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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Structure and Solution Speciation of U IV Linked Phosphomolybdate (Mo V ) Clusters

Crystals of [NaU(Mo 6 P 4 O 31 H 7 ) 2 ]·5Na·(H 2 O)$_n$ (NaUMo 6 ) have been synthesized by slow evaporation of an aqueous mixture containing uranyl nitrate, sodium molybdate, phosphoric acid, and sodium dithionate. Single crystal diffraction of NaUMo 6 reveals the assembly of {Mo 6 P 4 } clusters linked into one-dimensional chains with alternating Na + and U 4+ cations. To our knowledge, NaUMo 6 is a unique example of Mo 5+ based polyoxometalate associated with actinides. With the use of similar synthesis conditions but without uranium in the aqueous solution, [Na(Mo 6 P 4 O 31 H 10 ) 2 ]·5Na·(H 2 PO 4 )·(H 2 O)$_n$ (NaMo 6 ) is obtained. NaMo 6 is a sandwich type cluster which is built on the assemblage of two {Mo 6 P 4 } units linked by one sodium cation. Using small-angle X-ray scattering techniques and aqueous electrolyte based dissolution strategies, we can accurately observe chains of [UNa(Mo 6 P 4 O 31 H 7 ) 2 ]$_n$$^{5n}$, where $n = 7$ is the dominant soluble specie. Likewise, the dimeric form of [Na(Mo 6 P 4 O 31 H 10 ) 2 ] 5– dominates the aqueous solution, revealing the structural units observed in the crystal structure are also stable in solution, under appropriate dissolution conditions.

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

Advanced Analysis of X-ray Fluorescence Measurements of the Interfacial Density of Eu Ions at Liquid–Liquid Interfaces for Solvent Back-Extraction

X-ray fluorescence near total reflection (XFNTR) is the primary technique used to measure the element-specific interfacial density of ions at liquid−liquid interfaces. Fluorescence from ions in the bulk liquids can complicate the determination of the interfacial density; consequently, measurements have been previously limited to samples without ions in the upper phase and with concentrations on the order of 10 μM or less in the lower phase. We modify the analysis of XFNTR data to account for ions in both bulk phases, then demonstrate its use in the context of rare-earth separations processes. In a model of ion stripping (i.e., back-extraction), dodecane solutions of di(2-ethylhexyl)- phosphoric acid (HDEHP) loaded with Eu(III) at the 1 mM level are placed in contact with either pure water or aqueous solutions of nitric or citric acid at pH 3. XFNTR measurements of equilibrated, quiescent samples reveal that citric acid solutions produce a disproportionately large depletion of ions from the interface compared to that from the bulk organic solution, whereas stripping by pure water or nitric acid solutions is negligible. As a result, this advance in the methodology of XFNTR may have broad applicability to the investigation of metal ions in chemical and biological processes at liquid−liquid interfaces.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Vibrational Signatures of Unrealized Phosphorus Suboxide Intermediates in White Phosphorus Oxidation Reactions

White phosphorus ignition notoriously produces the phosphoric acid anhydride P 4 O 10 , yet the intermediate oxidation steps remain undetermined. Here, we report the first geometric and vibrational characterization of two P 4 O 2 isomers, P 3 OPO and P 3 PO 2 , and substantiate a previously proposed cyclic P 4 O 2 isomer. We formally assign the infrared bands observed by Andrews and Mielke at 898 and 891 cm −1 to the antisymmetric P− O−P vibrations of P 3 OPO species. Additional bands corresponding to terminal P=O and −PO 2 stretches of P 3 OPO and P 3 PO 2 discussed herein also went unrecognized due to the peculiar bonding of P 4 O 2 species compared to oxo-bridged P 4 O x (x = 3−6) species. Sequential addition of oxygen atoms to the P 4 tetrahedron appears to form P 3 OPO and P 3 PO 2 , while cyclic P 4 O 2 is formed from P 2 O dimerization. CCSD(T) geometries, CCSD(T) + MP2[δVPT2] fundamental frequencies, and enthalpies of formation extrapolated using focal-point analysis are reported. The predicted enthalpies of formation relative to tetrahedral P 4 plus 3 Σ g − O 2 for bent-P 3 OPO, extended-P 3 OPO, P 3 PO 2 , and cyclic-P 4 O 2 are −93, −88, −85, and −63 kcal mol −1 , respectively.

Molecular structure↗
DOE OSTI2021

Membrane-Induced Vanadium Crossover-Blocking Polybenzimidazole Copolymer with Exceptional Proton Selectivity

Broad deployment of redox flow batteries is hindered, in part, due to the lack of highly selective ion-exchange membranes with high proton conductivity. We report a post-functionalization strategy for polybenzimidazole copolymer (PBI-co) membranes by a reacting mixture of concentrated sulfuric and phosphoric acids that led to improved membrane selectivity while retaining high proton conductivity. Fourier-transform infrared spectroscopy confirmed successful sulfonation and protonation of benzimidazole functionalities. PBI-co exhibits a very high room-temperature proton conductivity of 0.138 S cm -1 , as measured by electrochemical impedance spectroscopy. PBI-co also demonstrates electromigration crossover mitigation under applied current densities up to 500 mA cm -2 , and voltage pulses up to 1.4 V, while also inhibiting diffusion-driven vanadium crossover for over 20 days. Single-cell vanadium flow battery testing on post-functionalized PBI-co further confirms state-of-the-art battery performance with an ~99.5% Coulombic efficiency at 100 mA cm -2 and an area-specific resistance of ~20 mO cm 2 lower than Nafion-212 membrane.

25 ENERGY STORAGE↗
DOE OSTI2020

Catalytic Dynamic Kinetic Resolutions in Tandem to Construct Two-Axis Terphenyl Atropisomers

The defined structure of molecules bearing multiple stereogenic axes is of increasing relevance to materials science, pharmaceuticals, and catalysis. However, catalytic enantioselective approaches to control multiple stereogenic axes remain synthetically challenging. Here, we report the catalytic synthesis of two-axis terphenyl atropisomers, with complementary strategies to both chlorinated and brominated variants, formed with high diastereo- and enantioselectivity. The chemistry proceeds through a sequence of two distinct dynamic kinetic resolutions: first, an atroposelective ring opening of Bringmann-type lactones produces a product with one established axis of chirality, and second, a stereoselective arene halogenation delivers the product with the second axis of chirality established. In order to achieve these results, a class of Brønsted basic guanidinylated peptides, which catalyze an efficient atroposelective chlorination, is reported for the first time. In addition, a complementary bromination is reported, which also establishes the second stereogenic axis. These bromo-terphenyls are accessible following the discovery that chiral anion phase transfer catalysis by C 2 -symmetric phosphoric acids allows catalyst control in the second stereochemistry-determining event. Accordingly, we established the fully catalyst-controlled stereodivergent synthesis of all possible chlorinated stereoisomers while also demonstrating diastereodivergence in the brominated variants, with significant levels of enantioselectivity in all cases.

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

Quantitative and mechanistic insights into proton dynamics for fast energy storage

Proton conduction in hydrogen-bond-rich protic electrolytes enables fast mass and charge transport, crucial for electrochemical energy storage and power conversion. Such transport can give proton-based batteries exceptional rate capability and low-temperature operation beyond other working ions. Here we show that in phosphoric acid (H 3 PO 4 ) electrolytes, vehicular and structural proton transport coexist, and their contributions to conductivity can be quantitatively distinguished. We link structural diffusion directly to hydrogen-bond strength, enabling the precise tuning of proton migration. Guided by this, we reveal a double conductivity peak from regulated structural diffusion. The optimal electrolyte (5.8-M H 3 PO 4 ) achieves high overall (232.9 mS cm −1 ) and structural (164.9 mS cm−1) conductivity. A MoO 3 ‖CuFe-TBA battery with this electrolyte outperforms a deep-eutectic benchmark (8.3-M H 3 PO 4 ), delivering >17,474 W kg −1 at room temperature and retaining 15.1 Wh kg −1 at −75 °C. These findings provide a framework for designing advanced protic electrolytes across electrochemical systems.

Li, Ziyue [Fudan University, Shanghai (China, Peop↗
DOE OSTI2021

Recovery of high specific activity molybdenum-99 from accelerator-induced fission on low-enriched uranium for technetium-99m generators

Abstract A new process was developed to recover high specific activity (no carrier added) 99 Mo from electron-accelerator irradiated U 3 O 8 or uranyl sulfate targets. The process leverages a novel solvent extraction scheme to recover Mo using di(2-ethylhexyl) phosphoric acid following uranium and transuranics removal with tri- n -butyl phosphate. An anion-exchange concentration column step provides a final purification, generating pure 99 Mo intended for making 99 Mo/ 99m Tc generators. The process was demonstrated with irradiated uranium targets resulting in more than 95% 99 Mo recovery and without presence of fission products or actinides in the product.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Search for a Grotthuss mechanism through the observation of proton transfer

The transport of protons is critical in a variety of bio- and electro-chemical processes and technologies. The Grotthuss mechanism is considered to be the most efficient proton transport mechanism, generally implying a transfer of protons between ‘chains’ of host molecules via elementary reactions within the hydrogen bonds. Although Grotthuss proposed this concept more than 200 years ago, only indirect experimental evidence of the mechanism has been observed. Here we report the first experimental observation of proton transfer between the molecules in pure and 85% aqueous phosphoric acid. Employing dielectric spectroscopy, quasielastic neutron, and light scattering, and ab initio molecular dynamic simulations we determined that protons move by surprisingly short jumps of only ~0.5–0.7 Å, much smaller than the typical ion jump length in ionic liquids. Our analysis confirms the existence of correlations in these proton jumps. However, these correlations actually reduce the conductivity, in contrast to a desirable enhancement, as is usually assumed by a Grotthuss mechanism. Furthermore, our analysis suggests that the expected Grotthuss-like enhancement of conductivity cannot be realized in bulk liquids where ionic correlations always decrease conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Extraction of lanthanides using 1-hydroxy-6- N -octylcarboxamido-2(1 H )-pyridinone as an extractant via competitive ligand complexations between aqueous and organic phases

Here, the ability to selectively extract lanthanides is crucial in hydrometallurgy and the nuclear fuel cycle. The capabilities of 1-hydroxy-6- N -octylcarboxamido-2(1 H )-pyridinone (octyl-HOPO) as an extractant for the separation of lanthanides and actinides were studied for the first time. Octyl-HOPO greatly outperformed the traditional ligand di-2-ethylhexyl phosphoric acid (DEHPA).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Water-soluble Schiff base-actinyl complexes and their effect on the solvent extraction of f-elements

Conventional solvent extraction of selected f-element cations by bis(2-ethylhexyl)phosphoric acid (HDEHP) yields increased extraction from aqueous to organic solution along the series Np(V) < Cm(III) < Eu(III) < U(VI), with distribution ratios all within two orders of magnitude. However, in the presence of the water-soluble tetradentate Schiff base (N,N'-bis(5-sulfonatosalicylidene)-ethylenediamine or H 2 salenSO 3 ), selective complexation of the two actinyl cations (Np(V) and U(VI)) resulted in an extraction order of Np(V) < U(VI) << Eu(III) < Cm(III). The extraction of neither Cm(III) or Eu(III) by HDEHP are significantly impacted by the presence of the aqueous phase Schiff base. Despite observed hydrolytic decomposition of H 2 salenSO 3 in aqueous solutions, the calculated high conditional stability constant (β 11 = 26) for the complex [UO 2 (salenSO 3 )] 2- demonstrates its capacity for aqueous hold-back of U(VI). UV-visible-NIR spectroscopy of solutions prepared with a Np(VI) stock and H 2 salenSO 3 suggest that reduction of Np(VI) to Np(V) by the ligand was rapid, resulting in a pentavalent Np complex that was substantially retained in the aqueous phase. Lastly, results from 1 H NMR of aqueous solutions of H 2 salenSO 3 with U(VI) and La(III), Eu(III), and Lu(III) provides additional evidence that the ligand readily chelates U(VI), but has only weak interactions with trivalent lanthanide ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Inner versus Outer Sphere Metal-Monoamide Complexation: Ramifications for Tetravalent & Hexavalent Actinide Selectivity

Extraction of tetravalent and hexavalent plutonium by straight and branched chained monoamides was studied using UV-Vis spectroscopy. It was determined that predominantly anionic, outer sphere species are, formed, in all instances instead of Pu4+ recovery by acyl branched monoamides. Distribution values calculated from UV-Vis analysis were compared to tracer level LSC measurements, and were found to agree. Distribution values of hexavalent Am were also assessed. Good distribution values were achieved with straight monoamides and bis-2-ethyl hexyl phosphoric acid.

actinide separation, amide extractant↗
DOE OSTI2026

Opportunities and challenges for the expansion of LFP battery supply chains

Global markets for energy storage are growing rapidly, with some applications transitioning from traditional LiNi x Mn y Co 1−x−y O 2 (NMC) toward LiFePO 4 (LFP) due to cost, safety, and performance advantages. Battery growth has seeded interest in critical material supplies such as high-purity lithium precursors. In contrast, challenges in securing high-purity iron and phosphorus, historically not considered critical materials, are often overlooked. Precursors must remain inexpensive to maintain LFP's current cost advantage, which leverages the low-cost (∼$\$100$ per t) FeSO 4 byproduct from titanium dioxide manufacturing and will not be available as LFP manufacturing expands. As an alternative, iron is mined primarily for steel manufacturing, for which the existing supply chain and beneficiation process is optimized. LFP batteries require small iron volumes compared to steel (0.11%), but profit margins associated with existing low-cost iron ores and high costs (∼$27 000 per t) associated with low volume high-purity iron oxides may limit interest in manufacturing small volumes of high-purity, specialized iron battery precursors. The complementary LFP precursor, phosphoric acid (H 3 PO 4 ), is primarily utilized in fertilizers. Of the current phosphate ore demand for fertilizers, 4–22.8% would be required to meet projected 2045 LFP H 3 PO 4 demand, suggesting significant supply chain planning is needed to achieve projected demand. If only higher-grade material is considered, demand jumps to 15–77% of current world production. While lithium precursor purity requirements have been evaluated (Li 2 CO 3 is commonly defined as ≥99.5%), “battery grade” iron and phosphorus precursors remain poorly defined, with no internationally accessible and widely adopted standard, further challenging expanding industry by creating manufacturing uncertainty and increasing potential costs.

25 ENERGY STORAGE↗
DOE OSTI2014

Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry

TALSPEAK is a liquid/liquid extraction process designed to separate trivalent lanthanides (Ln3+) from minor actinides (MAs) Am3+ and Cm3+. Traditional TALSPEAK organic phase is comprised of a monoacidic dialkyl bis(2-ethylhexyl)phosphoric acid extractant (HDEHP) in diisopropyl benzene (DIPB). The aqueous phase contains a soluble aminopolycarboxylate diethylenetriamine-N,N,N’,N”,N”-pentaacetic acid (DTPA) in a concentrated (1.0-2.0 M) lactic acid (HL) buffer with the aqueous acidity typically adjusted to pH 3.0. TALSPEAK balances the selective complexation of the actinides by DTPA against the electrostatic attraction of the lanthanides by the HDEHP extractant to achieve the desired trivalent lanthanide/actinide group separation. Although TALSPEAK is considered a successful separations scheme, recent fundamental studies have highlighted complex chemical interactions occurring in the aqueous and organic phases during the extraction process. Previous attempts to model the system have shown thermodynamic models do not accurately predict the observed extraction trends in the p[H+] range 2.5-4.8. In this study, the aqueous phase is modified by replacing the lactic acid buffer with a variety of simple and longer-chain amino acid buffers. The results show successful trivalent lanthanide/actinide group separation with the aqueous-modified TALSPEAK process at pH 2. The amino acid buffer concentrations were reduced to 0.5 M (at pH 2) and separations were performed without any effect on phase transfer kinetics. Successful modeling of the aqueous-modified TALSPEAK process (p[H+] 1.6-3.1) using a simplified thermodynamic model and an internally consistent set of thermodynamic data is presented.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2014

Radiolysis of Tributyl Phosphate by Particles of High Linear Energy Transfer

Tributyl Phosphate (TBP), used in chemical separation processes for used nuclear fuel, is susceptible to radiolysis causing losses in process performance. Here, we have studied its degradation by exposing dry 1M TBP/n-dodecane solutions to gamma radiation from a cesium-137 source and in a mix of low and high linear energy transfer (LET) radiation by irradiating samples in the UC Irvine TRIGA® reactor and utilizing the 10 B(n,α) 7 Li reaction. In a 1 M solution of TBP in n-dodecane the degradation of TBP (G - TBP ) was found to be 0.36 and 0.14 μmol/J for low and high LET radiation, respectively. The formation of dibutyl phosphoric acid, DBP, (G + DBP ) in this solution was found to be 0.18 and 0.047 μmol/J for low and high LET radiation, respectively. In samples exposed to low LET as well as a mix of low and high LET a variety of TBP degradation products containing phosphorus were observed indicating that other degradation products than DBP and the monobutyl diacid (MBP) were formed. Our results for both low and high LET radiation compare well with previous studies on these systems indicating that high LET degrades TBP to a lesser extent than gamma radiation. Available data for high LET is not as abundant as for low LET making such comparisons challenging. Nevertheless, our method yields a value for G + DBP that agrees well with previous alpha radiolysis studies indicating that our method shows promise for studying high LET radiolysis in liquid-liquid extraction systems.

10B(n,α)7Li reaction↗
DOE OSTI2014

The chemistry of TALSPEAK: A review of the science

Here, the TALSPEAK Process (Trivalent Actinide Lanthanide Separation with Phosphorus-reagent Extraction from Aqueous Komplexes) was originally developed at Oak Ridge National Laboratory by B. Weaver and F.A. Kappelmann in the 1960s. It was envisioned initially as an alternative to the TRAMEX process (selective extraction of trivalent actinides by tertiary or quaternary amines over fission product lanthanides from concentrated LiCl solutions). TALSPEAK proposed the selective extraction of trivalent lanthanides away from the actinides, which are retained in the aqueous phase as aminopolycarboxylate complexes. After several decades of research and development, the conventional TALSPEAK process (based on di-(2-ethylhexyl) phosphoric acid (extractant) in 1,4-di-isopropylbenzene (diluent) and a concentrated lactate buffer containing diethylenetriamine-N,N,N',N",N"-pentaacetic acid (actinide-selective holdback reagent)) has become a widely recognized benchmark for advanced aqueous partitioning of the trivalent 4f/5f elements. TALSPEAK chemistry has also been utilized as an actinide-selective stripping agent (Reverse TALSPEAK) with some notable success. Under ideal conditions, conventional TALSPEAK separates Am 3+ from Nd 3+ (the usual limiting pair) with a single-stage separation factor of about 100; both lighter and heavier lanthanides are more completely separated from Am 3+ . Despite this apparent efficiency, TALSPEAK has not seen enthusiastic adoption for advanced partitioning of nuclear fuels at process scale for two principle reasons: 1) all adaptations of TALSPEAK chemistry to process scale applications require rigid pH control within a narrow range of pH, and 2) phase transfer kinetics are often slower than ideal. To compensate for these effects, high concentrations of the buffer (0.5-2 M H/Na lactate) are required. Acknowledgement of these complications in TALSPEAK process development has inspired significant research activities dedicated to improving understanding of the basic chemistry that controls TALSPEAK (and related processes based on the application of actinide-selective holdback reagents). In the following report, advances in understanding of the fundamental chemistry of TALSPEAK that have occurred during the past decade will be reviewed and discussed.

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

The photochemistry of pyrimidine in realistic astrophysical ices and the production of nucleobases

Nucleobases, together with deoxyribose/ribose and phosphoric acid, are the building blocks of DNA and RNA for all known life. The presence of nucleobase-like compounds in carbonaceous chondrites delivered to the Earth raises the question of an extraterrestrial origin for the molecules that triggered life on our planet. Whether these molecules are formed in interstellar/protostellar environments, in small parent bodies in the solar system, or both, is currently unclear. Recent experiments show that the UV irradiation of pyrimidine (C{sub 4}H{sub 4}N{sub 2}) in H{sub 2}O-rich ice mixtures that contain NH{sub 3}, CH{sub 3}OH, or CH{sub 4} leads to the formation of the pyrimidine-based nucleobases uracil, cytosine, and thymine. In this work, we discuss the low-temperature UV irradiation of pyrimidine in realistic astrophysical ice mixtures containing H{sub 2}O, CH{sub 3}OH, and NH{sub 3}, with or without CH{sub 4}, to search for the production of nucleobases and other prebiotic compounds. These experiments show the presence of uracil, urea, glycerol, hexamethylenetetramine, small amino acids, and small carboxylic acids in all samples. Cytosine was only found in one sample produced from ices irradiated with a higher UV dose, while thymine was not found in any sample, even after irradiation with a higher UV dose. Results are discussed to evaluate the role of the photochemistry of pyrimidine in the inventory of organic molecules detected in meteorites and their astrophysical/astrobiological implications.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

A FeCrAl-Al2O3 Composite Produced via Laser Powder Bed Fusion of a Mixed Powder for Porous Catalyst Scaffolds

This study proposes a novel approach for synthesizing and etching bicontinuous FeCrAl-Al2O3 composites as a means for replacing FeCrAl foams as catalyst scaffolds in bio-driven alcohol reactors for jet-fuel production. Conventional FeCrAl foams suffer from poor availability and consequent high costs. New additive manufacturing techniques provide an opportunity to produce tailored foams in reasonable times and at acceptable costs. This research aimed to generate a porous FeCrAl structure by etching a bicontinuous FeCrAl-Al2O3 composite produced by laser powder bed fusion of amalgamated FeCrAl and Al2O3 powders. The composite powder for laser powder bed fusion is created by ball-milling FeCrAl and Al2O3 powders. This research focuses on achieving a bi-continuous FeCrAl-Al2O3 structure, essential for the selective removal of the ceramic phase. The influence of laser processing parameters on the microstructure was examined across a range of laser powers (60-120 W) and scan speeds (100-400 mm/s), showing that higher powers and speeds produce finer metal struts. A bi-continuous microstructure was consistently obtained, marking a key achievement. The Al2O3 removal process involved a two-step etching method using hydrochloric and phosphoric acids, tested across various etching times. The alumina phase was reduced from 36 vol% to 17 vol% (corresponding to an increase in porosity from 24 vol% to 43 vol%), showing the potential for use as a porous catalyst scaffold. This research demonstrates the potential for using additive manufacturing to produce porous FeCrAl structures capable of replacing hard-to-source FeCrAl foams.

Son, Kwangtae↗