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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8

Goethite and Hematite Nucleation and Growth from Ferrihydrite: Effects of Oxyanion Surface Complexes

The presence of oxyanions, such as nitrate (NO 3 – ) and phosphate (PO 4 3– ), regulates the nucleation and growth of goethite (Gt) and hematite (Hm) during the transformation of ferrihydrite (Fh). Our previous studies showed that oxyanion surface complexes control the rate and pathway of Fh transformation to Gt and Hm. However, how oxyanion surface complexes control the mechanism of Gt and Hm nucleation and growth during the Fh transformation is still unclear. Here, we used synchrotron scattering methods and cryogenic transmission electron microscopy to investigate the effects of NO 3 – outer-sphere complexes and PO 4 3– inner-sphere complexes on the mechanism of Gt and Hm formation from Fh. Our TEM results indicated that Gt particles form through a two-step model in which Fh particles first transform to Gt nanoparticles and then crystallographically align and grow to larger particles by oriented attachment (OA). In contrast, for the formation of Hm, imaging shows that Fh particles first aggregate and then transform to Hm through interface nucleation. This is consistent with our X-ray scattering results, which demonstrate that NO 3 – outer-sphere and PO 4 3– inner-sphere complexes promote the formation of Gt and Hm, respectively. These results have implications for understanding the coupled interactions of oxyanions and iron oxy-hydroxides in Earth-surface environments.

54 ENVIRONMENTAL SCIENCES↗

Influence of Aqueous Phase Acidity on Ln(III) Coordination by N , N , N ', N '-Tetraoctyldiglycolamide

Here, this study highlights the importance of combining distribution ratio measurements with multiple spectroscopic techniques to provide a more comprehensive understanding of organic phase Ln coordination chemistry. Solvent extraction investigations with N,N,N',N'-tetraoctyldiglycolamide (TODGA) in n-heptane reveal the sensitivity of Ln complexation to the HNO 3 concentration. Distribution ratio measurements in tandem with UV–Vis demonstrated that increasing the concentration of HNO3 above 0.5 M with a constant NO 3 – of 1 M increases the number of coordinating TODGA molecules, from a 1:2 to a 1:3 Ln:TODGA complex. At each concentration of HNO 3 considered herein (from 0.01 to 1 M), Eu lifetime analysis demonstrated no evidence of H 2 O coordination. Results from Fourier transform infrared investigations suggest the presence of inner-sphere NO 3 – under low concentrations of HNO 3 when the 1:2 Ln:TODGA complex is present. Increasing the HNO 3 concentration above 0.5 M increases the propensity for outer-sphere interactions by removing the coordinated NO 3 – and saturating the Ln coordination sphere with three TODGA molecules, resulting in the well-established cationic, trischelate homoleptic [Ln(TODGA) 3 ] 3+ complex. This work demonstrates the importance in considering the NO 3 – source for solvent extraction systems. In particular, for systems with an affinity for outer-sphere interactions with molar concentrations of HNO 3 , changing the NO 3 – source can change the inner-sphere coordination of the Ln complex, which, in turn, affects the separation efficacy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling Pb(II) Adsorption on Mineral Surfaces: Bridging Density Functional Theory and Experiment with Thermodynamic Insights

Despite decades of work on aqueous lead (Pb) adsorption on a-Fe2O3 (hematite) and a-Al2O3 (alumina), gaps between measurements and modeling obscure molecular-level understanding. Achieving well-matched geometries between theory and experimental for mineral-water interfaces is a hurdle, as surface functional group type and distribution must be accounted for in determining mechanisms. Additionally, computational methods that can describe the substrate are often not appropriate to capture aqueous effects. Progress requires focusing on well-studied and relevant systems, such as key facets (001),(012), and (110) of hematite and alumina, and ubiquitous contaminants such as aqueous Pb. In the past, bulk-parametrized bond-valence principles were used to rationalize Pb(II) adsorption trends. These approaches can break down at surfaces, where flexible bonding environments and adsorption-induced surface relaxations play a critical role. Here, we adapt and apply a density functional theory (DFT) and thermodynamics framework, integrating DFT-calculated energies with experimental data and electrochemical principles, to predict Pb(II) adsorption. Our model results capture trends across the full set of surfaces and predict that inner-sphere Pb(II) sorption on (001) alumina varies from unfavorable to weakly favorable across a range of pH conditions. This aligns with experiment insights that Pb(II) interacts at that surface through outer-sphere interactions. Extending to Fe(II) adsorption, we demonstrate a coverage-dependent site preference, potentially explaining disorder in overlayers grown by the oxidative adsorption of Fe(II) on hematite (001).

lead contamination↗

Molecular-Level Insights into the NMR Relaxivity of Gadobutrol Using Quantum and Classical Molecular Simulations

MRI is an indispensable diagnostic tool in modern medicine; however, understanding the molecular-level processes governing NMR relaxation of water in the presence of MRI contrast agents remains a challenge, hindering the molecular-guided development of more effective contrast agents. By using quantum-based polarizable force fields, the first-of-its-kind molecular dynamics (MD) simulations of Gadobutrol are reported where the 1 H NMR longitudinal relaxivity r 1 of the aqueous phase is determined without any adjustable parameters. The MD simulations of r 1 dispersion (i.e., frequency dependence) show good agreement with measurements at frequencies of interest in clinical MRI. Importantly, the simulations reveal key insights into the molecular level processes leading to r 1 dispersion by decomposing the NMR dipole–dipole autocorrelation function G(t) into a discrete set of molecular modes, analogous to the eigenmodes of a quantum harmonic oscillator. The molecular modes reveal important aspects of the underlying mechanisms governing r 1 , such as its multiexponential nature and the importance of the second eigenmodal decay. By simply analyzing the MD trajectories on a parameter-free approach, the Gadobutrol simulations show that the outer-shell water contributes ∼50% of the total relaxivity r 1 compared to the inner-shell water, in contrast to simulations of (nonchelated) gadolinium-aqua where the outer shell contributes only ∼15% of r 1 . The deviation between simulations and measurements of r 1 below clinical MRI frequencies is used to determine the low-frequency electron-spin relaxation time for Gadobutrol, in good agreement with independent studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Competitive Valerate Binding Enables RuO 2 -Mediated Butene Electrosynthesis in Water

The (non)-Kolbe oxidation of valeric acid, sourced from a hydrolysis product of cellulose, provides a sustainable synthetic route to access value-added products, such as butene. An essential mechanistic step preceding product formation involves the oxidative and decarboxylative cleavage of a C–C bond. Yet, the role of the electrode surface in mediating this oxidative step remains an open question: the electron transfer can occur either via an inner-sphere or outer-sphere mechanism. Here, we report the electrochemical, in situ spectroscopic, computational, and reactivity studies of RuO 2 -mediated oxidative decarboxylation of valeric acid to butene in aqueous electrolytes. We find that carboxylates bind to RuO 2 anode surfaces at potential values where decarboxylation products are observed. Our results are consistent with a reaction scheme where the competitive and catalytic oxygen evolution reaction (OER) is impeded by these bound carboxylate species while these species are inert toward butene formation. Our results implicate an outer-sphere electron transfer mechanism for decarboxylation where the surface chemistry of the RuO 2 electrode serves to enable higher non-Kolbe reaction selectivity by suppressing the parasitic OER. Furthermore, our findings delineate interfacial design principles for selective electrochemical systems that utilize water as the ultimate oxidant for sustainable decarboxylation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Neutron Reflectometry Reveals the Interfacial Microenvironment Driving Electrochemical Ammonia Synthesis

Electrified interfaces are critical to the performance of energy systems and often demonstrate substantial complexity under operating conditions. A nanoscale understanding of the interfacial microenvironment, i.e., the solid-electrolyte interphase (SEI), in lithium-mediated nitrogen reduction (Li–N 2 R) is key for realizing efficient ammonia (NH 3 ) production. Herein, we used time-resolved neutron reflectometry (NR) to observe SEI formation under Li–N 2 R conditions. We found that the LiBF 4 -based electrolyte provided a substantially more well-defined SEI layer than previous SEI NR interrogations that used LiClO 4 , highlighting the underlying chemistry that dictates electrolyte design and enabling new NR-based studies. Using in situ NR, we found that the LiBF 4 -derived SEI under Li–N 2 R conditions comprises a thick, diffuse outer layer and a thin, compact inner layer at low current cycling (<2 mA/cm 2 ), revealing a structure which ex situ studies have not been able to probe. Increased current cycling and sustained current cycling led to the merging of the layers into a single-layer SEI. Here, we used isotope contrast methods with d 6 -EtOH and d 8 -THF to drive time-resolved tracking of SEI growth at low current cycling, revealing that the proton donor modifies the inner layer, and the solvent modifies the outer layer. Li dendritic growth was observed in the absence of a proton donor. Neutron absorption also indicated the presence of boron in the SEI, underscoring the value of neutron-based interrogation. Our results inform Li-based systems and reaction microenvironments, and these methods can be applied broadly to interfacial energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring the Selective Oxidation of Hydroxyl-Containing Compounds via Precisely Tuning the Hydrogen-Bond Strength of Catalyst H-Bond Acceptors

The unique performance of the enzyme is mainly achieved via weak interactions between the “outer coordination sphere” and the substrate. Inspired by this process, we developed 3D encapsulated-structure catalysts with hydrogen-bond engineering on the shell, which mimics the “outer coordination sphere” of an enzyme. Various hydrogen bond acceptors (C=O, S=O, and N–O groups) are imparted in the shell. Concentration-dependent 1H NMR, inverse-phase gas Chromatography (IGC) measurements, and DFT calculations underscore that the hydrogen bond strength between the acceptor groups and alcohol follows the order of C=O < S=O < N–O. The hydroxyl compound oxidation rate vs the hydrogen bond strength follows a volcano behavior, reminiscent of Sabatier’s principle. The performance variation among catalysts is attributed to the adsorption strength of the substrate. The proposed bioinspired design principle expands the scope of encapsulated catalysts, enabling fine regulation of catalytic activity through precise microenvironment control via weak interactions with substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetotail Variability During Magnetospheric Substorms

Abstract In this work, we present a statistical study of substorms covering a five‐year period 2016–2020. Substorm phases were identified from time series of the SuperMAG AL (SML) index using a list of 5,077 previously identified substorm onsets, the SML peak value marking transition from expansion to recovery phase, and the recovery identified as return to activity less than −100 nT in the SML index. Magnetic field observations from THEMIS, RBSP, and MMS missions were used to study the magnetotail characteristics during the substorm evolution. A superposed epoch analysis indicates that the substorm onset occurs almost simultaneously with a few minutes of uncertainty throughout the magnetotail, ranging from geostationary orbit to 20 RE. The onset in the transition region precedes the ground onset by a few minutes. The peak SML time coincides with the peak of the outer transition region Δ B Z , which suggests that the field‐aligned currents driving the SML activity arise from the outer transition region. Analysis of 2D maps of the tail magnetic field shows that the magnetotail current changes are limited to the center of the tail within | Y | < 10 R E . The substorm recovery is fastest in the inner transition region and lasts longer when moving further out. We did not find major asymmetries in the substorm signatures associated with IMF B Y or B Z .

Kumar, S.↗

Derivations of the Total Radiation Belt Electron Content

Abstract We present multiple derivations of the Total Radiation Belt Electron Content (TRBEC), an indicator of the global number of electrons that instantaneously occupy the radiation belts. Derived from electron flux measurements, the TRBEC reduces the spatial information into a scalar quantity that concisely describes global aspects of the system. This index provides a simple, global, and long‐term assessment of the radiation belts that enables systematic analysis. In this work, we examine the TRBEC using the adiabatic invariants of which has been used in previous articles as this coordinate system removes reversible adiabatic effects. We then introduce a new expression to compute the TRBEC using the non‐adiabatic coordinates of , relevant in the contexts of energetic electron precipitation, chorus, and hiss scattering where adiabatic invariant quantities are no longer conserved. From both expressions of the TRBEC we demonstrate that an erroneous factor of that appeared in previous works using the adiabatic derivation led to an overestimate of the reported electron populations. In addition, we quantify electron loss in the outer radiation belt via a case study using the Van Allen Probes data over a 20‐day period from March 2013 specifying particle populations both in terms of the aforementioned adiabatic and non‐adiabatic variables. The total number of electrons in the outer radiation belt reached upwards of electrons at the peak of the storm, a rest mass of roughly 10 g.

Astronomy & Astrophysics↗

PreMevE‐MEO: Predicting Ultra‐Relativistic Electrons Using Observations From GPS Satellites

Abstract Ultra‐relativistic electrons with energies greater than or equal to two megaelectron‐volt (MeV) pose a major radiation threat to spaceborne electronics, and thus specifying those highly energetic electrons has a significant meaning to space weather communities. Here we report the latest progress in developing our predictive model for MeV electrons in the outer radiation belt. The new version, primarily driven by electron measurements made along medium‐Earth‐orbits (MEO), is called PREdictive MEV Electron (PreMevE)‐MEO model that nowcasts ultra‐relativistic electron flux distributions across the whole outer belt. Model inputs include >2 MeV electron fluxes observed in MEOs by a fleet of GPS satellites as well as electrons measured by one Los Alamos satellite in the geosynchronous orbit. We developed an innovative Sparse Multi‐Inputs Latent Ensemble NETwork (SmileNet) which combines convolutional neural networks with transformers, and we used long‐term in situ electron data from NASA's Van Allen Probes mission to train, validate, optimize, and test the model. It is shown that PreMevE‐MEO can provide hourly nowcasts with high model performance efficiency and high correlation with observations. This prototype PreMevE‐MEO model demonstrates the feasibility of making high‐fidelity predictions driven by observations from longstanding space infrastructure in MEO, thus has great potential of growing into an invaluable space weather operational warning tool.

79 ASTRONOMY AND ASTROPHYSICS↗

Mesh-like structure integrated core-shell-shell nanocomposites for enhanced stability and performance in carbon capture

Carbon capture is essential for mitigating climate change, yet most sorbents struggle to combine high capacity with chemical stability. Here we report core-shell-shell (CSS) nanocomposites that integrate adsorption efficiency with exceptional robustness. The design couples a metal-organic framework (MOF) core, which enriches local CO 2 concentration, with a polyamine shell that is reorganized into a porous, ordered network through entanglement with an outer covalent organic framework (COF) shell. This hierarchical architecture enables dual amine functionalization via sequential “click” and Schiff-base reactions, achieving a CO 2 uptake of 3.4 mmol g −1 at 1 bar. The COF outer layer also acts as a protective barrier, suppressing humidity interference and doubling cycling stability under simulated flue gas. Remarkably, the nanocomposites maintain structural integrity after one week in strongly acidic (3 M HNO 3 ) or basic (NaOH, pH=14) environments, underscoring their chemical resilience. By uniting high capacity, cycling durability, and environmental tolerance, this CSS strategy offers a versatile platform for next-generation carbon capture materials.

Yang, Sizhuo [Lawrence Berkeley National Laborator↗

Abundant ammonia and nitrogen-rich soluble organic matter in samples from asteroid (101955) Bennu

Organic matter in meteorites reveals clues about early Solar System chemistry and the origin of molecules important to life, but terrestrial exposure complicates interpretation. Samples returned from the B-type asteroid Bennu by the Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer mission enabled us to study pristine carbonaceous astromaterial without uncontrolled exposure to Earth’s biosphere. Here we show that Bennu samples are volatile rich, with more carbon, nitrogen and ammonia than samples from asteroid Ryugu and most meteorites. Nitrogen-15 isotopic enrichments indicate that ammonia and other N-containing soluble molecules formed in a cold molecular cloud or the outer protoplanetary disk. We detected amino acids (including 14 of the 20 used in terrestrial biology), amines, formaldehyde, carboxylic acids, polycyclic aromatic hydrocarbons and N-heterocycles (including all five nucleobases found in DNA and RNA), along with ~10,000 N-bearing chemical species. All chiral non-protein amino acids were racemic or nearly so, implying that terrestrial life’s left-handed chirality may not be due to bias in prebiotic molecules delivered by impacts. The relative abundances of amino acids and other soluble organics suggest formation and alteration by low-temperature reactions, possibly in NH 3 -rich fluids. Bennu’s parent asteroid developed in or accreted ices from a reservoir in the outer Solar System where ammonia ice was stable.

79 ASTRONOMY AND ASTROPHYSICS↗

The variety and origin of materials accreted by Bennu’s parent asteroid

The first bodies to form in the Solar System acquired their materials from stars, the presolar molecular cloud and the protoplanetary disk. Asteroids that have not undergone planetary differentiation retain evidence of these primary accreted materials. However, geologic processes such as hydrothermal alteration can dramatically change their bulk mineralogy, isotopic compositions and chemistry. Here we analyse the elemental and isotopic compositions of samples from asteroid Bennu to uncover the sources and types of material accreted by its parent body. We show that some primary accreted materials escaped the extensive aqueous alteration that occurred on the parent asteroid, including presolar grains from ancient stars, organic matter from the outer Solar System or molecular cloud, refractory solids that formed close to the Sun, and dust enriched in neutron-rich Ti isotopes. We find Bennu to be richer in isotopically anomalous organic matter, anhydrous silicates, and light isotopes of K and Zn than its closest compositional counterparts, asteroid Ryugu and Ivuna-type (CI) carbonaceous chondrite meteorites. We propose that the parent bodies of Bennu, Ryugu and CI chondrites formed from a common but spatially and/or temporally heterogeneous reservoir of materials in the outer protoplanetary disk.

Kuiper belt↗

Probing the active sites of oxide encapsulated electrocatalysts with controllable oxygen evolution selectivity

Electrocatalysts encapsulated by nanoscopic overlayers can control the rate of redox reactions at the outer surface of the overlayer or at the buried interface between the overlayer and the active catalyst, leading to complex behavior in the presence of two competing electrochemical reactions. This study investigated oxide encapsulated electrocatalysts (OECs) comprised of iridium (Ir) thin films coated with an ultrathin (2–10 nm thick) silicon oxide (SiO x ) or titanium oxide (TiO x ) overlayer. The performance of SiO x |Ir and TiO x |Ir thin film electrodes towards the oxygen evolution reaction (OER) and Fe(II)/Fe(III) redox reactions were evaluated. An improvement in selectivity towards the OER was observed for all OECs. Overlayer properties, namely ionic and electronic conductivity, were assessed using a combination of electroanalytical methods and molecular dynamics simulations. SiO x and TiO x overlayers were found to be permeable to H 2 O and O 2 such that the OER can occur at the MO x |Ir (M = Ti, Si) buried interface, which was further supported with molecular dynamics simulations of model SiO 2 coatings. In contrast, Fe(II)/Fe(III) redox reactions occur to the same degree with TiO x overlayers having thicknesses less than 4 nm as bare electrocatalyst, while SiO x overlayers inhibit redox reactions at all thicknesses. This observation is attributed to differences in electronic transport between the buried interface and outer overlayer surface, as measured with through-plane conductivity measurements of wetted overlayer materials. These findings reveal the influence of oxide overlayer properties on the activity and selectivity of OECs and suggest opportunities to tune these properties for a wide range of electrochemical reactions.

08 HYDROGEN↗

Source shape estimation for neutron imaging systems using convolutional neural networks

Neutron imaging systems are important diagnostic tools for characterizing the physics of inertial confinement fusion reactions at the National Ignition Facility (NIF). In particular, neutron images give diagnostic information on the size, symmetry, and shape of the fusion hot spot and surrounding cold fuel. Images are formed via collection of neutron flux from the source using a system of aperture arrays and scintillator-based detectors. Currently, reconstruction of fusion source geometry from the collected neutron images is accomplished by solving a computationally intensive maximum likelihood estimation problem via expectation maximization. In contrast, it is often useful to have simple representations of the overall source geometry that can be computed quickly. In this work, we develop convolutional neural networks (CNNs) to reconstruct the outer contours of simple source geometries. We compare the performance of the CNN for penumbral and pinhole data and provide experimental demonstrations of our methods on both non-noisy and noisy data.

Machine learning, neutron imaging, source reconstr↗

First-wall fluxes from large and small ELMs

Experimental analysis at DIII-D shows that small edge localized modes (ELMs) deposit a larger fraction of their energy to the first wall, compared to type-I ELMs in similar magnetic configuration and input power. The energy (λQ) and particle (λΓ) flux decay lengths in the scrape-off layer (SOL) are up to 3 and 5 times larger, respectively, for small ELMs than for larger type-I ELMs. Transport dynamics of ELM filaments in the SOL are found to be related to divertor conditions, where high divertor collisionality, typical for partially detached plasmas, is associated with increased cross field ELM radial fluxes. Results show that a sufficiently large outer wall gap and/or limiters might be needed in future scenarios to protect the first wall, if operating with small ELMs and a cold divertor. This might also have implications for RF heating in future devices, where the coupling efficiency is dependent to some degree to the outer-wall gap.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Experimental demonstration of transient CHI start-up using a floating biased electrode configuration

Transient coaxial helicity injection (CHI) current start-up in a spherical tokamak (ST) has been demonstrated for the first time using a reactor-relevant floating single biased (FSB) electrode configuration on QUEST. Unlike previous applications of CHI on HIT-II and on NSTX in which the entire ST vessel was split in two using two toroidal ceramic rings as vacuum breaks, in the FSB electrode configuration on QUEST, only the lower outer divertor plate is electrically insulated from the rest of the vessel. This is the CHI injector region. A CHI discharge is generated by driving current, using an external power supply, along magnetic field lines that connect the inner and outer divertor plates in the CHI injector region. The CHI plasma evolution and closed flux formation on QUEST are very similar to those on NSTX and have generated toroidal currents of 150 kA with 100 kA of current flowing on closed flux surfaces. An alternate, force-free model approach has been used to derive the CHI scaling relations. The resulting CHI scaling relations from the model are consistent with the conventional CHI scaling relations, which state that the CHI generated toroidal current is proportional to the CHI injector flux and the CHI injector current is inversely proportional to the toroidal field. These results from QUEST bode well for the application of CHI in a new generation of compact high field STs and low aspect ratio tokamaks in which the space for the central solenoid is very restricted.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Numerical investigation of magneto-inertial fusion targets magnetized by dynamic enforcement of helical current flow

Magnetized Liner Inertial Fusion (MagLIF) targets require premagnetization to reduce thermal conduction losses from the laser-heated fuel to the liner material during implosion. MagLIF targets are typically magnetized by external magnetic field coils which are technologically limited to providing <20 T axial magnetic fields in the fusion fuel. We present a novel target design, AutoMag-D, which employs dynamic enforcement of helical current in the liner, resulting in >20 T axial magnetic field in the fuel region prior to implosion without the need of external magnetic field coils. These self-magnetizing liners are made of helically oriented alternating electrically conductive material and electrically insulating material surrounded by a thin, conductive outer radial layer. As the liner is pulsed with a ∼ 20 MA, ∼ 100 ns rise time drive current from Z, the outer layer of conductive material is shocked and intensely Joule heated, causing it to melt, vaporize, and turn to plasma. This allows the magnetic drive field to diffuse radially inward which dynamically enforces current flow in the helical conduction paths in the liner and produces axial magnetic field in the fuel region prior to implosion of the inner liner surface. AutoMag-D liner designs do not require dielectric breakdown of electrically insulating material (as in traditional auto-magnetizing helical liners) and do not require helical return current geometries (as in dynamic screw pinches). We present results from three-dimensional radiation-magnetohydrodynamic simulations of MagLIF implosions employing AutoMag-D liner designs. Simulated AutoMag-D targets demonstrate improved fuel conditions and thermonuclear yield compared to traditional MagLIF.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗