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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Reactivities of Interstitial Hydrides in a Cu 11 Template: En Route to Bimetallic Clusters

In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu + , Ag + , and Au + ), the stable CuI dihydride template [Cu 11 H 2 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 ] (H 2 Cu 11 ) generates surprisingly three very different compounds, namely [CuH 2 Cu 11 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 ] + (1), [AgH 2 Cu 14 {S 2 P(OiPr) 2 } 6 ((C≡CPh) 6 ] + (2), and [AuCu 11 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H 2 Cu 11 precursor. Neutron diffraction revealed the first time a trigonal-pyramidal hydride coordination mode in the AgCu 3 environment of 2. 3 has no hydride and exhibits a mixed-valent [AuCu 11 ] 10+ metal core, making it a two-electron superatom.

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

Synthesis and Surface Attachment of Molecular Re(I) Hydride Species with Silatrane Functionalized Bipyridyl Ligands

Three molecular Re hydrides of the form ( R bpy)Re(CO) 3 H with 2,2′-bipyridine (bpy) ligands containing silatrane functional groups for surface attachment on metal oxide surfaces were synthesized. IR spectroscopy and cyclic voltammetry (CV) demonstrated that the complexes containing the silatrane functional groups have electronic properties similar to those of a control compound, which did not contain functional groups for attachment. Additionally, in a similar fashion to the control compound, the silatrane containing Re hydrides are electrocatalysts for the reduction of CO 2 to CO in solution. The silatrane containing complexes were immobilized on a thin layer of TiO 2 on Si, and the resulting composites were characterized using X-ray photoelectron and IR spectroscopy as well as cyclic voltammetry in the dark and under illumination. Control experiments indicated that the hydride complexes are not stable on the surface and degrade to species which contain a bpy ligand, three CO ligands, and an unknown ligand in the sixth site. Similarly, when one of the silatrane containing Re hydride complexes was immobilized on Si nanoparticles with a thin layer of SiO 2 or silica nanoparticles, the hydride ligand was lost. Density functional theory calculations were used to corroborate the observed behavior of hydride species on a surface. Altogether, this work demonstrates the difficulties associated with attaching well-defined molecular hydride complexes to metal oxide surfaces.

Anions↗
DOE OSTI2022

Predicting and Controlling Corrosion (Abbreviated Final Report)

Corrosion accumulates significant replacement costs in the transportation, utility, manufacturing, and infrastructure sectors. It also underpins several of LLNL’s core missions in stockpile stewardship, defense, and energy security. Whereas most corrosion and aging models are empirically parameterized to describe well-defined conditions late in the reaction, the factors that determine the early stages of corrosion—during which mitigation could be most impactful— are poorly understood. This project addressed the critical need for new approaches to predict the kinetics of corrosion initiation based on firm physical and chemical understanding. The activities encompassed degradation of relevant metals in both hydrogen-rich and environmental corrosion scenarios. The team integrated state-of-the-art multiscale simulation, in situ characterization, and data science within three technical thrusts: hydriding of Ti alloys; aqueous corrosion of Al and Ni-Cr alloys; and degradation of additively manufactured 316L stainless steel. In each case, novel capabilities were developed to identify and track the impacts of key atomistic, compositional, and microstructural features on the metal systems. For hydriding, protocols were developed to tightly integrate multiscale models, advanced multimodal characterization, and machine learning to determine how hydrogen interacts with native passivating surface oxides and nucleates new undesired phases, shedding new light on the critical role of grain boundaries, interfaces, and atomically disordered regions. For aqueous corrosion, the project demonstrated methods to predict dissolution rates of metal surfaces in corrosive solutions, to measure and understand microstructural and grain orientation effects on corrosion susceptibility, and to investigate competing growth and dissolution kinetics of surface oxides. For additively manufactured metals, analysis using state-of-the-art microscopy techniques revealed the role of specific heterogeneities invoked during laser processing, including cellular structure, dislocations, and precipitates, on corrosion susceptibility. In addition to new capabilities and understanding, the project provided an avenue for workforce development, as well as key partnerships with stakeholders in corrosion science.

08 HYDROGEN↗
DOE OSTI2021

Ethane Dehydrogenation on Single and Dual Centers of Ga-modified γ-Al 2 O 3

Density-functional theory calculations and microkinetic analysis are used to investigate the efficacy of Ga-modified γ-Al 2 O 3 (110) surfaces for the catalytic dehydrogenation of ethane and elucidate the synergy between Ga and Al sites. The model surfaces are modified by either Ga grafting or doping. We consider and analyze numerous active sites and rank them using microkinetic analysis. The kinetic parameters obtained from microkinetic modelling are compared with experimental values for ethane dehydrogenation over Ga 2 O 3 -Al 2 O 3 mixed oxides prepared by co-precipitation. The dominant reaction pathway proceeds via heterolytic C-H bond dissociation to a surface proton and a metal-carbanion intermediate that undergoes β-hydride elimination. We find that grafted Ga sites are catalytically inactive. In contrast, Ga-doped sites exhibit fivefold enhancement in catalytic activity when compared to the sites on pristine Al 2 O 3 , owed to the synergy between neighboring AlIII and GaIV sites. Furthermore, we model and investigate the effect of surface hydroxylation, demonstrate how surface water interferes with the aforementioned synergy between AlIII and GaIV sites and discuss the implications for the catalytic activity of the modified surfaces. Here, an increase in the partial pressure of H 2 O significantly increases the apparent activation energies of dehydrogenation and interestingly changes the most active site.

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

Superconductivity Observed in Tantalum Polyhydride at High Pressure

We report experimental discovery of tantalum polyhydride superconductor. It was synthesized under high-pressure and high-temperature conditions using diamond anvil cell combined with in situ high-pressure laser heating techniques. The superconductivity was investigated via resistance measurements at pressures. The highest superconducting transition temperature T c was found to be ∼ 30 K at 197 GPa in the sample that was synthesized at the same pressure with ∼ 2000 K heating. The transitions are shifted to low temperature upon applying magnetic fields that support the superconductivity nature. The upper critical field at zero temperature μ 0 H c2 (0) of the superconducting phase is estimated to be ∼ 20 T that corresponds to Ginzburg–Landau coherent length ∼ 40 Å. Our results suggest that the superconductivity may arise from I 4 ¯ 3 d phase of TaH 3 . It is, for the first time to our best knowledge, experimental realization of superconducting hydrides for the VB group of transition metals.

Physics↗
DOE OSTI2020

Measurement of Palladium Hydride and Palladium Deuteride Isotherms Between 130 K and 393 K

The data collected in the present work extend the measured phase diagram for palladium hydride and palladium deuteride to a region that has been sparsely reported in open literature. Absorption isotherms were measured using a 2.5-g bed of palladium powder at temperatures between 130 K and 393 K and pressures less than 1.3 x 10 5 Pa. Such low-pressure and low-temperature measurements are useful for characterizing palladium beds used for tritium pumping and storage. For tritium storage, pressures are kept below a few millibar for safety reasons. Low temperatures increase the tritium storage capacity of palladium. The measured absorption isotherms show the well-documented, two-phase behavior for this system: two solubility regions and a mixed, hydride-forming region. The isotherms show that an increased quantity of hydride is formed at lower temperatures, as marked by an increase in the hydride-forming region. This region exceeds hydrogen to metal ratios of 0.75 for T ≤ 273 K. Equilibrium pressures in the mixed region decrease with decreasing temperatures until a critical temperature is reached for each isotope. Below these critical temperatures, the rate of pressure decrease with decreasing temperature is significantly reduced. This change in trend suggests hydrogen isotopes are adsorbed onto the palladium surface, rather than forming a hydride. Using the equilibrium pressures recorded at temperatures between 236 K and 393 K for protium and between 211 K and 354 K for deuterium, the van’t Hoff constants were calculated to be A = –36 ± 1 kJ/mol and B = 88 ± 3 J/K for protium and A = -32 ± 2 kJ/mol and B = 88 ± 9 J/K for deuterium. As a result, these constants agree favorably with literature in the range where the temperatures of the measured isotherms overlap.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Sensitivity study of hydrogen Soret transport in yttrium Hydride-Based nuclear fuel

Yttrium hydride is an excellent solid neutron moderator material for high temperature nuclear reactor applications due to its high hydrogen density and exceptional hydride stability at high temperatures. Despite these attractive characteristics, the details of how hydrogen behaves within yttrium hydride while temperature gradients exist are still not well understood. The evolution of the hydrogen composition profile resulting from a temperature gradient requires knowledge of hydrogen’s heat of transport, a critical parameter that has not yet been measured for this material. In this work, we perform hydride redistribution, hydrogen dissociation, and hydrogen leakage calculations while varying the Soret heat of transport of hydrogen in yttrium hydride to elucidate the sensitivity of hydride stability under temperature gradients to this parameter. This study analyzes hydride stability of a hypothetical uranium-yttrium hydride nuclear fuel design during operation of a high temperature liquid metal-cooled nuclear reactor. Assuming U-YH x could be fabricated in a physically stabilized manner, this fuel system can likely maintain hydride stability while operating at very high power densities and temperatures. We find that even though the hydrogen dissociation pressure in the gas gap does vary by several percent as the heat of transport temperature parameter is varied, the hydrogen content in the U-YH x fuel meat is relatively insensitive to this parameter over the course of a high burnup fuel cycle; this is due to yttrium hydride’s excellent hydrogen retention under the high temperature conditions considered here. Here, this suggests that hydride stability analyses are insensitive to the value of the Soret heat of transport in U-YH x under steady state liquid metal-cooled reactor conditions. However, the susceptibility to internal gas overpressurization-induced stress-rupture of the cladding during a high temperature transient is more sensitive to this parameter due to the non-linear dependence of hydrogen gas dissociation pressure vs. composition and temperature.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Catalytic Activity of Ti-based MXenes for the Hydrogenation of Furfural

Here, we report on the catalytic activity of Ti-based MXenes (Ti 3 CNT z and Ti 3 C 2 T z ) for biomass transformation. MXenes were found to be active catalysts for the hydrogenation of furfural using either gaseous hydrogen or 2-propanol as solvent and hydrogen source. Both catalysts showed good activity in the conversion of furfural to furfuryl alcohol, with furfuryl ether as the main by-product. Stability tests indicated that Ti 3 CNT z is more stable than Ti 3 C 2 T z against deactivation. Ab initio calculations were used to examine the hydrogenation and etherification reactions pathways and their corresponding reaction energetics on the Ti 3 CNT z MXene. The results indicate that the hydrogenation of the carbonyl bond efficiently proceeds via the heterolytic activation of hydrogen over the metal-oxygen site pair followed by the addition of the proton and hydride to the C and O atoms of the carbonyl. The subsequent hydrogenation of the unsaturated furan ring via metal bound hydrogen, however, is calculated to be much more difficult. Protons bound to the oxygen of the MXene are acidic and can also catalyze the etherification of the resulting alcohols. Finally, the bifunctional acid-metal site pairs also selectively catalyze the hydrogenolysis of the furfuryl alcohol to form 2-methyl furan.

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

A stress-based fracture model for reacting metal ejecta

The evolution of reacting metal ejecta continues to be a topic of interest at the forefront of metals in reactive and extreme environments. Ejecta are small particles formed when the surface of a metal undergoes Richtmyer–Meshkov instability from a strong shock. Experiments have shown that in the case where ejecta are in ambient conditions that induce a reaction, the ejecta behave irregularly. The ejecta temperature rises and then plateaus, and the acceleration profile shows unexpected jumps. These variations are assumed to be related to the exothermic heat release and particle mass loss caused by the reaction. To explain this phenomenon, efforts to model this in simulations have increased. While current models can capture many of these physical processes, they currently assign a constant reaction shell thickness with little physical reasoning. This work remedies this problem by assigning a dynamic physically informed shell thickness to the reacting particles, using solid analysis. The shell thickness of the particles impacts the rate of change of reacted mass in the system, as well as the rate at which the particles react. The model is based on a simple stress–strain relationship and gives a dynamic assignment for when the reacting particle should begin to fracture. We compare our model to the previous computational and simulation data to analyze the effects of different model parameters.

42 ENGINEERING↗
DOE OSTI2023

The deformation and burst behavior of Zircaloy-4 cladding tubes with hydride rim features subject to internal pressure loads

This study is motivated by the desire to conduct a separate effects test replicating specific aspects of an in-pile pulse reactor test on high exposure light water reactor (LWR) fuel rods. The principal purpose of the tests was to determine whether temperature and or hydrogen concentration thresholds exist in assessing the vulnerability of a stress relieved zirconium alloy cladding tubes to low strain ruptures. A secondary objective was to determine whether observations of the cladding stress during deformation could aid in the understanding of the crack formation and propagation in cladding tubes with hydride rim features. Here, the study utilized artificially hydrided Zircaloy-4 cladding tubes and an isothermal, internal pressure test that was controlled with an in-situ strain measurement. The test results show a clear transition in failure vulnerability between room temperature and 150 °C. Below 150 °C, cladding tubes rupture at very low uniform plastic strain—even at relatively modest cladding hydrogen levels. At and above 150 °C, cladding tubes only rupture at low uniform plastic strain if the cladding hydrogen content is greater than 500 ppm and usually experience at least some modest amount of plastic deformation prior to rupture. Post-test metallographs from non-ruptured cladding tubes show numerous primary cracks forming in the hydride rim and arresting at the metal/hydride interface. This observation combined with the decrease in bulk yielding of hydrided cladding tubes when compared to fresh non-hydrided tubes leads to the conclusion that the fracture stress of the hydride rims is related to and bounded by the yield stress of the zirconium metal. Some evidence is presented for a change in crack propagation mechanism from one of void formation on hydride plates and linkage at temperatures below 150 °C to more classical ductile shearing beneath the primary crack tip at temperatures above 150 °C. This apparent change in crack propagation mechanism may help explain the observed temperature and hydrogen concentration thresholds.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Combining pressure and electrochemistry to synthesize superhydrides

Significance Superhydrides are a materials system where near–room-temperature superconductivity has been achieved but only at very high (megabar) pressures. This work proposes an approach that combines pressure and electrochemistry to stabilize superhydrides at moderate pressures. Through a computational study of the palladium–hydrogen system, we construct electrochemical phase diagrams and show that electrochemically synthesizing superhydrides may be possible when combined with moderate pressures. We generalize this to other binary metal superhydrides of interest for superconductivity, including La, Y, and Mg hydrides.

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

Impact of Pendant Amine Basicity on Electrochemically-Promoted Cobalt Hydride Formation: Kinetic and Mechanistic Analysis

Here, we report the role of pendant amine basicity on the proton-coupled electron transfer (PCET) reactivity for the conversion of [Co III Cp(P Ph 2 N R 2 )(CH 3 CN)] 2+ complexes to [HCo III Cp(P Ph 2 N R 2 )] + , which is a key transformation involved in catalytic CO 2 conversion to formate and in H 2 evolution. Three complexes were studied, where the amine substituent (R) varies from benzyl, methoxyphenyl, or phenyl. In previous work on the benzyl system, we showed that the amine on the P Ph 2 N Bn 2 ligand serves as a kinetically accessible protonation site and enables three participating hydride formation mechanisms. In this work, a combination of electrochemical measurements and theoretical calculations were used to show that the electronic donation at the pendant amine influences the accessible PCET mechanism and proton transfer kinetics related to cobalt hydride formation under analogous reaction conditions. Notably, the amine with the most electron-donating substituent correlates to the lowest barrier for amine protonation, and specific cobalt hydride formation mechanisms can be shut off for the amine with the least electron-donating substituent. The mechanistic and kinetic changes upon modulation of the amine substituent have great implications for overall catalytic efficiency and selectivity, especially to generate the cobalt hydride intermediate involved in selective CO 2 reduction to formate. This work shows how to exploit kinetic basicity using ligand-cooperative design to facilitate PCET reactions involved in energy related transformations.

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

Biocatalytic Synthesis of α-Amino Esters via Nitrene C–H Insertion

α-Amino esters are precursors to noncanonical amino acids used in developing small-molecule therapeutics, biologics, and tools in chemical biology. α-C–H amination of abundant and inexpensive carboxylic acid esters through nitrene transfer presents a direct approach to α-amino esters. Methods for nitrene-mediated amination of the protic α-C–H bonds in carboxylic acid esters, however, are underdeveloped. This gap arises because hydrogen atom abstraction (HAA) of protic C–H bonds by electrophilic metal-nitrenoids is slow: metal-nitrenoids preferentially react with polarity-matched, hydridic C–H bonds, even when weaker protic C–H bonds are present. This study describes the discovery and evolution of highly stable protoglobin nitrene transferases that catalyze the enantioselective intermolecular amination of the α-C–H bonds in carboxylic acid esters. We developed a high-throughput assay to evaluate the activity and enantioselectivity of mutant enzymes together with their sequences using the Every Variant Sequencing (evSeq) method. Furthermore, the assay enabled the identification of enantiodivergent enzymes that function at ambient conditions in Escherichia coli whole cells and whose activities can be enhanced by directed evolution for the amination of a range of substrates.

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

Preliminary Observations on the Hydrogen Redistribution Feedback in YH-Moderated Monolithic Microreactors.

Nuclear microreactors promise to open new markets for nuclear industry. This is due to their potential competitive cost in non-traditional market segments, e.g., mines, forward military basis, extraterrestrial surfaces and remote areas, and inherently safe characteristics that make them deployable where other power sources are not available or difficult to exploit. Transition metal dihydrides have been considered among the most promising candidates for moderating nuclear microreactors. In particular, yttrium hydride (YH\textsubscript{x}) has been selected for high temperature applications due to its high thermal stability and relatively high hydrogen retention at temperatures exceeding $870^\circ C$. One of the main issues associated with the use of hydrides is that, when exposed to temperature, stress, or concentration gradients, the hydrogen contained in the metallic matrix tends to redistribute and leak from the moderating elements, potentially leading to reactivity losses and power swings. The purpose of this paper is to gain a better physical understanding of the neutronic feedback associated with the hydrogen redistribution in YH\textsubscript{x}, by using Griffin and Bison. This feedback is inherently multiphysics, since the hydrogen distribution is strongly dependent on the moderator temperature spatial distribution. In particular, we want to understand the sign (+/-) of the neutronic feedback, its order of magnitude, and its underlying physical causes.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2023

Bonding and Acidity of the Formal Hydride in the Prototypical Au 9 (PPh 3 ) 8 H 2+ Nanocluster

The role of hydrogen atoms as surface ligands on metal nanoclusters is of profound importance but remains difficult to directly study. While hydrogen atoms often appear to be incorporated formally as hydrides, evidence suggests that they donate electrons to the cluster's delocalized superatomic orbitals and may consequently behave as acidic protons that play key roles in synthetic or catalytic mechanisms. Here we directly test this assertion for the prototypical Au 9 (PPh 3 ) 8 H 2+ nanocluster, formed by addition of a hydride to the well-characterized Au 9 (PPh 3 ) 8 3+ . Using gas-phase infrared spectroscopy, we were able to unambiguously isolate Au 9 (PPh 3 ) 8 H 2+ and Au 9 (PPh 3 ) 8 D 2+ , revealing an Au–H stretching mode at 1528 cm –1 that shifts to 1038 cm –1 upon deuteration. This shift is greater than the maximum expected for a typical harmonic potential, suggesting a potential governing cluster-H bonding that has some square-well character consistent with the hydrogen nucleus behaving as a metal atom in the cluster core. Complexing this cluster with very weak bases reveals a redshift of 37 cm –1 in the Au–H vibration, consistent with those typically seen for moderately acidic groups in gas phase molecules and providing an estimate of the acidity of Au 9 (PPh 3 ) 8 H 2+ , at least with regard to its surface reactivity.

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

Formation and characterization of hydride rim structures in Zircaloy-4 nuclear fuel cladding tubes

Zirconium alloy tubes used as nuclear fuel cladding are subject to oxidation and subsequent hydrogen pickup during their long service in commercial light water reactors. The hydrogen picked up in the cladding can precipitate as a brittle hydride rim feature on the cladding outer surface. Here, to better understand the effect of hydride rims on the fracture behavior of stress-relieved zirconium alloy cladding tubes, a procedure to produce these rim-like structures has been developed and is described herein. Extensive characterization of the ‘as hydrided’ tubes is performed. The hydrogen charging apparatus consists of a tube furnace with a quartz chamber that is connected to a vacuum pump as well as a bottle of pure hydrogen gas. The charging station uses a static charge of hydrogen as opposed to a flowing gas. The chief advantage of this approach is the ability to monitor the pressure drop in the hydriding chamber and correlate this pressure drop to a known rate of hydrogen pickup in the cladding tube. It was found that the hydrogen partial pressure, metal temperature, and surface treatment all clearly played a role in whether a hydride rim was formed. Extensive characterization of the hydride rims shows they consist of needle like platelets of δ phase hydrides (ZrH1.66) oriented in the circumferential direction with a radial spacing of several microns in a sandwich-like structure.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗