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At least 19 records

Single rhenium atoms on nanomagnetite: Probing the recharge process that controls the fate of rhenium in the environment

Understanding the redox transitions that control rhenium geochemistry is central to paleoredox and geochronology studies, as well as predicting the fate of chemically similar hazardous oxyanions in the environment such as pertechnetate. However, detailed mechanistic information regarding rhenium redox transitions in anoxic systems is scarce. Here, we performed a comprehensive laboratory study of rhenium redox transitions on variably oxidized magnetite nanoparticle surfaces. Through high-end spectroscopic and microscopic tools, we propose an abiotic transition pathway in which aqueous iron(II) ions in the presence of pure or preoxidized magnetite serve as an electron source to reduce rhenium(VII) to individual rhenium(IV) atoms or small polynuclear species on nanoparticle surfaces. Notably, iron(II) ions recharged preoxidized magnetite nanoparticles exhibit a maghemite core and a magnetite shell, challenging the traditional core-shell magnetite-maghemite model. This study provides a fundamental understanding of redox processes governing rhenium fate and transport in the environment and enables an improved basis for predicting its speciation in geochemical systems.

Science & Technology - Other Topics↗

Rhenium-Selenido Corroles: Reflections on 5d Metalloporphyrins and Metallocorroles as Triplet Emitters and Photosensitizers

Following the successful synthesis of rhenium-oxido, rhenium-imido, and rhenium-sulfido corroles, a series of para-X-substituted rhenium-selenido triarylcorroles (X = OCH 3 , CH 3 , H, F, CF 3 ) have been prepared in 70–76% yields. A one-pot, two-step procedure was used, analogous to that used for ReS corroles, involving rhenium insertion via high-temperature reaction of Re 2 (CO) 10 and free-base corroles in refluxing decalin, followed by exposure to PCl 3 (which is thought to deoxygenate ReO corroles formed under the reaction) and elemental selenium. An analogous procedure, however, failed to yield rhenium-tellurido corroles, presumably reflecting, according to DFT calculations, the limited stability of these species. Unlike ReO corroles, ReS and ReSe corroles were found not to exhibit phosphorescence in the NIR-I regime (600–1000 nm); nor did they sensitize singlet oxygen formation. In the hope of obtaining a broader perspective of this negative result, we also examined ReN porphyrins and found them not to phosphoresce or to sensitize singlet oxygen formation. These results were explained by DFT and TDDFT calculations in terms of low-energy triplet states, which are not energetic enough to excite molecular oxygen to its lowest singlet state. Whether some of the new Re corroles exhibit phosphorescence in the NIR-II regime remains an interesting question for future investigation.

Aromatic compounds↗

Ambient Aging of Epitaxial and Polycrystalline Rhenium Thin Films

Extending the lifetime of superconducting qubits requires materials that are resistant to surface oxide formation. Rhenium has emerged as one such promising material. Because grain boundaries can promote material degradation, this project compares epitaxial (single-crystal, no grain boundaries) and polycrystalline (many grain boundaries) rhenium thin films after three years of ambient environmental exposure. Epitaxial rhenium remained free of undesired particles, while polycrystalline rhenium developed higher-oxide surface particles. Epitaxial rhenium demonstrated greater resistance to aging and oxidation, making it a more promising candidate for superconducting qubits. Surface characterization using scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy revealed localized oxygen and nitrogen enrichment together with a Re⁷⁺ oxidation state in the polycrystalline surface particles, consistent with the proposed formation of ammonium perrhenate. Ongoing cleaning and XPS depth profiling will further determine the identity and origin of the surface crystallites.

Wiacek, Wiktoria [William Rainey Harper Coll.]↗

Ambient Aging of Epitaxial and Polycrystalline Rhenium Thin Films

Extending the lifetime of superconducting qubits requires materials that are resistant to surface oxidation. Rhenium has emerged as one such promising candidate that forms a sub-nanometer oxide. Grain boundaries are known to promote material degradation, and thus, we compare epitaxial (single crystal, no grain boundaries) and polycrystalline (many grain boundaries) rhenium thin films after three years of ambient environmental exposure. Epitaxial rhenium remained free of undesired particles, while polycrystalline rhenium developed surface oxide crystallites. Surface characterization using scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy reveals localized oxygen and nitrogen enrichment, together with a Re⁷⁺ oxidation state in the polycrystalline surface particles, consistent with the proposed formation of ammonium perrhenate. Epitaxial rhenium demonstrated greater resistance to aging and oxidation, making it a more promising candidate for superconducting qubits. Ongoing cleaning and XPS depth profiling will further determine the identity and origin of the surface crystallites.

Wiacek, Wiktoria [Fermilab]↗

Ambient Aging of Epitaxial and Polycrystalline Rhenium Thin Films

Extending the lifetime of superconducting qubits requires materials that are resistant to surface oxidation. Rhenium has emerged as one such promising candidate that forms a sub-nanometer oxide. Grain boundaries are known to promote material degradation, and thus we compared epitaxial (single crystal, no grain boundaries) and polycrystalline (many grain boundaries) rhenium thin films after three years of ambient environmental exposure. Epitaxial rhenium remained free of undesired particles, while polycrystalline rhenium developed surface oxide crystallites. Surface characterization using scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy reveals localized oxygen and nitrogen enrichment together with a Re⁷⁺ oxidation state in the polycrystalline surface particles, consistent with the proposed formation of ammonium perrhenate. Epitaxial rhenium demonstrated greater resistance to aging and oxidation, making it a more promising candidate for superconducting qubits. Ongoing cleaning and XPS depth profiling will further determine the identity and origin of the surface crystallites.

Wiacek, Wiktoria [William Rainey Harper Coll.]↗

Rhenium-Sulfido and -Dithiolato Corroles: Reflections on Chalcophilicity

The high-temperature (~180 °C) reaction between free-base meso-triarylcorroles and Re 2 (CO) 10 , followed by exposure to PCl 3 and thiols (or elemental sulfur), affords rhenium-sulfido (ReS) corroles in 67-76% yields. The use of shorter reaction times, lower temperatures (~130 °C), and a dithiol (e.g., ethane-1,2-dithiol) also allows the isolation of rhenium-dithiolato corroles, presumptive intermediates on the path to ReS corroles. The ReS corroles exhibit high thermal stability and two reversible oxidations and reductions in their cyclic voltammograms, with redox potentials nearly identical to those observed for analogous ReO corroles. The electrochemical HOMO-LUMO gaps of the complexes, at 2.2 eV, are consistent with ligand-centered oxidation and reduction. The UV-vis spectra of ReS corroles, on the other hand, differ significantly from those of their ReO counterparts. Scalar-relativistic DFT calculations suggest that this difference reflects low-energy LUMO+2 and LUMO+3 levels, consisting of Re-S π-antibonding interactions; the ReO corroles, in contrast, exhibit a larger LUMO+1/LUMO+2 gap, as expected for a relatively classical Gouterman-type metalloporphyrin analogue. The high stability of ReS corroles is consistent with geochemists' view of rhenium as a moderately chalcophilic element (i.e., one that partitions into sulfide melts) as well as with a recent quantitative analysis of thiophilicity, which indicates that rhenium's oxophilicity and thiophilicity are essentially evenly balanced.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and characterization of rhenium chalcogenides for nuclear waste management

A new synthetic approach to binary rhenium (Re) chalcogenides was investigated to aid in the preparation of analogous technetium (Tc) compounds for Tc waste management efforts. The Boron-Chalcogen Mixture (BCM) method was utilized for the first time to prepare polycrystalline powders of ReS 2 , ReSe 2 , and Re 2 Te 5 using a perrhenate, NaReO4, as a rhenium source. Single crystals of ReS 2 were also synthesized using the combined BCM and molten flux methods by adding a K 2 CO 3 flux to the reagent mixture. Thermal analysis using TGA/DSC revealed negligible changes from ambient temperature up to ∼300 °C followed by the oxidation of the Re chalcogenides. High Temperature PXRD was used to investigate the crystallinity of ReS 2 at various temperatures revealing an increase in crystallinity up to 275 °C followed by a decrease in crystallinity due to oxidation. The research presented herein demonstrates a significant step towards technetium waste treatment efforts.

Boron chalcogen mixture (BCM) method↗

A high-temperature heat flux sensor using the transverse Seebeck effect in elemental rhenium

Heat flux sensors compatible with hot environments are critical to advance aerospace, materials, and energy generation technologies that cope with extreme thermal conditions. In this work, we report on the development and characterization of a high-temperature heat flux sensor using the transverse Seebeck effect in rhenium single crystals. The sensor leverages refractory alloys and ceramics compatible with temperatures exceeding 1000 °C. The heat flux sensor was characterized from room temperature to 500 °C using a temperature-controlled calibration facility. At constant temperature, the sensor’s voltage output is linear with respect to the absorbed heat flux. The responsivity of the sensor varies with temperature, from 1.3 μV/(W/cm 2 ) at room temperature to −3.2 μV/(W/cm 2 ) at 500 °C, increasing monotonically in magnitude after changing sign from positive to negative at approximately 300 °C. The experimental results are in good agreement with analytical predictions of the sensor’s temperature-dependent responsivity, which suggest a further increase in magnitude up to −7.4 μV/(W/cm 2 ) at 1000 °C. These results highlight the unique characteristics of rhenium as a TSE transducer. The design offers compatibility with a wide range of operating temperatures and yields a measurement sensitivity that increases as the environmental conditions become more challenging.

20 FOSSIL-FUELED POWER PLANTS↗

Infrared Spectroelectrochemical Insights into Rhenium-Based Supramolecular Assemblies for Electron Storage and Transfer

Three supramolecular square assemblies featuring Re(CO)3Cl corners and monodentate pyridyl linkers [4,4′-bipyridine, (1a), pyrazine (2a), and 1,2-di(4-pyridyl)ethylene (3a), where a denotes the native state] were synthesized and studied via infrared spectroelectrochemistry (IR-SEC). IR-SEC revealed that the length of the bridging ligand and degree of electronic coupling in rhenium squares greatly impact the reduction pathway in both inert and CO2 atmospheres; notably, the squares are capable of interacting with CO2 after only ligand reduction, thereby avoiding the need for an additional reductive event to generate the rhenium anion. This mechanism differs from that of mononuclear complexes, highlighting how unique redox properties can be endowed by electronic coupling in supramolecular systems.

Koehne, Sydney Marie↗

Raman scattering of rhenium for secondary pressure calibration

With the increasing number of 100 s GPa experiments in the diamond anvil cell (DAC), improved accuracy in secondary pressure calibrations to extreme pressures is essential. The rhenium equation of state has been proposed as a pressure calibrant via x-ray diffraction with potentially broad applications as it is commonly used as a gasket material in DAC experiments. In this work, we conducted Raman spectroscopy experiments on rhenium in the DAC and report the pressure shift of the E2g mode, a refined high-pressure C44 and mode-Grüneisen parameter above 200 GPa. We used flat, beveled, and toroidal diamond anvils under quasi-hydrostatic and non-hydrostatic conditions. By measuring the E2g mode from the culet edge to the center, we analyzed pressure distribution based on culet type and distance from the anvil center. The shift in the E2g mode can be expressed as a function of pressure, and diamond edge measurements appear reliable across all anvil types. Comparing the center and edge pressures reveals anvil cupping, offering insights into predicting or preventing anvil failure during materials properties measurements at extreme conditions.

Diamond anvil cells↗

High-Quality Factor Microwave Resonators using Rhenium

Coplanar waveguide resonators are a perfect tool to evaluate the losses induced by defects and interfaces in superconducting devices. Even if niobium is the most used superconductor for resonators and qubits, its native oxide at the metal-air (MA) interface limits the device results. Tantalum has recently significantly improved qubit performances due to a thinner and less disordered oxide layer compared to Nb. To further improve the MA interface, we used rhenium, a superconducting material with 1.7 K critical temperature resistant to oxidation: it forms an oxide layer thinner than 1 nm. In this study, we will present a thorough investigation of rhenium CPW resonator measurements with internal quality factors at the single photon level exceeding 2 million. The devices have been fabricated on a sapphire substrate while the processing parameters have been varying and optimized. The measurements have been performed as a function of power and temperature to disentangle different sources of losses, such as two-level systems (TLS) and quasi-particles. A peculiar TLS temperature dependence has been measured and analyzed. In this work, we also vary the participation ratio of the devices to extract the losses introduced by the involved interfaces with higher fidelity and precision. We carried on a deep material characterization effort to link the results to the differences in the fabrication steps, and we will present material characterization measurements performed via AFM, ToF-SIMS, XPS, and TEM.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Validating the rhenium proxy for rock organic carbon oxidation using weathering profiles

Chemical weathering over geological timescales acts as a source or sink of atmospheric carbon dioxide (CO 2 ), while influencing long-term redox cycling and atmospheric oxygen (O 2 ) at Earth's surface. There is a growing recognition that the oxidative weathering of rock organic carbon (OC petro ) can release more CO 2 than is locally drawn down by silicate weathering, and may vary due to changes in erosion and climate. The element rhenium (Re) has emerged as a proxy to track the oxidative weathering of OC petro , yet uncertainties in its application remain namely that we lack a systematic assessment of the comparative mobility of Re and OC petro during sedimentary rock weathering. Here we measure Re and OC petro loss across gradients in rock weathering at 9 global sites, spanning a range of initial OC petro values from ~0.2 % to >10 %. We use titanium to account for volume changes during weathering and assess Re and OC petro loss alongside major elements that reflect silicate (Na, Mg), carbonate (Ca, Mg) and sulfide (S) weathering. Across the dataset, Re loss is correlated with OC petro loss but not with loss of any other major element. Further, across the weathering profiles, the average molar ratio of OC petro to Re loss was 0.84 ± 0.15, with 8 out of 9 sites having a ratio >0.74. At one site (Marcellus Shale), the average ratio was lower at 0.58 ± 0.11. The excess loss of Re matches expectations that, typically, between ~0 and 20 % of the Re liberated by sedimentary rock weathering derives from silicate or sulfide phases, while some OC petro may be physically or chemically protected from weathering. Overall, our measurements provide validation for the Re proxy of OC petro oxidation and allow future work to further improve our knowledge of regional and global-scale rates of this important source of CO 2 in the geochemical carbon cycle.

58 GEOSCIENCES↗

Synthesis of rhenium coatings on 316 stainless steel and their electrochemical behavior towards water oxidation in saline environments

The production of electrolytic hydrogen or Green Hydrogen has attracted the attention of scientists as a potential enabler of sustainable energy production. The cleavage of the water molecule requires high energy, in order to produce hydrogen and oxygen through their corresponding half reactions, the hydrogen evolution and oxygen evolution reactions. Further, this latter reaction has been studied in more detail, since its slow kinetics make the water electrolysis less efficient, and, for instance, delay the formation of hydrogen in the counter compartment of the electrolytic cell. In this work, a study of the oxygen evolution reaction is presented. For this, a series of rhenium catalysts deposited onto stainless steel 316 are studied with the aim of analyzing the effect of the pure metal (Re) and the metal with heteroatoms (Re-C, Re-B, and Re-O). As one of the problems worldwide is the scarcity of freshwater, the study focuses on the performance of this series of catalysts in highly saline environments, representative of seawater. The synthesis and electrochemical performance is shown, giving high expectations that these electrocatalysts could be potential electrocatalysts in marine environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rhenium Isotope Reconnaissance of Uranium Ore Concentrates

Exploration of natural isotopic variations of the element rhenium (Re) is in its infancy, with initial studies revealing isotopic fractionation in a variety of geological materials. Here, in this work, we investigate Re isotope variation as a new geochemical tool, given its redox-sensitive properties and affinity for organic matter and sulfides. In this work, Re abundance and isotope ratio data were collected from uranium ore concentrates (UOCs) across a variety of depositional ages, locations, geologic settings, and deposit types. Ore types from which the UOC were derived include sandstone, unconformity, and quartz-pebble (QP) conglomerate. To isolate Re from the U-rich matrix of UOCs, a new purification method utilizing DGA ion exchange resin was developed. We found that UOCs exhibit a wide range of Re isotope ratios, with sandstone ore-derived UOCs having the isotopically lightest values, QP conglomerate ore-derived UOCs having the heaviest, and unconformity ore-derived UOCs in between (with some overlap with sandstone UOCs). The Re isotope ratio range observed in UOCs extends previously reported values by more than a factor of two. Industrial processing (e.g., incomplete recovery of Re from ore, contamination, fractionation during processing) may play a role in the isotopic variability in the UOCs. However, systematic differences between ore types suggest that the depositional setting is a significant factor. For nuclear forensic investigations, Re isotopic compositions combined with data from other isotopic systems provide geochemical signatures that can aid in provenance assessment of UOCs. Regardless of the specific causes for the wide range of Re isotope ratios in UOCs, these initial data indicate Re is a promising tool for nuclear forensic investigations on samples from early in the nuclear fuel cycle.

58 GEOSCIENCES↗

Enhanced Electrocatalytic and Selective CO 2 -to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-Bipyridines

The electrochemical reduction of CO 2 (CO 2 RR) into value-added chemicals offers a promising route toward a circular carbon economy and reduced reliance on fossil fuels. A detailed understanding of the structural and electronic factors governing the performance of molecular CO 2 RR electrocatalysts is essential for the design of efficient, tunable systems. Here, in this study, we report a series of rhenium(I) complexes, fac-[Re I (6,6′-(R) 2 -bpy)(CO) 3 Cl] (bpy = 2,2′-bipyridine; R = mesityl (mes), 2,4,6-triisopropylphenyl (trip), or isophthalic acid (phth)) and evaluate their electrocatalytic activity. Among these, fac-[Re I (6,6′-(mes) 2 -bpy)(CO) 3 Cl] exhibited the highest performance, enabling selective CO 2 -to-CO conversion for 1 hour with Faradaic efficiency (FE) > 97%, representing an unprecedented activity level for a Re-bpy catalysts. Single-crystal X-ray diffraction and density functional theory (DFT) calculations indicated that favorable CO 2 binding could be promoted by the tilting of the 6,6′-(mes)2-bpy ligand (from the Re-CO coordination plane), providing mechanistic insight into the observed enhancement. The study consequently demonstrates a rational correlation between the CO 2 electrocatalytic performance of Re-bpy catalysts and their structural variations, as derived from X-ray data and corroborated by computational modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Global Biogeochemical Cycle of Rhenium

Here, this paper is the first comprehensive synthesis of what is currently known about the different natural and anthropogenic fluxes of rhenium (Re) on Earth's surface. We highlight the significant role of anthropogenic mobilization of Re, which is an important consideration in utilizing Re in the context of a biogeochemical tracer or proxy. The largest natural flux of Re derives from chemical weathering and riverine transport to the ocean (dissolved = 62 × 10 6 g yr -1 and particulate = 5 × 10 6 g yr -1 ). This review reports a new global average [Re] of 16 ± 2 pmol L -1 , or 10 ± 1 pmol L -1 for the inferred pre-anthropogenic concentration without human impact, for rivers draining to the ocean. Human activity via mining (including secondary mobilization), coal combustion, and petroleum combustion mobilize approximately 560 × 10 6 g yr -1 Re, which is more than any natural flux of Re. There are several poorly constrained fluxes of Re that merit further research, including: submarine groundwater discharge, precipitation (terrestrial and oceanic), magma degassing, and hydrothermal activity. The mechanisms and the main host phases responsible for releasing (sources) or sequestrating (sinks) these fluxes remain poorly understood. This study also highlights the use of dissolved [Re] concentrations as a tracer of oxidation of petrogenic organic carbon, and stable Re isotopes as proxies for changes in global redox conditions.

58 GEOSCIENCES↗

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↗

Neutral rhenium(i) tricarbonyl complexes with sulfur-donor ligands: anti-proliferative activity and cellular localization

Rhenium(I) tricarbonyl complexes are widely studied for their cell imaging properties and anticancer and anti-microbial activities, but the complexes with S-donor ligands remain relatively unexplored. A series of six fac-[Re(NN)(CO) 3 (SR)] complexes, where (NN) is 2,2'-bipyridyl (bipy) or 1,10-phenanthroline (phen), and RSH is a series of thiocarboxylic acid methyl esters, have been synthesized and characterized. Cellular uptake and anti-proliferative activities of these complexes in human breast cancer cell lines (MDA-MB-231 and MCF-7) were generally lower than those of the previously described fac-[Re(NN)(CO) 3 (OH 2 )] + complexes; however, one of the complexes, fac-[Re(CO) 3 (phen)(SC(Ph)CH 2 C(O)OMe))] (3b), was active (IC 50 ~ 10 μM at 72 h treatment) in thiol-depleted MDA-MB-231 cells. Moreover, unlike fac- [Re(CO) 3 (phen)(OH 2 )] + , this complex did not lose activity in the presence of extracellular glutathione. Taken together these properties show promise for further development of 3b and its analogues as potential anti-cancer drugs for co-treatment with thiol-depleting agents. Conversely, the stable and non-toxic complex, fac-[Re(bipy)(CO) 3 (SC(Me)C(O)OMe)] (1a), predominantly localized in the lysosomes of MDA-MB-231 cells, as shown by live cell confocal microscopy (λ ex = 405 nm, λ em = 470-570 nm). It is strongly localized in a subset of lysosomes (25 μM Re, 4 h treatment), as shown by co-localization with a Lysotracker dye. Longer treatment times with 1a (25 μM Re for 48 h) resulted in partial migration of the probe into the mitochondria, as shown by co-localization with a Mitotracker dye. These properties make complex 1a an attractive target for further development as an organelle probe for multimodal imaging, including phosphorescence, carbonyl tag for vibrational spectroscopy, and Re tag for X-ray fluorescence microscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗