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Results for “molecular evolution”

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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Alkali cation-induced cathodic corrosion in Cu electrocatalysts

The reconstruction of Cu catalysts during electrochemical reduction of CO 2 is a widely known but poorly understood phenomenon. Herein, we examine the structural evolution of Cu nanocubes under CO 2 reduction reaction and its relevant reaction conditions using identical location transmission electron microscopy, cyclic voltammetry, in situ X-ray absorption fine structure spectroscopy and ab initio molecular dynamics simulation. Our results suggest that Cu catalysts reconstruct via a hitherto unexplored yet critical pathway - alkali cation-induced cathodic corrosion, when the electrode potential is more negative than an onset value (e.g., –0.4 V RHE when using 0.1 M KHCO 3 ). Having alkali cations in the electrolyte is critical for such a process. Consequently, Cu catalysts will inevitably undergo surface reconstructions during a typical process of CO 2 reduction reaction, resulting in dynamic catalyst morphologies. While having these reconstructions does not necessarily preclude stable electrocatalytic reactions, they will indeed prohibit long-term selectivity and activity enhancement by controlling the morphology of Cu pre-catalysts. Alternatively, by operating Cu catalysts at less negative potentials in the CO electrochemical reduction, we show that Cu nanocubes can provide a much more stable selectivity advantage over spherical Cu nanoparticles.

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

Nature of molybdenum carbide surfaces for catalytic hydrogen dissociation using machine-learned potentials: an ensemble-averaged perspective

Molybdenum carbides with an electronic structure similar to noble metals have gained attention as a promising low-cost catalyst for biomass valorization and the hydrogen evolution reaction. However, our fundamental understanding of the catalyst surface and how different phases of these catalysts behave at varying reaction conditions is limited to ground state density functional theory calculations as ab initio molecular dynamics (AIMD) is computationally prohibitive at relevant length and time scales. Here, in this work, we train a multi-atomic cluster expansion (MACE) machine-learned interatomic potentials (MLIP) to study hydrogen dissociation and dynamics over Mo, δ-MoC, α-Mo 2 C, and β-Mo 2 C surfaces at varying temperatures and hydrogen partial pressures. Our simulations identify unique and different molecular and atomic hydrogen adsorption sites on different surfaces that do not depend on the temperature. At low hydrogen pressures, the surface coverage is monolayer, which transitions to two-layer adsorption at higher pressures. We find that atomic hydrogen diffusion and recombinations are preferred over molybdenum atom hollow sites, while the diffusion over carbon-terminated facets was negligible, signifying particularly strong C–H interactions. In contrast, molecular hydrogen adsorption occurs mostly atop Mo or the bridging sites. At a comparable hydrogen loading, β-Mo 2 C (001) is the most active surface for hydrogen dissociation reaction. This work provides insights into the dynamic nature of the hydrogen dissociation chemistry and the diversity of hydrogen adsorption sites on molybdenum carbides.

08 HYDROGEN↗
DOE OSTI2020

From Atom to Engine: Understanding Fundamental Effects of Structure on Combustion Using Tandem Experiment and Computation

The ability to tie structural features to a fuel candidate’s ignition properties provides a path for rational design of advantaged fuels that facilitate higher-efficiency, lower-emitting combustion in engines. The time evolution of a fuel’s radical population directly correlates with global combustion parameters, and because the generated radicals depend on the initial structure and reaction pathways of the fuel molecule, it follows that the molecular structure of a fuel has a direct impact on this cascade, and therefore salient ignition-tied fuel properties. This work aims to understand the impact of structural features in the context of global combustion properties for direct application to emerging engine technologies. Specifically, we highlight the ability to identify potential fuel blendstocks for specific engine strategies by examining and elucidating the radical cascade tied to ignition. A representative subset of alcohols possessing a variety of structural features (e.g. branching, chain length) was selected for study using a robust combination of experimental and computational methods. The approach begins with identifying short-lived radicals and likely abstraction sites upon pyrolysis in a microreactor coupled with photoionization mass spectrometry for direct detection of product species. In tandem, electronic structure calculations were performed to calculate the relevant potential energy surfaces for fuel pyrolysis as well as the subsequent O2 addition-isomerization reactions, which govern ignition behavior. Furthermore, the theoretical energetic and ro-vibrational data are used to calculate rate constants for direct ignition modeling to explore how structural effects impact NTC behavior. The microreactor data combined with electronic structure theory calculations provide a well-informed picture of the reactions relevant to ignition for each fuel in this study, as well as the most likely radicals generated under engine conditions. This thorough fundamental picture of fuel decomposition and ignition chemistry is used to correlate the observed ignition behavior to molecular structural effects.

advanced biofuels↗
DOE OSTI2023

The evolution of anaerobic growth in Saccharomycotina yeasts

Humans rely on the ability of budding yeasts to grow without oxygen in industrial scale fermentations that produce beverages, foods, and biofuels. Oxygen is deeply woven into the energy metabolism and biosynthetic capabilities of budding yeasts. While diverse ecological habitats may provide wide varieties of different carbon and nitrogen sources for yeasts to utilize, there is no direct substitute for molecular oxygen, only a range of availability. Understanding how a small subset of budding yeasts evolved the ability to grow without oxygen could expand the set of useful species in industrial scale fermentations as well as provide insight into the cryptic field of yeast ecology. Furthermore, we still do not yet appreciate the full breadth of species that can growth without oxygen, what genes underlie this adaptation, and how these genes have evolved.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Dynamical preparation of an atomic condensate in a Hofstadter band

The creation of a Hamiltonian in the quantum regime which has nontrivial topological features is a central goal of the cold-atom community, enabling widespread exploration of novel phases of quantum matter. A general scheme to synthesize such Hamiltonians is based on dynamical modulation of optical lattices which thereby generate vector potentials. At the same time, the modulation can lead to heating and serious difficulties with equilibration. Here we show that these challenges can be overcome by demonstrating how a Hofstadter Bose-Einstein condensate (BEC) can be dynamically realized, using experimental protocols. From Gross-Pitaevskii simulations our study reveals a complex, multistage evolution; this includes a chaotic intermediate "heating" stage followed by a spontaneous reentrance to the BEC. The observed behavior is reminiscent of evolution in cosmological models.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Construction of Lattice Strain in Bimetallic Nanostructures and Its Effectiveness in Electrochemical Applications

Bimetallic nanocrystals (NCs), associated with various surface functions such as ligand effect, ensemble effect, and strain effect, exhibit superior electrocatalytic properties. The stress-induced surface strain effect can alter binding strength between the surface active sites and reactants as well as their intermediates, and the electrochemical performance of bimetallic NCs can be significantly facilitated by the lattice-strain modification via their morphologies, sizes, shell-thickness, surface defectiveness as well as compositions. Here in this review, an overview of fundamental principles, characterization techniques, and quantitative determination of the surface lattice strain is provided. Various strategies and synthesis efforts on creating lattice-strain-engineered bimetallic NCs, including the de-alloying process, atomic layer-by-layer deposition, thermal treatment evolution, one-pot synthesis, and other efforts are also discussed. It is further outlined how the lattice strain effect promotes electrochemical catalysis through the selected case studies. The reactions on oxygen reduction reaction, small molecular oxidation, water splitting reaction, and electrochemical carbon dioxide reduction reactions are focused. In particular, studies of lattice strain arisen from core–shell nanostructure and defectiveness are highlighted. Lastly, the potential challenges are summarized and the prospects of lattice-strain-based engineering on bimetallic nanocatalysts with suggestion and guidance of the future electrocatalyst design are envisioned.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Probing Attosecond Bound Electron Dynamics Driven by Strong-Field Light Transients

The project aimed to drive strong-field excitation of bound electronic coherences in gas-phase atoms and molecules using a novel source of near-single-cycle optical field transients, based on industrial-grade Yb:solid-state laser technology. Key objectives included generating near-single cycle field transients and isolated attosecond pulses, reconstructing time-dependent wave packets in atoms and molecules, probing their decoherence using attosecond interferometry, and controlling the dynamic evolution of systems on attosecond to few-femtosecond timescales. A secondary goal of the project was to develop field-resolved measurement platforms as a novel approach for studying electron dynamics in atomic and molecular systems.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Large-scale atomistic studies of sliding friction in polycrystalline aluminum interfaces

In this work, we discuss large-scale non-equilibrium molecular dynamics (NEMD) simulations of ductile metal sliding comprising up to 1.8 × 10 9 atoms over time scales of 100 ns. The results of these simulations have identified a variety of physical mechanisms that are important in determining the steady-state frictional force for a wide range of velocities at compressed metal–metal interfaces. These include grain growth and refinement, the evolution of large plastic strains and strain rates, material mixing, and melting. These phenomena can be included in a strain, strain rate, and grain size model that gives good agreement with the NEMD simulations and can be applied to macroscopic continua.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Nanoscale visualization of the thermally driven evolution of antiferromagnetic domains in FeTe thin films

Antiferromagnetic order, being a ground state of a number of exotic quantum materials, is of immense interest both from the fundamental physics perspective and for driving potential technological applications. For a complete understanding of antiferromagnetism in materials, nanoscale visualization of antiferromagnetic domains, domain walls, and their robustness to external perturbations is highly desirable. Here, we synthesize antiferromagnetic FeTe thin films using molecular-beam epitaxy. We visualize local antiferromagnetic ordering and domain formation using spin-polarized scanning tunneling microscopy. From the atomically resolved scanning tunneling microscopy topographs, we calculate local structural distortions to find a high correlation with the distribution of the antiferromagnetic order. This is consistent with the monoclinic structure in the antiferromagnetic state. Interestingly, we observe a substantial domain-wall change by small temperature variations, unexpected for the low-temperature changes used compared to the much higher antiferromagnetic ordering temperature of FeTe. This is in contrast to electronic nematic domains in the cousin FeSe multilayer films, where we find no electronic or structural change within the same temperature range. Further, our experiments provide the atomic-scale imaging of perturbation-driven magnetic domain evolution simultaneous with the ensuing structural response of the system. The results reveal surprising thermally driven modulations of antiferromagnetic domains in FeTe thin films well below the Néel temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Mechanisms of ion irradiation induced ordering in amorphous TiO 2 nanotubes: Effects of ion mass and energy

Here, amorphous TiO 2 nanotubes were irradiated in-situ in a transmission electron microscope (TEM) with Kr + ions at energies of 46 keV, 150 keV, and 1 MeV and with 46 keV Xe + ions, to investigate the structural and morphological evolution of the nanotubes under irradiation. At all irradiation conditions, amorphous TiO 2 nanotubes exhibited significant morphological instability, and tended to undergo volumetric swelling with increasing ion counts, often until collapse of the original nanotube structure. Molecular dynamics (MD) simulations confirmed that irradiation-induced defects can explain the observed swelling. Structurally, nanotubes remain amorphous following all Kr + irradiation conditions, but irradiation with 46 keV Xe + leads to the formation of anatase nanocrystallites. Importantly, through systematically varying ion energy and ion species, we try to elucidate the influence of nuclear and electronic stopping power on ion irradiation induced changes. By contextualizing these results within the existing literature, we propose that the observed changes in TiO 2 nanotube morphology and structure could be due to a competition between two mechanisms: (1) disorder-induced swelling and (2) irradiation-induced amorphous-to-crystalline transformation.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Universal progression of structure and dynamics in colloidal nanocrystal gels during salt-accelerated aging

Controlling the structure and function of colloidal gels requires a detailed understanding of how the various components govern network formation and aging. In particular, molecular additives like salts are widely used to tune interparticle interactions, yet their influence on gelation pathways in complex systems such as colloidal nanocrystal gels remains inadequately understood. Here, we investigate how noncoordinating salts modulate the evolution of gels formed using chemically linked tin-doped indium oxide nanocrystals. Through combined structural, dynamic, and kinetic analyses, we demonstrate that increasing salt concentration accelerates gelation. When rescaled by salt-dependent characteristic times, the evolution collapses onto universal trajectories, revealing a time-salt superposition principle. The universality extends across length scales, suggesting a consistent salt-dependent mechanism that controls both local structuring and macroscopic network formation. This observed salt modulation of structure and dynamics provides a predictive basis for controlling the kinetics of nonequilibrium nanocrystal gel assembly, enhancing the rational design of functional nanomaterials with tunable properties.

36 MATERIALS SCIENCE↗
DOE OSTI2022

New Clues to the Evolution of Dwarf Carbon Stars From Their Variability and X-Ray Emission

As main-sequence stars with C > O, dwarf carbon (dC) stars are never born alone but inherit carbon-enriched material from a former asymptotic giant branch (AGB) companion. In contrast to M dwarfs in post-mass-transfer binaries, C 2 and/or CN molecular bands allow dCs to be identified with modest-resolution optical spectroscopy, even after the AGB remnant has cooled beyond detectability. Accretion of substantial material from the AGB stars should spin up the dCs, potentially causing a rejuvenation of activity detectable in X-rays. Indeed, a few dozen dCs have recently been found to have photometric variability with periods under a day. However, most of those are likely post-common-envelope binaries, spin–orbit locked by tidal forces, rather than solely spun-up by accretion. Here, we study the X-ray properties of a sample of the five nearest-known dCs with Chandra. Two are detected in X-rays, the only two for which we also detected short-period photometric variability. We suggest that the coronal activity detected so far in dCs is attributable to rapid rotation due to tidal locking in short binary orbits after a common-envelope phase, late in the thermally pulsing (TP) phase of the former C-AGB primary (TP-AGB).

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Complex Structure of Molten FLiBe (2 Li F – Be F 2 ) Examined by Experimental Neutron Scattering, X-Ray Scattering, and Deep-Neural-Network Based Molecular Dynamics

The use of molten salts as coolants, fuels, and tritium breeding blankets in the next generation of fission and fusion nuclear reactors benefits from furthering the characterization of the molecular structure of molten halide salts, paving the way to predictive capability of the chemical and thermophysical properties of molten salts. Due to its neutronic, chemical, and thermochemical properties, 2 Li F - Be F 2 is a candidate molten salt for several fusion- and fission-reactor designs. We performed neutron and x-ray total-scattering measurements to determine the atomic structure of liquid 2 Li F - Be F 2 . We also performed and neural-network molecular-dynamics simulations to predict the structure obtained by neutron- and x-ray-diffraction experiments. The use of machine learning provides improvements to the efficiency in predicting the structure at a longer length scales than is achievable with simulations at significantly lower computational expense while retaining near accuracy. We found that the NNMD simulations accurately predicted the Be F 4 2 − oligomer formations seen in the experimental first-structure-factor peak. Our combination of high-resolution measurements with large-scale molecular dynamics provided an avenue to explore and experimentally verify the intermediate-range ordering beyond the first-nearest neighbor that has posed too many experimental and computational challenges in previous works. With a deeper understanding of the salt structure and ion ordering, the evolution of salt chemistry over the lifetime of a reactor can be better predicted, which is crucial to the licensing and operation of advanced fission and fusion reactors that employ molten salts. To this end, this work will serve as a reference for future studies of salt structure and macroscopic properties with and without the addition of solutes. Published by the American Physical Society 2024

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

A physically based mechanical model for Mullins effect in thermoplastic polyurethanes

Despite decades of research, connecting the chemical and physical structure of thermoplastic polyurethanes to their mechanical properties remains highly challenging. Of particular note are their large-deformation and rate-dependent behaviors, which vary greatly with molecular chemistry, including the type and relative content of soft and hard segments. In this work, we develop a physically motivated mechanical theory for predicting the behavior of thermoplastic polyurethanes. The theory incorporates a representation of microstructural evolution during mechanical deformation, which captures the signatures of stress softening over cyclic loading (commonly referred to as the Mullins effect). There are only eight physically motivated fitting parameters, including a direct dependence on the hard segment fraction. The model predicts that increasing the hard segment fraction leads to higher stiffness and greater energy dissipation, in quantitative agreement with published experimental data. Furthermore, we provide a comprehensive analysis of the model and validate its predictions across several independent datasets focused on mechanical characterization. Direct comparisons to experimental data demonstrate its predictive capability on the effect of loading rate, cyclic deformations, and applied tension or compression. Altogether, this work establishes a predictive framework that connects polymer chemistry and microstructure to emergent mechanical behaviors.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Atomic Layer Deposition of Ruthenium Films Using Ruthenium Diketonates and O 2 , H 2 , or N 2 O: The Role of Ruthenium Etching

In this work, the evolution of the surface during the steps that comprise the atomic layer deposition (ALD) of ruthenium films on a nickel substrate using tris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium(III) (Ru(tmhd) 3 ) and molecular oxygen was characterized using a combination of X-ray photoelectron (XPS) and reflection–absorption infrared (RAIRS) spectroscopies. The uptake of the Ru metalorganic precursor was determined to be activated, involving the average loss of two out of the three ligands (and the retention of the third, in molecular form, at the surface–vacuum interface), and self-limited, as required in ALD. The reaction of the resulting layer from that first half of the ALD cycle with O 2 proved to be more complex: in addition to the desired removal of the carbon-containing material, the Ni substrate becomes oxidized, and some Ru is etched away in the form of the volatile RuO 4 gas. By testing different combinations of exposures and temperatures it was determined that Ru film growth was possible, but tuning and optimizing the ALD or atomic layer etching (ALE) process conditions for maximum film growth or removal rate per cycle proved difficult. Replacing O 2 with H 2 was shown not to be viable either, as such an agent can reduce the nickel oxide formed after O 2 treatments (in fact, Ru(tmhd) 3 can do this as well) but not remove the carbonaceous material deposited on the surface by the Ru precursor. The use of N 2 O, on the other hand, showed much promise, being capable of removing most of the surface carbon without affecting the Ru film or the Ni substrate.

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

Thermal Hydroquinone Oxidation on Co/N-doped Carbon Proceeds by a Band-Mediated Electrochemical Mechanism

Molecules catalyze aerobic oxidation reactions via redox cycling at the metal center to effect sequential activation of O 2 and the substrate. Metal surfaces can catalyze the same transformations by coupling independent half-reactions for oxygen reduction and substrate oxidation mediated via the exchange of band-electrons. Metal/nitrogen-doped carbons (MNCs) are promising catalysts for aerobic oxidation that consist of molecule-like active sites embedded in a conductive carbon host. Owing to their combining molecular and metallic features, it remains unclear whether they proceed via the sequential redox cycling pathways of molecules or the band-mediated pathways of metals. Herein, we simultaneously track the potential of the catalyst and the rate of the turnover of aerobic hydroquinone oxidation on a cobalt-based MNC catalyst contacted to a catalytically inactive carbon electrode. By comparing operando measurements of rate and potential with the current-voltage behavior of each constituent half-reaction under identical conditions, we show that these molecular materials can display the band-mediated reaction mechanisms of extended metallic solids. Further, we show that the action of these band-mediated mechanisms explains fractional reaction orders in both oxygen and hydroquinone, the time evolution of catalyst potential and rate, and the dependence of rate on overall reaction free energy. Selective poisoning experiments suggest that oxygen reduction proceeds at cobalt sites, whereas quinone oxidation proceeds at native oxidic defects on the carbon. These findings highlight that molecule-like active sites can take advantage of band-mediated mechanisms when coupled to conductive hosts.

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

Transportome remodeling of a symbiotic microalga inside a planktonic host

Abstract Metabolic exchange is one of the foundations of symbiotic associations between organisms and is a driving force in evolution. In the ocean, photosymbiosis between heterotrophic hosts and microalgae is powered by photosynthesis and relies on the transfer of organic carbon to the host (e.g. sugars). Yet, the identity of transferred carbohydrates as well as the molecular mechanisms that drive this exchange remain largely unknown, especially in unicellular photosymbioses that are widespread in the open ocean. Combining genomics, single-holobiont transcriptomics, and environmental metatranscriptomics, we revealed the transportome of the marine microalga Phaeocystis in symbiosis within acantharia, with a focus on sugar transporters. At the genomic level, the sugar transportome of Phaeocystis is comparable to non-symbiotic haptophytes. By contrast, we found significant remodeling of the expression of the transportome in symbiotic microalgae compared to the free-living stage. More particularly, 36% of sugar transporter genes were differentially expressed. Several of them, such as GLUTs, TPTs, and aquaporins, with glucose, triose-phosphate sugars, and glycerol as potential substrates, were upregulated at the holobiont and community level. We also showed that algal sugar transporter genes exhibit distinct temporal expression patterns during the day. This reprogramed transportome indicates that symbiosis has a major impact on sugar fluxes within and outside the algal cell, and highlights the complexity and the dynamics of metabolic exchanges between partners. This study improves our understanding of the molecular players of the metabolic connectivity underlying the ecological success of planktonic photosymbiosis and paves the way for more studies on transporters across photosymbiotic models.

Environmental Sciences & Ecology↗