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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 1,279 records · Page 71
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Electrochemical reduction of europium(iii) using tetra- n -octyl diglycolamide functionalized ordered mesoporous carbon microelectrodes

This work investigates the one-electron reduction of Eu(III) to Eu(II) with ordered mesoporous carbon (OMC) in cavity microelectrode (CME) systems. OMC materials with and without tetra-n-octyl diglycolamide (TODGA) functionalization were subjected to voltammetric measurements and compared with commercial carbon black Vulcan® XC-72. The electrochemical reduction of solution Eu(III) with unfunctionalized OMC, XC-72, and TODGA-functionalized OMC—both within the electrode matrix and on the electrode surface—is reported. The complexation of Eu(III) by TODGA-functionalized OMC prior to electrode preparation incorporates Eu(III) as part of the bulk electrode matrix. Under these conditions, the high capacitance obscures the Eu(III)/Eu(II) redox couple. A signal emerges above the background (capacitive) currents when 2-octanol is added to the TODGA-functionalized OMC as a wetting agent. In contrast, surface Eu(III)–TODGA complexation, when Eu(III) contacts the electrode surface exclusively after electrode preparation, provides a strong response. The addition of 2-octanol to TODGA reduces the capacitance of the electrode and narrows the Eu(III)/Eu(II) redox peak widths. In conclusion, the desorption by reductive stripping of Eu(II) was demonstrated using a 2-octanol modified TODGA OMC CME, opening the possibility for selective separation of Eu from adjacent trivalent lanthanides.

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

Overcoming the phase separation within high-entropy metal carbide by poly(ionic liquid)s

High-entropy crystalline materials are attracting more attention. In principle, high-entropy metal carbides (HMCs) that contain five or more metal ions, possess more negative free energy value during catalysis. But its preparation is challenging because of the immiscibility of multi metal cations in a single carbide solid solution. Here, a rational strategy for preparing HMC is proposed via a coordination-assisted crystallization process in the presence of Br-based poly(ionic liquids). Through this method, Mo 0.2 W 0.2 V 0.2 Cr 0.2 Nb 0.2 C nanoparticles, with a single cubic phase structure, incorporated on porous carbon, are obtained (HMC@NC). By combination of well dispersed small particle size (~4 nm), high surface area (~270 m 2 g –1 ), and high-entropy phase, HMC@NC can function as a promising catalyst for the dehydrogenation of ethylbenzene. Here, unexpected activity (EB conv.: 73%) and thermal stability (>100 h on steam) at 450 °C are observed. Such a facile synthetic strategy may inspire the fabrication of other types of HMCs for more specific tasks.

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

Mechanochemical synthesis and structural analysis of trivalent lanthanide and uranium diphenylphosphinodiboranates

Phosphinodiboranates (H 3 BPR 2 BH 3 – ) are a class of borohydrides that have merited a reputation as weakly coordinating anions, which is attributed in part to the dearth of coordination complexes known with transition metals, lanthanides, and actinides. We recently reported how K(H 3 BP t Bu 2 BH 3 ) exhibits sluggish salt elimination reactivity with f-metal halides in organic solvents such as Et 2 O and THF. Here we report how this reactivity appears to be further attenuated in solution when the t Bu groups attached to phosphorus are exchanged for R = Ph or H, and we describe how mechanochemistry was used to overcome limited solution reactivity with K(H 3 BPPh 2 BH 3 ). Grinding three equivalents of K(H 3 BPPh 2 BH 3 ) with UI 3 (THF) 4 or LnI 3 (Ln = Ce, Pr, Nd) allowed homoleptic complexes with the empirical formulas U(H 3 BPPh 2 BH 3 ) 3 (1), Ce(H 3 BPPh 2 BH 3 ) 3 (2), Pr(H 3 BPPh 2 BH 3 ) 3 (3), and Nd(H 3 BPPh 2 BH 3 ) 3 (4) to be prepared and subsequently crystallized in good yields (50–80%). Single-crystal XRD studies revealed that all four complexes exist as dimers or coordination polymers in the solid-state, whereas 1 H and 11 B NMR spectra showed that they exist as a mixture of monomers and dimers in solution. Treating 4 with THF breaks up the dimer to yield the monomeric complex Nd(H 3 BPPh 2 BH 3 ) 3 (THF) 3 (4-THF). XRD studies revealed that 4-THF has one chelating and two dangling H 3 BPPh 2 BH 3 – ligands bound to the metal to accommodate binding of THF. In contrast to the results with K(H 3 BPPh 2 BH 3 ), attempting the same mechanochemical reactions with Na(H 3 BPH 2 BH 3 ) containing the simplest phosphinodiboranate were unsuccessful; only the partial metathesis product U(H 3 BPH 2 BH 3 )I 2 (THF) 3 (5) was isolated in poor yields. Here, despite these limitations, our results offer new examples showing how mechanochemistry can be used to rapidly synthesize molecular coordination complexes that are otherwise difficult to prepare using more traditional solution methods.

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

Prussian blue as a co-catalyst for enhanced Cr (VI) photocatalytic reduction promoted by titania-based nanoparticles and aerogels

Hexavalent chromium (Cr(VI)) is an noxious and highly toxic heavy metal that presents a serious threat to human health if present even in low concentrations in drinking water. Photocatalytic reduction of Cr(VI) to its less toxic Cr(III) state is a potential strategy to combat Cr(VI) pollution, but the efficiency of the process is low, especially in the absence of hole scavenger organic reagents. To address this issue and prepare efficient photocatalysts for Cr(VI) removal from water, in this study, we explored Prussian blue (PB) as a co-catalyst for improving the photoreduction performance of different high surface area TiO 2 -based materials (titania or silica–titania nanoparticles and aerogels). Here, the photocatalyst nanomaterials were surface-modified with nanocrystalline PB using the photodeposition route. The PB layer acts as an effective electron acceptor/mediator between the semiconductor photocatalyst and Cr(VI) species. All the PB-modified photocatalysts exhibit higher photocatalytic activity (up to 9 times faster) as compared to the unmodified photocatalysts towards reduction of Cr(VI). Importantly, the PB-modified photocatalysts exhibited high photocatalytic performance (98–99% reduction in 40 min for pH = 5.6 and in 10 min for pH = 3) without addition of organic reagents. The simple approach reported herein can be followed to prepare new PB-photocatalyst systems with improved photocatalytic performance towards Cr(VI) reduction and other target applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Magnetic and dielectric property control in the multivalent nanoscale perovskite Eu 0.5 Ba 0.5 TiO 3

We report nanoscale Eu 0.5 Ba 0.5 TiO 3 , a multiferroic in the bulk and candidate in the search to quantify the electric dipole moment of the electron. Eu 0.5 Ba 0.5 TiO 3 , in the form of nanoparticles and other nanostructures is interesting for nanocomposite integration, biomedical imaging and fundamental research, based upon the prospect of polarizability, f-orbital magnetism and tunable optical/radio luminescence. We developed a [non-hydrolytic]sol–[H 2 O-activated]gel route, derived from in-house metallic Ba (s) /Eu (s) alkoxide precursors and Ti{(OCH(CH 3 ) 2 } 4 . Two distinct nanoscale compounds of Ba:Ti:Eu with the parent perovskite crystal structure were produced, with variable dielectric, magnetic and optical properties, based on altering the oxidizing/reducing conditions. Eu 0.5 Ba 0.5 TiO 3 prepared under air/O 2 atmospheres produced a spherical core–shell nanostructure (30–35 nm), with perovskite Eu 0.5 Ba 0.5 TiO 3 nanocrystal core-insulating oxide shell layer (~3 nm), presumed a pre-pyrochlore layer abundant with Eu 3+ . Fluorescence spectroscopy shows a high intensity 5 D 0 → 7 F 2 transition at 622 nm and strong red fluorescence. The core/shell structure demonstrated excellent capacitive properties: assembly into dielectric thin films gave low conductivity (2133 GΩ mm -1 ) and an extremely stable, low loss permittivity of ε eff ~25 over a wide frequency range (tan δ < 0.01, 100 kHz–2 MHz). Eu 0.5 Ba 0.5 TiO 3 prepared under H 2 /argon produced more irregular shaped nanocrystals (20–25) nm, with a thin film permittivity around 4 times greater ( ε eff 101, tan δ < 0.05, 10 kHz–2 MHz, σ ~59.54 kΩ mm -1 ). Field-cooled magnetization values of 0.025 emu g -1 for EBTO-Air and 0.84 emu g -1 for EBTO-Argon were observed. X-ray photoelectron spectroscopy analysis reveals a complex interplay of Eu II/III /Ti III/IV configurations which contribute to the observed ferroic and fluorescence behavior.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Unveiling the complex configurational landscape of the intralayer cavities in a crystalline carbon nitride

The in-depth understanding of the reported photoelectrochemical properties of the layered carbon nitride, poly(triazine imide)/LiCl (PTI/LiCl), has been limited by the apparent disorder of the Li/H atoms within its framework. To understand and resolve the current structural ambiguities, an optimized one-step flux synthesis (470 °C, 36 h, LiCl/KCl flux) was used to prepare PTI/LiCl and deuterated-PTI/LiCl in high purity. Its structure was characterized by a combination of neutron/X-ray diffraction and transmission electron microscopy. The range of possible Li/H atomic configurations was enumerated for the first time and, combined with total energy calculations, reveals a more complex energetic landscape than previously considered. Experimental data were fitted against all possible structural models, exhibiting the most consistency with a new orthorhombic model (Sp. Grp. Ama2) that also has the lowest total energy. In addition, a new Cu(I)-containing PTI (PTI/CuCl) was prepared with the more strongly scattering Cu(I) cations in place of Li, and most closely matching with the partially-disorder structure in Cmc2 1 . Thus, a complex configurational landscape of PTI is revealed to consist of a number of ordered crystalline structures that are new potential synthetic targets, such as with the use of metal-exchange reactions.

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

Diffusion of Hydrophilic to Hydrophobic Forms of Nile Red in Aqueous C 12 EO 10 Gels by Variable Area Fluorescence Correlation Spectroscopy

In this work, solute diffusion within lyotropic liquid crystal gels prepared from a series of water and decaethylene glycol monododecyl ether (C 12 EO 10 ) mixtures was explored by variable area fluorescence correlation spectroscopy. Aqueous C 12 EO 10 gels were prepared in concentrations ranging from 55:45 to 70:30 wt% of surfactant and water. Small angle X-ray scattering revealed that these gels comprise hexagonal mesophases of cylindrical micelles. Micelle spacing was found to decrease with increasing C 12 EO 10 concentration. Three different Nile red (NR) dyes were employed as model solutes and were separately doped into the gels at nanomolar levels. These include a hydrophilic form of NR incorporating an anionic sulfonate group (NRSO 3 - ), a hydrophobic form incorporating a fourteen-carbon alkane tail (NRC 14 ), and commercial NR as an intermediate case. FCS data acquired from the gels revealed that NRSO 3 - diffused primarily in 3D. Its diffusion coefficient exhibited a monotonic decrease with increasing gel concentration and micelle packing density, consistent with confinement of its motions as a result of its exclusion from the micelle cores. NRC 14 exhibited the smallest diffusion coefficient, most likely due to its larger size and enhanced interactions with the micelle cores. NR yielded an intermediate diffusion coefficient and the most anomalous behavior of the three dyes, attributable to its facile partitioning between core and corona regions, and greater participation by 1D diffusion. The results of these studies afford an improved understanding of molecular mass transport through soft-matter nanomaterials like those being developed for use in drug delivery and membrane based chemical separations.

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

Facile synthesis and phase stability of Cu-based Na 2 Cu(SO 4 ) 2 · x H 2 O ( x = 0–2) sulfate minerals as conversion type battery electrodes

Mineral exploration forms a key approach for unveiling functional battery electrode materials. The synthetic preparation of naturally found minerals and their derivatives can aid in designing of new electrodes. Herein, saranchinaite Na 2 Cu(SO 4 ) 2 and its hydrated derivative kröhnkite Na 2 Cu(SO 4 ) 2 ·2H 2 O bisulfate minerals have been prepared using a facile spray drying route for the first time. The phase stability relation during the (de)hydration process was examined synergising in situ X-ray diffraction and thermochemical studies. Kröhnkite forms the thermodynamically stable phase as the hydration of saranchinaite to kröhnkite is highly exothermic (-51.51 ± 0.63 kJ mol -1 ). Structurally, kröhnkite offers a facile 2D pathway for Na+ ion migration resulting in 20 times higher total conductivity than saranchinaite at 60 °C. Both compounds exhibited a conversion redox mechanism for Li-ion storage with the first discharge capacity exceeding 650 mA h g -1 (at 2 mA g -1 vs. Li + /Li) upon discharge up to 0.05 V. Post-mortem analysis revealed that the presence of metallic Cu in the discharged state is responsible for high irreversibility during galvanostatic cycling. This study reaffirms the exploration of Cu-based polyanionic sulfates, which while having limited (de)insertion properties, can be harnessed for conversion-based electrode materials for batteries.

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

Challenges in synthesis of heterostructures

Developing the ability to reproducibly prepare materials drives the advancement of human technology. Trends in historical advances and extrapolation of current technologies suggest that the next logical step is developing the ability to control structure and composition at near atomic scales in device manufacturing to take advantage of emergent properties discovered in 2D materials and heterostructures. This article reviews a subset of synthetic approaches used to prepare heterostructures, outlining key reaction steps, and how experimental parameters are used to control which product forms. The positive attributes of each synthesis approach are discussed along with some of their limitations. The elemental reactant (MER) approach is discussed in more depth.

36 MATERIALS SCIENCE↗
DOE OSTI2023

New advances in chiral nanographene chemistry

This review will highlight several recent and lesser-reviewed works related to the preparation of chiral nanographenes, specifically focusing on structures prepared by non-Scholl methods.

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

Exploring a new synthesis route to lithium-excess disordered rock salt (DRX) cathode materials

Lithium-excess disordered rock salt (DRX) materials are promising candidates for Co/Ni-free Li-ion cathodes due to their high specific energy (800+ W h kg −1 ) and compositional flexibility. DRX cathodes are typically synthesized using solid-state reactions, which are difficult to scale and provide little-to-no control over particle morphology. Here, to address this bottleneck, the present study reports a two-step, solution-based reaction route to prepare Mn/Ti-based DRX oxyfluoride cathodes with nominal compositions of Li 1.25 Mn 0.5 Ti 0.3 O 1.95 F 0.05 and Li 1.35 Mn 0.7 Ti 0.1 O 1.85 F 0.15 . More specifically, a glycine–nitrate combustion reaction is used to produce a lithiated transition metal oxide, which is further reacted with LiF to produce high-purity DRX powders. Remarkably, this route yields 80–90% pure DRX after annealing for 1 h at 800–1000 °C, and 19 F solid-state nuclear magnetic resonance (ssNMR) spectra demonstrate that F− anions are successfully incorporated into the DRX structure. Cathodes prepared using this approach exhibit promising electrochemical performance, with Li 1.35 Mn 0.7 Ti 0.1 O 1.85 F 0.15 attaining reversible capacities ∼210 mA h g −1 and moderate cycling stability in half cells (65% capacity retention over 150 cycles). Overall, these results demonstrate that utilizing novel metal oxide precursors presents a viable and largely unexplored method to produce high-performance Co/Ni-free DRX cathodes.

25 ENERGY STORAGE↗
DOE OSTI2024

Aluminosilicate colloidal gels: from the early age to the precipitation of zeolites

Aluminosilicate hydrogels are often considered to be precursors for the crystallisation of zeolites carried out under hydrothermal conditions. The preparation of mechanically homogeneous aluminosilicate gels enables the study of these materials through bulk rheology and observation of the aging dynamics until the precipitation of crystalline zeolites. The first part of this study deals with the establishment of ternary state diagrams, in order to identify the range of chemical formulations that enable preparation of single-phase homogeneous gels. Then, by studying the viscoelastic moduli during the gelation reaction, and by yielding the gel under large deformation, we propose an empirical law considering the partial order of reaction on each chemical element, to predict the gelation time according to the chemical formulation. The scaling behavior of the elastic properties of this colloidal gel shows a transition from a strong link behavior to a weak link regime. Long term aging results in the shrinkage of the gel, accompanied by syneresis of interstitial liquid at the surface. Zeolites precipitate through crystallisation by a particle attachment mechanism, when thermodynamic equilibrium is reached. The stoichiometry of the precipitated zeolites is not only consistent with the concentration of the remaining species in the supernatant but, surprisingly, it is also very close to the partial order of the reaction of the chemical elements involved in the determination of the critical gel point. This indicates a strong correlation between the morphology of the soft amorphous gel network that is formed at an early age and those of the final solid precipitated crystals.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A multivariate library of zirconia metal–organic frameworks with dissolved p -nitroaniline dipoles and concentration-dependent optical and dielectric response

In this work, we show how the combination of soluble non-polar and polar links allows for the preparation of multivariate metal–organic frameworks (MTV MOFs) that exhibit dipolar solid-solution behavior. We prepared a library of PIZOF-2 MOFs with varied concentrations of p -nitroaniline (PNA)-containing moiety embedded within the MTV links. This library forms a partial solid solution up to 30 mol% with input/output composition ratio of 0.536 ± 0.018. MOFs with x > 5 mol% PNA show concentration-dependent hypsochromic dipole–dipole coupling (H-coupling) in the solid-state UV-visible spectra. The MTV library also exhibits a dielectric relaxation event in the broadband dielectric spectra with activation enthalpies and entropies that vary with temperature and PNA content and follow linear Meyer–Neldel compensation relations.

Langlois, Kyle R. [Univ. of Central Florida, Orlan↗
DOE OSTI2026

Microstructure-dependent particulate populations in ODS steels revealed by single-particle ICP-TOF-MS

In this work, we evaluated the ability of single-particle inductively coupled plasma time-of-flight mass spectrometry (SP-ICP-TOF-MS) to characterize particulates generated from 300 series stainless steels and oxide dispersion–strengthened (ODS) steels. Particulates were produced using two different rotary tools (cutting disk and grinding bit) to assess the influence of particle generation on effluent particulates. Across all materials and preparation techniques, SP-ICP-TOF-MS detected a substantial population of particles containing the expected constituent elements, with average compositions closely matching the nominal alloy values. A secondary population of Y-bearing particles was evident in ODS steels; their formation is strongly favored in particulates generated using the grinding bit. Specifically, in PM2000, Y-bearing particles were predominantly colocated with Al, whereas in 14YWT, Y-bearing particles were less frequently Fe-free but showed stronger colocation with Ti. These trends are consistent with the known microstructural differences between Y–Al–O oxide particles in PM2000 and finer Y–Ti–O nanoclusters in 14YWT. Together, these results demonstrate that SP-ICP-TOF-MS can resolve distinct particulate populations in complex, multicomponent steels at the femtogram mass scale, enabling particle-resolved insight into microstructure-driven phase separation and preparation-dependent particle generation.

Brubaker, Zach E. [Oak Ridge National Laboratory (↗
DOE OSTI2024

Overview of the distributed image processing infrastructure to produce the Legacy Survey of Space and Time

The Vera C. Rubin Observatory is preparing to execute the most ambitious astronomical survey ever attempted, the Legacy Survey of Space and Time (LSST). Currently the final phase of construction is under way in the Chilean Andes, with the Observatory’s ten-year science mission scheduled to begin in 2025. Rubin’s 8.4-meter telescope will nightly scan the southern hemisphere collecting imagery in the wavelength range 320–1050 nm covering the entire observable sky every 4 nights using a 3.2 gigapixel camera, the largest imaging device ever built for astronomy. Automated detection and classification of celestial objects will be performed by sophisticated algorithms on high-resolution images to progressively produce an astronomical catalog eventually composed of 20 billion galaxies and 17 billion stars and their associated physical properties. In this article we present an overview of the system currently being constructed to perform data distribution as well as the annual campaigns which reprocess the entire image dataset collected since the beginning of the survey. These processing campaigns will utilize computing and storage resources provided by three Rubin data facilities (one in the US and two in Europe). Each year a Data Release will be produced and disseminated to science collaborations for use in studies comprising four main science pillars: probing dark matter and dark energy, taking inventory of solar system objects, exploring the transient optical sky and mapping the Milky Way. Also presented is the method by which we leverage some of the common tools and best practices used for management of large-scale distributed data processing projects in the high energy physics and astronomy communities. We also demonstrate how these tools and practices are utilized within the Rubin project in order to overcome the specific challenges faced by the Observatory.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Scale tests of the new DUNE data pipeline

In preparation for the second runs of the ProtoDUNE detectors at CERN (NP02 and NP04)[1], DUNE has established a new data pipeline for bringing the data from the EHN-1 experimental hall at CERN to primary tape storage at Fermilab and CERN, and then spreading it out to a distributed disk data store at many locations around the world. This system includes a new Ingest Daemon and a new Declaration Daemon. The Rucio[2] replica catalog, and FTS3 transport are used to transport all files. All file metadata is declared to the new MetaCat[3] metadata service. All of these new components have been successfully tested at a scale equal to the expected output of the detector data acquisition system (~2-4 GB/s), and the expected network bandwidth out of the experimental hall. We present the procedure that was used to test and the results of the test.

Timm, Steven↗
DOE OSTI2024

Godiva IV central cavity neutron environment characterization with threshold neutron detectors

Godiva IV is a cylindrical fast burst reactor comprised of approximately 65 kg of highly enriched uranium that is operated by Los Alamos National Laboratory and sited at the National Criticality Experiments Research Center at the Nevada National Security Site in Nevada in the United States. Godiva IV is typically operated at delayed critical and in the regime spanning from sub-prompt to super-prompt bursts. Godiva IV is used for sample irradiations, criticality safety demonstrations, dosimetry studies, and for studying super-prompt behavior. In preparation for both an upcoming experiment to reduce uncertainties in the prompt fission spectrum for 235U using threshold neutron detectors, and for future research using Godiva IV, it was desired to exercise the process of the selection of threshold neutron detectors/activation foils, radiation metrology, and the subsequent adjustment of the neutron spectrum. For this exercise, nine high purity threshold neutron detectors/activation foils were irradiated in a Godiva IV burst. The foils were then analyzed using a high-purity germanium detector in the NCERC counting laboratory to determine end of irradiation specific activities for available IRDFF-II reactions. This work summarizes the Godiva IV foil irradiation, radiation metrology results, and adjusted neutron spectrum. The results of this exercise ultimately characterized the neutron environment inside the sample irradiation cavity inside Godiva IV to a higher degree than previously performed, informed decisions for the upcoming larger scale experiment, and will inform future neutron spectrum characterizations at NCERC.

Whitman, Nicholas H.↗