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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 1,675 records · Page 93
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Aspartate transformation at 200 °C with brucite [Mg(OH) 2 ], NH 3 , and H 2 : Implications for prebiotic molecules in hydrothermal systems

Hydrothermal systems may have been favorable environments for the evolution of prebiotic chemistry on early Earth due to the presence of chemical, temperature, and redox gradients that could promote the formation of biomolecules. However, the relevance of these environments in origins of life scenarios has been debated due to rapid decomposition of biologically essential species, such as amino acids, at high temperatures. Little is known about the reactivity of amino acids in the presence of mineral surfaces and reducing conditions, which reflect the geochemical complexities of environments such as serpentinite-hosted hydrothermal vents. We investigated the decomposition of 25 mM aspartate at 200 °C and 15.5 bars (P SAT ) in gold capsules both with and without brucite [Mg(OH) 2 ], a mineral product of serpentinization, and reducing conditions (NH 4 Cl and H 2(aq) ). Here we observed that the reaction products of aspartate vary significantly with the initial reaction conditions. Fluids containing aspartate only decomposed to fumarate, maleate, malate, acetate, and trace amounts of succinate and glycine. However, under reducing conditions, the main product was succinate (8 mM) and also approximately 1 mM total of the amino acids glycine, α-alanine, and β-alanine. The amount of α-alanine increased three-fold with brucite. Furthermore, we detected a two-fold decrease in the fumarate concentration, whereas total maleate concentration dramatically decreased over ten-fold and resulted in an overall increase in the trans/cis ratio of these deamination products of aspartate from 0.9 to 4.5 as a function of brucite loading. This net decrease in fumarate and maleate concentration and the five-fold increase in the trans/cis ratio might have been caused by a combination of a pH increase and the formation of magnesite due to increased Mg 2 + ion concentration. The results of this study provide evidence that the fundamental properties of a hydrothermal system, including mineral assemblages, reducing conditions, and dissolved species concentrations, will influence the fate of amino acids at high temperature.

58 GEOSCIENCES↗
DOE OSTI2021

Influence of ethylenediaminetetraacetic acid on the long-term oxidation state distribution of plutonium

Here, spectrophotometry was used to study the effect of EDTA on plutonium oxidation state distribution as a function of time, pH, and ligand-to-metal ratio (L/M) under anoxic conditions. Novel Pu(V)-EDTA absorption bands were identified at 571, 993, 1105, and 1150 nm with molar absorption coefficients of 15 ± 1, 6 ± 1, 10 ± 1, and 10 ± 1 cm –1 M –1 , respectively. Pu(V)-EDTA spectral changes occurred at L/M < 1, indicating only Pu V O 2 (EDTA) 3- formed with logK = 3.6 ± 0.3. Time-resolved experiments showed EDTA drastically increased the Pu(V/VI) reduction rate, which we propose is driven by amine lone-pair electron donation and the oxidative decarboxylation of EDTA. Oxidation of Pu(III)-EDTA to Pu(IV)-EDTA occurred on a slower time scale (110–237 days) than previously reported (<15 min) and is hypothesized to be radiolysis driven. Pu(V/VI)-EDTA and Pu(III)-EDTA both approached Pu(IV)-EDTA stabilization over time, yet Pu(V/VI)-EDTA solubility data was ≥ 1.0 log 10 units higher than predicted by Pu(IV)-EDTA solubility models, indicating that current thermodynamic models are incomplete. Ultimately, the data show EDTA preferentially stabilizes Pu(IV) over time regardless of initial oxidation state, but Pu(V)-EDTA can persist under environmentally-relevant conditions, emphasizing the need to continue investigating redox reactions, speciation, and behavior of these complexes to support the transuranic waste disposal and surface remediation/containment efforts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2018

Radiocesium interaction with clay minerals: Theory and simulation advances Post–Fukushima

Insights at the microscopic level of the process of radiocesium adsorption and interaction with clay mineral particles have improved substantially over the past several years, triggered by pressing social issues such as management of huge amounts of waste soil accumulated after the Fukushima Dai-ichi nuclear power plant accident. In particular, computer-based molecular modeling supported by advanced hardware and algorithms has proven to be a powerful approach. Its application can now generally encompass the full complexity of clay particle adsorption sites from basal surfaces to interlayers with inserted water molecules, to edges including fresh and weathered frayed ones. On the other hand, its methodological schemes are now varied from traditional force-field molecular dynamics on large-scale realizations composed of many thousands of atoms including water molecules to first-principles methods on smaller models in rather exacting fashion. In this article, we overview new understanding enabled by simulations across methodological variations, focusing on recent insights that connect with experimental observations, namely: 1) the energy scale for cesium adsorption on the basal surface, 2) progress in understanding the structure of clay edges, which is difficult to probe experimentally, 3) cesium adsorption properties at hydrated interlayer sites, 4) the importance of the size relationship between the ionic radius of cesium and the interlayer distance at frayed edge sites, 5) the migration of cesium into deep interlayer sites, and 6) the effects of nuclear decay of radiocesium. Key experimental observations that motivate these simulation advances are also summarized. Furthermore, some directions toward future solutions of waste soil management are discussed based on the obtained microscopic insights.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Cations controlled growth of β-MnO 2 crystals with tunable facets for electrochemical energy storage

Engineering crystal facets to enhance their functionalities often require complex processing routes to suppress the growth of surfaces with the lowest thermodynamic energies. Herein, we report a unique method to control the morphologies of β-MnO 2 crystals with different occupancy of {100}/{111} facets through the effect of K + cations. Combining aberration-corrected scanning transmission electron microscopy (STEM), ultramicrotomy, and dynamic functional theory (DFT) simulation, we clarified that the β-MnO 2 crystals were formed through a direct solid-state phase transition process. Increasing the concentration of K + cations in the precursor gradually changed the morphology of β-MnO 2 from bipyramid prism ({100}+{111} facets) to an octahedron structure ({111} facets). The K + cations controlled the morphology of β-MnO 2 by affecting the formation of α-K 0.5 Mn 4 O 8 intermediate phase and the subsequent phase transition. Utilizing the β-MnO 2 crystals as the cathode for Li-ion batteries showed that highly exposed {111} facets offered β-MnO 2 crystal better rate performance, with ~70% capacity retention when the charge-discharge rate increased from 20 mA/g to 200 mA/g. Furthermore, our work revealed a new mechanism to tune the morphology of this earth-abundant metal oxide crystal, which could be used to adjust its electrochemical performance for different applications, such as supercapacitors and catalysts for metal-air batteries and fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2019

Synthesis of Ni-Rich Thin-Film Cathode as Model System for Lithium Ion Batteries

We demonstrate a process to prepare model electrodes of the Ni-rich layered compound LiNi 0.6 Mn 0.2 Co 0.2 O 2 . These thin-film cathodes are compared with the composite materials to demonstrate the system is a viable platform for isolating interfacial phenomena between the electrolyte and active material without the influence of binders and conductive additives. The appropriate choice of heterolayers was found to influence the preferential orientation of the (101) and (104) planes relative to the (003) plane of the layered R-3m crystal structure, enhancing Li + diffusion and improving electrochemical performance. The addition of a Co interlayer between the Pt current collecting layer and alumina substrate increased the (101) and (104) texturing of the 500 nm Ni-rich film and allowed cells to deliver greater than 50% of their theoretical capacity. This work provides an architecture for isolating complex mechanisms of active materials that suffer from surface reconstruction and degradation in electrochemical cells.

25 ENERGY STORAGE↗
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 OSTI2022

Monolayer Molecular Functionalization Enabled by Acid–Base Interaction for High-Performance Photochemical CO 2 Reduction

We report the development of a hybrid catalyst consisting of carbon nitride (CN x ) and cobalt phthalocyanine tetracarboxylic acid (CoPc-COOH), which converts CO 2 to CO with high reaction rate (1067 μmol/g·h) and high selectivity (over 98%), under simulated solar irradiation. The carboxylic acid substituents on the phthalocyanine ligands play a critical role as they bind to the amine groups of CN x to enable nearly ideal monolayer coverage of the molecular co-catalyst on the semiconductor surface and promote catalytic activity from the molecular complex. Specifically, the CN x /CoPc-COOH hybrid material achieves a reaction rate 16 times higher than a CN x material containing unsubstituted CoPc molecules. We further show that activation and deactivation of the CN x /CoPc-COOH composite, which are associated with the reduction and decomposition of CoPc-COOH, respectively, both proceed at a nearly constant rate regardless of the CO 2 reduction reaction rate. Here, the decoupling of charge carrier injection and CO 2 reduction catalysis has important mechanistic implications for future performance optimization and materials design of photocatalysts for CO 2 reduction.

14 SOLAR ENERGY↗
DOE OSTI2025

Tracking Local pH Dynamics during Water Electrolysis via In-Line Continuous Flow Raman Spectroscopy

The performance of electrochemical devices, which play a critical role in decarbonization efforts, is often governed by proton-coupled electron transfer reactions at the electrode–electrolyte interface. These reactions are highly sensitive to the complex and dynamic microenvironment present at the electrode surface. However, characterizing this environment─particularly monitoring interfacial pH and its evolution under reaction conditions─remains challenging, necessitating the development of advanced analytical tools. Here, in this study, we introduce in-line continuous flow Raman spectroscopy (CFRS) as a spectroelectrochemical platform for quantifying interfacial pH swings generated during water-splitting. By monitoring phosphate ion speciation and controlling the hydrodynamics with a flow cell, we measure pH swings as a function of current density, flow rate, and distance from the electrode. Comparison with theoretical models reveals the impact of bulk pH, boundary layer thickness, and bubble dynamics at high current densities. Collectively, these findings establish CFRS as a platform for quantitatively investigating pH dynamics, offering critical insights for advancing electrochemical energy conversion technologies.

Marquez, Raul A. [Univ. of Texas, Austin, TX (Unit↗
DOE OSTI2020

Atomically Dispersed Iron–Nitrogen Sites on Hierarchically Mesoporous Carbon Nanotube and Graphene Nanoribbon Networks for CO 2 Reduction

Atomically dispersed metal and nitrogen co-doped carbon (M-N/C) catalysts hold great promise for electrochemical CO 2 conversion. However, there is a lack of cost-effective synthesis approaches to meet the goal of economic mass production of single-atom M-N/C with desirable carbon support architecture for efficient CO 2 reduction. Herein, we report facile transformation of commercial carbon nanotube (CNT) into isolated Fe-N 4 sites anchored on carbon nanotube and graphene nanoribbon (GNR) networks (Fe-N/CNT@GNR). The oxidization-induced partial unzipping of CNT results in the generation of GNR nanolayers attached to the remaining fibrous CNT frameworks, which reticulates a hierarchically mesoporous complex and thus enables a high electrochemical active surface area and smooth mass transport. The Fe residues originating from CNT growth seeds serve as Fe sources to form isolated Fe-N-4 moieties located at the CNT and GNR basal plane and edges with high intrinsic capability of activating CO 2 and suppressing hydrogen evolution. The Fe-N/CNT@GNR delivers a stable CO Faradaic efficiency of 96% with a partial current density of 22.6 mA cm -2 at a low overpotential of 650 mV, making it one of the most active M-N/C catalysts reported. This work presents an effective strategy to fabricate advanced atomistic catalysts and highlights the key roles of support architecture in single-atom electrocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Three-dimensional imaging of vortex structure in a ferroelectric nanoparticle driven by an electric field

Topological defects of spontaneous polarization are extensively studied as templates for unique physical phenomena and in the design of reconfigurable electronic devices. Experimental investigations of the complex topologies of polarization have been limited to surface phenomena, which has restricted the probing of the dynamic volumetric domain morphology in operando. Here, we utilize Bragg coherent diffractive imaging of a single BaTiO 3 nanoparticle in a composite polymer/ferroelectric capacitor to study the behavior of a three-dimensional vortex formed due to competing interactions involving ferroelectric domains. Our investigation of the structural phase transitions under the influence of an external electric field shows a mobile vortex core exhibiting a reversible hysteretic transformation path. We also study the toroidal moment of the vortex under the action of the field. Our results open avenues for the study of the structure and evolution of polar vortices and other topological structures in operando in functional materials under cross field configurations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Ce stabilized Ni–SrO as a catalytic phase transition sorbent for integrated CO 2 capture and CH 4 reforming

Integration of carbon dioxide capture from flue gas with dry reforming of CH 4 represents an attractive approach for CO 2 utilization. The selection of a suitable bifunctional material serving as a catalyst/sorbent is the key. This paper reports Ni decorated and CeO x -stabilized SrO (SrCe 0.5 Ni 0.5 ) as a multi-functional, phase transition catalytic sorbent material. The effect of CeO x on the morphology, structure, decarbonation reactivity, and cycling stability of the catalytic sorbent was determined with TEM-EDX, XRD, in situ XRD, CH 4 -TPR and TGA. Here, cyclic process tests were conducted in a packed bed reactor. The results indicate that large Ni clusters were present on the surface of the SrNi sorbent, and the addition of CeO 2 promoted even distribution of Ni on the surface. Moreover, the Ce–Sr interaction promoted a complex carbonation/decarbonation phase-transition, i.e. SrCO 3 + CeO 2 ↔ Sr 2 CeO 4 + CO 2 as opposed to the conventional, simple carbonation/decarbonation cycles (e.g. SrCO 3 ↔ SrO + CO 2 ). This double replacement crystalline phase transition mechanism not only adjusts the carbonation/calcination thermodynamics to facilitate SrCO 3 decomposition at relatively low temperatures but also inhibits sorbent sintering. As a result, excellent activity and stability were observed with up to 91% CH 4 conversion, >72% CO 2 capture efficiency and ~100% residual O 2 capture efficiency from flue gas by utilizing the CeO 2 ↔ Ce 2 O 3 redox transition. This renders an intensified process with zero coke deposition. Moreover, the SLDRM with SrCe 0.5 Ni 0.5 has the flexibility to produce concentrated CO via CO 2 -splitting while co-producing a syngas with tunable H 2 /CO ratios.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Understanding the anharmonic vibrational structure of the carbon dioxide dimer

Understanding the vibrational structure of the CO 2 system is important to confirm the potential energy surface and interactions in such van der Waals complexes. In this work, we use our previously developed mbCO2 potential function to explore the vibrational structure of the CO 2 monomer and dimer. The potential function has been trained to reproduce the potential energies at the CCSD(T)-F12b/aug-cc-pVTZ level of electronic structure theory. The harmonic approximation, as well as anharmonic corrections using vibrational structure theories such as vibrational self-consistent field, vibrational second-order Moller-Plesset perturbation, and vibrational configuration interaction (VCI), is applied to address the vibrational motions. We compare the vibrational results using the mbCO2 potential function with traditional electronic structure theory results and to experimental frequencies. The anharmonic results for the monomer most closely match the experimental data to within 3 cm -1 , including the Fermi dyad frequencies. The intermolecular and intramolecular dimer frequencies were treated separately and show good agreement with the most recent theoretical and experimental results from the literature. The VCI treatment of the dimer vibrational motions accounts for vibrational mixing and delocalization, such that we observe the dimer Fermi resonance phenomena, both in the intramolecular and intermolecular regions.

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

Direct functionalization of C-H bonds by electrophilic anions

Bond formation between two of the most inert molecules, alkanes and [B12X12]2- (X = Cl, Br), is performed in a two step process. Fragmentation of [B12X12]2- in the gas phase generates highly reactive [B12X11]- ions which spontaneously react with alkanes. The reaction mechanism was investigated using tandem mass spectrometry and gas-phase vibrational spectroscopy combined with electronic structure calculations. This effort revealed the unprecedented and counterintuitive electrophilic substitution of a proton in an alkane by a negatively charged ion resulting in a B-C bond formation. The product is a dianionic [B12X11CnH2n+1]2- species, in which H+ is electrostatically bound to the dianion. High flux ion soft-landing was performed to co-deposit [B12X11]- and complex organic molecules (phthalates) in thin layers on surfaces. Molecular structure analysis of the product films revealed that C-H functionalization by [B12X11]- occured in the presence of other more reactive functional groups. This observation demonstrates the utility of highly reactive fragment ions for defined bond formation processes and may pave the way to the use of gas phase ion chemistry for chemical synthesis in the condensed phase.

Warneke, Jonas↗
DOE OSTI2019

Mitigating the Threat of Nuclear-Weapon Proliferation via Nuclear-Submarine Programs

Brazil is building a nuclear-powered attack submarine, South Korea has in the past asserted its need for nuclear-powered attack submarines to deal with the threat of North Korean nuclear-armed submarine-launched ballistic missiles, and Iran has asserted more vaguely its need for naval nuclear propulsion. All three countries are non-weapon-state parties to the Nuclear Nonproliferation Treaty (NPT). Their interest in naval reactors brings with it two challenges to the NPT: 1) The safeguards “loophole” under which a country can withdraw nuclear materials from IAEA safeguards indefinitely for allowed “non-peaceful activities;” and 2) A justification for the acquisition of national uranium-enrichment facilities because the international suppliers of enrichment services have peaceful-use requirements. In fact, Brazil’s acquisition of enrichment was driven by its navy. It is argued, however, that nuclear-powered attack submarines have advantages over modern conventional attack submarines primarily in their ability to transit great distances at high speed whereas only a few countries have foreign military commitments requiring such capabilities. For defense of nearby waters against foreign navies, attack submarines are merely one component of a complex system of anti-submarine aircraft and surface vessels and underwater sensor networks. Conventional attack submarines are no less effective and much less costly than nuclear-powered attack submarines in this role.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2018

On-shot characterization of single plasma mirror temporal contrast improvement

Here, we report on the setup and commissioning of a compact recollimating single plasma mirror (PM) for temporal contrast enhancement at the Draco 150 TW laser during laser-proton acceleration experiments. The temporal contrast with and without PM is characterized single-shot by means of self-referenced spectral interferometry with extended time excursion at unprecedented dynamic and temporal range. This allows for the first single-shot measurement of the PM trigger point, which is interesting for the quantitative investigation of the complex pre-plasma formation process at the surface of the target used for proton acceleration. As a demonstration of high contrast laser plasma interaction we present proton acceleration results with ultra-thin liquid crystal targets of ~ 1 μm down to 10 nm thickness. Focus scans of different target thicknesses show that highest proton energies are reached for the thinnest targets at best focus. This indicates that the contrast enhancement is effective such that the acceleration process is not limited by target pre-expansion induced by laser light preceding the main laser pulse.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

State-to-state rate coefficients for HCS+ in rotationally inelastic collisions with H2 at low temperatures

ABSTRACT HCS+ ions have been detected in several regions of the interstellar medium (ISM), but an accurate determination of the chemical-physical conditions in the molecular clouds where this molecule is observed requires detailed knowledge of the collisional rate coefficients with the most common colliders in those environments. In this work, we study the dynamics of rotationally inelastic collisions of HCS+ + H2 at low temperature, and report, for the first time, a set of rate coefficients for this system. We used a recently developed potential energy surface for the HCS+–H2 van der Waals complex and computed state-to-state rotational rate coefficients for the lower rotational states of HCS+ in collision with both para- and ortho-H2, analysing the influence of the computed rate coefficients on the determination of critical densities. Additionally, the computed rate coefficients are compared with those obtained by scaling the ones from HCS+ in collision with He (an approximation that is sometimes used when data is lacking), and large differences are found. Furthermore, the approximation of using the rates for the HCO+ + H2 collision as a rough approximation for those of the HCS+ + H2 system is also evaluated. Finally, the complete set of de-excitation rate coefficients for the lowest 30 rotational states of HCS+ by collision with H2 is reported from 5 to 100 K.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Validating sequential Monte Carlo for gravitational-wave inference

Nested sampling (NS) is the preferred stochastic sampling algorithm for gravitational-wave inference for compact binary coalescences. It can handle the complex nature of the gravitational-wave likelihood surface and provides an estimate of the Bayesian model evidence. However, there is another class of algorithms that meets the same requirements, but has not been used for gravitational-wave analyses: sequential Monte Carlo (SMC), an extension of importance sampling that maps samples from an initial density to a target density via a series of intermediate densities. In this work, we validate a type of SMC algorithm, called persistent sampling (PS), for gravitational-wave inference. We consider a range of different scenarios including binary black holes and binary neutron stars and real and simulated data and show that PS produces results that are consistent with NS whilst being, on average, 2 times more efficient and 2.74 times faster. This demonstrates that PS is a viable alternative to NS that should be considered for future gravitational-wave analyses.

black hole mergers↗
DOE OSTI2025

Electronic structure complexity and extremely large magnetoresistance in antiferromagnetic semimetal SmAgSb 2

SmAgSb 2 , a layered magnetic semimetal in the tetragonal 𝑅⁢𝑇⁢ Sb 2 family (𝑅 = Y, Sc, rare earth; 𝑇 = transition metal), is known to exhibit extremely large magnetoresistance (XMR) below its antiferromagnetic (AFM) transition temperature. Here, in this work, we present a comprehensive investigation combining magnetotransport measurements, density functional theory calculations accounting for electron correlation, and angle-resolved photoemission spectroscopy. Our results reveal a complex electronic structure characterized by a multiband Fermi surface and intricate magnetic ground states. We demonstrate that simple two-band models, previously employed in the literature, fail to consistently describe the observed transport phenomena. Notably, we report an XMR of approximately 25200% at 2 K under a 14 T magnetic field, significantly exceeding earlier reports for this material family and rivaling the performance of prominent nonmagnetic XMR systems. This pronounced enhancement below 𝑇 𝑁 suggests that the XMR originates from a combination of multiband electron-hole compensation and enhanced magnetic scattering in this correlated AFM semimetal.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗