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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 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Enhanced delivery of engineered Fe-Mn binary oxides in heterogeneous porous media for efficient arsenic stabilization

Heterogeneity in sediment and aquifer is universal, resulting in preferential flows of injected materials in the high permeability regions and forming flow by-passed zones in the low permeability regions during in-situ subsurface remediation. This adverse effect can considerably delay the completion of remedial operations and significantly increase the cost. Column experiments were designed and conducted to study the transport of starch- and starch-xanthan gum modified Fe-Mn binary oxide particles (SFM and SXFM) in saturated heterogeneous porous media and to reveal the particles’ arsenic (As) stabilization performance. Fine-in-Coarse (FIC) and Coarse-in-Fine (CIF) patterns of heterogeneous packings were set up in the columns. Testing results demonstrated that starch-xanthan gum dual treatment on Fe-Mn binary oxides successfully improved the particles’ migration capability in heterogeneous porous media and their distribution uniformity attributed to the profound shear thinning behavior of xanthan gum solution. The addition of xanthan gum to the system increased the viscosity and shear thinning property of SXFM suspension, making it a better candidate for delivery. Both SFM and SXFM stabilized As in heterogeneously packed sediment collected from a contaminated site, with SXFM showing better stabilization performance than SFM. The stabilization effects of SXFM were 90.7-97.0%, compared to 82.0-95.2% of SFM.

Yan, Xiulan↗
DOE OSTI2018

Dynamic imaging of metastable reaction pathways in lithiated cobalt oxide electrodes

Understanding how lithium-ion batteries function down to the atomic level during charge and discharge cycling can provide valuable guidance to optimize structure-property relationships and to design and understand new electrode materials. Lithium insertion and reactions with the electrodes during charge and discharge cycling can occur via metastable structures with complex ordering and related non-equilibrium phenomena. Remarkably, these processes remain still poorly understood despite their significance in the operation of lithium battery systems in critical technologies. In this communication, we present the dynamics of lithium insertion into Co3O4 and the evolution of metastable phases as probed by in-situ transmission electron microscopy, in concert with first principles density functional theory calculations. We show that the initial lithium intercalation reaction occurs with the formation of several metastable and intermediate phases, followed by a sequence of conversion reactions that perturb and expand the cubic-close-packed oxygen array, ultimately generating an end-product of finely dispersed cobalt metal clusters within a Li2O matrix. The calculated non-equilibrium lithiation pathways corroborate with the experimental lithiation voltages, and explain the significant hysteresis that occurs during electrochemical cycling. The data provide new insights into the complexity of solid state lithium electrochemistry in metal oxides that are relevant to advancing lithium battery technology.

conversion reaction electrode↗
DOE OSTI2016

Processable conductive graphene/polyethylene nanocomposites: Effects of graphene dispersion and polyethylene blending with oxidized polyethylene on rheology and microstructure

Poor dispersion of graphene in non-polar polymer matrices creates composites with limited applications. A method to improve the dispersion of graphene in polyethylene (PE) via blending PE with oxidized PE (OPE) is examined. Graphene was produced by simultaneous thermal exfoliation and reduction of graphite oxide. Nanocomposites of graphene with PE as well as graphene with PE/OPE-blends were prepared by solvent blending. Improved dispersion of graphene in PE/OPE blends substantially decreases percolation from both rheological (0.3 vol%) and electrical (0.13 vol%) measurements compared to neat PE nanocomposites (1 and 0.29 vol%), respectively. A universal Brownian dispersion of graphene in polymers was concluded similar to that of nanotubes, following the Doi-Edwards theory. Micromechanical models, such as Mori-Tanaka and Halpin-Tsai models, modeled the mechanical properties of the nanocomposites. The nanocomposites microstructure, studied by small angle x-ray scattering, confirmed better dispersion of graphene at lower loadings and the formation of surface fractals in the blend/graphene nanocomposites; whereas only mass fractals were observed in neat PE/graphene nanocomposites.

graphene↗
DOE OSTI2023

Targeting Oxide Concentration in Tantalum Oxide-Fluoride Anions

The design of both molecular and non-molecular solid materials with specific properties fundamentally relies on the controlled synthesis of crystals with desired functional groups, bonding motifs, polarity, chirality, and more. To this end, fluoride and oxide-fluoride anions have been utilized as basic building units (BBUs) in the synthesis of noncentrosymmetric racemic materials for their ability to create polar axes that facilitate the breaking of an inversion center as demonstrated in a series of compounds with [MF6]2- anions (M = Ti, Zr, Hf). Targeting an analog with a [TaOF5]2- anion, the phase space of (CuO, Ta2O5)/bpy/HF(aq)/H2O (bpy = 2,2′-bipyridine) was investigated and three new compounds with Cu-bpy cations and Ta-fluoride or Ta-oxyfluoride anions were synthesized: [Cu(bpy)2][TaF6], [Cu(bpy)2][Ta2OF10], and [Cu(bpy)F(H2O)2]2[TaF7]∙H2O with the anions [TaF6]-, [Ta2OF10]2-, and [TaF7]2-, respectively. The formation of these anions was found to be a product of both the concentration of hydrofluoric acid in solution and the ratio of metal-oxide starting materials to ligand. This work contributes to the understanding of mixed anion formation in the solid state.

Kamp, Kendall R.↗
DOE OSTI2018

Carrier transport through the ultrathin silicon-oxide layer in tunnel oxide passivated contact (TOPCon) c-Si solar cells

The carrier transport through the silicon-oxide (SiO x ) layer in tunnel oxide passivated contact (TOPCon) c-Si solar cells has been studied experimentally and by simulation. The current intensity versus voltage (J-V) characteristics of GaIn/n-c-Si/SiO x /n + -poly-Si/Al structures shows a linear Ohmic characteristic, while a non-Ohmic behavior is observed in the samples without the n + -poly-Si contact layer. Conductive Atomic Force Microscopy (c-AFM) images reveal some current spikes on the surface of the samples, which could be related to the transport through pinholes. The simulation results show that 1) a rectification characteristic is obtained when only the tunneling mechanism is included, 2) both the reverse saturation current and the forward current increase when a small amount of transport through pinholes is introduced, and 3) finally a linear Ohmic behavior is observed when the pinhole transport component reaches a certain level. Furthermore, the simulation for whole TOPCon solar cells provides some useful results. For very thin SiO x (< 1.2 nm), the tunneling provides sufficient high tunneling probability and high efficiency TOPCon solar cells can be obtained without transport through pinholes if the passivation is ensured; while for a relatively thick SiO x (> 1.2 nm) without the transport through pinholes, the TOPCon solar cell shows a poor fill factor (FF) with a high series resistance (Rs) because the tunneling does not provide a sufficient high transport channel for carrier transport, and the introduction of a small number of transports through pinholes improves the FF and reduces the Rs, hence improves the PCE. However, a high possibility for carrier going through pinholes reduces all of the performance parameters and degrades PCE for all the cases simulated. Therefore, an optimized pinhole density and size distribution is critical engineering for solar cell performance optimization. However, the establishment of an optimized method to precisely control the pinhole formation and characterization is still on the way.

14 SOLAR ENERGY↗
DOE OSTI2018

Facet-Dependent Rock-Salt Reconstruction on the Surface of Layered Oxide Cathodes

The surface configuration of pristine layered oxide cathode particles for Li-ion batteries significantly affects the electrochemical behavior, which is generally considered to be a thin rock-salt layer in the surface. Unfortunately, aside from its thin nature and spatial location on the surface, the true structural nature of this surface rock-salt layer remains largely unknown, creating the need to understand its configuration and the underlying mechanisms of formation. Using scanning transmission electron microscopy, we have found a correlation between the surface rock-salt formation and the crystal facets on pristine LiNi0.80Co0.15Al0.05O2 primary particles. It is found that the originally (01 $ \overline{4}\ $) and (003) surfaces of the layered phase result in two kinds of rock-salt reconstructions: the (002) and (111) rock-salt surfaces, respectively. Stepped surface configurations are generated for both reconstructions. The (002) configuration is relatively flat with monoatomic steps while the (111) configuration shows significant surface roughening. Both reconstructions reduce the ionic and electronic conductivity of the cathode, leading to a reduced electrochemical performance.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2021

LaNi x Fe 1– x O 3–δ as a Robust Redox Catalyst for CO 2 Splitting and Methane Partial Oxidation

The current study reports LaNi 0.5 Fe 0.5 O 3–δ as a robust redox catalyst for CO 2 splitting and methane partial oxidation at relatively low temperatures (~700 °C) in the context of a hybrid redox process. Specifically, perovskite-structured LaNi x Fe 1–x O 3–δ (LNFs) with nine different compositions (x = 0.05–0.5) were prepared and investigated. Among the samples evaluated, LaNi 0.4 Fe 0.6 O 3–δ and LaNi 0.5 Fe 0.5 O 3–δ showed superior redox performance, with ~90% CO 2 and methane conversions and >90% syngas selectivity. The standalone LNFs also demonstrated performance comparable to that of LNF promoted by mixed conductive Ce 0.85 Gd 0.1 Cu 0.05 O 2–δ (CGCO). Long-term testing of LaNi 0.5 Fe 0.5 O 3–δ indicated that the redox catalyst gradually loses its activity over repeated redox cycles, amounting to approximately 0.02% activity loss each cycle, averaged over 500 cycles. This gradual deactivation was found to be reversible by deep oxidation with air. Further characterizations indicated that the loss of activity resulted from a slow accumulation of iron carbide (Fe 3 C and Fe 5 C 2 ) phases, which cannot be effectively removed during the CO 2 splitting step. Reoxidation with air removed the carbide phases, increased the availability of Fe for the redox reactions via solid-state reactions with La 2 O 3 , and decreased the average crystallite size of La 2 O 3 . As a result, reactivating the redox catalyst periodically, e.g., once every 40 cycles, was shown to be highly effective, as confirmed by operating the redox catalyst over 900 cumulative cycles while maintaining satisfactory redox performance.

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

Autothermal Chemical Looping Oxidative Dehydrogenation of Ethane: Redox Catalyst Performance, Longevity, and Process Analysis

Energy-efficient upgrading of stranded ethane from shale gas to olefins holds the promise of increasing the supply of useful chemical feedstocks while reducing flaring-based CO 2 emissions. Previously, we reported a modular ethane-to-liquids (M-ETL) system based on a chemical looping oxidative dehydrogenation (CL-ODH) scheme. In this article, we present long-term (>1200 h) results of Li 2 CO 3 -promoted La 0.8 Sr 0.2 FeO 3 corresponding to ~4125 CL-ODH cycles in a large laboratory-scale packed bed reactor. Temperature monitoring along the bed length confirmed the exothermicity of both the oxidative dehydrogenation and regeneration steps, enabling an autothermal operation. Product gas analysis indicated that the redox catalyst maintains a high C 2+ selectivity (~90%) and ethane conversion (~67%) at 735 °C after continuous cycling of >1000 h. As a result, product distributions and heats of reactions were used to update our M-ETL process model for revised techno-economic analysis, demonstrating that the current system is economically viable with relatively low required selling prices across a wide range of operating scenarios.

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

Integrated Two-Stage Alkaline-Oxidative Pretreatment of Hybrid Poplar. Part 1: Impact of Alkaline Pre-Extraction Conditions on Process Performance and Lignin Properties

We previously demonstrated that a two-stage pretreatment comprising of an alkaline pre-extraction followed by a Cu-catalyzed alkaline–oxidative treatment is effective at pretreating hardwoods under relatively mild reaction conditions. In this work, we focus on characterizing how biomass source and reaction conditions used during the alkaline pre-extraction impact the subsequent processing stages as well as lignin yields and properties. Specifically, three hybrid poplars were subjected to the first stage alkaline pre-extraction under various conditions including differences in time (15–300 min), temperature (95–155 °C), and alkali loadings (50–200 mg NaOH/g biomass), and the impact on total mass solubilization, lignin recovery, and lignin purity was determined. Empirical correlations were developed between reaction conditions and mass solubilization and lignin recovery during the pre-extraction stage. For select conditions, lignin properties were assessed and include β-O-4 content determined by 13C NMR, molecular mass distributions as determined by gel permeation chromatography, and susceptibility to depolymerization to aromatic monomers using thioacidolysis and formic acid catalyzed depolymerization. We found alkaline pre-extraction performed at higher temperatures generated lignins exhibiting lower contamination by polysaccharides, lower aromatic monomer yields from depolymerization, lower molar masses, and lower β-O-4 contents relative to the lower temperature pre-extractions. Lastly, the pre-extracted biomass from select conditions was assessed for its response to the subsequent Cu-catalyzed alkaline–oxidative treatment and enzymatic hydrolysis. It was demonstrated that minor differences in delignification during pre-extraction have quantifiable impacts on the subsequent efficacy of the second stage of pretreatment and enzymatic hydrolysis with improved lignin removal during the first pre-extraction stage resulting in improved hydrolysis yields.

09 BIOMASS FUELS↗
DOE OSTI2017

Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials

A series of mixed-valent, heterometallic (mixed-transition metal) diketonates that can be utilized as prospective volatile single-source precursors for the low-temperature preparation of M x M' 3–x O 4 spinel oxide materials is reported. Three iron–cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal–oxygen bonds with those in homometallic analogues, heterometallic compounds were formulated as [Fe III (acac) 3 ][Co II (hfac) 2 ] (1), [Co II (hfac) 2 ][Fe III (acac) 3 ][Co II (hfac) 2 ] (2), and [Fe II (hfac) 2 ][Fe III (acac) 3 ][Co II (hfac) 2 ] (3). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated CoII/FeII centers chelated by two hexafluoroacetylacetonate (hfac) ligands maintain bridging interactions with oxygen atoms of acetylacetonate (acac) groups that chelate the neighboring Fe III metal ion. Preliminary assignment of Fe and Co positions/oxidation states in 1–3 drawn from X-ray structural investigation was corroborated by a number of complementary techniques. Single-crystal resonant synchrotron diffraction and neutron diffraction experiments unambiguously confirmed the location of Fe and Co sites in the molecules of dinuclear (1) and trinuclear (2) complexes, respectively. Direct analysis in real time mass spectrometry revealed the presence of Fe III - and Co II -based fragments in the gas phase upon evaporation of precursors 1 and 2 as well as of Fe III , Fe II , and Co II species for complex 3. Theoretical investigation of two possible “valent isomers”, [Fe II I(acac) 3 ][Co II (hfac) 2 ] (1) and [Co III (acac) 3 ][Fe II (hfac) 2 ] (1'), provided an additional support for the metal site/oxidation state assignment giving a preference of 6.48 kcal/mol for the experimentally observed molecule 1. Magnetic susceptibility measurements data are in agreement with the presence of high-spin FeIII and CoII magnetic centers with weak anti-ferromagnetic coupling between those in molecules of 1 and 2. Highly volatile heterometallic complexes 1–3 were found to act as effective single-source precursors for the low-temperature preparation of iron–cobalt spinel oxides Fe x Co 3–x O 4 known as important materials for diverse energy-related applications.

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

Modulating Hole Transport in Multilayered Photocathodes with Derivatized p-Type Nickel Oxide and Molecular Assemblies for Solar-Driven Water Splitting

We report here a new photocathode composed of a bi-layered doped NiO film topped by a macro-mesoporous ITO (ioITO) layer with molecular assemblies attached to the ioITO surface. The NiO film containing a 2% K+ doped NiO inner layer and a 2% Cu2+ doped NiO outer layer provides sufficient driving force for hole transport after injection to NiO by the molecular assembly. The tri-layered oxide, NiK0.02O | NiCu0.02O | ioITO, sensitized by a ruthenium polypyridyl dye and functionalized with a nickel-based hydrogen evolution catalyst, outperforms its counterpart, NiO | NiO | ioITO, in photocatalytic hydrogen evolution from water over a period of several hours with a Faradaic yield of ~90%.

Shan, Bing↗
DOE OSTI2017

Interplay between Terminal and Bridging Diiron Hydrides in Neutral and Oxidized States

This study describes the structural, spectroscopic, and electrochemical properties of electronically unsymmetrical diiron hydrides. The terminal hydride Cp*Fe(pdt)Fe(dppe)(CO)H ([1(t-H)]0, Cp*– = Me5C5 –, pdt2– = CH2(CH2S–)2, dppe = Ph2PC2H4PPh2) was prepared by hydride reduction of [Cp*Fe(pdt)Fe(dppe)(CO)(NCMe)]+. As established by X-ray crystallography, [1(t- H)]0 features a terminal hydride ligand. Unlike previous examples of terminal diiron hydrides, [1(t-H)]0 does not isomerize to the bridging hydride [1(µ-H)]0. Oxidation of [1(t-H)]0 gives [1(t- H)]+, which was also characterized crystallographically as its BF4 – salt. Density functional theory (DFT) calculations indicate that [1(t-H)]+ is best described as containing an Cp*Fe(III) center. In solution, [1(t-H)]+ isomerizes to [1(µ-H)]+ as anticipated by DFT. Reduction of [1(µ- H)]+ by Cp2Co affords the diferrous bridging hydride [1(µ-H)]0. Electrochemical measurements and DFT calculations indicate that the couples [1(t-H)]+/0 and [1(µ-H)]+/0 differ by 210 mV. Qualitative measurements indicate that [1(t-H)]0 and [1(µ-H)]0 are close in free energy. Protonation of [1(t-H)]0 in MeCN solution affords H2 even with weak acids via hydride transfer.

Yu, Xin↗
DOE OSTI2018

Electrophilic Impact of High-Oxidation State Main-Group Metal and Ligands on Alkane C–H Activation and Functionalization Reactions

High-oxidation state main-group metal complexes are potential alternatives to transition metals for electrophilic alkane C–H functionalization reactions. Yet, there is little known about how selection of the p-block, main-group metal and ligand impact alkane C–H activation and functionalization thermodynamics and reactivity. This work reports density functional theory calculations used to determine qualitative and quantitative features of C–H activation and metal-methyl functionalization energy landscapes for reaction between high-oxidation state d 10 s 0 In III , Tl III , Sn IV , and Pb IV carboxylate complexes with methane. While the main-group metal influences the C–H activation barrier height in a periodic manner, the carboxylate ligand has a much larger quantitative impact on C–H activation with stabilized carboxylate anions inducing the lowest barriers. For metal-methyl reductive functionalization reactions, the main-group metal dramatically influences the barrier heights, which are correlated to reaction thermodynamics and bond heterolysis energies as a model for two-electron reduction energies. Generally, this work begins to outline which main-group metals and carboxylate ligands could be useful for alkane functionalization systems that utilize electrophilic C–H activation and metal-alkyl functionalization reactions.

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

Feasibility of Metal Oxide Glasses and Polymer Membranes as Sorbents for Gaseous Oxidized Mercury

Mass spectrometry methods are currently under development by the atmospheric mercury (Hg) research community to elucidate the identity of atmospheric oxidized mercury (Hg II ) compounds. Due to high instrument detection limits, materials that can quantitatively preconcentrate atmospheric Hg II without facilitating compound-altering chemical reactions are needed to support these methods. Cation exchange membranes (CEM) and nylon membranes are currently used to preconcentrate ambient Hg II for concentration measurements and Hg II compound estimation, respectively. However, CEM and nylon membranes are poor candidates for observations by mass spectrometry methods due to release of interfering compounds upon heating; glasses do not have this problem. Here, three metal oxide glasses were explored as potential alternatives for Hg II preconcentration for future use with mass spectrometry methods: calcium phosphate (CaP), iron phosphate (FeP), and calcium aluminate (CaAl). The glasses demonstrated quantitative selective capture of HgBr 2 without capture of Hg 0 . Under ambient conditions, the CaP, FeP, and CaAl sorbed 36.4 ± 12.6% of the total HgII as the CEM. However, when Hg concentrations were normalized to surface area, CaP, FeP, and CaAl sorbed more HgBr 2 in the laboratory and ambient HgII compared to CEM. The CEM and CaP retained similar concentrations of HgBr 2 when preloaded samples were deployed in the field. Additionally, a permeation tube-based calibrator was used to load sorbents with HgBr 2 for investigation of HgII retention on CEM and thermal desorption profile changes on nylon membranes during active sampling. Nylon membranes were purchased from three vendors and used to compare HgBr 2 retention; a different HgBr 2 thermal desorption profile was achieved for each vendor’s nylon membrane.

Amides↗