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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Nanoscopic Titanium Dioxide Overlayers Improve the Durability of Porphyrin Molecular Electrocatalysts while Maintaining Molecular Structure and Redox Activity

Molecular catalysts, such as metalated porphyrins, are attractive cocatalysts for photocatalytic water splitting owing to their potential to simultaneously catalyze target reactions at their metal center, extend charge-separated-state lifetimes, and accumulate the requisite charge for product formation. However, porphyrin catalysts, like most molecular catalysts, are often limited by poor stability associated with demetalation, inactivation by undesired bonding (e.g., O2 coordination/redox/dimerization), and detachment from electrode supports or semiconducting photoabsorbers. In this study, nanoscopic titanium dioxide (TiO2) overlayers, deposited by atomic layer deposition (ALD), are demonstrated to encapsulate cobalt(III) meso-tetra(4-carboxyphenyl) porphyrin chloride (CoTCPP) molecular catalysts and thereby improve their adhesion to electrode surfaces over a wide range of electrode potentials spanning from -1.0 V vs RHE to +1.8 V vs RHE. Through analysis of Raman and ultraviolet-visible spectroscopy, it was confirmed that the metalloporphyrin structure was maintained when the surface-bound CoTCPP was encapsulated by 10 - 250 ALD cycles (~2 - 18 nm thick) of TiO2. Additional characterization of CoTCPP catalysts before and after electrochemical measurements reveals that up to 97% of the encapsulated CoTCPP remains tethered to the electrode surface after chronoamperometry tests under hydrogen evolution reaction (HER) conditions, compared to <36% for unencapsulated CoTCPP. This study also shows that encapsulated CoTCPP molecules remain partially redox active for overlayers up to 8 nm, which can also attenuate undesired redox mediator back reactions like ferricyanide reduction.

08 HYDROGEN↗
DOE OSTI2020

Water-Fed Hydroxide Exchange Membrane Electrolyzer Enabled by a Fluoride-Incorporated Nickel–Iron Oxyhydroxide Oxygen Evolution Electrode

Here, we have developed a dissolved oxygen and galvanic corrosion method to synthesize vertically aligned fluoride-incorporated nickel–iron oxyhydroxide nanosheet arrays on a compressed Ni foam as an efficient self-supported oxygen evolution electrode. It is integrated with poly(aryl piperidinium) hydroxide exchange membrane and ionomers with high ion exchange capacity into a hydroxide exchange membrane electrolyzer fed with pure water, which achieves a performance of 1020 mA cm –2 at 1.8 V and prevents the detachment of catalysts during continuous operation (>160 h at 200 mA cm –2 ). Furthermore, this work provides a potential pathway for massively producing low-cost hydrogen using intermittent renewable energy sources.

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

Interpenetrating 3D Electrodes for High-Rate Alkaline Water Splitting

Mass transfer is critical for the reaction kinetics and efficiency of alkaline water splitting (AWS). For AWS to operate at high current densities (hundreds of mA/cm 2 ), the device architecture must ensure a large catalytic surface area, rapid ion diffusion, and minimal solution and charge transfer resistances. Effective electrodes should also facilitate gas bubble detachment and release. 3D-printed electrodes have shown promise, but stacking them increases the ion diffusion length and solution resistance. Here we demonstrate a new device architecture with interpenetrating gyroid electrodes, providing a large ion-accessible surface area and gas diffusion channels. This design significantly reduces the interelectrode distance, lowering ion diffusion length and solution resistance. Simulations show faster ion diffusion and higher current density in the interpenetrating configuration compared with separate electrodes. This improved performance, especially at low temperatures and high current densities, highlights a promising strategy for enhancing AWS and other electrochemical systems limited by slow ion diffusion.

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

Beyond Volume Variation: Anisotropic and Protrusive Lithiation in Bismuth Nanowire

Materials storing energy via an alloying reaction are promising anode candidates in rechargeable lithium-ion batteries (LIBs) due to their much higher energy density than the current graphite anode. Until now, the volumetric expansion of such electrode particles during lithiation has been considered as solely responsible for cycling-induced structural failure. Here, we report different structural failure mechanisms using single-crystalline bismuth nanowires as the alloying-based anode. The Li–Bi alloying process exhibits a two-step transition, that is, Bi–Li 1 Bi and Li 1 Bi–Li 3 Bi. Interestingly, the Bi–Li 1 Bi phase transition occurs not only in the bulk Bi nanowire but also on the particle surface showing its characteristic behavior. The bulk alloying kinetics favors a Bi-(012)-facilitated anisotropic lithiation, whose mechanism and energetics are further studied using the density functional theory calculations. More importantly, the protrusion of Li 1 Bi nanograins as a result of anisotropic Li–Bi alloying is found to dominate the surface morphology of Bi particles. The growth kinetics of Li 1 Bi protrusions is understood atomically with the identification of two different controlling mechanisms, that is, the dislocation-assisted strain relaxation at the Bi/Li 1 Bi interface and the short-range migration of Bi supporting the off-Bi growth of Li 1 Bi. As loosely rooted to the bulk substrate and easily peeled off and detached into the electrolyte, these nanoscale protrusions developed during battery cycling are believed to be an important factor responsible for the capacity decay of such alloying-based anodes at the electrode level.

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

Metal–Metal Bonding in Actinide Dimers: U 2 and U 2 –

Understanding direct metal–metal bonding between actinide atoms has been an elusive goal in chemistry for years. Here we report for the first time the anion photoelectron spectrum of U 2 – . The threshold of the lowest electron binding energy (EBE) spectral band occurs at 1.0 eV, which corresponds to the electron affinity (EA) of U 2 , whereas the vertical detachment energy of U 2 – is found at EBE ~ 1.2 eV. Electronic structure calculations on U 2 and U 2 – were carried out with state-of-the-art theoretical methods. The computed values of EA(U 2 ) and EA(U) and the difference between the computed dissociation energies of U 2 and U 2 – are found to be internally consistent and consistent with experiment. Analysis of the bonds in U 2 and U 2 – shows that while U 2 has a formal quintuple bond, U 2 – has a quadruple bond, even if the effective bond orders differ only by 0.5 unit instead of one unit. Furthermore, the resulting experimental-computational synergy elucidates the nature of metal–metal bonding in U 2 and U 2 – .

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

Au as a Surrogate for F: The Case of UAu 6 vs UF 6

Here, anion photoelectron spectroscopy and first-principles quantum chemistry are used to demonstrate to what degree Au can act as a surrogate for F in UF6 and its anion. Unlike UF6, UAu6 exhibits strong ligand–ligand, i.e., Au–Au, interactions, resulting in three low-lying isomers, two of which are three-dimensional while the third isomer has a ring-like quasi two-dimensional structure. Additionally, all the UAu6 isomers have open-shell electrons, which in nearly all cases are localized on the central U atom. As a result, the adiabatic electron affinity and vertical detachment energy are measured to be 3.05 ± 0.05 and 3.28 ± 0.05 eV, respectively, and are in very good agreement with calculations.

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

Chemical and Structural Evolution of AgCu Catalysts in Electrochemical CO 2 Reduction

Silver–copper (AgCu) bimetallic catalysts hold great potential for electrochemical carbon dioxide reduction reaction (CO 2 RR), which is a promising way to realize the goal of carbon neutrality. Although a wide variety of AgCu catalysts have been developed so far, it is relatively less explored how these AgCu catalysts evolve during CO 2 RR. The absence of insights into their stability makes the dynamic catalytic sites elusive and hampers the design of AgCu catalysts in a rational manner. Here, in this study, we synthesized intermixed and phase-separated AgCu nanoparticles on carbon paper electrodes and investigated their evolution behavior in CO 2 RR. Our time-sequential electron microscopy and elemental mapping studies show that Cu possesses high mobility in AgCu under CO 2 RR conditions, which can leach out from the catalysts by migrating to the bimetallic catalyst surface, detaching from the catalysts, and agglomerating as new particles. Besides, Ag and Cu manifest a trend to phase-separate into Cu-rich and Ag-rich grains, regardless of the starting catalyst structure. The composition of the Cu-rich and Ag-rich grains diverges during the reaction and eventually approaches thermodynamic values, i.e., Ag 0.88 Cu 0.12 and Ag 0.05 Cu 0.95 . The separation between Ag and Cu has been observed in the bulk and on the surface of the catalysts, highlighting the importance of AgCu phase boundaries for CO 2 RR. In addition, an operando high-energy-resolution X-ray absorption spectroscopy study confirms the metallic state of Cu in AgCu as the catalytically active sites during CO 2 RR. Taken together, this work provides a comprehensive understanding of the chemical and structural evolution behavior of AgCu catalysts in CO 2 RR.

Chen, Peng-Cheng↗
DOE OSTI2025

Structural Transformation and Degradation of Cu Oxide Nanocatalysts during Electrochemical CO 2 Reduction

The electrochemical CO 2 reduction reaction (CO 2 RR) holds enormous potential as a carbon-neutral route to the sustainable production of fuels and platform chemicals. The durability for long-term operation is currently inadequate for commercialization, however, and the underlying deactivation process remains elusive. A fundamental understanding of the degradation mechanism of electrocatalysts, which can dictate the overall device performance, is needed. In this work, we report the structural dynamics and degradation pathway of Cu oxide nanoparticles (CuO x NPs) during the CO 2 RR by using in situ small-angle X-ray scattering (SAXS) and X-ray absorption spectroscopy (XAS). The in situ SAXS reveals a reduction in the size of NPs when subjected to a potential at which no reaction products are detected. At potentials where the CO 2 RR starts to occur, CuO x NPs are agglomerated through a particle migration and coalescence process in the early stage of the reaction, followed by Ostwald ripening (OR) as the dominant degradation mechanism for the remainder of the reaction. As the applied potential becomes more negative, the OR process becomes more dominant, and for the most negative applied potential, OR dominates for the entire reaction time. The morphological changes are linked to a gradual decrease in the formation rate for multicarbon products (C 2 H 4 and ethanol). Other reaction parameters, including reaction intermediates and local high pH, induce changes in the agglomeration process and final morphology of the CuO x NPs electrode, supported by post-mortem ex situ microscopic analysis. The in situ XAS analysis suggests that the CuO x NPs reduced into the metallic state before the structural transformation was observed. The introduction of high surface area carbon supports with ionomer coating mitigates the degree of structural transformation and detachment of the CuO x NPs electrode. These findings show the dynamic nature of Cu nanocatalysts during the CO 2 RR and can serve as a rational guideline toward a stable catalyst system under electrochemical conditions.

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

Field-Coupled Water Splitting with Metal-Free Donor–Acceptor Covalent Organic-Framework Junctions

Advancing metal-free electrocatalysts for hydrogen and oxygen evolution reactions (HER/OER) across acidic and alkaline media requires coordinated control of intermediate binding thermodynamics, interfacial charge delivery, and near-electrode transport dynamics. Here, we design amide-linked benzene–triazine covalent organic frameworks (BTA/TzTA-Hz COFs) and integrate them with carbon nanotubes (CNTs) to form COF–CNT junctions that establish a built-in interfacial electric field. Density functional theory (DFT) and electrostatic potential maps indicate complementary active motifs, with benzene-proximal fragments associated with HER and triazine-proximal motifs associated with OER. CNT integration shifts the contact-potential difference by ≈0.20 V, while operando electrochemical impedance spectroscopy suggests partially separable high-frequency junction-charging and lower-frequency Faradaic/transport responses. A 300 mT static magnetic field lowers the HER and OER overpotentials by tens of millivolts. Under anodic bias, the effective interfacial charging capacitance increases, and Mott–Schottky analysis shows an apparent ∼0.15 V flat-band shift with an essentially unchanged slope. Together, these observations are consistent with field-perturbed interfacial charging and altered bias partitioning. Field-dependent impedance and bubble imaging are consistent with magnetohydrodynamic convection that promotes bubble detachment and near-electrode mass transport for both half-reactions, and they reveal an OER-specific high-frequency perturbation under anodic bias. Under field, the heterostructure reaches an OER onset overpotential of ∼261 mV and requires an overpotential of 366 mV at 10 mA cm –2 in alkaline electrolyte. These results illustrate how reticular-framework chemistry, junction engineering, and both built-in and applied fields can program reactivity through interfacial electrostatics and near-electrode transport in organic-framework electrocatalysts.

Garcia-Enriquez, Lissette [Univ. of Texas at El Pa↗
DOE OSTI2021

Activity of Cu-Al-oxo extra-framework clusters for selective methane oxidation on Cu exchanged zeolites

Cu-zeolites are able to directly convert methane to methanol via a 3-step process using O2 as oxidant. Among the different zeolite topologies, Cu-exchanged mordenite (MOR) shows the highest methanol yields, attributed to a preferential formation of active Cu-oxo species in its 8-MR pores. The presence of extra-framework or partially detached Al species entrained in the micropores of MOR leads to the formation of nearly homotopic redox active Cu-Al-oxo nanoclusters with the ability to activate CH4. Studies of the activity of these sites together with characterization by 27Al NMR and IR spectroscopy leads to the conclusion that the active species are located in the 8-MR side pockets of MOR and it consists of two Cu ions and one Al linked by O. This Cu-Al oxo cluster shows an activity per Cu in methane oxidation significantly higher than of any previ-ously reported active Cu-oxo species. In order to determine unambiguously the structure of the active Cu-Al-oxo cluster, we combine experimental XANES of Cu K- and L- edges, Cu K-edge HERFD-XANES and Cu K-edge EXAFS with TDDFT and AIMD-assisted simulations. Our results provide evidence of a [Cu2AlO3]2+ cluster exchanged on MOR Al pairs that is able to oxidize up to two methane molecules per cluster at ambient pressure.

Methane oxidation, Cu L3-edge XANES, HERFD, TDDFT,↗
DOE OSTI2026

Mass Spectrometric Determination of Site-Specific O -Acetylation in Rhamnogalacturonan I Oligomers

O-acetylation, a common modification in rhamnogalacturonan I (RG-I), is critical for various biological processes, including plant growth, stress responses, and pathogen defense. Precise determination of the degree and specific positions of acetylation is therefore essential. To date, nuclear magnetic resonance (NMR) and tandem mass spectrometry have been employed to identify O-acetyl positions in pectin oligosaccharides. Although NMR is effective, it requires pure, high-concentration samples. Tandem mass spectrometry (MS), which uses smaller sample amounts, faces challenges due to O-acetyl migration between monosaccharide positions. The multiple steps in pectin sample analysis can further promote O-acetyl migration, especially near free hydroxyl groups. Moreover, during tandem MS, O-acetyl groups may detach, complicating the accurate tracking. This study presents an approach to lock O-acetyl groups by introducing trideuteroacetyl and propionyl substituents onto free hydroxyls of RG-I or partially acetylated RG-I. By combining matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) MS and electrospray ionization (ESI) MS with MS/MS or tandem mass spectrometry (MSn), we devised a way to determine the monosaccharide sequence in the oligomer and the precise positions of O-acetyl groups in partially acetylated RG-I. This method enables the study of the regiospecificity of recombinant pectin O-acetyltransferases and can be applied to other oligosaccharides to determine acyl positions.

O-acetylation↗
DOE OSTI2021

Generation of Subauroral Longitudinally Extended Emissions Following Intensifications of the Poleward Boundary of the Substorm Bulge and Streamer Production

Observations showing the development of Subauroral Longitudinally Extended Emigerssions on a global scale are presented. It is demonstrated that they occur as a separation of an east-west arc-like band of luminosity that detaches away from the equatorward edge of the auroral distribution following episodes of auroral streamer production. They persist for time intervals on the order of ~30 min and devolve into patchy disjointed segments before they fade. Emissions are seen in both 557.7 nm OI and 391.4 nm N + 2 1NG lines, and 630.0 nm emissions are often observed equatorward. The 391.4 nm emissions are typically weaker and fade away more quickly than the 557.7 nm emissions, suggesting that an auroral precipitation source is initially present but is rapidly depleted as the forms age. All cases are associated with enhanced Subauroral Polarization Stream (SAPS) flows, and one event shows clear association with large-scale Giant Undulations (GUs) and the formation of spur-like forms that fold equatorward under the main oval. A model is proposed for the production of subauroral longitudinally extended forms in which nonlinear growth of SAPS-induced surface waves on the plasmapause results in a disruption of the boundary. It is suggested that hot plasma of plasma sheet origin becomes entrained in the plasmasphere to produce transient precipitation-associated auroral emissions that may decay into STEVE emissions and that cold dense plasma from the plasmasphere becomes entrained onto open drift paths to feed long-lived drainage plumes. This process may occur quasi periodically during intense substorms and storm-time conditions.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Evolution of the Horizontal Winds in Jupiter's Great Red Spot From One Jovian Year of HST/WFC3 Maps

We measured the horizontal winds in Jupiter's Great Red Spot (GRS) using data from the WFC3/UVIS instrument on board the Hubble Space Telescope (HST). The data cover 11 epochs from 2009 to 2020. Long-term monotonic trends in size and shape previously noted from the visible cloud appearance are paralleled by changes in the high-speed ring around the vortex. The circularization of the GRS cannot be explained by changes in the horizontal wind shear of the surrounding environment. The velocity fields suggest no long-term trend in the static stability inside or outside the vortex. Instead, the changes are accompanied by a 4%–8% increase in the mean wind speeds of the high-speed ring from 2009 to 2020. Changes in the wind field coincided with the South Equatorial Belt Outbreak storms of 2016–2017, but not with 2019 "flaking" events involving detachment of red material from the main oval.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Can Glacial Sea‐Level Drop‐Induced Gas Hydrate Dissociation Cause Submarine Landslides?

Abstract We conducted two‐dimensional numerical simulations to investigate the mechanisms underlying the strong spatiotemporal correlation observed between submarine landslides and gas hydrate dissociation due to glacial sea‐level drops. Our results suggest that potential plastic deformation or slip could occur at localized and small scales in the shallow‐water portion of the gas hydrate stability zone (GHSZ). This shallow‐water portion of the GHSZ typically lies within the area enclosed by three points: the BGHSZ–seafloor intersection, the seafloor at ∼600 m below sea level (mbsl), and the base of the GHSZ (BGHSZ) at ∼1,050 mbsl in low‐latitude regions. The deep BGHSZ (>1,050 mbsl) could not slip; therefore, the entire BGHSZ was not a complete slip surface. Glacial hydrate dissociation alone is unlikely to cause large‐scale submarine landslides. Observed deep‐water (much greater than 600 mbsl) turbidites containing geochemical evidence of glacial hydrate dissociation potentially formed from erosion or detachment in the GHSZ pinch‐out zone.

58 GEOSCIENCES↗
DOE OSTI2026

Climatology of Cloud‐Land‐Surface Coupling Across Different ARM Sites

Land-atmosphere interactions play a critical role in the evolution and formation of low-level clouds. The different states of coupling between low-level clouds and the surface are uncertain, primarily over continental regions, where complex thermodynamics complicates their investigation. This study uses observations from the Atmospheric Radiation Measurement User Facility to explore cloud-surface coupling and perform a climatological analysis of this interaction in five countries across three continents. The results reveal consistent coupling thresholds and average percentages across the five sites, with coupled clouds accounting for 66% of the cases and decoupled clouds for 34%. Thermodynamic and dynamic evaluations show distinct differences between coupled and decoupled clouds. Coupled clouds are characterized by humid environments, in which vertical motions connect the surface and lower atmosphere to the cloud base, conditions that favor the formation of boundary layer clouds. Decoupled clouds prefer to occur in a drier and colder environment with vertical motions inside the boundary layer being detached from the cloud base, under which boundary layer clouds are hard to form. Coupled clouds peak during warmer hours and seasons, and vice versa for decoupled clouds. This study underscores the complexity of cloud-land-surface interactions and paves the way for further investigations into cloud formation and evolution under different atmospheric environments.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

The electron affinity of astatine

One of the most important properties influencing the chemical behavior of an element is the electron affinity (EA). Among the remaining elements with unknown EA is astatine, where one of its isotopes, 211 At, is remarkably well suited for targeted radionuclide therapy of cancer. With the At - anion being involved in many aspects of current astatine labeling protocols, the knowledge of the electron affinity of this element is of prime importance. Here we report the measured value of the EA of astatine to be 2.41578(7) eV. This result is compared to state-of-the-art relativistic quantum mechanical calculations that incorporate both the Breit and the quantum electrodynamics (QED) corrections and the electron–electron correlation effects on the highest level that can be currently achieved for many-electron systems. The developed technique of laser-photo detachment spectroscopy of radioisotopes opens the path for future EA measurements of other radioelements such as polonium, and eventually super-heavy elements.

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

Synthesis of molecular metallic barium superhydride: pseudocubic BaH 12

Following the discovery of high-temperature superconductivity in the La–H system, we studied the formation of new chemical compounds in the barium-hydrogen system at pressures from 75 to 173 GPa. Using in situ generation of hydrogen from NH 3 BH 3 , we synthesized previously unknown superhydride BaH 12 with a pseudocubic (fcc) Ba sublattice in four independent experiments. Density functional theory calculations indicate close agreement between the theoretical and experimental equations of state. In addition, we identified previously known P6/mmm-BaH 2 and possibly BaH 10 and BaH 6 as impurities in the samples. Ab initio calculations show that newly discovered semimetallic BaH 12 contains H 2 and H 3 – molecular units and detached H 12 chains which are formed as a result of a Peierls-type distortion of the cubic cage structure. Barium dodecahydride is a unique molecular hydride with metallic conductivity that demonstrates the superconducting transition around 20 K at 140 GPa.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

A unifying criterion of the boiling crisis

Abstract We reveal and justify, both theoretically and experimentally, the existence of a unifying criterion of the boiling crisis. This criterion emerges from an instability in the near-wall interactions of bubbles, which can be described as a percolation process driven by three fundamental boiling parameters: nucleation site density, average bubble footprint radius and product of average bubble growth time and detachment frequency. Our analysis suggests that the boiling crisis occurs on a well-defined critical surface in the multidimensional space of these parameters. Our experiments confirm the existence of this unifying criterion for a wide variety of boiling surface geometries and textures, two boiling regimes (pool and flow boiling) and two fluids (water and liquid nitrogen). This criterion constitutes a simple mechanistic rule to predict the boiling crisis, also providing a guiding principle for designing boiling surfaces that would maximize the nucleate boiling performance.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗