been known that ABO 3 perovskites can manifest an arrangement of m-DOFs in the form of octahedral tilting, bond dimerization, Jahn-Teller distortions, and ordering of local magnetic moments. It appears reasonable that such structural and magnetic local degrees of freedom need to be allowed to compete with purely electronic strong correlation. To answer this question, we explored a range of d-electron oxide perovskites exemplified by the archetypes LaTiO 3 , LaVO 3 , SrMnO 3 , and LaMnO 3 with 1, 2, 3, or 4 d -electrons, respectively. Using a mean-field-like electronic structure method (here, density functional theory), we find that a combination of magnetic symmetry breaking with structural distortions can account for insulating band gaps in this series while at the same time correctly predicting for the control case an intrinsic paramagnetic metal in SrVO 3 as symmetry-breaking is insufficiently strong to remove the degeneracy. Finally, this indicates that calculating quantitatively local magnetic and positional symmetry-breaking motifs in unit cells that avoid averaging at the outset over the low symmetry motifs can provide consistent trends in a Mott transition without Mott U.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Oxygen Affinity: The Missing Link Enabling Prediction of Proton Conductivities in Doped Barium Zirconates

Proton-conducting oxides, specifically doped barium zirconates, have garnered much attention as electrolytes for solid-state electrochemical devices operable at intermediate temperatures (400–600 °C). In chemical terms, hydration energy, E hyd , and proton–dopant association energy, E as , are two key parameters that determine whether an oxide exhibits fast proton conduction, but to date ab initio studies have for the most part studied each parameter separately, with no clear correlation with proton conductivity identified in either case. Here, we demonstrate that the oxygen affinity, E O.dopant , defined as the energy released when an oxide ion enters an oxygen vacancy close to a dopant atom, is the missing link between these two parameters and correlates well with experimental proton conductivities in doped barium zirconates. Ab initio calculations of point defects and their complexes in Sc-, In-, Lu-, Er-, Y-, Gd-, and Eu-doped barium zirconates are used to determine E hyd , E as , E O.dopant , and the hydrogen affinity, E H.host , of each system. These four energy terms are related by E hyd = E O.dopant + 2E H.host + 2E as . Complementary impedance spectroscopy measurements reveal that the stronger the calculated oxygen affinity of a system, the higher the proton conductivity at 350 °C. Although the proton trapping site is also an important factor, the results show that oxygen affinity is an excellent predictor of proton conductivity in these materials.

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

Engineering metal oxidation using epitaxial strain

The oxides of platinum group metals are promising for future electronics and spintronics due to the delicate interplay of spin-orbit coupling and electron correlation energies. However, their synthesis as thin films remains challenging due to their low vapour pressures and low oxidation potentials. Here we show how epitaxial strain can be used as a control knob to enhance metal oxidation. Using Ir as an example, we demonstrate the use of epitaxial strain in engineering its oxidation chemistry, enabling phase-pure Ir or IrO 2 films despite using identical growth conditions. The observations are explained using a density-functional-theory-based modified formation enthalpy framework, which highlights the important role of metal-substrate epitaxial strain in governing the oxide formation enthalpy. We also validate the generality of this principle by demonstrating epitaxial strain effect on Ru oxidation. The IrO 2 films studied in our work further revealed quantum oscillations, attesting to the excellent film quality. The epitaxial strain approach we present could enable growth of oxide films of hard-to-oxidize elements using strain engineering.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Hund’s flat band in a frustrated spinel oxide

Electronic flat bands associated with quenched kinetic energy and heavy electron mass have attracted great interest for promoting strong electronic correlations and emergent phenomena such as high-temperature charge fractionalization and superconductivity. Intense experimental and theoretical research has been devoted to establishing the rich nontrivial metallic and heavy fermion phases intertwined with such localized electronic states. Here, in this study, we investigate the transition metal oxide spinel LiV 2 O 4 , an enigmatic heavy fermion compound lacking localized f orbital states. We use angle-resolved photoemission spectroscopy and dynamical mean-field theory to reveal a kind of correlation-induced flat band with suppressed interatomic electron hopping arising from intra-atomic Hund’s coupling. The appearance of heavy quasiparticles is ascribed to a proximate orbital-selective Mott state characterized by fluctuating local moments as evidenced by complementary magnetotransport measurements. The spectroscopic fingerprints of long-lived quasiparticles and their disappearance with increasing temperature further support the emergence of a high-temperature “bad” metal state observed in transport data. This work resolves a long-standing puzzle on the origin of heavy fermion behavior and unconventional transport in LiV 2 O 4 . Simultaneously, it opens a path to achieving flat bands through electronic interactions in d-orbital systems with geometrical frustration, potentially enabling the realization of exotic phases of matter such as the fractionalized Fermi liquids.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Substituted SrFeO 3 as robust oxygen sorbents for thermochemical air separation: correlating redox performance with compositional and structural properties

Thermochemical air separation via cyclic redox reactions of oxide-based oxygen sorbents has the potential to achieve high energy efficiency. Although a number of promising sorbents have been investigated, further improvements in sorbent performance through a fundamental understanding of the structure–performance relationships are highly desirable. In this study, we systematically investigated the effects of A and B site dopants on the oxygen uptake/release properties (i.e., vacancy formation energy, reduction enthalpy, oxygen release temperature, and oxygen capacity) of the SrFeO 3 family of perovskites as oxygen sorbents. A monotonic correlation between DFT calculated oxygen vacancy formation energy and oxygen release temperature demonstrates the effectiveness of DFT for guiding sorbent selection. Combining vacancy formation energy with stability analysis, dopants such as Ba and Mn have been identified for tuning the redox property of SrFeO 3 sorbents, and increasing the oxygen capacity for temperature and pressure swings when compared to undoped SrFeO 3 . The Mn doped sample proved to be highly stable, with less than a 3% decrease in capacity over 1000 cycles. Although the dynamic nature of the redox process makes it difficult to use a single vacancy formation energy as the descriptor, a systematic approach was developed to correlate the oxygen storage capacities with the sorbents’ compositional properties and vacancy formation energies. The combination of DFT calculations with experimental studies from this study provides a potentially effective strategy for developing improved sorbents for thermochemical air separation.

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

Nanoporous Fe 2 O 3 and Soluble Fe(II) Intermediates Accelerate the Electrodeposition of Fe in NaOH(aq)

Electrochemical conversion of iron oxide to iron metal can enable low-cost batteries for long duration energy storage and zero-emissions ironmaking for steel. Iron oxides, such as hematite, can be electrochemically reduced to metallic iron in concentrated alkaline electrolytes at modest temperatures, but the relative influences of solid-state and dissolved intermediates at practical reaction rates remains unclear. Here, in this study, we prepare a homologous set of well-defined hematite particles to measure how the nanoscale morphology of oxides controls both their reactivity and apparent reduction mechanism in concentrated hydroxide. Correlated electron microscopy and rotating-ring-disk-electrode measurements revealed that nanoporous hematite and solid intermediates formed iron via a dissolution-redeposition pathway. In contrast, dense hematite particles directly formed iron metal via reactive fracture. While previous studies on iron electrowinning have primarily emphasized the role of particle diameter at the micron scale, these results demonstrate the importance of the dissolution-redeposition pathway to support rapid reaction rates and suggest that nanoscale porosity controls iron oxide reactivity at temperatures <100 °C. Therefore, iron-oxide-to-metal electrolyzers and fast-charging iron-air batteries supported by curtailed electricity can increase the rate of metal formation by accelerating fracture and dissolution in reactant oxides.

TEM↗
DOE OSTI2024

Critical Assessment of Electronic Structure Descriptors for Predicting Perovskite Catalytic Properties

The discovery and design of materials which can efficiently catalyze the oxygen reduction and evolution reactions at reduced temperatures is important for facilitating the widespread adoption of fuel cell and electrolyzer technologies. Numerous studies have produced correlations between catalytic properties, such as oxygen surface exchange or electrode area specific resistance (ASR), and properties of the catalyst material. However, correlations have historically been limited in scope (e.g., using only a few materials or at a single temperature) and it has been difficult to provide detailed assessments of their robustness. Here, in this study, we assess the ability of the O p-band center electronic structure descriptor, obtained from density functional theory (DFT) calculations, to correlate with oxygen surface exchange rates, diffusivities, and area specific resistances for a large database of perovskite oxide catalytic properties. By data mining the literature, we obtain 747 catalytic property value data points spanning 299 unique perovskite compositions from 313 studies. We assess linear correlations of each property with the O p-band center and find generally modest correlations that are qualitatively useful (prediction mean absolute errors of about 0.5 log units are typical), where the correlations are improved at higher temperatures (e.g., 800 °C vs. 500 °C) and significantly improve when considering fits to the subset of materials which have multiple independent measurements. These findings suggest that the spread of property data is significantly influenced by experimental uncertainty, and subsequent measurements of additional materials will likely improve the O p-band center correlations.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2025

In Situ/Operando Probing of Dynamic Phase Structures of Alumina‐Supported Ultrasmall Copper‐Gold Alloy Nanoparticles Under Reaction Conditions

Abstract The ability to control phase structures and surface sites of ultrasmall alloy nanoparticles under reaction conditions is essential for preparing catalysts by design. This is, however, challenging due to limited understanding of the atomic‐scale phases and their correlation with the ensemble‐averaged structures and activities of catalysts during catalytic reactions. We reveal here a dynamic structural stability of alumina‐supported ultrasmall and equiatomic copper‐gold alloy nanoparticles under reaction conditions as a model system in the in situ/operando study. In situ atomic‐scale morphological tracking under oxygen reveals temperature‐dependent dynamic crystalline‐amorphous dual‐phase structures, showing dynamic stability over an elevated temperature range. This atomic‐scale dynamic phase stability coincides with a “conversion plateau” observed for carbon monoxide oxidation on the catalyst. It is substantiated by the stable lattice ordering/disordering structures and surface sites with oscillatory characteristics shown by operando ensemble‐average structural tracking of the catalyst during the oxidation reaction. The understanding of the atomic‐scale dynamic phase structures in correlation with the ensemble‐average dynamic ordering/disordering phase structures and surface sites provides fresh insights into the unique synergy of the supported alloy nanoparticles. This understanding has implications for the design and structural tuning of active and stable ultrasmall alloy catalysts under elevated temperatures.

Chemistry↗
DOE OSTI2020

Wannier–Koopmans method calculations for transition metal oxide band gaps

The widely used density functional theory (DFT) has a major drawback of underestimating the band gaps of materials. Wannier–Koopmans method (WKM) was recently developed for band gap calculations with accuracy on a par with more complicated methods. WKM has been tested for main group covalent semiconductors, alkali halides, 2D materials, and organic crystals. Here we apply the WKM to another interesting type of material system: the transition metal (TM) oxides. TM oxides can be classified as either with d 0 or d 10 closed shell occupancy or partially occupied open shell configuration, and the latter is known to be strongly correlated Mott insulators. We found that, while WKM provides adequate band gaps for the d0 and d10 TM oxides, it fails to provide correct band gaps for the group with partially occupied d states. This issue is also found in other mean-field approaches like the GW calculations. We believe that the problem comes from a strong interaction between the occupied and unoccupied d-state Wannier functions in a partially occupied d-state system. We also found that, for pseudopotential calculations including deep core levels, it is necessary to remove the electron densities of these deep core levels in the Hartree and exchange–correlation energy functional when calculating the WKM correction parameters for the d-state Wannier functions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Pairing correlations in the cuprates: A numerical study of the three-band Hubbard model

We study the three-band Hubbard model for the copper oxide plane of the high-temperature superconducting cuprates using determinant quantum Monte Carlo and the dynamical cluster approximation (DCA) and provide a comprehensive view of the pairing correlations in this model using these methods. Specifically, we compute the pair-field susceptibility and study its dependence on temperature, doping, interaction strength, and charge-transfer energy. Using the DCA, we also solve the Bethe-Salpeter equation for the two-particle Green's function in the particle-particle channel to determine the transition temperature to the superconducting phase on smaller clusters. Our calculations reproduce many aspects of the cuprate phase diagram and indicate that there is an “optimal” value of the charge-transfer energy for the model where T c is largest. Finally, these results have implications for our understanding of superconductivity in both the cuprates and other doped charge-transfer insulators.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Promoting the cleavage of C-O bonds at the interface between a metal oxide cluster and a Co(0001) support

As a first step toward the rational design of Co-based catalysts with a higher activity and selectivity, we determine how one can activate a C-O bond at the interface between a metal oxide cluster and a Co(0001) support. The hypothesis here is that the metal ions in metal oxide clusters on a Co(0001) support enhance the adsorption of CO and weaken the C-O bond strength, which can then facilitate the dissociation of the CO reactant. To test this hypothesis, we developed three computational models of Ti4O8/Co(0001), Zr4O8/Co(0001), and Mn8O8/Co(0001). We quantify the CO adsorption behavior at the interface sites between an oxide cluster and the Co(0001) support as well as the corresponding IR spectra. We correlate the computed CO stretch frequencies with their CO adsorption energies, as well as the CO stretch frequency with the C-O bond length, and related these findings to the changes in the chemical bonding in the bound CO. The interface is the most favorable site for CO adsorption. Adsorption results in an increase of the C-O bond length and a decrease in its vibrational frequency. From a chemical bonding analysis, the bond order in CO at this site drops from 3 (in the gas phase) to 1. This decrease in bond order is a necessary precursor stage for CO dissociation. The experimental measurements of the corresponding FTIR spectra support this point. The favorability of CO adsorption at the interface sites is due to an electron transfer from the metal ion in the metal oxide cluster to the O atom in CO. We establish a linear relationship between C-O bond length and CO frequency and this relationship is found to be independent of the support, type of metal oxide cluster, or the adsorption site.

Fischer-Tropsch Synthesis, Heterogeneous Catalysis↗
DOE OSTI2023

Enthalpies of formation for Criegee intermediates: A correlation energy convergence study

Criegee intermediates, formed from the ozonolysis of alkenes, are known to have a role in atmospheric chemistry, including the modulation of the oxidizing capacity of the troposphere. Although studies have been conducted since their discovery, the synthesis of these species in the laboratory has ushered in a new wave of investigations of these structures, both theoretically and experimentally. In some of these theoretical studies, high-order corrections for correlation energy are included to account for the mid multi-reference character found in these systems. Many of these studies include a focus on kinetics; therefore, the calculated energies should be accurate (<1 kcal/mol in error). In this research, we compute the enthalpies of formation for a small set of Criegee intermediates, including higher-order coupled cluster corrections for correlation energy up to coupled cluster with perturbative quintuple excitations. The enthalpies of formation for formaldehyde oxide, anti-acetaldehyde oxide, syn-acetaldehyde oxide, and acetone oxide are presented at 0 K as 26.5, 15.6, 12.2, and 0.1 kcal mol−1, respectively. Additionally, we do not recommend the coupled cluster with perturbative quadruple excitations [CCSDT(Q)] energy correction, as it is approximately twice as large as that of the coupled cluster with full quadruple excitations (CCSDTQ). Half of the CCSDT(Q) energy correction may be included as a reliable, cost-effective estimation of CCSDTQ energies for Criegee intermediates.

Chemistry↗
DOE OSTI2025

Impact of Hydrogen Combustion on the Oxidation-induced Degradation of Heavy-duty Diesel Engine Piston Materials

High temperature ferritic-martensitic steels are candidate materials for heavy-duty diesel engine pistons. The envisioned transition to hydrogen blended fuels is expected to alter the post-combustion atmosphere in the engines, primarily resulting in a higher water vapor content (> 20 vol%) and potentially higher exhaust gas temperatures. The oxidation resistance of existing and newly developed alloys will be a critical life-limiting mechanism under these conditions. In the present work, the oxidation behavior of candidate piston alloys was evaluated in air+10 vol.% H2O and air+30 vol.% H2O at 700°C. Thermal cyclic (1h cycle) exposures were conducted for two variants of commercial UNSS42200 ferritic-martensitic steel and two developmental alloy steels for up to 300h. The developmental alloys each have similar compositions but with one containing elevated Cu levels of 3 wt.%, A significant reduction in resistance to breakaway oxidation was observed for the commercial alloys in the higher water vapor atmosphere. Microstructural characterization (optical metallography, scanning electron microscopy and electron microprobe analysis) revealed the formation of thick Fe-rich oxides even for the high Cr (~12 wt.%) steels after an initial stage of protective oxidation with MnCr-rich spinels. The impact of the evaporation-induced loss of Cr on the time and temperature dependent compositional changes in the alloys was correlated with experimental findings. For the developmental alloys, Cu additions appear to play a role in significantly reducing oxidation kinetics in air+30 vol.% H2O at 700°C.

Pillai, Rishi [ORNL] (ORCID:0000000243688197)↗
DOE OSTI2021

Enhanced Interface-Driven Perpendicular Magnetic Anisotropy by Symmetry Control in Oxide Superlattices

Perpendicular magnetic anisotropy (PMA) has recently been shown to emerge at interfaces of 3d and 5d transition-metal oxides (TMOs). However, strategies to systematically stabilize such interface-driven PMA still remains elusive, hindering further applications of this design approach. Here, tuning crystal symmetry is shown to be an effective means to engineer this interfacial phenomenon. The evolution of PMA strength as a function of ferromagnetic oxide thickness quantitatively reveals the competition between volume- and interface-specific contributions that determine the magnetic anisotropy. By applying different degrees of epitaxial strain, the relative contributions to PMA are modulated, clearly revealing their correlations with crystal symmetries. To be more specific, the volume anisotropy energy is found to be correlated with the tetragonal distortion of the ferromagnetic layer, while the interface anisotropy energy is mainly modulated by the octahedral tilting at the interface. With these insights, superlattices with enhanced interface-driven PMA and higher Curie temperature are realized. These findings reveal a route to engineering interface-driven PMA and associated magnetic phenomena in TMO heterostructures for future spintronic applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

A Superconducting Praseodymium Nickelate with Infinite Layer Structure

A variety of nickel oxide compounds have long been studied for their manifestation of various correlated electron phenomena. Recently, superconductivity was observed in nanoscale infinite layer nickelate thin films of Nd 0.8 Sr 0.2 NiO 2 , epitaxially stabilized on SrTiO 3 substrates via topotactic reduction from the perovskite precursor phase. In this paper, we present the synthesis and properties of PrNiO 2 thin films on SrTiO 3 . Upon doping in Pr 0.8 Sr 0.2 NiO 2 , we observe superconductivity with a transition temperature of 7–12 K and robust critical current density at 2 K of 334 kA/cm 2 . These findings indicate that superconductivity in the infinite layer nickelates is relatively insensitive to the details of the rare earth 4 f configuration. Furthermore, they motivate the exploration of a broader family of compounds based on two-dimensional NiO 2 planes, which will enable systematic investigation of the superconducting and normal state properties and their underlying mechanisms.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

WACCM6 Projections of Polar Mesospheric Cloud Abundance Over the 21st Century

Polar mesospheric clouds (PMC), or noctilucent clouds, can be observed over high latitudes with the naked eye from the ground or from space near the summer solstice. PMC are considered a direct and sensitive indicator of climate change and have been reported to appear more frequently in recent decades. How PMC will change in the future under the influence of natural variability and anthropogenic forcing is uncertain. In this study, we utilize model output from the Whole Atmosphere Community Climate Model under several shared socioeconomic pathway (SSP) scenarios and input the water vapor, temperature, and pressure information into a 0-d PMC model to project the trend and variation of PMC over the 21st century, and their relationship to future changes of temperature, water vapor, and the solar cycle. The 0-d model calculations indicate that PMC ice water content (IWC) will increase and PMC will extend to lower latitudes under high SSP scenarios. Under these scenarios, more mesospheric water vapor leads to an increased IWC of PMC over the polar region, and colder mesopause temperature leads to more PMC over the mid-latitudes. There is a significant anti-correlation between the solar cycle and PMC IWC over the 21st century, but the anti-correlation is not always significant on the decadal scale. Finally, methane oxidation in the stratosphere and water vapor entering from the troposphere are both responsible for future changes in mesospheric water vapor and thus PMC.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

In situ x-ray and electron scattering studies of oxide molecular beam epitaxial growth

We perform the first in situ synchrotron X-ray ray diffraction (SXRD) / reflection high energy electron diffraction (RHEED) studies on the growth of complex oxide thin films by molecular beam epitaxy. The unique deposition chamber, located at the Advanced Photon Source, allows the preparation of complex oxide samples with monolayer precision and facilitates the formation of direct correlations between in situ X-ray studies and the more prevalent RHEED investigations. Importantly, because SXRD and RHEED probe different atomic-scale processes during thin film synthesis, their concomitant use enables the extraction of details concerning growth behavior than one cannot determine from either probe alone. We describe the results of such in situ studies on the epitaxial growth of perovskite LaNiO3on (La 0.18 Sr 0.82 )(Al 0.59 Ta 0.41 )O 3 (001). We find that during the earliest stages of growth, the RHEED and X-ray signals do not agree with each other, demonstrating that while regular RHEED oscillations may imply high quality growth, the film-substrate interface can undergo significant changes during deposition due to the occurrence of interdiffusion at the growth temperature.

36 MATERIALS SCIENCE↗