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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Mechanistic Investigations of Gas-Phase Catalytic Hydrogenation in Metal–Organic Frameworks: Cooperative Activity of the Metal and Linker Sites in Cu x Rh 3– x (BTC) 2

We report the Cu x Rh 3–x (BTC) 2 catalyst (abbreviated CuRhBTC, BTC 3– = benzene tricarboxylate) provides excellent dispersion of active metal sites coupled with well-defined, robust structures for propylene hydrogenation reactions. This material therefore serves as a unique prototype for understanding catalytic activity in metal organic frameworks (MOFs). The mechanism of gas-phase hydrogenation at the bimetallic metal nodes of a MOF has been investigated in detail for the first time using in situ spectroscopy and diffraction experiments combined with density functional theory (DFT) calculations. The reaction occurs via a cooperative process in which the metal and linker sites play complementary roles; specifically, H 2 is dissociated at a Rh 2+ site with a missing Rh–O bond, while protonation of the decoordinated carboxylate linker stabilizes the active sites and promotes H 2 dissociation. In situ X-ray diffraction experiments show that the crystalline structure of the MOF is retained under reaction conditions at 20–100 °C. In situ Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments demonstrate that propylene adsorbs at both Rh 2+ and Cu 2+ sites via π bonding. Cu 2+ is catalytically inactive, but at Rh 2+ sites, a propyl intermediate is observed when H 2 is introduced into the propylene feed. Furthermore, the appearance of the O–H stretch of COOH at ~3690 cm –1 in the DRIFT spectra is characteristic of defects consisting of missing Rh–O bonds. These experimental results are in general agreement with a reaction mechanism proposed by DFT, in which the decoordinated carboxylate linker is protonated, and the active Rh 2+ site remains available for readsorption of reactants in the subsequent catalytic cycle.

36 MATERIALS SCIENCE↗
DOE OSTI2020

White dwarf pollution by hydrated planetary remnants: hydrogen and metals in WD J204713.76–125908.9

ABSTRACT WD J204713.76–125908.9 is a new addition to the small class of white dwarfs with helium-dominated photospheres that exhibit strong Balmer absorption lines and atmospheric metal pollution. The exceptional abundances of hydrogen observed in these stars may be the result of accretion of water-rich rocky bodies. We obtained far-ultraviolet and optical spectroscopy of WD J204713.76–125908.9 using the Cosmic Origin Spectrograph on-board the Hubble Space Telescope and X-shooter on the Very Large Telescope, and identify photospheric absorption lines of nine metals: C, O, Mg, Si, P, S, Ca, Fe, and Ni. The abundance ratios are consistent with the steady-state accretion of exo-planetesimal debris rich in the volatile elements carbon and oxygen, and the transitional element sulphur, by factors of 17, 2, and 4, respectively, compared to the bulk Earth. The parent body has a composition akin to Solar system carbonaceous chondrites, and the inferred minimum mass, 1.6 × 1020 g, is comparable to an asteroid 23 km in radius. We model the composition of the disrupted parent body, finding from our simulations a median water mass fraction of 8 per cent.

Hoskin, Matthew J.↗
DOE OSTI2023

Probing of the Noninnocent Role of P in Transition-Metal Phosphide Hydrogen Evolution Reaction Electrocatalysts via Replacement with Electropositive Si

Transition-metal phosphides (TMP) have been identified as promising electrocatalysts for the hydrogen evolution reaction (HER). Despite recent computational investigations identifying P sites as being crucial for hydrogen adsorption, the main mode of optimization for TMPs has been focused on changing the metal sites. Here, to experimentally verify computational hypotheses and provide a route for HER electrocatalyst optimization via ternary compounds, we performed systematic experimental studies of structurally related NiSi 1–x P x phases, namely, Ni 2 SiP, Ni 5 Si 2 P 3 , Ni 3 SiP 2 , and Ni 7 Si 2 P 5 , which are ordered derivatives of the NiSi structure (Pnma, oP-8, MnP structure type). We found that P played a significant role in modulating HER activity in an acidic electrolyte because the incorporation of P in NiSi reduced the overpotential at current density j = 10 mA/cm 2 from η 10 = 529 mV (NiSi) to η 10 = 97 mV (Ni 2 SiP). Ni 2 SiP outperformed the current state-of-the-art Ni5P4 electrocatalyst prepared and studied in identical conditions both in terms of activity and stability, which is attributed to the presence of covalent Ni–Si bonding in the structure. Within the family of ternary Ni–Si–P compounds, electrocatalytic activity correlates with the number of Ni-3d states at the Fermi energy.

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

Facile Generation of Active Sites in Nodes of Ni-MFU-4l Metal–Organic Framework for Hydrogenation Reaction

Metal–organic frameworks (MOFs) represent a well-defined class of materials capable of incorporating catalytically active sites for gas-phase catalysis. However, the reducing conditions of hydrogenation catalysis can lead to nanoparticle formation in MOFs, which can significantly diminish the catalytic activity of single-site metals and reduce the longevity of MOF-based hydrogen solutions. In this work, we present a straightforward approach to accessing catalytically active single metal sites in a robust Ni-MFU-4l MOF for gas-phase hydrogenation without the formation of Ni nanoparticles. By carefully tuning the local node chemistry through postsynthetic exchange of the terminal ligand coordinated to the Ni(II) centers in the MOF, from −Cl to −OH or −HCOO, we can readily generate Ni–H active species. We further demonstrate, using in situ pair-distribution function analysis, that these Ni–H sites are the sole catalytically active sites in the terminal ligand-exchanged counterparts, whereas nanoparticles readily form in the parent Ni-MFU-4l-Cl under otherwise identical catalytic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Gas-solid reaction pathway for chlorination of rare earth and actinide metals using hydrogen and chlorine gas

Hydriding and chlorination of buttons of metallic cerium have been tested as a head-end step to separating metal impurities from actinides. The objective here was to achieve complete conversion to chlorides while maintaining high surface area via small particles and open porosity. Hydriding by reaction with 100% H 2 gas at 573 K was successful at reducing cm-scale metal buttons into small particles/fragments. This step was followed by reaction with flowing 99.5% anhydrous Cl 2 gas at temperatures ranging from 423 to 573 K for 60 min. In experiments reported here, up to 92% conversion to cerium chloride was achieved from reacting with the anhydrous chlorine gas. The final chloride product has high porosity coupled with small particle sizes (microns to 1600 μm), which makes it suitable for subsequent purification processes. Higher chlorine concentrations in the gas favor higher conversion to chloride. The optimal temperature to achieve high chlorination is 523 K. Oxygen is a minor impurity in the chlorine gas which appears to prevent complete chlorination from being achieved.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Charge trapping at Al/Al 2 ⁢O 3 interface facilitates hydrogen-induced superabundant metal vacancy formation

Hydrogen is a ubiquitous impurity that deteriorates the metal/oxide interface, causing challenges such as current leakage and blistering. Here, in this work, we uncover the mechanisms behind hydrogen-induced damage at the prototypical Al/A⁢l 2 ⁢O 3 interface. The precursor that we identify is charge trapping at the interface, which facilitates hydrogen segregation to the interface plane as H – . Presence of hydrogen increases aluminum vacancy concentration at the interfacial metal and oxide planes. Each Al vacancy can trap multiple hydrogen atoms. As a result, the interfacial aluminum vacancy and hydrogen concentrations increase by orders of magnitude. Additionally, hydrogen behaves as an n-type dopant and increases electronic conductivity at the oxide layer adjacent to the interface by forming H + , and the [V Al –H] complex is the predominant defect at this layer. These findings provide the precursor mechanisms of hydrogen-induced damage at the metal-oxide interfaces and have implications for advancing Al/A⁢l 2 ⁢O 3 –based coatings and electronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2010

Empirical Method to Estimate Hydrogen Embrittlement of Metals as a Function of Hydrogen Gas Pressure at Constant Temperature

High pressure Hydrogen (H) gas has been known to have a deleterious effect on the mechanical properties of certain metals, particularly, the notched tensile strength, fracture toughness and ductility. The ratio of these properties in Hydrogen as compared to Helium or Air is called the Hydrogen Environment Embrittlement (HEE) Index, which is a useful method to classify the severity of H embrittlement and to aid in the material screening and selection for safety usage H gas environment. A comprehensive world-wide database compilation, in the past 50 years, has shown that the HEE index is mostly collected at two conveniently high H pressure points of 5 ksi and 10 ksi near room temperature. Since H embrittlement is directly related to pressure, the lack of HEE index at other pressure points has posed a technical problem for the designers to select appropriate materials at a specific H pressure for various applications in aerospace, alternate and renewable energy sectors for an emerging hydrogen economy. Based on the Power-Law mathematical relationship, an empirical method to accurately predict the HEE index, as a function of H pressure at constant temperature, is presented with a brief review on Sievert's law for gas-metal absorption.

Lee, Jonathan A.↗
NASA NTRS1990

The temperature variation of hydrogen diffusion coefficients in metal alloys

Hydrogen diffusion coefficients were measured as a function of temperature for a few metal alloys using an electrochemical evolution technique. Results from these measurements are compared to those obtained by the time-lag method. In all cases, diffusion coefficients obtained by the electrochemical method are larger than those by the time-lag method by an order of magnitude or more. These differences are attributed mainly to hydrogen trapping.

Danford, M. D.↗
DOE OSTI2023

Mechanisms of adsorbing hydrogen gas on metal decorated graphene

Hydrogen is a key player in global strategies to reduce greenhouse gas emissions. In order to make hydrogen a widely used fuel, we require more efficient methods of storing it than the current standard of pressurized cylinders. An alternative method is to adsorb H 2 in a material and avoid the use of high pressures. Among many potential materials, layered materials such as graphene present a practical advantage as they are lightweight. However, graphene and other 2D materials typically bind H 2 too weakly to store it at the typical operating conditions of a hydrogen fuel cell, meaning that high pressure would still be required. Modifying the material, for example by decorating graphene with adatoms, can strengthen the adsorption energy of H 2 molecules, but the underlying mechanisms are still not well understood. In this work, we systematically screen alkali and alkaline-earth metal decorated graphene sheets for the static thermodynamic adsorption of hydrogen gas from first principles and focus on the mechanisms of binding. We show that there are three mechanisms of adsorption on metal decorated graphene and each leads to distinctly different hydrogen adsorption structures. The three mechanisms can be described as weak van der Waals physisorption, metal adatom facilitated polarization, and Kubas adsorption. Among these mechanisms, we find that Kubas adsorption is easily perturbed by an external electric field, providing a way to tune H 2 adsorption. In conclusion, this work is foundational and builds our understanding of H 2 adsorption under idealized conditions.

36 MATERIALS SCIENCE↗
NASA NTRS1969

Effects of hydrogen on metals

Several rules to guide choice of materials, and methods of welding, electroplating, and heat treatment will provide a method for minimizing failures in storage tanks and related hardware. Failures are caused by high-pressure hydrogen effects, the formation of hydrides in titanium, and hydrogen absorption through various metals processing techniques.

Cataldo, C. E.↗
DOE OSTI2021

Solid electrolyte technology with rearrangeable bonds for metal and metal-ion batteries

In an embodiment, a metal or metal-ion battery cell, includes anode and cathode electrodes, a separator electrically separating the anode and the cathode, and a solid electrolyte ionically coupling the anode and the cathode, wherein the solid electrolyte comprises a material having one or more rearrangeable chalcogen-metal-hydrogen groups that are configured to transport at least one metal-ion or metal-ion mixture through the solid electrolyte, wherein the solid electrolyte exhibits a melting point below about 350° C. In an example, the solid electrolyte may be produced by mixing different dry metal-ion compositions together, arranging the mixture inside of a mold, and heating the mixture while arranged inside of the mold at least to a melting point (e.g., below about 350° C.) of the mixture so as to produce a material comprising one or more rearrangeable chalcogen-metal-hydrogen groups.

Yushin, Gleb↗
NASA NTRS1984

Solubility of hydrogen in metals and its effect of pore-formation and embrittlement

The effect of alloying elements on hydrogen solubility were determined by evaluating solubility equations and interaction coefficients. The solubility of dry hydrogen at one atmosphere was investigated in liquid aluminum, Al-Ti, Al-Si, Al-Fe, liquid gold, Au-Cu, and Au-Pd. The design of rapid heating and high pressure casting furnaces used in meta foam experiments is discussed as well as the mechanism of precipitation of pores in melts, and the effect of hydrogen on the shrinkage porosity of Al-Cu and Al-Si alloys. Hydrogen embrittlement in iron base alloys is also examined.

Shahani, H. R.↗
NASA NTRS1977

The dynamics and helium distribution in hydrogen-helium fluid planets

The simple case of a homogeneous planet without first-order phase transitions is considered and an investigation is conducted concerning a pure hydrogen planet in which a first-order phase transition takes place from fluid molecular hydrogen to fluid metallic hydrogen. Attention is also given to convection in the presence of a compositional gradient, the effects of helium insolubility in a cooling hydrogen-helium planet, a hydrogen-helium planet in its early evolution, and the case in which influence of phase transition occurs much later in the evolution of the planet.

Stevenson, D. J.↗
NASA NTRS2013

Characterizing Uranus with an Ice giant Planetary Origins Probe (Ice-POP)

We now know from studies of planetary transits and microlensing that Neptune-mass planets are ubitquitous and may be the most common class of planets in the Galaxy. As such it is crucial that we understand the formation and evolution of the ice giant planets in our own solar system so that we can better understand planet formation throughout the galaxy. An entry probe mission to Uranus would help accomplish this goal. In fact the Planetary Decadal Survey recommended a Uranus orbiter with entry probe but did not explore in detail the specifications for the entry probe. NASA Ames is currently studying thermal protection system requirements for such a mission and this has led to questions regarding the minimum interesting science payload of such an entry probe. The single most important in-situ measurement for an ice giant entry probe is a measurement of atmospheric composition. For Uranus this would specifically include the methane and noble gas abundances. An in situ measurement of the methane abundance, from below the methane cloud, would constrain the atmospheric carbon abundance, which is believed to be roughly 30 to 50 times solar. There are hints from the transiting planets that extrasolar ice giants show comparable or even greater enhancements of heavy elements compared to their primary stars. However the origin of this carbon enhancement is controversial. Is Uranus a "failed core" of a larger gas giant or was the atmosphere enhanced by accretion of icy planetesimals' Constraining atmospheric abundances of C and perhaps S or even N from below 5 bars would provide badly needed data to address such issues. A measurement of the N abundance would provide clues on the origin of the planetesimals that formed Uranus. Low N-abundance indicates planetesimals from 'warmer' regions where N was mainly in form of NH3, whereas a strong enrichment could indicate planetesimals / cometary material from the colder outer regions of the nebula. Furthermore CO and HCN have been detected in Neptune but not in Uranus. A measurement of the abundance of either would constrain the source mechanisms for these molecules (exogenic or internal). A major surprise from the Galileo Entry Probe was that the heavier noble gases Ar, Kr, and Xe are enhanced in Jupiter's atmosphere at a level comparable to what was seen for the chemically active volatiles N, C, and S. It had been generally expected that Ar, Kr, and Xe would be present in solar abundances, as all were expected to accrete with hydrogen during the gravitational capture of nebular gases. Enhanced abundances of Ar, Kr, and Xe is equivalent to saying that these noble gases have been separated from hydrogen. There are several mechanisms that could accomplish this but these hypotheses require further testing. Measurement of noble gas abundances in an ice giant would constrain the planetary formation and nebular mechanisms responsible for this enhancement. Standard three-layer models of Uranus find that the outer, predominantly H/He layer of Uranus does not reach pressures high enough (approximately 1 Mbar) for H2 to transition to liquid metallic hydrogen. However, valid models can also be constructed with a smaller intermediate water-rich layer, with hydrogen then reaching the metallic hydrogen phase. If this occurs, He should phase separate from the hydrogen and ``rain out," taking along a substantial abundance of Ne, as suggested for Jupiter (and likely also for Saturn). Hence He and Ne depletions could be probes of the planet's structure in the much deeper interior. A determination of Uranus' atmospheric abundances, particularly of the noble gasses, is thus critical to understanding the formation of Uranus, and giant planets in general. These measurements can only be performed with an entry probe. The second key measurement would be a temperature-pressure sounding to provide ground truth for remote measurements of atmospheric temperature and composition and to constrain the internal heat flow. This would also establish that the methane abundance measurements have indeed been made below any possible methane cloud. Finally an ultra stable oscillator would measure wind speeds and constrain atmospheric dynamics. In our presentation we will discuss the importance of all of these measurements and argue that an entry probe is a crucial component of any ice giant mission.

Marley, Mark S.↗
NASA NTRS1977

The phase diagram and transport properties for hydrogen-helium fluid planets

The properties of pure hydrogen and helium are examined, taking into account metallic hydrogen, molecular hydrogen, and the molecular-metallic transition. Metallic hydrogen-helium mixtures are considered along with molecular hydrogen-helium mixtures, the total phase diagram, and minor constituents, including deuterium. The transport properties of the metallic and the molecular phase are also discussed, giving attention to electrical conductivity, thermal conductivity, viscosity, self-diffusion, interdiffusion, radiative opacity, and second-order transport coefficients.

Stevenson, D. J.↗