Reactivity of Titanium Additives towards Hydrogen and their Incorporation into Complex Metal Hydrides.
Abstract not provided.
SEARCH · Search NASA
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Abstract not provided.
Abstract not provided.
Surface contrast solution NMR and reaction kinetic assays reveal an active role for H 2 spillover in the phenol hydrogenation reaction catalyzed by Pd on reducible metal oxides.
This project endeavors to design and demonstrate an integrated CSP system that meets the Department of Energy’s 6¢/kW-hr LCOE goal. This design is based on the 10 MW e Supercritical Transformational Electric Power (STEP) engine specifications, but adaptable to any sCO 2 power module up to 10 MW e . The enabling technology to be tested is a new class of metal hydride based thermal energy storage materials which can store thermal energy in the hydrogen bonds between the metal hydride and hydrogen. This thermochemical energy storage solution provides a much greater energy density than sensible and latent energy storage enabling an integrated system design that closely linked the metal hydride to the power block. This allows the entire system to be mounted up tower to provide cost reductions.
Although transition metal (M) alloying with platinum (Pt) is a promising approach to reduce the Pt dosage required in the hydrogen evolution reaction (HER), the catalytic activity and durability of PtM alloy are often unsatisfactory for acidic HER, especially at high currents, due to a reduced number of highly active sites (Pt) at the atomic level and challenges in stabilizing them to prevent detachment and aggregation. Herein, we report a robust functional structure integrated electrode (D-PtCu/CF) with abundant edge dislocations and very low platinum content (0.1 mg cm -2 ) to achieve high activity and stability in acidic HER within a proton exchange membrane water electrolysis cell (PEMWE). D-PtCu/CF exhibits high Pt mass activity (10.28 A mg Pt -1 ) and excellent operational stability (negligible decay after 200 h). X-ray absorption spectroscopy and in situ electrochemical experiments reveal that the lattice distortion caused by edge dislocations in PtCu mainly affects Pt atoms by compressing strain, reducing their ability to adsorb H. At the same time, Cu atoms are subjected to tensile strain, enhancing the bonding between Cu and H. Therefore, edge dislocations not only improve the intrinsic catalytic activity of Pt atoms but also increase the number of active sites (Cu) available for hydrogen adsorption, which synergistically accelerates the kinetics of the HER reaction. Finally, the PEMWE employing the D-PtCu/CF catalytic electrode can operate stably for 100 h at an industrial-level current density of 500 mA cm -2 with 1.63 V.
This project focused on the development bimetallic metal-organic frameworks (MOFs) as gas phase heterogeneous catalysts for hydrogenation and hydroformylation reactions. MOFs are a new class of hybrid inorganic/organic materials that are highly crystalline, with structures consisting of metal nodes of specific geometries connected by organic linkers. Although there have been a number of studies of catalysis at MOF nodes in solution, there is little experimental data in the literature for gas phase reactions despite the fact that industrial heterogeneous catalysis on MOFs is more economically viable than homogeneous catalysis. The use of MOFs as heterogeneous catalysts presents the unique opportunity to carefully control the composition, geometry and ensemble sizes of the active sites, which are all critical factors for the rational design of new catalysts. Specific objectives of the project are as follows: (1) to tailor the geometry, composition and ensemble size of the active sites; (2) to understand how the adsorption of molecules at metal sites can be modified by interactions with a neighboring metal site; (3) to determine how oxidation states of the metal change during reaction and how these states can be modified by metal-metal electronic interactions; and (4) to elucidate reaction mechanisms and intermediates. For these studies, we have chosen to investigate selective hydrogenation of hydrocarbons and hydroformylation, which are industrially relevant reactions. Our interdisciplinary team of Chen, Shustova and Vogiatzis/Henkelman provides critical expertise in novel MOF synthesis (Shustova), atomic-scale surface science and catalysis (Chen) and computational studies of reaction mechanisms (Vogiatzis/Henkelman) that are necessary for the development of these catalysts. We believe that this work will lead directly to the rational design of new catalysts that are versatile, highly active/selective and suitable for industrial processes.
Integrating plasmonic nanoparticles into the photoactive metal-organic matrix is highly desirable due to the plasmonic near field enhancement, complementary light absorption, and accelerated separation of photogenerated charge carriers at the junction interface. The construction of a well-defined, intimate interface is vital for efficient charge carrier separation, however, it remains a challenge in synthesis. Here we synthesize a junction bearing intimate interface, composed of plasmonic Ag nanoparticles and matrix with silver node via a facile one-step approach. The plasmonic effect of Ag nanoparticles on the matrix is visualized through electron energy loss mapping. Moreover, charge carrier transfer from the plasmonic nanoparticles to the matrix is verified through ultrafast transient absorption spectroscopy and in-situ photoelectron spectroscopy. The system delivers highly efficient visible-light photocatalytic H 2 generation, surpassing most reported metal-organic framework-based photocatalytic systems. This work sheds light on effective electronic and energy bridging between plasmonic nanoparticles and organic semiconductors.
Motivated by increased awareness about nitrate contamination of surface waters and its deleterious effects in human and animal health, we sought an alternative, non-noble metal catalyst for the chemical degradation of nitrate. First row transition metal phosphides recently emerged as excellent alternatives for hydrogen evolution and hydrotreating reactions. We demonstrate that a key member of this family, Ni 2 P, readily hydrogenates nitrate (NO 3 – ) to ammonia (NH 3 ) near ambient conditions with very high selectivity (96%). One of the few non-precious metal-based catalysts for this transformation, and among ca. 1% of catalysts with NH 3 selectivity, Ni 2 P can be recycled multiple times with limited loss of activity. Both nitrite (NO 2 – ) and nitric oxide (NO) intermediates are also hydrogenated. Density functional theory (DFT) indicates that—in the absence of a catalyst—nitrite hydrogenation is the reaction bottleneck. A variety of adsorbates (H, O, N, NO) induce surface reconstruction with top-layer Ni-rich surface stoichiometry. Critically, H saturation coverage on Ni 2 P(001) is only ca. 3 nm –2 , significantly less than that on Pd(111) and Ni(111) of ca. 15–18 nm –2 , which may play a key role in allowing coadsorption of NO x – . Here the ability of Earth-abundant, binary metal phosphides such as Ni 2 P to catalyze nitrate hydrogenation could transform and help us to better understand the basic science behind catalytic hydrogenation and, in turn, advance the next generation of oxyanion removal technologies.
Uranium nitride has been under consideration at NASA and the Department of Energy for nuclear thermal propulsion applications intended for deep space exploration vehicles. It is critical to the success of the technology development that the behavior of the fuel system is properly characterized in operational environments. This body of work fabricated ceramic metal composites consisting of uranium ceramic fuel in a molybdenum and molybdenum–tungsten metal matrix, both with and without an exterior molybdenum barrier. Specimens were introduced to a high temperature hydrogen environment and characterized through x-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy to identify characteristic changes. A portion of the specimens was fabricated with a 1.27 mm thick molybdenum barrier in order to isolate the material from the hydrogen environment. Instability of the uranium nitride occurred as low as 2073 K, leading to aggressive instability approaching 2658 K. Carbon reactions with the metal matrix were observed as well as alloying between the uranium and metal matrix constituents. The liquid uranium resulting from the instability of the uranium nitride was observed to attack the grain boundaries of the refractory metal, resulting in the formation of a liquid uranium molybdenum eutectic melt. Specimens encased in a barrier experienced similar results. The authors conclude this is a significant challenge to applications of this cermet at these temperatures. Alternate configurations with resilient hermetic seals or lower temperature applications such as power reactors may have more success.
The development and comprehension of supported metal catalysts for CO 2 hydrogenation is of paramount importance in mitigating the net CO 2 emissions. Supported Ru catalysts have been widely recognized in facilitating CO 2 methanation, on which recent findings suggest that the CO 2 hydrogenation process can be manipulated to favor the reverse water–gas shift (RWGS) pathway by precisely adjusting the size of Ru particles. However, the size-dependent impact of Ru remains a topic of lively debate. In this work, Ru/MgO catalysts with Ru in the form of single atoms (Ru 1 ) and few-atom cluster (Ru FAC ) structures were prepared for CO 2 hydrogenation. The 1.0Ru/MgO catalyst (with 1 wt.% of Ru), featuring a mixture of Ru 1 and Ru FAC with a size of 0.6–1.0 nm, showed the highest CO yield (38% at 500 °C) with balanced CO 2 conversion and CO selectivity. Transient CO 2 hydrogenation and temperature-programmed surface reaction (TPSR) studies suggested that the adsorbed CO 2 species participated in CO 2 hydrogenation. On Ru 1 sites, CO 2 hydrogenation followed the RWGS pathway, resulting in the production of CO. In contrast, on Ru FAC sites, the enhanced H 2 dissociation ability, along with the presence of adsorbed bidentate and monodentate carbonate species at the Ru-MgO interfaces, facilitated the formation of CH 4 through the CO 2 methanation pathway. In conclusion, this study highlights the critical roles of Ru structure and local environment in defining the CO 2 hydrogenation pathways and provides new design principles for highly active Ru-based catalysts.
Understanding the interaction of hydrogen with microstructural features in metallic materials is crucial for designing hydrogen-resistant alloys. Although thermal desorption spectroscopy (TDS) is widely used for investigating the hydrogen binding behavior of various microstructural features, its application to face-centered cubic (fcc) metals and alloys that exhibit low hydrogen diffusivity is limited due to the lumped TDS desorption signals. This paper shows that, by coupling a Sofronis–McMeeking type hydrogen transport model with a microstructure-informed finite-element model, TDS data can be deconvoluted to reveal the underlying adsorption–diffusion–desorption processes, hydrogen diffusivity, and trap-binding energies. In conclusion, the austenitic steel SS316L in solution-annealed condition is used as a demonstration material, and we focused on investigating the interaction of deuterium (hydrogen isotope) with grain boundaries, which is difficult to investigate from experiments alone but critical for design of alloys for hydrogen infrastructure.
Photocatalytic hydrogen production is a promising alternative to traditional hydrogen production. To implement photocatalytic hydrogen production the development of efficient, sustainable, and stable catalysts is necessary, and overcoming the current challenges surrounding high dimensional search spaces requires both computational and experimental efforts. Utilizing photo driven processes, stable colloidal metal catalysts can be formed in situ for efficient hydrogen production from water. When considering colloidal catalysts, stability is typically a concern solved through the addition of supports or ligands. In this work, poly(ethylene glycol) methyl ether thiol acts as a stabilizing ligand eliminating the need for catalyst supports while providing stable and active nanoparticle catalysts for more than 45 hours of reaction time and illumination. These systems utilize molecular photosensitizers, water reduction catalysts, stabilizing ligands, water, a sacrificial reductant, and organic solvents, posing new challenges pertaining to the optimization of multi-variable systems. Design of experiments (DOE) is applied to accelerate the understanding of variable interactions and is used as a tool to rapidly optimize the compositions of Au, Cu, Ni, and Fe containing systems. Through a collaboration leveraging computation and experimentation (both high throughput and characterizations), optimized performance peaks were obtained for each of these metals alongside distinct mapping of expected activity associated with photosensitizer, metal, and ligand concentration variations. With the highly digitized workflow, this study allowed for comparative generalizations to be made regarding photo driven hydrogen production for all four metals.
Hydrogen is the most common element in the universe, comprising nearly 75% of all normal matter, and it has been used by scientists for centuries, but it was not fully recognized as an element until 1766, when it was isolated by Henry Cavendish. Early work focused on the generation of hydrogen through the oxidation of metals in water, which released hydrogen gas. Hydrogen’s lighter-than-air and flammable properties were immediately used in engines, zeppelins, and as feedstock for a wide variety of chemical reactions. Several approaches were developed for the production of hydrogen with the most common being associated with the production and conversion of hydrocarbon-based fuels. Coal gasification, steam methane reforming, and other reformation processes provide the majority of current hydrogen production due to the relatively low cost of hydrogen produced through these processes. More than 95% of hydrogen production is used for industrial processes rather than energy storage. To facilitate affordable decarbonization of these industrial processes and to advance the use of hydrogen as a fuel in transportation, DOE launched the Hydrogen Shot as part of the Energy Earthshots Initiative. The goal of the Hydrogen Shot is to reduce the cost of clean hydrogen by 80% to $1/kg of clean hydrogen production within one decade (known as the “1 1 1” goal). This is distinct from the Long-Duration Storage Shot, which is the primary focus of this report; however, it is intrinsically linked to bidirectional hydrogen storage. Several important chemical synthesis processes are dependent upon hydrogen, and the production and use of hydrogen is generally driven by its connection to one of these markets. For example, ammonia is one of the most highly produced chemicals in the world and it depends chiefly on hydrogen. Ammonia is primarily used for agricultural fertilizer and is considered to be largely responsible for a doubling of agricultural production per unit of land over the last century. Another one of hydrogen’s primary uses is as a catalyst in petroleum refining during the desulfurization process. Beyond chemical production, hydrogen is used as a reductant in the production of steel and has been demonstrated as a substitute for metallurgical coal in the production of raw iron. It is even used in the hydrogenation reaction for food products to create more shelf-stable semi-solid fats. However, while hydrogen is produced on the order of 100 million metric tons/year globally to feed these industries, more than 95% of hydrogen is produced from hydrocarbons that emit CO2 during the process. Conversely, electrolysis is a process by which electricity is used to separate hydrogen and oxygen in water molecules, usually across a membrane. Hydrogen production via electrolysis lowers the carbon intensity of produced hydrogen when coupled with low-carbon electricity. Currently, global electrolysis capacity is on the order of 1 GW, which equates to about 500 metric tons/day of hydrogen production. To support large-scale industrial decarbonization, capacity will likely need to increase by two to three orders of magnitude. Electrolysis technology is broadly separated into groups that are defined by the electrolyte used, with further subdivision based on the operating characteristics. The majority of commercial electrolyzer systems are based around three main technology groups: liquid alkaline, proton exchange membrane, and solid oxide. Liquid Alkaline (LA) electrolysis is the oldest, most mature, least expensive, and most common commercial technology, with 400 plants in operation by 1902. Its hydrogen output is low relative to the size of the system due to a low current density. LA electrolysis utilizes a liquid potassium hydroxide solution as the electrolyte. Proton exchange membrane (PEM) electrolysis (also known as polymer electrolyte membrane electrolysis), described in 1960, relies on an acid-impregnated polymer membrane as the electrolyte and typically offers three to six times higher hydrogen production per unit cell area than LA electrolysis. Solid oxide electrolysis, or high-temperature electrolysis, utilizes a ceramic cell as the electrolyte and operates on steam rather than liquid water, enabling electrical efficiencies of more than 90%, which is up from 60% with PEM. Two pre-commercial electrolyzer technologies to note are alkaline exchange membrane (AEM) and proton-conducting solid oxide electrolysis cell (SOEC). AEM potentially has the advantages of both LA and PEM technologies in that it is able to use low-cost materials like LA but with the ability to operate at higher output pressures with a smaller footprint like PEM. Proton-conducting SOEC is similar to commercial SOEC, which uses an oxide-conducting ceramic; however, it uses a proton-conducting ceramic that has the potential to operate at lower temperatures and has lower capital costs. Each of these technologies is experiencing a rapid improvement in performance and a reduction in installed cost, and each appears to be well suited to specific applications. Besides differences in the type of electrolyzer used, the main difference in the architecture of bidirectional hydrogen systems is how the hydrogen is stored. Currently, the most cost-effective way to store large amounts of hydrogen gas is underground, such as in large salt caverns that have been hollowed out. These salt caverns are geographically concentrated in small portions of the United States and are not generally near large metropolitan areas; however, other subsurface architectures are being investigated to expand this reach. A more widely deployable option is aboveground pressurized tanks. These systems are about 10 times as expensive because of the materials and safety margins required to hold hydrogen at high pressures. A third option is using materials-based storage, such as liquid organic hydrogen carriers. By reversibly attaching the produced hydrogen to other molecules, it can be stored at near atmospheric pressure and room temperature. This has the potential to reduce the material cost of storage but may result in a reduction in the efficiency of the process because there are both hydrogen uptake and release processes. While materials-based storage has not been used extensively for large-scale hydrogen storage in the past, there is currently significant activity regarding developing materials and processes for use in large-scale hydrogen storage applications. Electrolysis-produced hydrogen offers an unusual opportunity for energy storage applications. Unlike more conventional energy storage approaches, such as batteries, which operate entirely within electrical markets, hydrogen is a valuable product beyond the electric market and can be directed to the most lucrative use. Hydrogen also can be directly converted back to electricity using either a fuel cell or turbine, or it can be sold to other markets, such as chemical synthesis, steel production, or even export. In this way, excess electricity can be upgraded to the most valuable product. Finally, its use can be actively managed between multiple off-takers; for example, local hydrogen storage can provide a specific amount of stored electricity and any excess can be exported to ammonia production. This flexibility is amplified by the fact that hydrogen storage has fully decoupled power and energy components, which allows for affordable scaling options. Together, this allows a substantial amount of creativity to enable the economic utilization of variable power resources while supporting decarbonization of the industry.
A trilateral agreement has been finalized involving research institutions in Korea, Japan, and the U.S. The project partners are Sandia, LLNL, KIST, KAIST, and AIST. The project title is “Structure-Property Relationships in Metal Alloys for Hydrogen Storage and Processing.” Funding for the U.S. portion of the effort is through NNSA; the PI is Vitalie Stavila. The overall objective of this project is to identify detailed structure-property relationships governing hydrogen separation, purification, storage, and compression in compositionally complex metal alloys.
Austenitic stainless steels are used extensively in harsh environments, including for high-pressure gaseous hydrogen service. However, the tensile ductility of this class of materials is very sensitive to materials and environmental variables. While tensile ductility is generally insufficient to qualify a material for hydrogen service, ductility is an effective tool to explore microstructural and environmental variables and their effects on hydrogen susceptibility, to inform understanding of the mechanisms of hydrogen effects in metals, and to provide insight to microstructural variables that may improve relative performance. In this study, hydrogen precharging was used to simulate high-pressure hydrogen environments to evaluate hydrogen effects on tensile properties. Several austenitic stainless steels were considered, including both metastable and stable alloys. Room temperature and subambient temperature tensile properties were evaluated with three different internal hydrogen contents for type 304L and 316L austenitic stainless steels and one hydrogen content for XM-11. Significant ductility loss was observed for both metastable and stable alloys, suggesting the stability of the austenitic phase is not sufficient to characterize the effects of hydrogen. Internal hydrogen does influence the character of deformation, which drives local damage accumulation and ultimately fracture for both metastable and stable alloys. While a quantitative description of hydrogen-assisted fracture in austenitic stainless steels remains elusive, these observations underscore the importance of the hydrogen-defect interactions and the accumulation of damage at deformation length scales.
A low-cost cathode catalyst based on a NiMo alloy was examined here to replace noble metals for the hydrogen production in microbial electrolysis cells (MECs). Two NiMo catalysts were synthesized through either an electrochemical assisted (NiMo Elec) or a hydrothermal (NiMo Ht) approach. The NiMo Ht method enriched the electrocatalyst with Mo atoms compared to the NiMo Elec approach, producing a similar current density with a minimal overpotential of 50mV compared to Pt. Further, in MEC tests using the NiMo Ht catalyst, H 2 was generated at a highest rate of 81±3 L H2 /L-d (current density of 44.4 ± 0.9 A/m 2 ) at a cell voltage of -0.86 V, and a Coulombic efficiency of >97%. Modifying the closely stacked MEC design to include a reference electrode, and analysis of the electrode potentials using the electrode potential slope method, revealed a large contribution of the cathode resistance (5.3±0.5mΩm 2 ) compared to the anode (1.4±0.2mΩm 2 ) and ohmic resistance (0.83mΩm 2 ) for a total internal resistance of 7.6±0.5mΩm 2 . The high performance of the NiMo Ht catalyst coupled with its low cost provides an economically viable approach to advance the generation of biohydrogen in MECs.
Metal hydrides can store hydrogen isotopes with high volumetric density. In metal tritides, tritium beta decay can result in accumulation of helium within the solid, in some cases exceeding 10 at.% helium after only 4 years of aging. Helium is insoluble in most materials, but often does not readily escape, and instead coalesces to form nanoscale bubbles when helium concentrations are near 1 at.%. Blistering or spallation often occurs at higher concentrations. Radioactive particles shed during this process present a potential safety hazard. This study investigates the effects of high helium concentrations on erbium deuteride (ErD 2 ), a non-radioactive surrogate material for erbium tritide (ErT 2 ). To simulate tritium decay in the surrogate, high doses of 120 keV helium ions were implanted into ErD 2 films at room temperature. Scanning and transmission electron microscopy indicated spherical helium bubble formation at a critical concentration of 1.5 at.% and bubble linkage leading to nanoscale crack formation at a concentration of 7.5 at.%. Additionally, crack propagation occurred through the nanocrack region, resulting in spallation extending from the implantation peak to the surface. Electron energy loss spectroscopy was utilized to confirm the presence of high-pressure helium in the nanocracks, suggesting that helium gas plays a predominant role in deformation. This work improves the overall understanding of helium behavior in ErD 2 by using modern characterization techniques to determine: the critical helium concentration required for bubble formation, the material failure mechanism at high concentration, and the nanoscale mechanisms responsible for material failure in helium implanted ErD 2 .
Magnetic nanoplatelets hold significant potential for various technical applications due to their ability to switch between a fully magnetized state with high magnetization and a vortex‐like configuration that eliminates stray fields in the absence of an external field. This study presents the synthesis of uniform CoNi nanoplatelets through the topotactic reduction of metal hydroxides using hydrogen plasma. The reduction process is analyzed via magnetometry, leveraging the transition from paramagnetic hydroxide to ferromagnetic metal. Lorentz transmission electron microscopy and scanning transmission X‐ray microscopy confirm the presence of magnetic vortex‐like structures in isolated Co 0.85 Ni 0.15 nanoplatelets at ambient temperature. Additionally, micromagnetic simulations are conducted to further explore the magnetic properties of the nanoplatelets, revealing the formation of magnetic vortex remanent states at diameters between 200 nm and 1 μm and a thickness of around 12 nm. Notably, structural defects and thickness variations do not directly destabilize the magnetic vortex configurations.