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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

In-situ HRTEM observations of intermediate phase transformation in lattice reorientation in HCP rhenium

In-situ high-resolution transmission electron microscopy (HRTEM) is performed to investigate the deformation behavior of hexagonal close-packed rhenium (Re) which is compressed along the $\langle1\overline{1}00\rangle$ direction. Atomistic simulations are also conducted to better understand the deformation mechanisms. Two types of lattice reorientation are observed during compression. The first type involves the reorientation of one lattice by ~90° around $\langle1\overline{1}00\rangle$, which is accomplished by the formation of an intermediate face-center-cubic (FCC) phase at the interface. This transformation sequence can be described as {$1\overline{1}00$} matrix → {$111$} FCC → ($0001$) twin . In the second type, a new grain is formed but does not satisfy any known twin relationship with the matrix, and an intermediate FCC phase is also formed. The transformation sequence can be described as {$1\overline{1}00$} matrix → {$111$} FCC → ($0001$) grain . Mechanisms responsible for the observed lattice reorientation and sequential phase transitions are analyzed by conducting lattice correspondence analyses on the simulation results. Strain accommodation is also analyzed to explain the mechanisms for lattice reorientation and the intermediate phase transformations. In conclusion, the results provide new insight into the deformation behavior of HCP metals

36 MATERIALS SCIENCE↗
DOE OSTI2020

Thermal diffusivity of irradiated tungsten and tungsten-rhenium alloys

The Japan-US PHENIX project irradiated tungsten materials in the RB-19J capsule experiment in the High Flux Isotope Reactor (HFIR). A gadolinium (Gd) shielding was used to absorb the thermal neutrons and reduce rhenium and osmium generation in tungsten. Pure tungsten and K-doped W-3% Re samples were irradiated at 532 – 662 °C to dose of 0.21-0.46 dpa, with the grain orientation perpendicular or parallel to the disk surface. Thermal diffusivity measurements were performed from 100 °C to 500 °C. Furthermore, additional measurements followed after annealing up to 900 °C. Irradiated pure tungsten specimens showed similar thermal diffusivity results compared with an unirradiated W-1% Re specimen in another study. The transmutation amount of Re was calculated to be about 0.52% for those specimens that showed good agreement with this study. Specimens irradiated in this study to different doses presented almost the same thermal diffusivity. Annealing up to 800 °C resulted in no recovery of thermal diffusivity. These results show that the contribution of crystalline defects to degradation of thermal diffusivity is quite limited. In addition, the thermal diffusivity of the irradiated specimens was getting close to that of the unirradiated specimens at elevated temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Highly Active Rhenium-, Ruthenium-, and Iridium-Based Dichalcogenide Electrocatalysts for Oxygen Reduction and Oxygen Evolution Reactions in Aprotic Media

Transition metal dichalcogenides (TMDCs) have garnered much attention recently due to their remarkable performance for different electrochemical systems. In this study, we report on the synthesis and catalysis of less studied TMDC nanoflakes (NFs) with a design space comprised of three transition metals (rhenium, ruthenium, and iridium) and three chalcogens (sulfur, selenium, and tellurium) for the oxygen reduction and evolution reactions (ORR and OER) in an aprotic hybrid electrolyte containing 0.1 M lithium bis(trifluoromethanesulfonypimide salt in 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid and dimethyl sulfoxide. Our results indicate that among the tested catalysts, ReS2 exhibits the highest current density for both ORR and OER, beyond those of the state-of-the-art catalysts used in aprotic media with Li salts. We performed density functional calculations to provide a mechanistic understanding of the reactions in the ReS2 NFs/ionic liquid system. These novel bifunctional catalyst results could open a way for exploiting the unique properties of these materials in Li-O-2 batteries as well as other important electrochemical systems.

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

A Rhenium Bis -tetramethylphenanthroline Catalyst for CO 2 Reduction to Formate

Catalytic CO 2 reduction reactions featuring high selectivity toward formate are relatively rare. In some homogeneous molecular CO 2 -reducing electrocatalysis, using triethylamine (TEA) and isopropanol (IPA) as additives improves catalytic performance in producing formate. In this paper, we investigate whether the rhenium(I) bis-diimine dicarbonyl complexes, cis-[Re(N^N) 2 (CO) 2 ] + , where N^N is 2,2’-bipyridine ([1] + ) or 3,4,7,8-tetramethyl-1,10-phenanthroline ([2] + ), are capable of electrocatalytically reducing CO 2 to formate in acetonitrile containing TEA and IPA. Catalyst [1] + was ineffective at CO 2 reduction, yielding formate quantities comparable to those produced in experiments without the catalyst. Catalyst [2] + , however, is a promising electrocatalyst for the CO 2 reduction reaction in the presence of TEA and IPA, with formate being produced in millimolar concentrations (10.5 mM), as detected by 1 H NMR spectroscopy after 6 h electrolysis (formate Faradaic efficiency = 11%, with the major balance going to H 2 ). Upon more detailed examination, [2] + exhibited a turnover frequency (TOF) of 12 s –1 for formate, comparable to other leading molecular catalysts that competently execute this reduction. Combinations of spectroscopy, electrochemistry, and theory were used to better understand the mechanism of CO 2 reduction by [2] + . Fourier transform infrared spectroelectrochemical (FTIR-SEC) data provided no evidence for CO ligand dissociation or substitution upon one- and two-electron reduction of [2] + , suggesting that a mechanism distinct from one that is metal-hydride-based is operative in catalysis. Computational studies guide mechanistic investigations toward the proposed formation of a hydrophenanthroline-based intermediate responsible for hydride transfer to CO 2 and electrocatalytic formate production from [2] + .

Beverages↗
DOE OSTI2020

Temperature and Solvent Effects on H 2 Splitting and Hydricity: Ramifications on CO 2 Hydrogenation by a Rhenium Pincer Catalyst

The catalytic hydrogenation of carbon dioxide holds immense promise for applications in sustainable fuel synthesis and hydrogen storage. Mechanistic studies that connect thermodynamic parameters with the kinetics of catalysis can provide new understanding and guide predictive design of improved catalysts. Reported here are thermochemical and kinetic analyses of a new pincer-ligated rhenium complex ( tBu POCOP)Re(CO) 2 ( tBu POCOP = 2,6-bis(di-tert-butylphosphinito)phenyl) that catalyzes CO 2 hydrogenation to formate with faster rates at lower temperature. Because the catalyst follows the prototypical “outer sphere” hydrogenation mechanism, comprehensive studies of temperature and solvent effects on the H 2 splitting and hydride transfer steps are expected to be relevant to many other catalysts. Strikingly large entropy associated with cleavage of H2 results in a strong temperature dependence on the concentration of [( tBu POCOP)Re(CO) 2 H] – present during catalysis, which is further impacted by changing the solvent from toluene to tetrahydrofuran to acetonitrile. New methods for determining the hydricity of metal hydrides and formate at temperatures other than 298 K were developed, providing insight into how temperature can influence the favorability of hydride transfer during catalysis. These thermochemical insights guided the selection of conditions for CO 2 hydrogenation to formate with high activity (up to 364 h –1 at 1 atm or 3330 h –1 at 20 atm of 1:1 H 2 CO 2 ). In cases where hydride transfer is the highest individual kinetic barrier, entropic contributions to outer sphere H 2 splitting lead to a unique temperature dependence: catalytic activity increases as temperature decreases in tetrahydrofuran (200-fold increase upon cooling from 50 to 0 °C) and toluene (4-fold increase upon cooling from 100 to 50 °C). Furthermore, the ramifications on catalyst structure-function relationships are discussed, including comparisons between “outer sphere” mechanisms and metal–ligand cooperation mechanisms.

14 SOLAR ENERGY↗