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At least 163 records · Page 9

Performance analysis of advanced spacecraft TPS

The analysis on the feasibility for using metal hydrides in the thermal protection system of cryogenic tanks in space was based on the heat capacity of ice as the phase change material (PCM). It was found that with ice the thermal protection system weight could be reduced by, at most, about 20 percent over an all LI-900 insulation. For this concept to be viable, a metal hydride with considerably more capacity than water would be required. None were found. Special metal hydrides were developed for hydrogen fuel storage applications and it may be possible to do so for the current application. Until this appears promising further effort on this feasibility study does not seem warranted.

Pitts, William C.↗

WEC Irradiation Can Thermal Testing Report

With renewed interest for the next generation of small modular reactors and space-based nuclear reactors, metal hydrides have been a focus of research for moderating materials to reduce the need for highly enriched fuel to maintain small core sizes. Yttrium hydride (YH) is an attractive candidate for these metal hydrides due to its ability to retain hydrogen at elevated temperatures as well as the low neutron absorption cross section of yttrium metal. Given the necessity for reactors to operate at elevated temperatures for extended periods of time, understanding hydrogen retention in moderator channels in simulated operating thermal conditions is paramount in predicting reactor performance and the long-term stability of YH. Additionally, coating strategies on the moderator encapsulating will be explored to ascertain if it aids in retention of hydrogen within the capsule and moderator.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Hydrogen transport in yttrium hydride under asymmetric heat

Metal hydrides are a promising moderator material for high temperature fission reactors. Yttrium hydride can be loaded to a high hydrogen density with relatively high hydrogen stability at temperatures up to 800°C. This makes yttrium hydride a potential moderator material for microreactors as foreseen in the fission surface power program. However, during the operation of such advanced reactors temperature gradients are expected which can change the local hydrogen density in the moderator. Hydrogen diffusion in metals is driven by a concentration gradient (Fick’s law) and thermal diffusion (Soret diffusion). Thermal diffusion is the transport of hydrogen, or other species, due to a temperature gradient. For example, hydrogen might migrate from the hot side of a sample to the cold side of a sample. Measuring Fickian diffusion is achieved through various permeation or absorption experiments, however measuring thermal diffusion is challenging and has rarely been performed. The Hydrogen Experimental Apparatus for Thermal Diffusion (HEATD) experiment is designed to induce thermal diffusion in samples and quench those samples so that the hydrogen distribution can be analyzed using hot vacuum extraction (HVE). One side of the sample was heated to a high temperature e.g., 800°C, while the other side of the sample is at a lower temperature. The sample was held under the applied temperature gradient for a given time until the anticipated hydrogen diffusion has occurred. The actual time depends depend on the sample composition and hydrogen concentration. The results from HVE showed that thermal diffusion took place in the specimen and the Soret coefficient was calculated.

36 MATERIALS SCIENCE↗

Chemically Separable Ruthenium Hydride Isomers with Distinct Hydride Transfer Properties

Transition metal hydrides are key intermediates in biological and industrial catalysis, where control over hydride donor ability (hydricity) is essential for optimizing reactivity. Herein, we report a series of isomeric ruthenium hydrides in which the ligand trans to the ruthenium hydride bond–either an N-heterocyclic carbene or pyridine–modulates the thermodynamic hydricity by up to 8 kcal mol –1 . These hydrides exhibited distinct reactivity toward CO 2 and various organic hydride acceptors, enabling detailed kinetic and mechanistic analysis. Stopped-flow experiments, isotopic labeling, and computational studies supported an outer-sphere hydride transfer mechanism. Linear free energy relationships (LFERs) and Marcus relationships were utilized to correlate the changes in thermodynamics and kinetics, revealing that ligands with strong trans effects and trans influence can disrupt conventional scaling relationships, which can be a powerful strategy for promoting new reactivity paradigms in hydride transfer reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Combustion synthesis of nanoscale magnesium borides with improved hydrogen uptake and release

The overarching goal of the reported project was to develop reversible metal hydrides that can be dehydrogenated and recharged at relatively low temperatures and pressures. The project complemented the research on reversible metal hydrides for hydrogen storage conducted by the Hydrogen Materials – Advanced Research Consortium (HyMARC). The students involved were trained at both the University of Texas at El Paso (UTEP) and Sandia National Laboratories (SNL). The research objectives were to fabricate nanoscale magnesium boride powders with different B/Mg atomic ratios and to investigate the effects of B/Mg ratio and particle size on the hydrogenation properties of the obtained materials. Magnesium diboride (MgB 2 ) and tetraboride (MgB 4 ) were synthesized by using combustion synthesis and by heating in a tube furnace. The latter method resulted in materials with significantly reduced impurity levels. An effective method for the removal of magnesium oxide impurities was identified. High-energy ball milling produced submicron MgB 2 and MgB 4 powders. However, hydrogenation experiments at pressures up to 700 bar have not shown any uptake of hydrogen. Thermogravimetric analysis of the decomposition of the obtained MgB 2 and MgB 4 demonstrated higher thermodynamic stability of the latter. Thus, the boron-rich nature and phase stability of magnesium borides with high B/Mg ratios make them poor candidates for direct hydrogenation. However, the synthesized MgB 4 is a promising energetic additive to solid fuels for high-speed air-breathing propulsion as it offers a lower oxidation onset temperature and greater energy density than MgB 2 .

08 HYDROGEN↗

Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides

The kinetics of hydride transfer from Re( R bpy)(CO) 3 H (bpy = 4,4'-R-2,2'-bipyridine; R = OMe, t Bu, Me, H, Br, COOMe, CF 3 ) to CO 2 and seven different cationic N-heterocycles were determined. Additionally, the thermodynamic hydricities of complexes of the type Re( R bpy)(CO) 3 H were established primarily using computational methods. Linear free-energy relationships (LFERs) derived by correlating thermodynamic and kinetic hydricities indicate that, in general, the rate of hydride transfer increases as the thermodynamic driving force for the reaction increases. Kinetic isotope effects range from inverse for hydride transfer reactions with a small driving force to normal for reactions with a large driving force. Hammett analysis indicates that hydride transfer reactions with greater thermodynamic driving force are less sensitive to changes in the electronic properties of the metal hydride, presumably because there is less buildup of charge in the increasingly early transition state. Bronsted α values were obtained for a range of hydride transfer reactions and along with DFT calculations suggest the reactions are concerted, which enables the use of Marcus theory to analyze hydride transfer reactions involving transition metal hydrides. It is notable, however, that even slight perturbations in the steric properties of the Re hydride or the hydride acceptor result in large deviations in the predicted rate of hydride transfer based on thermodynamic driving forces. This indicates that thermodynamic considerations alone cannot be used to predict the rate of hydride transfer, which has implications for catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unexpected Roles of Triethanolamine in the Photochemical Reduction of CO 2 to Formate by Ruthenium Complexes

We show a series of 4,4'-dimethyl-2,2'-bipyridyl ruthenium complexes with carbonyl ligands were prepared and studied using a combination of electrochemical and spectroscopic methods with infrared detection to provide structural information on reaction intermediates in the photochemical reduction of CO 2 to formate in acetonitrile (CH 3 CN). An unsaturated 5-coordinate intermediate was characterized, and the hydride-transfer step to CO 2 from a singly reduced metal-hydride complex was observed with kinetic resolution. While triethanolamine (TEOA) was expected to act as a proton acceptor to ensure the sacrificial behavior of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as an electron donor, time-resolved infrared measurements revealed that about 90% of the photogenerated one-electron reduced complexes undergo unproductive back electron transfer. Furthermore, TEOA showed the ability to capture CO 2 from CH 3 CN solutions to form a zwitterionic alkylcarbonate adduct and was actively engaged in key catalytic steps such as metal-hydride formation, hydride transfer to CO 2 to form the bound formate intermediate, and dissociation of formate ion product. Collectively, the data provide an overview of the transient intermediates of Ru(II) carbonyl complexes and emphasize the importance of considering the participation of TEOA when investigating and proposing catalytic pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA: Structure and Thermophysical Properties of Delta and Epsilon Zry4H x

Small-modular and micro-reactors are part of an emerging nuclear technology aimed to provide power to decentralized grids in civilian, industrial, and defense energy sectors. Resurgence in microreactor research is partly driven by demands for a mobile, safe, and compact energy platform for remote and strategic locations. The defining characteristics of the microreactor include its high-power density on a small footprint, its highly transportable design, and the use of high-assay low-enriched uranium (HALEU) fuel. Solid-state metal hydride neutron moderator components are considered for microreactor designs where the moderator functions to thermalize neutrons into lower energies for the fuel to achieve high fission rates. Zirconium hydride (ZrH x where x denotes the atomic hydrogen-to-metal ratio) is a leading moderator candidate material due to the combination of its low neutron absorption cross section, irradiation resistance, high hydrogen atomic density (upwards of 7.5 x 10 22 H atoms/cm 3 at low temperatures), and high hydrogen desorption (dissociation) temperature around 600 °C (873 K) compared to other metal hydrides. Its high-temperature stability enables operation of fuel temperatures into several hundred degrees Celsius for overall increased efficiency.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

In-Situ Spatial Mapping of Hydrogen in Yttrium Hydrides at LANSCE

This report summarizes the neutron imaging techniques and experimental activities performed at the Los Alamos Neutron Science Center (LANSCE) with the main goal of measuring temperature driven hydrogen diffusion within bulk-yttrium hydride (YH x ) materials. The experimental results and technique developments reported herein support the US Department of Energy Office of Nuclear Energy’s (DOE-NE) Microreactor Program under Technology Maturation. In particular, the critical need to experimentally validate and verify hydrogen-diffusion models of metal hydrides used in hightemperature microreactor designs is addressed by means of high-spatial-resolution neutron imaging coupled with custom-built and application-specific furnaces. These capabilities were designed to apply large temperature gradients across centimeter-sized YH x pellets to simulate conditions faced in the microreactor environment. Neutron imaging, combined with in-situ sample heating, enables near real-time tracking of hydrogen diffusion in YH x on the sub-millimeter scale. In this report, an overview of neutron imaging methodology and technologies are given in the context of recent spatial measures of hydrogen concentrations in similar metals hydrides. Additionally, the commissioning and operation of a custom-built compact dual-zone furnace is given along with details on the first two in-situ heating measurements of YH x performed over the 2020 and 2021 LANSCE operation cycles. In parallel with in-situ heating measurements, neutron computed tomography scans were performed to visualize hydrogen aggregates in post-heated YH x samples. Analysis and results from these neutron imaging measurements are given along with outlooks and plans for improving future hydrogen diffusion measurements at LANSCE.

47 OTHER INSTRUMENTATION↗

Mechanistic roles of metal- and ligand-protonated species in hydrogen evolution with [Cp*Rh] complexes

Protonation reactions involving organometallic complexes are ubiquitous in redox chemistry and often result in the generation of reactive metal hydrides. However, some organometallic species supported by η 5 -pentamethylcyclopentadienyl (Cp*) ligands have recently been shown to undergo ligand-centered protonation by direct proton transfer from acids or tautomerization of metal hydrides, resulting in the generation of complexes bearing the uncommon η 4 -pentamethylcyclopentadiene (Cp*H) ligand. Here, time-resolved pulse radiolysis (PR) and stopped-flow spectroscopic studies have been applied to examine the kinetics and atomistic details involved in the elementary electron- and proton-transfer steps leading to complexes ligated by Cp*H, using Cp*Rh(bpy) as a molecular model (where bpy is 2,2′-bipyridyl). Stopped-flow measurements coupled with infrared and UV-visible detection reveal that the sole product of initial protonation of Cp*Rh(bpy) is [Cp*Rh(H)(bpy)] + , an elusive hydride complex that has been spectroscopically and kinetically characterized here. Tautomerization of the hydride leads to the clean formation of [(Cp*H)Rh(bpy)] + . Variable-temperature and isotopic labeling experiments further confirm this assignment, providing experimental activation parameters and mechanistic insight into metal-mediated hydride-to-proton tautomerism. Spectroscopic monitoring of the second proton transfer event reveals that both the hydride and related Cp*H complex can be involved in further reactivity, showing that [(Cp*H)Rh] is not necessarily an off-cycle intermediate, but, instead, depending on the strength of the acid used to drive catalysis, an active participant in hydrogen evolution. Identification of the mechanistic roles of the protonated intermediates in the catalysis studied here could inform design of optimized catalytic systems supported by noninnocent cyclopentadienyl-type ligands.

08 HYDROGEN↗

A Review on Advanced Manufacturing for Hydrogen Storage Applications

Hydrogen is a notoriously difficult substance to store yet has endless energy applications. Thus, the study of long-term hydrogen storage, and high-pressure bulk hydrogen storage have been the subject of much research in the last several years. To create a research path forward, it is important to know what research has already been done, and what is already known about hydrogen storage. In this review, several approaches to hydrogen storage are addressed, including high-pressure storage, cryogenic liquid hydrogen storage, and metal hydride absorption. Challenges and advantages are offered based on reported research findings. Since the project looks closely at advanced manufacturing, techniques for the same are outlined as well. There are seven main categories into which most rapid prototyping styles fall. Each is briefly explained and illustrated as well as some generally accepted advantages and drawbacks to each style. An overview of hydrogen adsorption on metal hydrides, carbon fibers, and carbon nanotubes are presented. The hydrogen storage capacities of these materials are discussed as well as the differing conditions in which the adsorption was performed under. Concepts regarding storage shape and materials accompanied by smaller-scale advanced manufacturing options for hydrogen storage are also presented.

36 MATERIALS SCIENCE↗

Kinetics of Hydrogen Diffusion in LaNi(sub 5-x)Sn(sub x) Alloys

Solid-state diffusion of hydrogen in metal hydride (MH) alloys is recognized as the rate determining step in the discharge of MH alloys in alkaline Ni-MH rechargeable cells. In our pursuit of new ternary solutes in LaNi(sub 5) for extended cycle lifetimes, we have observed noticeable improvement in the cycle life with small substitutions of Sn and Ge for Ni. Furthermore, these substituents also facilitate enhanced charge transfer kinetics for hydriding-dehydriding process. In this paper, we report our studies on the kinetics of hydrogen diffusion in LaNi(sub 5-x) Sn(sub x) alloys by electrochemical pulse techniques, chronoamperometry and chronocoulometry.

electrochemical cycling↗

Reversing the Irreversible: Thermodynamic Stabilization of LiAlH 4 Nanoconfined Within a Nitrogen-Doped Carbon Host

A general problem when designing functional nanomaterials for energy storage is the lack of control over the stability and reactivity of metastable phases. Using the high-capacity hydrogen storage candidate LiAlH4 as an exemplar, we demonstrate an alternative approach to the thermodynamic stabilization of metastable metal hydrides by coordination to nitrogen binding sites within the nanopores of N-doped CMK-3 carbon (NCMK-3). The resulting LiAlH 4 @NCMK-3 material releases H 2 at temperatures as low as 126 °C with full decomposition below 240 °C, bypassing the usual Li 3 AlH 6 intermediate observed in bulk. Moreover, >80% of LiAlH 4 can be regenerated under 100 MPa H 2 , a feat previously thought to be impossible. Nitrogen sites are critical to these improvements, as no reversibility is observed with undoped CMK-3. Density functional theory predicts a drastically reduced Al–H bond dissociation energy and supports the observed change in the reaction pathway. Finally, the calculations also provide a rationale for the solid-state reversibility, which derives from the combined effects of nanoconfinement, Li adatom formation, and charge redistribution between the metal hydride and the host.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

System for operating solid oxide fuel cell generator on diesel fuel

A system is provided for operating a solid oxide fuel cell generator on diesel fuel. The system includes a hydrodesulfurizer which reduces the sulfur content of commercial and military grade diesel fuel to an acceptable level. Hydrogen which has been previously separated from the process stream is mixed with diesel fuel at low pressure. The diesel/hydrogen mixture is then pressurized and introduced into the hydrodesulfurizer. The hydrodesulfurizer comprises a metal oxide such as ZnO which reacts with hydrogen sulfide in the presence of a metal catalyst to form a metal sulfide and water. After desulfurization, the diesel fuel is reformed and delivered to a hydrogen separator which removes most of the hydrogen from the reformed fuel prior to introduction into a solid oxide fuel cell generator. The separated hydrogen is then selectively delivered to the diesel/hydrogen mixer or to a hydrogen storage unit. The hydrogen storage unit preferably comprises a metal hydride which stores hydrogen in solid form at low pressure. Hydrogen may be discharged from the metal hydride to the diesel/hydrogen mixture at low pressure upon demand, particularly during start-up and shut-down of the system.

Singh, Prabhu↗

Metal–Metal Bonding Influences Hydride Reactivity in [Sn–Rh] 3+ and [Sn–Ni] 2+ Bimetallics

Heavier group 14 metal hydrides serve as key intermediates in catalytic transformations, such as hydroboration. Regenerating such intermediates via a clean hydride source like dihydrogen could provide catalytic processes with a more economical alternative to, e.g., silanes and hydridoborane reagents. Herein, we report our efforts toward this goal using a [Sn–Rh] 3+ bimetallic system with the formal Rh I center acting as a potential dihydrogen activator. Targeting the introduction of a hydride ligand to the bimetallic core, our reactivity studies have revealed a preference for the hydride ligand to be bound to the Rh center, instead of the Sn center. Finally, examination of the electronic structures of these complexes via theoretical and experimental methods has revealed the electron acceptor nature of the Rh center within the bimetallic core and offers an explanation for the localization of the hydride between metal centers.

anions↗

Assessment of Materials-Based Options for On-Board Hydrogen Storage for Rail Applications

The objective of this project was to evaluate material- and chemical-based solutions for hydrogen storage in rail applications as an alternative to high-pressure hydrogen gas and liquid hydrogen. Three use cases were assessed: yard switchers, long-haul locomotives, and tenders. Four storage options were considered: metal hydrides, nanoporous sorbents, liquid organic hydrogen carriers, and ammonia, using 700 bar compressed hydrogen as a benchmark. The results suggest that metal hydrides, currently the most mature of these options, have the highest potential. Storage in tenders is the most likely use case to be successful, with long-haul locomotives the least likely due to the required storage capacities and weight and volume constraints. Overall, the results are relevant for high-impact regions, such as the South Coast Air Quality Management District, for which an economical vehicular hydrogen storage system with minimal impact on cargo capacity could accelerate adoption of fuel cell electric locomotives. The results obtained here will contribute to the development of technical storage targets for rail applications that can guide future research. Moreover, the knowledge generated by this project will assist in development of material-based storage for stationary applications such as microgrids and backup power for data centers.

08 HYDROGEN↗

Thermodynamic Modeling of Complex Solid Solutions in the Lu-H-N System via Graph Neural Network Accelerated Monte Carlo Simulations

Metal hydrides are important across diverse applications, such as hydrogen storage, batteries, gas sensors, nuclear reactions, and high-temperature superconductivity. Previous computational studies of metal hydrides under extreme pressures, e.g., 𝑂⁡(10 2 ) ⁢GPa, usually treat them as stoichiometric compounds without considering interstitial lattice disorder. As pressures become more moderate in the 𝑂⁡(10 0 ) ⁢GPa and below range, hydrogen disorder at interstitial lattice sites becomes prominent, e.g., in the N-doped Lu hydride that was recently claimed superconducting near 1 GPa. Further adding compositional complexity from alloying and/or multielement interstitial occupation makes elucidating pressure- and temperature-dependent observables intractable by first-principles calculations alone. We therefore propose a lattice graph neural-network surrogate modeling approach to predict configuration- and pressure-dependent equation-of-state properties. Their efficiency permits Monte Carlo simulations to calculate Gibbs energies and pressure-dependent phase diagrams, thereby revealing insights into the synthesis conditions required for achieving desired phase equilibria. We demonstrate this concept for the compositionally complex cubic Lu(H,N,Va) 3 system where three constituents (hydrogen, nitrogen and vacancy) have disordered multielement interstitial occupancies and insights into pressure-dependent phase equilibria are critically needed, e.g., N-doping levels can significantly lower dehydrogenation temperatures and provide a new strategy to optimize hydrogen-storage alloys. This work can improve the thermodynamic understanding of the Lu-H-N system and help rational synthesis of N-doped Lu hydrides, but more generally demonstrates an efficient approach to model pressure-dependent thermodynamics of multicomponent solid solutions.

Monte Carlo methods↗

Fundamental Studies of Tritium Formation and Diffusivity in Pure and Defective Zircaloy-4 Getters

Zirconium (Zr) alloys have excellent mechanical properties at high temperature and are resistant to corrosion in different environmental conditions. These alloys are used as tritium (3H or T) getters in nuclear reactors due to their low absorption cross section to thermal neutrons and excellent thermo-mechanical properties. Zr alloys have better mechanical and thermal properties than many other refractory alloys including stainless steel. After the irradiation of TPBAR by neutron flux, 3H produced during irradiation diffuses though the pellets and is captured by the getter. 3H chemically reacts with Zr metal to form metal hydride (ZrTx). Hydrides thus formed are brittle and adversely affect the mechanical and thermal properties of alloys. The lattice mismatch at the interface of alloy and metal hydrides also creates a stress that significantly reduces the alloy’s performance and operation life. Therefore, understanding the behavior of 3H and its species becomes significant as fuel burnup is increased, which leads to increase in hydrogen pickup and oxide formation.

Duan, Yuhua↗