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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 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

From Micro-environments to Macroscopic Effects: How the Alkaline Hydrogen Evolution Reaction Drives Cu Cathodic Corrosion

Cathodic corrosion of copper (Cu) has posed a significant challenge for over a century, impeding various technological progresses such as electrochemical conversion of CO 2 (eCO 2 RR) into fuels and other value-added carbon products. Here, in this study, employing a combined Density Functional Theory (DFT) and kinetic Monte Carlo (kMC) simulation approach, we delve into the atomistic level mechanism driving this phenomenon in Cu. Our hypothesis posits the pivotal role of alkaline hydrogen evolution reaction (HER) in facilitating cathodic corrosion in Cu. We rigorously develop a pH-dependent hydroxide (OH) adsorption mechanism and calculate the equilibrium OH coverage (𝜃 OH ) at varying pH levels, the thermodynamic stability of subsurface oxygen (O sub ), as well as the Cu-vacancy mediated diffusion of subsurface oxygens (O sub ). Through comprehensive analysis, we establish correlation among various microenvironments, including oxygen diffusion in subsurface layers, pH-dependent OH adsorption, and Cu dissolution into the electrolyte as (Cu-OH) complexes. Furthermore, our investigation explores the correlation between surface coordination environment of active sites and cathodic corrosion of Cu. Finally, by integrating DFT-derived thermodynamic data into a kMC model, we successfully predict the formation of experimentally observed corrosion pits on Cu-surfaces. This combined approach not only advances our fundamental understanding of Cu cathodic corrosion but also offers insights crucial for developing effective corrosion mitigation strategies.

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

Surface Vacancy Engineering Re-Routes First-Cycle Redox for Stabilized Li-Rich Layered Cathodes

We demonstrate that atomic-scale surface disorder can control the first-cycle redox sequence of Li-rich layered oxides, eliminating the detrimental process of oxygen release and lattice collapse that degrades performance. In Li1.14Ni0.32Mn0.54O2 (LNMO), a simple chemical treatment introduces oxygen and transition metal (TM) vacancies confined to the particle surface while preserving the bulk layered framework. Multi-modal synchrotron analyses reveal that these vacancies trigger an early oxygen oxidation below 4.4 V, delay nickel oxidation to higher potential, and suppress the formation of covalent Ni4+─O states. This modified pathway prevents irreversible oxygen release, suppresses manganese dissolution, and maintains metal-oxygen coordination at high voltages. Consequently, the treated cathode delivers higher first-cycle Coulombic efficiency (CE), mitigated voltage fade, and superior capacity retention. By directly linking engineered surface disorder to redox reactions and associated structural transformations, this work establishes a general design principle for durable, high-energy-density cathodes.

Kang, Seongkoo↗
DOE OSTI2026

Atomic-scale vacancy engineering unlocks basal-plane catalytic activity in metallic WSe 2 for reversible oxygen electrocatalysis

Two-dimensional metallic transition metal dichalcogenides offer high electrical conductivity and large surface areas for electrocatalysis, yet their inherent basal planes are catalytically inert. Here, we present an atomic-scale vacancy engineering strategy to activate the basal surfaces of metallic WSe 2 for reversible oxygen electrocatalysis. This approach, based on intentionally designed substitutional metal doping, promotes the spontaneous formation of selenium vacancies while preserving the metallic 1 T′ phase, thereby creating highly reactive and oxygen-affinitive sites. Density functional theory calculations reveal that these vacancy-mediated metal complexes dramatically lower the energy barriers for initial oxygen adsorption, enabling dissociative oxygen adsorption. Operando and ex-situ spectroscopic analyses confirm that vacancy-mediated metal complexes transform into dynamic Se/W-oxide intermediates under operating conditions. Se/W-oxides on the surface experimentally and theoretically prove electrocatalytic activity and reversibility. Applying this strategy in lithium–oxygen batteries, the basal-plane activated WSe 2 shows high discharge capacities (9868 mA h g −1 , corresponding to 3947 mA h g$^{-1}_{cathode}$), impressive cycle retention over 550 cycles at 1000 mA h g −1 , and outstanding rate–capability over a wide current–density range (100–3000 mA g −1 ) during 256 cycles.

2D materials↗
DOE OSTI2022

A multimodal approach to revisiting oxidation defects in Cr 2 O 3

The oxidation of chromium in air at 700 °C was investigated with a focus on point defect behavior and transport during oxide layer growth. A comprehensive set of characterization techniques targeted characteristics of chromium oxide microstructure and chemical composition analysis. TEM showed that the oxide was thicker with longer oxidation times and that, for the thicker oxides, voids formed at the metal/oxide interface. PAS revealed that the longer the oxidation time, there was an overall reduction in vacancy-type defects, though chromium monovacancies were not found in either case. EIS found that the longer oxidized material was more electrochemically stable and that, while all oxides displayed p-type character, the thicker oxide had an overall lower charge carrier density. Together, the results suggest anion oxygen interstitials and chromium vacancy cluster complexes drive transport in an oxidizing environment at this temperature, providing invaluable insight into the mechanisms that regulate corrosion.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Origin of proton irradiation-induced deep acceptors in Al 0.70 Ga 0.30 N

Deep level defect introduction and carrier removal were characterized using steady-state photocapacitance (SSPC), deep level transient spectroscopy (DLTS) and lighted capacitance–voltage for proton irradiated n-type Al 0.70 Ga 0.30 N Schottky diodes grown by metal-organic vapor phase epitaxy on AlN-on-sapphire templates. SSPC observed deep levels in the as-grown diode with zero-phonon transition energies of 2.20, 2.65, 3.10, 3.40, and 4.65 eV relative to the conduction band minimum (E c ), and an additional deep level emerged at 1.20 eV with irradiation. Lighted capacitance–voltage measurements quantified the deep level concentration (N t ) of states detected by SSPC, and it was observed that N t increased with proton fluence only for the 1.2 and 4.65 eV levels. Carrier removal was much larger than the increase in N t of the 1.2 and 4.65 eV deep levels, suggesting that radiation-induced deep level compensators existed beyond what was detected with SSPC. DLTS detected additional, proton-induced deep acceptors at E c —0.55, 0.82, and 1.16 eV, the latter of which is likely the same 1.20 eV deep state observed by SSPC. The concentration of the E c —0.82 eV defect state was large enough to reconcile carrier removal with total deep level introduction. Comparing the E c —0.82 and 1.16 eV deep acceptor levels to previous experimental and theoretical reports suggests that their atomistic origins could be the nitrogen vacancy (V N ) and oxygen substituting on the nitrogen sub-lattice (O N ), respectively. This defect behavior contrasts starkly with GaN, where V N and O N are shallow donors, and demonstrates that the electronic properties of defects can evolve drastically within the AlGaN alloy system ranging from wide bandgap GaN to ultra-wide bandgap AlN.

Armstrong, Andrew Michael [Sandia National Laborat↗
DOE OSTI2024

Atomistic Probing of Defect-Engineered 2H-MoTe 2 Monolayers

Point defects dictate various physical, chemical, and optoelectronic properties of two-dimensional (2D) materials, and therefore, a rudimentary understanding of the formation and spatial distribution of point defects is a key to advancement in 2D material-based nanotechnology. In this work, we performed the demonstration to directly probe the point defects in 2H-MoTe 2 monolayers that are tactically exposed to (i) 200 °C-vacuum-annealing and (ii) 532 nm-laser-illumination; and accordingly, we utilize a deep learning algorithm to classify and quantify the generated point defects. We discovered that tellurium-related defects are mainly generated in both 2H-MoTe 2 samples; but interestingly, 200 °C-vacuum-annealing and 532 nm-laser-illumination modulate a strong n-type and strong p-type 2H-MoTe 2 , respectively. While 200 °C-vacuum-annealing generates tellurium vacancies or tellurium adatoms, 532 nm-laser-illumination prompts oxygen atoms to be adsorbed/chemisorbed at tellurium vacancies, giving rise to the p-type characteristic. This work significantly advances the current understanding of point defect engineering in 2H-MoTe 2 monolayers and other 2D materials, which is critical for developing nanoscale devices with desired functionality.

2H-MoTe 2↗
DOE OSTI2026

Tandem bulk oxygen diffusion and surface reactions in reducible metal oxides control redox cycle dynamics

The interplay between bulk oxygen diffusion and surface reactions in reducible metal oxides is key in heterogeneous catalysts, but direct measurements of oxygen mobility, transient kinetics, and in situ spectroscopies have been lacking. Here, we reveal complex dynamic behavior of ceria-zirconia by H 2 using transient kinetics via mass spectrometry and in situ Raman and near-ambient pressure x-ray photoelectron spectroscopies. Molecular dynamics simulations with a machine learning potential delineate competitive oxygen diffusion mechanisms, with an optimal mobility at intermediate reductions. We expose a compensation between vacancy availability and lattice distortion at intermediate to high reductions and Frenkel defects at low reductions, underscoring a potential deficiency of 16 O/ 18 O exchange experiments in deducing oxygen mobility. Vacancies in proximity require electron localization on Ce atoms further away. The continuous replenishment of surface oxygen results in a varying reduction rate, with H 2 dissociation being the rate-limiting step. Multiscale transient simulations, consistent with experiments, indicate catalysts of potentially spatially varying oxidation states. The approach is broadly applicable to reducible oxide materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Insights into the Oxygen Evolution Reaction on Graphene-Based Single-Atom Catalysts from First-Principles-Informed Microkinetic Modeling

Single-atom transition metals embedded in nitrogen-doped graphene have emerged as promising electrocatalysts due to their high activity and low material cost. These materials have been shown to catalyze a variety of electrochemical reactions, but their active sites under reaction conditions remain poorly understood. Using first-principles density functional theory calculations, we develop a pH-dependent microkinetic model to evaluate the relative performance of transition metal catalysts embedded in fourfold N-substituted double carbon vacancies in graphene for the oxygen evolution reaction. We find that reaction pathways involving intermediates co-adsorbed on the metal site are preferred on all transition metals. These pathways lead to enhancements in catalytic activity and broaden the activity peak when compared with purely thermodynamics-based predictions. Furthermore, these findings demonstrate the importance of investigating reaction pathways on graphene-based catalysts and other two-dimensional (2D) materials that involve metal active centers decorated by spectator intermediate species.

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

Influence of Oxygen Flow and Stoichiometry on Optical Properties and Damage Resistance of Hafnium Oxide Thin Films

Hafnium oxide (HfO 2 ) is predominantly used as a high-index material in multi-layer dielectric coatings for high-peak- and high-average-power lasers, but laser damage often initiates within the HfO 2 layers despite their wide bandgap. Oxygen deficiency during deposition can introduce vacancy-related sub-bandgap states and absorptive defects, lowering damage resistance. This study investigates how oxygen flow during HfO 2 deposition with ion beam sputtering (IBS) affects its stoichiometry, defect formation, and nanosecond laser-induced damage threshold (LIDT) and whether single-layer trends predict multilayer performance. Single layers were deposited at varying oxygen flows, characterized for optical and structural properties, and tested for the LIDT at 1064 nm and 355 nm. Increasing oxygen flow drove the layer toward near-stoichiometric HfO 2 , reduced the refractive index, and altered the density of surface pinhole-like features. The single-layer LIDT at 355 nm increased with oxygen, whereas the 1064 nm LIDT was comparatively less sensitive to oxygen flow, consistent with the wavelength-dependent roles of absorptive precursors and microstructural defects. In contrast, a HfO 2 -based high-reflector (HR) showed a higher LIDT at lower oxygen flow, indicating that the family of damage precursors changes between single layers and multilayers; in stacks, structural properties such as stress, gas entrapment and thermal dissipation may outweigh the isolated absorptive defects found in single layers. These results demonstrate that the optimal oxygen flow condition depends on both LIDT wavelength and film architecture. We identified, for single layers, a 15–35 sccm window for maximizing the 1064 nm LIDT and a high-flow optimum (45 sccm) for the 355 nm LIDT and, for 355 nm HR stacks, a distinct lower-flow regime (~10 sccm).

Optics and optical instruments↗
DOE OSTI2025

Atomic-Scale Insights into Carbon Dissolution in α-, γ-, and θ-Al 2 O 3 : Phase-dependent Transport Dynamics from First-Principles Calculations

α-Al 2 O 3 exhibits superior carburizing corrosion resistance compared to metastable γ-Al 2 O 3 and θ-Al 2 O 3 phases in high-temperature CO 2 environments, yet its atomic-scale origins remain unclear. Using first-principles density functional theory, we systematically investigate carbon dissolution and diffusion in α-Al 2 O 3 , γ-Al 2 O 3 , and θ-Al 2 O 3 , including the effects of oxygen (O) and aluminum (Al) vacancies. Our results show that α-Al 2 O 3 consistently exhibits higher carbon solution enthalpies than γ-Al 2 O 3 and θ-Al 2 O 3 in both pristine and defective structures, indicating lower intrinsic carbon solubility in α-Al 2 O 3 . Vacancies significantly enhance carbon incorporation: O vacancies reduce solution enthalpy, while Al vacancies further amplify this effect, with a strong preference for carbon at Al vacancy sites. Carbon diffusion barriers are also highest in α-Al 2 O 3 , reflecting slower carbon mobility. Al vacancies increase diffusion barriers across all phases, while O vacancies raise barriers in α- and γ-Al 2 O 3 but slightly lower them in θ-Al 2 O 3 . These results reveal a dual mechanism behind the carburizing resistance of α-Al 2 O 3 : reduced carbon solubility and elevated diffusion barriers. Furthermore, this work provides atomic-scale insights to guide the design of alumina-based materials with improved carburizing resistance through phase selection and defect engineering.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ethanol Conversion over La 0.7 Sr 0.3 MnO 3–x (100): Autocatalysis, Adjacent O-Vacancies, Disproportionation, and Dehydrogenation

The mechanism for catalytic conversion of ethanol over La 0.7 Sr 0.3 MnO 3– x (100) surface to acetaldehyde and ethene was investigated. Pre-exposure temperature-programmed reaction (PE-TPR) experiments were performed in which ethanol was introduced to oxidized or reduced surfaces followed by heating. In particular, sequential PE-TPR experiments were conducted to incrementally and gradually reduce the surface. The products and their ratios were investigated as a function of surface reduction. The data show that acetaldehyde and ethene production is catalyzed with hydrogen abstraction and oxygen abstraction reactions occurring by intermediates in vacancies at various temperatures >400 K. Adsorption of acetaldehyde followed by a temperature-programmed reaction does not produce ethene, indicating that acetaldehyde is not an intermediate to ethene and that the hydrogen and oxygen abstraction from ethanol to ethene are decoupled steps. Further evidence for this mechanistic nuance was obtained using isotopically labeled ethanol (CD 3 CH 2 OH), which produces CD 3 CHO and CD 2 CH 2 . Additionally, the ratio of aldehyde production to alkene production increases with reduction, suggesting that aldehyde is produced from a disproportionation reaction between ethoxy species in adjacent O-vacancies, while ethene is produced from a dehydrogenation reaction with ethoxy species in vacancies without requiring adjacent O-vacancies. Counterintuitively, this finding indicates that the more oxygenated product (aldehyde vs ethene) is favored with more vacancies and that the net alcohol conversion is autocatalytic. Density functional theory calculations were able to find the previously unknown disproportionation pathway between ethoxies in adjacent O-vacancies, and kinetic Monte Carlo simulations support this interpretation by reproducing experimental selectivities. The activation energies for these pathways are estimated as 132 ± 10 kJ/mol for the disproportionation reaction (when occurring between ethoxies in adjacent vacancies) and as 148 ± 11 kJ/mol for the direct dehydrogenation reaction of an ethoxy in a vacancy. Based on these results, a mechanism with operative pathways based on elementary steps in O-vacancies is reported.

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

Density Functional Tight-Binding Simulations Reveal the Presence of Surface Defects on the Quartz (101)–Water Interface

Understanding the structure and reactivity of quartz–water interfaces is critical for numerous applications in the geological, environmental, and biological sciences. However, disagreements on the atomic-level structure of the interfaces between experiments and simulations are hampering our ability to predict the surface reactivity. Here, we used density functional tight-binding (DFTB)-based molecular dynamics to simulate a series of quartz (101) surfaces having different types and densities of surface defects in water and compared them with the structures determined by X-ray reflectivity measurements. The DFTB simulations are able to reproduce previous classical and quantum mechanical predictions of the pristine quartz (101)–water interface that disagree with experimental observations. To remedy this situation, a set of defective quartz surfaces having various surface silicon (Si) vacancies were built as indicated by recent experimental studies. We found that the rotation of surface [SiO 4 ] tetrahedra near Si vacancies can lead to outward displacements of Si atoms similar to those observed in the experiments. The presence of additional surface Si vacancies caused inward relaxations of terminal oxygens through the formation of hydrogen bonds. Finally, the overall results indicate that the quartz (101)–water interface may include a mixture of geminal (≡Si–(OH) 2 )- and vicinal (≡Si–OH)-type silanol groups together with the presence of surface Si vacancies.

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

Direct evidence for low-energy electron emission following O LVV Auger transitions at oxide surfaces

Abstract Oxygen, the third most abundant element in the universe, plays a key role in the chemistry of condensed matter and biological systems. Here, we report evidence for a hitherto unexplored Auger transition in oxides, where a valence band electron fills a vacancy in the 2s state of oxygen, transferring sufficient energy to allow electron emission. We used a beam of positrons with kinetic energies of $$\sim 1$$ ∼ 1 eV to create O 2s holes via matter-antimatter annihilation. This made possible the elimination of the large secondary electron background that has precluded definitive measurements of the low-energy electrons emitted through this process. Our experiments indicate that low-energy electron emission following the Auger decay of O 2s holes from adsorbed oxygen and oxide surfaces are very efficient. Specifically, our results indicate that the low energy electron emission following the Auger decay of O 2s hole is nearly as efficient as electron emission following the relaxation of O 1s holes in $$\hbox {TiO}_2$$ TiO 2 . This has important implications for the understanding of Auger-stimulated ion desorption, Coulombic decay, photodynamic cancer therapies, and may yield important insights into the radiation-induced reactive sites for corrosion and catalysis.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

First-principles determination of the phonon-point defect scattering and thermal transport due to fission products in ThO 2

This work presents the first-principles calculations of the lattice thermal conductivity degradation due to point defects in thorium dioxide using an iterative solution of the Pierels-Boltzmann transport equation. We have used the non perturbative Green’s function methodology to compute the phonon- point defect scattering rates that consider the local distortion around the point defect, including the mass difference changes, interatomic force constants, and structural relaxation near the point defects. The point defects considered in this work include the vacancy of thorium ($V$ $TH$ ) and oxygen ($V$ $O$ ), substitutions of helium ($He$ $Th$ ), krypton ($Kr$ $Th$ ), zirconium ($Zr$ $Th$ ), iodine ($I$ $Th$ ) and xenon ($Xe$ $Th$ ) in the thorium site, and the three different configurations of the Schottky defects. The results of the phonon-defect scattering rate reveal that, among all the considered intrinsic defects, the thorium vacancy and helium substitution in the thorium site scatter the phonon most due to the substantial changes in the force constant and structural distortions. The scattering of phonons due to the substitutional defects unveils that the zirconium atom scatters phonons the least, followed by xenon, iodine, krypton, and helium. This is contrary to the intuition that the scattering strength follows $He$ $Th$ > $Kr$ $Th$ > $Zr$ $Th$ > $I$ $Th$ > $Xe$ $Th$ based on the mass difference. This striking difference in the zirconium phonon scattering is due to the local chemical environment changes. Zirconium is an electropositive element with valency similar to thorium and, therefore, can bond with the oxygen atoms, thus creating less force constant variance compared to iodine, an electronegative element noble gas helium, xenon, and krypton. In conclusion, these results can serve as the benchmark for the analytical models and help the engineering-scale modeling effort for nuclear design.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Defect redistribution along grain boundaries in SrTiO 3 by externally applied electric fields

During thermal annealing at 1425 °C nominal electric field strengths of 50 V/mm and 150 V/mm were applied along the grain boundary planes of a near 45° (100) twist grain boundary in SrTiO 3 . Electron microscopy characterization revealed interface expansions near the positive electrode around 0.8 nm for either field strength. While the interface width decreased to roughly 0.4 nm after annealing at 50 V/mm, the higher field strength caused decomposition of the boundary structure close to the negative electrode. Electron energy-loss and X-ray photoelectron spectroscopies demonstrated an increased degree of oxygen sublattice distortion at the negative electrode side, and enhanced concentrations of Ti 3+ and Ti 2+ compared to bulk for both single crystals and bicrystals annealed with an external electric field, respectively. Oxygen migration due to the applied electric field causes the observed alteration of grain boundary structures. At sufficiently high field strength the agglomeration of anion vacancies may lead to the decomposition of the grain boundary.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Activating low-temperature diesel oxidation by single-atom Pt on TiO 2 nanowire array

Supported metal single atom catalysts (SACs) present an emerging class of low-temperature catalysts with high reactivity and selectivity, which, however, face challenges on both durability and practicality. Herein, we report a single-atom Pt catalyst that is strongly anchored on a robust nanowire forest of mesoporous rutile titania grown on the channeled walls of full-size cordierite honeycombs. This Pt SAC exhibits remarkable activity for oxidation of CO and hydrocarbons with 90% conversion at temperatures as low as ~160 °C under simulated diesel exhaust conditions while using 5 times less Pt-group metals than a commercial oxidation catalyst. Such an excellent low-temperature performance is sustained over hydrothermal aging and sulfation as a result of highly dispersed and isolated active single Pt ions bonded at the Ti vacancy sites with 5 or 6 oxygen ions on titania nanowire surfaces.

36 MATERIALS SCIENCE↗