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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 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Fast, purely growing collisionless reconnection as an eigenfunction problem related to but not involving linear whistler waves

If either finite electron inertia or finite resistivity is included in 2D magnetic reconnection, the two-fluid equations become a pair of second-order differential equations coupling the out-of-plane magnetic field and vector potential to each other to form a fourth-order system. The coupling at an X-point is such that out-of-plane even-parity electric and odd-parity magnetic fields feed off each other to produce instability if the scale length on which the equilibrium magnetic field changes is less than the ion skin depth. The instability growth rate is given by an eigenvalue of the fourth-order system determined by boundary and symmetry conditions. The instability is a purely growing mode, not a wave, and has growth rate of the order of the whistler frequency. The spatial profile of both the out-of-plane electric and magnetic eigenfunctions consists of an inner concave region having extent of the order of the electron skin depth, an intermediate convex region having extent of the order of the equilibrium magnetic field scale length, and a concave outer exponentially decaying region. If finite electron inertia and resistivity are not included, the inner concave region does not exist and the coupled pair of equations reduces to a second-order differential equation having non-physical solutions at an X-point.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Unfolding of the Villin Headpiece Domain: Revealing Structural Heterogeneity with Time‐Resolved X‐Ray Solution Scattering and Markov State Modeling

Understanding protein folding pathways is crucial to deciphering the principles of protein structure and function. Here, the unfolding dynamics of the 35‐residue villin headpiece (HP35) and a norleucine‐substituted variant (2F4K) using a combination of experimental and computational techniques is investigated. Time‐resolved X‐ray solution scattering coupled with equilibrium molecular dynamics simulations and Markov state modeling reveals distinct unfolding mechanisms between the two variants: HP35 and 2F4K. Specifically, HP35 exhibits a two‐state unfolding process, whereas an intermediate state is identified for the 2F4K mutant. A Markov state model constructed from simulations is used to map atomic‐level transitions to experimental observations, providing insights into the role of sequence variations in modulating folding pathways. The findings underscore the importance of integrating experimental and computational approaches to unravel protein unfolding mechanisms between heterogenous structural ensembles.

Nijhawan, Adam K. [Department of Chemistry Northwe↗
DOE OSTI2018

Combining Experiment and Theory To Unravel the Mechanism of Two-Electron Oxygen Reduction at a Selective and Active Co-catalyst

In this work, we present a combination of comprehensive experimental and theoretical evidence to unravel the mechanism of two-electron oxygen reduction reaction (ORR) on a catalyst composed of mildly reduced graphene oxide supported on P50 carbon paper (mrGO/P50). This catalyst is unique in that it shows >99% selectivity toward H 2 O 2 , the highest mass activity to date, and essentially zero overpotential in base. Furthermore, the mrGO catalytically active site is unambiguously identified and presents a unique opportunity to investigate mechanisms of carbon-based catalysis in atomistic detail. A wide range of experiments at varying pH are reported: ORR onset potential, Tafel slopes, H/D kinetic isotope effects, and O 2 reaction order. With DFT reaction energies and known thermodynamic parameters, we calculate the potential and pH-dependent free energies of all possible intermediates in this ORR and propose simple kinetic models that give semiquantitative agreement with all experiments. Our results show that mrGO is semiconducting and cannot support the conventional mechanism of coherently coupled proton–electron transfers. The conducting P50 provides electrons for initiating the ORR via outer sphere electron transfer to O 2 (aq), while the semiconducting mrGO provides the active catalytic sites for adsorption of O 2 – (aq) or HO 2 (aq), depending upon electrolyte pH. Due to this unique synergistic effect, we describe the mrGO/P50 as a co-catalyst. Lastly, this concept implies departure from the traditional picture of predicting catalytic activity trends based on a single descriptor, and the co-catalyst design strategy may generally enable other semiconductors to function as electrocatalysts as well.

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

Diversifying Isoprenoid Platforms via Atypical Carbon Substrates and Non-model Microorganisms

Isoprenoid compounds are biologically ubiquitous, and their characteristic modularity has afforded products ranging from pharmaceuticals to biofuels. Isoprenoid production has been largely successful in Escherichia coli and Saccharomyces cerevisiae with metabolic engineering of the mevalonate (MVA) and methylerythritol phosphate (MEP) pathways coupled with the expression of heterologous terpene synthases. Yet conventional microbial chassis pose several major obstacles to successful commercialization including the affordability of sugar substrates at scale, precursor flux limitations, and intermediate feedback-inhibition. Now, recent studies have challenged typical isoprenoid paradigms by expanding the boundaries of terpene biosynthesis and using non-model organisms including those capable of metabolizing atypical C1 substrates. Conversely, investigations of non-model organisms have historically informed optimization in conventional microbes by tuning heterologous gene expression. Here, we review advances in isoprenoid biosynthesis with specific focus on the synergy between model and non-model organisms that may elevate the commercial viability of isoprenoid platforms by addressing the dichotomy between high titer production and inexpensive substrates.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1993

Optical probing of cold trapped atoms

Transitions between excited states of laser-cooled and laser-trapped rubidium and cesium atoms are probed by use of fiber and diode lasers. High-resolution Doppler-free spectra are detected by observation of the absorption and fluorescence of light from the intermediate level of two-step cascade systems. The optical double-resonance spectra show Autler-Townes splitting in the weak probe limit and more complicated spectra for a strongly coupled three-level system.

Fox, R. W.↗
DOE OSTI2024

Stripe and bubble ratchets on asymmetric substrates

We show that various nonmonotonic ratchet effects can arise when mesophase pattern-forming systems, which exhibit anisotropic crystal, stripe, and bubble regimes, are coupled to one-dimensional asymmetric substrates under ac driving. The patterns emerge in the absence of a substrate when the ratio of attraction to repulsion is varied for particles with competing short-range attraction and long-range repulsion potentials. In the presence of the substrate, we find that the ratchet efficiency varies nonmonotonically with increasing attraction, depending upon how well the mesophase morphology matches the substrate spacing and periodicity. For strong repulsion, there is a weak but finite ratchet effect, while at intermediate attraction, there is a robust ratchet effect in which the system forms stripes aligned with the substrate symmetry direction. For strong attraction, large bubbles appear that have weak or no ratchet effects when the bubble width exceeds the substrate lattice spacing, causing the bubble to be only weakly coupled to the substrate. For very strong attraction, small bubbles form and undergo a strong ratchet effect with an efficiency that oscillates as a function of ac drive amplitude. Although the small bubble regime is a strongly correlated regime in which each bubble contains many particles, the system behaves as if it is in a single-particle regime since the bubble width is much smaller than the substrate lattice spacing. We map out the different rectification phases as a function of the pattern morphology, substrate strength, and ac drive amplitude. The pronounced ratchet effects that we observe in some regimes can be exploited for pattern sorting in hard and soft matter systems. Published by the American Physical Society 2024

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Thermal and Magnetic Field Switching in a Two-Step Hysteretic Mn III Spin Crossover Compound Coupled to Symmetry Breakings

In this work, a Mn III spin crossover complex with atypical two-step hysteretic thermal switching at 74 K and 84 K shows rich structural–magnetic interplay and magnetic-field-induced spin state switching below 14 T with an onset below 5 T. The spin states, structures, and the nature of the phase transitions are elucidated via X-ray and magnetization measurements. An unusual intermediate phase containing four individual sites, where 1\4 are in a pure low spin state, is observed. The splitting of equivalent sites in the high temperature phase into four inequivalent sites is due to a structural reorganization involving a primary and a secondary symmetry-breaking order parameter that induces a crystal system change from orthorhombic→monoclinic and a cell doubling. Further cooling leads to a reconstructive phase transition and a monoclinic low-temperature phase with two inequivalent low-spin sites. The coupling between the order parameters is identified in the framework of Landau theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Ultrafast Bulk Diffusion of AlHxin High-Entropy Dehydrogenation Intermediates of NaAlH4

Using first-principles molecular dynamics (FPMD) and total-energy calculations, we demonstrate low-barrier bulk diffusion of Al-bearing species in γ-NaAlH4, a recently proposed high-entropy polymorph of NaAlH4. For charged AlH4– and neutral AlH3 vacancies, the computed barriers for diffusion are <0.1 eV, and we directly observe the predicted diffusive pathways in FPMD simulations at picosecond time scales. In contrast, such diffusion in the α phase is inaccessible to FPMD, consistent with much higher barriers. The transport behavior of γ-NaAlH4, in addition to key dynamical and structural signatures, is consistent with experimental observations of high-mobility species, strongly supporting the idea that an intermediate transition from the α phase to a high-entropy polymorph facilitates the hydrogen-releasing decomposition of NaAlH4. Our results provide an answer to longstanding questions regarding the responsible agent for the experimentally observed efficient Al transport during dehydrogenation and suggest that mass transport and phase transformation kinetics are coupled. Implications for understanding the (de)hydrogenation of undoped and catalyzed NaAlH4 are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Thermodynamics, Kinetics and Structural Evolution of ε-LiVOPO 4 over Multiple Lithium Intercalation

ε -Li x VOPO 4 is a promising multi-electron cathode for rechargeable lithium-ion bat- teries that has an extremely high theoretical capacity of 318 mAh/g. In this w ork, we demonstrate the stable cycling of more than one Li in solid-state-syn thesized ε - LiVOPO 4 over more than 20 cycles for the first time. Using a combination of densit y functional theory (DFT) calculations, X-ray pair distribution funct ion (PDF) analy- sis and X-ray Absorption Near Edge Structure (XANES) measurements, we pre sent a comprehensive analysis of the thermodynamics, kinetics and stru ctural evolution of ε -Li x VOPO 4 over the entire lithiation range. We identify two intermediate ph ases at x = 1 . 5 and 1.75 in the low-voltage regime using DFT calculations, and the comput ed and electrochemically measured voltage profiles are in excellent agree ment. Operando PDF techniques show a reversible hysteretic change in the short ( < 2° A) V-O bond lengths coupled with an irreversible extension of the long V-O bond ( > 2.4 °A) dur- ing low-voltage cycling. These observations are confirmed with EXAFS spe ctra. We identify hydrogen intercalation from the electrolyte decomposition as a likely explana- tion for the ~ 2 . 4°A V-O bond and its irreversible extension. In terms of electronic conductivity, we find Li x VOPO 4 to be a large band gap insulator across the entire lithiation range, and calculated small polaron migration barriers are similar to those of the olivine LiMPO 4 cathodes. Finally, we demonstrate that ε -LiVOPO 4 is likely to be a one-dimensional diffuser using climbing-image nudged elastic ban d calculations. These results highlight the importance of nano-sizing and carbon coating in achieving good electrochemical performance in this material.

Lin, Yuh-Chieh↗
DOE OSTI2019

Aldol Condensation of Cyclopentanone on Hydrophobized MgO. Promotional Role of Water and Changes in the Rate-Limiting Step upon Organosilane Functionalization

Aldol condensation is a key C—C coupling reaction for upgrading of biomass-derived oxygenates to fuels and chemicals. In this work, we investigate the effects of added water on the condensation of cyclopentanone (CPO) on hydrophobized MgO catalysts. We have found that the role of water strongly depends on the degree of hydrophobic functionalization of the MgO surface. That is, on a nonfunctionalized (hydrophilic) high-surface-area MgO catalyst, the rate decreases with the addition of water, mostly due to active site blockage. By contrast, on MgO hydrophobized via silylation with octadecyltrichlorosilane (OTS), the rate actually increases with added water. A concomitant change in kinetics is observed from the pristine (hydrophilic) MgO to the hydrophobized sample. Specifically, on the hydrophilic sample, the reaction is first-order, as expected if the rate-limiting step is the formation of an enolate intermediate via α-H abstraction at a basic site, as widely reported in previous literature. By contrast, on the hydrophobized sample, the reaction becomes second-order, indicating a shift in rate-limiting step to the bimolecular C—C coupling. On pristine MgO, acid–base pairs are fully available on the surface, with the acid site polarizing the C=O group in the second cyclopentanone (electrophile) and making the attack by the enolate very favorable. It is proposed here that grafted OTS molecules interfere between active sites, making the adsorbate–adsorbate interaction on the surface less likely and reducing the rate of C—C coupling. Lastly, both isotope effect experiments and ab initio molecular dynamics simulations of cyclopentanone adsorption at the MgO/OTS interface further support this argument. Therefore, the promotional role of water seems to be the assistance of the C—C bond-forming step. It is proposed that, at low concentrations, water can help the second molecule (electrophile) be polarized from a remote Mg 2+ site through a chain of H-bonded molecules.

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

How Does Metal Spin State Affect Electronic Communication in Mixed-Valence Dimers? Insights from Ultrafast Near-Infrared and Soft X-ray Transient Absorption Spectroscopy

Recent advancements in photocatalysis, photovoltaics, and quantum information science take advantage of electron spin, and determining how spin multiplicity affects electron transfer is key to understanding these phenomena. Here, in this study, we examine how metal spin state affects electronic communication in an organometallic mixed-valence dimer, ferrocenyl cobaltocenium ([Fe II Cp 2 Co III Cp 2 ] + ). This complex can be photoexcited from its low-spin singlet Fe II ground state to form intermediate-spin triplet Fe II and high-spin quintet Fe II excited states. Using femtosecond optical transient absorption (OTA) spectroscopy with visible (vis), near-infrared (NIR), and short-wave IR (SWIR) probes, supported by time-dependent density functional theory (TD-DFT) calculations, we measure Fe II Co III →Fe III Co II intervalence charge transfer (IVCT) bands in each of the Fe II spin states. Mulliken–Hush analysis of the excited-state IVCT bands was used to compute the electronic coupling between the metal centers in all three spin states, which increased as quintet < triplet < singlet. Meanwhile, the peak energy of the bands, and thus the ΔG of the IVCT transition, increased as triplet < quintet < singlet. Then, to directly probe the electronic structure at each metal center, we employed picosecond soft X-ray transient absorption (XTA) spectroscopy at the Fe and Co L 3 edges. Our results show that the low-spin and high-spin states of [Fe II Cp 2 Co III Cp 2 ] + are valence-localized, while the intermediate-spin state is partially delocalized. The differences in charge delocalization are attributed to differences in orbital occupation and geometry that affect the free energy and superexchange coupling.

Burke, John H. [Univ. of Illinois at Urbana-Champa↗
DOE OSTI2015

The Role of Metal Halides in Enhancing the Dehydration of Xylose to Furfural

The dehydration of xylose yields furfural, a product of considerable value as both a commodity chemical and a platform for producing a variety of fuels. When xylose is dehydrated in aqueous solution in the presence of a Brønsted acid catalyst, humins are formed via complex side processes that ultimately result in a loss in the yield of furfural. Such degradative processes can be minimized via the insitu extraction of furfural into an organic solvent. The partitioning of furfural from water into a given extracting solvent can be enhanced by the addition of salt to the aqueous phase, a process that increases the thermodynamic activity of furfural in water. Although the thermodynamics of using salts to improve liquid-liquid extraction are well studied, their impact on the kinetics of xylose dehydration catalyzed by a Brønsted acid are not. The aim of the present study was to understand how metal halide salts affect the mechanism and kinetics of xylose dehydration in aqueous solution. We found that the rate of xylose consumption is affected by both the nature of the salt cation and anion, increasing in the order no salt < K + < Na + < Li + and no salt < Cl - < Br - < I - . Furfural selectivity increases similarly with respect to metal cations, but in the order no salt < I - < Br - < Cl - for halide anions. Multinuclear NMR was used to identify the interactions of cations and anions with xylose and to develop a model for explaining xylose-metal halide and water-metal halide interactions. The results of these experiments coupled with 18 O-labeling experiments indicate that xylose dehydration is initiated by protonation at the C 1 OH and C 2 OH sites, with halide anions acting to stabilize critical intermediates. Finally, the means by which metal halides affect the formation of humins was also investigated, and the role of cations and anions in affecting the selectivity to humins is discussed.

anions↗
DOE OSTI2015

High P-T Raman study of transitions in relaxor multiferroic Pb(Fe 0.5 Nb 0.5 )O 3

The vibrational and structural properties of Pb(Fe 0.5 Nb 0.5 )O 3 have been investigated using Raman spectroscopy up to 40 GPa at 300 K and from 300 to 415 K at selected pressures. The measurements reveal three phase transitions at 5.5, 8.7 and 24 GPa at room temperature. The temperature dependences of the spectra indicated transitions at 1.5 GPa, at 335 and 365 K. The results support the appearance of an intermediate tetragonal P 4mm phase between ferroelectric R 3m and paraelectric P m-3m phases. Furthermore, a P-T phase diagram is proposed that allows further insight into the magnetoelectric coupling present in this material.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides

Transformation of metastable Fe(III) oxyhydroxides is a prominent process in natural environments and can be significantly accelerated by the coexisting aqueous Fe(II) (Fe(II) aq ). Recent evidence points to the solution mass transfer of labile Fe(III) (Fe(III) labile ) as the primary intermediate species of general importance. However, a mechanistic aspect that remains unclear is the dependence of phase outcomes on the identity of the metastable Fe(III) oxyhydroxide precursor. Here, we compared the coupled evolution of Fe(II) species, solid phases, and Fe(III) labile throughout the Fe(II)-catalyzed transformation of lepidocrocite (Lp) versus ferrihydrite (Fh) at equal Fe(III) mass loadings with 0.2–1.0 mM Fe(II) aq at pH = 7.0. Similar to Fh, the conversion of Lp to product phases occurs by a dissolution–reprecipitation mechanism mediated by Fe(III) labile that seeds the nucleation of products. Though for Fh we observed a transformation to goethite (Gt), accompanied by the transient emergence and decline of Lp, for initial Lp we observed magnetite (Mt) as the main product. Further, a linear correlation between the formation rate of Mt and the effective supersaturation in terms of Fe(III) labile concentration shows that Fe(II)-induced transformation of Lp into Mt is governed by the classical nucleation theory. When Lp is replaced by equimolar Gt, Mt formation is suppressed by opening a lower barrier pathway to Gt by heterogeneous nucleation and growth on the added Gt seeds. The collective findings add to the mechanistic understanding of factors governing phase selections that impact iron bioavailability, system redox potential, and the fate and transport of coupled elements.

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

Recovery of Lithium from Geothermal Brine with Lithium–Aluminum Layered Double Hydroxide Chloride Sorbents

In this paper, we report a three-stage bench-scale column extraction process to selectively extract lithium chloride from geothermal brine. The goal of this research is to develop materials and processing technologies to improve the economics of lithium extraction and production from naturally occurring geothermal and other brines for energy storage applications. A novel sorbent, lithium aluminum layered double hydroxide chloride (LDH), is synthesized and characterized with X-ray powder diffraction, scanning electron microscopy, inductively coupled plasma optical emission spectrometry (ICP-OES), and thermogravimetric analysis. Each cycle of the column extraction process consists of three steps: (1) loading the sorbent with lithium chloride from brine; (2) intermediate washing to remove unwanted ions; (3) final washing for unloading the lithium chloride ions. Our experimental analysis of eluate vs feed concentrations of Li and competing ions demonstrates that our optimized sorbents can achieve a recovery efficiency of ~91% and possess excellent Li apparent selectivity of 47.8 compared to Na ions and 212 compared to K ions, respectively in the brine. Finally, the present work demonstrates that LDH is an effective sorbent for selective extraction of lithium from brines, thus offering the possibility of effective application of lithium salts in lithium-ion batteries leading to a fundamental shift in the lithium supply chain.

25 ENERGY STORAGE↗
DOE OSTI2019

Electrochemical CO Reduction: A Property of the Electrochemical Interface

Electrochemical CO reduction holds the promise to be a cornerstone for sustainable production of fuels and chemicals. However, the underlying understanding of the carbon–carbon coupling toward multiple-carbon products is not complete. Here we present thermodynamically realistic structures of the electrochemical interfaces, determined by explicit ab initio simulations. We investigate how key CO reduction reaction intermediates are stabilized in different electrolytes and at different pH values. We find that the catalytic trends previously observed experimentally can be explained by the interplay between the metal surface and the electrolyte. For the Cu(100) facet with a phosphate buffer electrolyte, the energy efficiency is found to be limited by blocking of a phosphate anion, while in alkali hydroxide solutions (MOH, M = Na, K, Cs), OH* intermediates may be present, and at high overpotential the H* coverage limits the reaction. Furthermore the results provide insight into the electrochemical interface structure, revealing the limitations for multiple-carbon products, and offer a direct comparison to experiments.

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

Constructing a square-like copper cluster to boost C–C coupling for CO 2 electroreduction to ethylene

The CO 2 electroreduction reaction (CO 2 ER) to ethylene (C 2 H 4 ) offers the dual promise of lowering CO 2 emission while storing energy from renewable electricity, for which the development of highly efficient electrocatalysts is of great significance. Herein, by means of density functional theory (DFT) computations, we designed an electrocatalyst for CO 2 -to-C 2 H 4 conversion by anchoring a Cu 5 cluster supported on a MoS 2 monolayer with an S monovacancy (Cu 5 @MoS 2 ). Our results revealed that one Cu atom of the Cu 5 cluster was embedded into the framework of the defective MoS 2 monolayer, while the other four Cu atoms form a square-like island over the substrate surface. Interestingly, the C–C coupling between two *CO species can easily occur on the unique square-like active site with a low kinetic barrier of 0.56 eV to form the key *C 2 O 2 intermediate, which can then be hydrogenated to the C 2 H 4 product with a very low limiting potential (–0.32 eV). Significantly, alkaline conditions (pH = 13) are beneficial to further promote C 2 H 4 synthesis. Finally, our work may offer a new avenue to precisely modulate the structures of Cu clusters for converting CO 2 into high-value target products.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2026

Ionic-content-driven restructuring of spirobisindane ionene networks: implications for mechanics, self-healing, and gas transport

Polymers of intrinsic microporosity (PIMs) offer exceptional gas permeability but remain brittle and susceptible to physical aging, limiting their durability in separation applications. Here, we introduce a reconfigurable microporous polymer network that uniquely integrates permanent PIM microporosity with autonomous, intrinsic self-healing driven by imidazolium-based ionic motifs. Spirobisindane units generate the intrinsic free-volume architecture, while an imidazolium-containing polyamide ionene supplies dynamic ionic and hydrogen-bonding interactions that reorganize under mild activation. Incorporation of imidazolium-based ionic liquids further tunes cohesion, mobility, and densification, enabling the network to relax, re-associate, and retain microporosity without structural collapse. Through a comprehensive multiscale approach combining spectroscopy, scattering, thermal and mechanical characterization with all-atom molecular dynamics and density functional theory calculations, we elucidate how ionic content, as a single control parameter that reshapes free-volume distributions, modulates local coordination environments, and governs relaxation and healing kinetics. At intermediate ionic loadings, the networks achieve rapid, repeatable self-healing while maintaining CO$_2$ selectivity, demonstrating an optimal balance between segmental mobility and structural integrity. By establishing how hierarchical ionic interactions couple structure, dynamics, and transport in microporous ionene networks, this work provides generalizable design rules for adaptive soft-matter systems that require simultaneous mechanical resilience, reconfigurability, and selective gas transport.

36 MATERIALS SCIENCE↗