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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Syngas Production at Si Hybrid Photoelectrodes Modified with Re(I) and Mn(I) Tricarbonyl Phenanthroline Complexes Containing Reactive Aryl Azide Groups

We installed molecular CO 2 reduction (CO 2 R) catalysts directly onto Si (photo)electrodes. The highly reactive M(5-azido-1,10-phenanthroline)(CO) 3 X (where M = Mn or Re, X = Br or Cl) complexes readily bubbled when dissolved in polar organic solvents, in both the presence and absence of an ultraviolet light source. When placed on hydrogen-terminated Si (H-Si) and native silicon oxide (SiOx), similar amounts of the complex were attached to the surface under illumination (367 nm, 50–200 mW/cm 2 ) or in the dark. Surprisingly, these films revealed submonolayer coverages instead of the multilayered structures we expected. DFT analyses support monolayer formation, showing that the triplet-state nitrene of the complex is more energetically favorable than the singlet state. Using controlled-potential electrolysis experiments, we showed that Re- and Mn-containing films on pSi photoelectrodes generated small amounts of CO when exposed to 1 atm of CO 2 and 1 sun illumination. These amounts of CO were an order of magnitude greater than control surfaces, producing 5.59 × 10 –7 mol CO/h for Re(az-phen) and 7.83 × 10 –7 mol CO/h for Mn(az-phen) films. Much of the charge passed at the pSi electrodes was consumed by the competing hydrogen evolution reaction, which we attribute to the low molecular coverage and the presence of native oxide on the electrode surface after attachment. Finally, this work demonstrates the feasibility of reacting azide-containing ligands with Si surfaces. Still, it highlights the need for alternative ligand structures and reaction conditions to form multilayer films.

azides↗
DOE OSTI2024

Lanthanide binding peptide surfactants at air–aqueous interfaces for interfacial separation of rare earth elements

Rare earth elements (REEs) are critical materials to modern technologies. They are obtained by selective separation from mining feedstocks consisting of mixtures of their trivalent cation. We are developing an all-aqueous, bioinspired, interfacial separation using peptides as amphiphilic molecular extractants. Lanthanide binding tags (LBTs) are amphiphilic peptide sequences based on the EF-hand metal binding loops of calcium-binding proteins which complex selectively REEs. We study LBTs optimized for coordination to Tb 3+ using luminescence spectroscopy, surface tensiometry, X-ray reflectivity, and X-ray fluorescence near total reflection, and find that these LBTs capture Tb 3+ in bulk and adsorb the complex to the interface. Molecular dynamics show that the binding pocket remains intact upon adsorption. We find that, if the net negative charge on the peptide results in a negatively charged complex, excess cations are recruited to the interface by nonselective Coulombic interactions that compromise selective REE capture. If, however, the net negative charge on the peptide is −3, resulting in a neutral complex, a 1:1 surface ratio of cation to peptide is achieved. Surface adsorption of the neutral peptide complexes from an equimolar mixture of Tb 3+ and La 3+ demonstrates a switchable platform dictated by bulk and interfacial effects. The adsorption layer becomes enriched in the favored Tb 3+ when the bulk peptide is saturated, but selective to La 3+ for undersaturation due to a higher surface activity of the La 3+ complex.

Ortuno Macias, Luis E. (ORCID:0000000284342192)↗
DOE OSTI2026

Climatology of Cloud‐Land‐Surface Coupling Across Different ARM Sites

Land-atmosphere interactions play a critical role in the evolution and formation of low-level clouds. The different states of coupling between low-level clouds and the surface are uncertain, primarily over continental regions, where complex thermodynamics complicates their investigation. This study uses observations from the Atmospheric Radiation Measurement User Facility to explore cloud-surface coupling and perform a climatological analysis of this interaction in five countries across three continents. The results reveal consistent coupling thresholds and average percentages across the five sites, with coupled clouds accounting for 66% of the cases and decoupled clouds for 34%. Thermodynamic and dynamic evaluations show distinct differences between coupled and decoupled clouds. Coupled clouds are characterized by humid environments, in which vertical motions connect the surface and lower atmosphere to the cloud base, conditions that favor the formation of boundary layer clouds. Decoupled clouds prefer to occur in a drier and colder environment with vertical motions inside the boundary layer being detached from the cloud base, under which boundary layer clouds are hard to form. Coupled clouds peak during warmer hours and seasons, and vice versa for decoupled clouds. This study underscores the complexity of cloud-land-surface interactions and paves the way for further investigations into cloud formation and evolution under different atmospheric environments.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Electrode-Ligand Interactions Dramatically Enhance CO 2 Conversion to CO by the [Ni(cyclam)](PF 6 ) 2 Catalyst

Dramatic enhancement of electrochemical CO 2 conversion to CO, catalyzed by [Ni(cyclam)](PF 6 ) 2 is confirmed on mercury/gold electrodes. We find that Hg provides favorable noncovalent dispersive interactions with the cyclam ligand. As a result, the Hg surface destabilizes the poisoned CO-bound form of the catalyst, leading to enhanced reaction kinetics. These effects are particularly relevant to the design of ligands that improve the electrocatalytic performance of transition-metal complexes on interaction with metallic surfaces under cell operating conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Spectral Induced Polarization-Biogeochemical Relationships for Remediation Amendment Monitoring

Geophysical tools such as electrical resistivity (ER) can indirectly monitor subsurface changes in response to remedial injections. These methods exhibit relatively low spatial resolution compared to sediment core characterization but are advantageous due to the ability to collect measurements non-intrusively over time across large volumes of the subsurface. Moreover, along with confirmatory groundwater or core sampling, geophysical methods can be used during active biogeochemical remedies to monitor short-term contaminant transformations and mobility, as well as part of an overall strategy for long-term monitoring of subsurface contaminated sites. The use of alternating current spectral induced polarization (SIP) provides significantly more information than conventional geophysical methods like direct current ER. SIP allows for monitoring changes in both solution and surface conductivity by separation of real and imaginary conductivity, respectively, as well as surface capacitance. In principle, SIP can measure indicators of remedy progression such as precipitation reactions that sequester contaminants, potentially providing a better indication of amendment delivery and reactivity as compared to conventional ER methods. However, multiple processes and material properties have overlapping (interacting) electrical responses across a range of frequencies. Hence, the purpose of this scoping study was to evaluate if SIP can be used to monitor (a) amendment delivery and (b) precipitation and reactivity of amendments under consideration at Hanford. SIP measurements were collected in fully saturated columns packed with sand and Hanford formation sediments containing (a) amendments that were highly conductive with significant capacitance (zero valent iron – ZVI, sulfur modified iron – SMI) and (b) amendments that exhibited low electrical conductivity with a small capacitance (calcite, apatite, bismuth). The sand was a quartz material with homogenous particle size that exhibited a relatively low surface conductivity. It was used as a control for comparison with the sediments from the Hanford Site, which have a greater surface conductivity because of their complex mineralogy and heterogeneous particle size distribution and may have complex interactions with amendments. The amendment mass fraction was varied to represent the different stages and subsurface locations associated with the delivery of a remedy. The primary objective was to identify the solution and solid surface changes associated with the delivery amendments and their secondary reactions within the subsurface. The figure below summarizes results for the amendments tested through this project. The SIP phase shift or imaginary conductivity change for the high conductivity amendments was more than 10 times that of the low conductivity amendments, highlighting the relative ease of detection of ZVI and SMI independent of the background signal from sand or Hanford sediments. The ZVI phase shift and imaginary conductivity changes occur primarily at high frequency (> 100 Hz) whereas SMI changes were at low frequency (0.01 to 10 Hz). SIP signals of SMI also increased over time and the maximum shifted to lower frequencies. The low conductivity amendments (calcite, abiotic and biotic apatite, bismuth subnitrate) exhibited relatively small phase and imaginary conductivity changes when added to sediments. The changes were above minimum detection limits (0.5 mrad for phase shift, 0.03 µS/cm for imaginary conductivity) for the highest concentration except for the commercial bismuth material. The lowest amendment concentration that can be detected is likely sediment specific, as minerals in sediments (clays, magnetite, Fe-oxides) have some capacitance and, therefore, exhibit a variable phase shift.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2013

Complex Indigenous Organic Matter Embedded in Apollo 17 Volcanic Black Glass Surface Deposits

Papers presented at the first Lunar Science Conference [1] and those published in the subsequent Science Moon Issue [2] reported the C content of Apollo II soils, breccias, and igneous rocks as rang-ing from approx.50 to 250 parts per million (ppm). Later Fegley & Swindle [3] summarized the C content of bulk soils from all the Apollo missions as ranging from 2.5 (Apollo 15) to 280 ppm (Apollo 16) with an overall average of 124+/- 45 ppm. These values are unexpectedly low given that multiple processes should have contributed (and in some cases continue to contribute) to the lunar C inventory. These include exogenous accretion of cometary and asteroidal dust, solar wind implantation, and synthesis of C-bearing species during early lunar volcanism. We estimate the contribution of C from exogenous sources alone is approx.500 ppm, which is approx.4x greater than the reported average. While the assessm ent of indigenous organic matter (OM) in returned lunar samples was one of the primary scientific goals of the Apollo program, extensive analysis of Apollo samples yielded no evidence of any significant indigenous organic species. Furthermore, with such low concentrations of OM reported, the importance of discriminating indigenous OM from terrestrial contamination (e.g., lunar module exhaust, sample processing and handling) became a formidable task. After more than 40 years, with the exception of CH4 [5-7], the presence of indigenous lunar organics still remains a subject of considerable debate. We report for the first time the identification of arguably indigenous OM present within surface deposits of black glass grains collected on the rim of Shorty crater during the Apollo 17 mission by astronauts Eugene Cernan and Harrison Schmitt.

Thomas-Keprta, Kathie L.↗
NASA NTRSDate not supplied

NASA’s Handheld Ionizer Tool for Astronauts

NASA’s next human lunar mission will require handheld tools to eliminate dust accumulation as well as electrostatic charge for the upcoming manned missions to the moon in the Artemis Program. The Moon’s lack of substantial atmosphere means the lunar surface is directly exposed to the solar wind, solar UV radiation, and cosmic rays which can cause dielectric charging of the lunar regolith via the photoelectric effect. The result is a layer of highly charged dust that is levitated and transported about a meter off the surface called the “horizon glow” as seen by the Apollo astronauts. The complex lunar electrostatic environment coupled with the surface dust behavior poses a concern for the longevity of surface infrastructures. The Electrostatics and Surface Physics Laboratory at NASA’S Kennedy Space Center retrofitted a commercial ionizer and successfully demonstrated that air ionizers are effective at removing dust particles and the static charge in high vacuum. Additional work is planned to establish the optimal voltage and flow characteristic to develop a high-fidelity ground prototype for future flight certification.

Electrostatics↗
NASA NTRS1983

An interactive method for surface fitting three-dimensional bodies

The paper discusses a computerized surface fitting procedure which, using interactive graphics, will surface fit mathematical relations to complex three-dimensional bodies. The program has been written so that it 'leads' the user step-by-step through the procedure, thus allowing a user of limited experience to rapidly digitize a body and obtain an accurate surface fit. Results are presented which indicate that the method yields accurate coordinates, slopes, and radii of curvature at any specified position on the body provided an adequate number of accurate cross section coordinates are available to adequately describe the body.

Perkins, J. N.↗
DOE OSTI2019

Fermi surface, possible unconventional fermions, and unusually robust resistive critical fields in the chiral-structured superconductor AuBe

The noncentrosymmetric superconductor (NCS) AuBe is investigated using a variety of thermodynamic and resistive probes in magnetic fields of up to 65 T and temperatures down to 0.3 K. Despite the polycrystalline nature of the samples, the observation of a complex series of de Haas–van Alphen (dHvA) oscillations has allowed the calculated band structure for AuBe to be validated. This permits a variety of BCS parameters describing the superconductivity to be estimated, despite the complexity of the measured Fermi surface. In addition, AuBe displays a nonstandard field dependence of the phase of dHvA oscillations associated with a band thought to host unconventional fermions in this chiral lattice. Overall, this result demonstrates the power of the dHvA effect to establish the properties of a single band despite the presence of other electronic bands with a larger density of states, even in polycrystalline samples. In common with several other NCSs, we find that the resistive upper critical field exceeds that measured by heat capacity and magnetization by a considerable factor. We suggest that our data exclude mechanisms for such an effect associated with disorder, implying that topologically protected superconducting surface states may be involved.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

An automated cluster surface scanning method for exploring reaction paths on metal-cluster surfaces

Metal-cluster surfaces present a wide variety of unique coordination environments. This complexity makes it difficult to manually probe the surface reactivity of such clusters. Here, we present a simple and automated method to systematically discover reaction pathways on cluster surfaces, based on the automated cluster surface scanning (ACSS) technique for mapping out potential energy surfaces. We showcase our method on 55-atom icosahedral Cu and Ag clusters, where we determine the activation energies of four elementary steps common in heterogeneous catalysis – hydrogen recombination (H* + H* → H 2 * + *), oxygen recombination (O* + O* → O 2 * + *), water formation (OH* + H* → H 2 O* + *), and CO oxidation (CO* + O* → CO 2 * + *) – with density functional theory calculations (DFT-PBE + D3). We show that the ACSS method requires significantly less human effort than the established manually performed climbing-image nudged elastic band (MP + CI-NEB) technique and locates transition states with comparable accuracy (root-mean-squared error of 0.10 eV) and similar computational cost. Rigorous sampling of the potential energy surface with the ACSS method allows one to locate all lowest-energy reaction pathways obtained via the MP+CI-NEB approach, as well as alternative pathways that one may have missed with the MP+CI-NEB approach due to the many possible pathways available on these clusters. The accuracy and efficiency afforded by the ACSS method could enable high-throughput exploration of the diverse reactivity of metal clusters.

36 MATERIALS SCIENCE↗
NASA NTRS1982

Evaluating near-surface soil moisture using Heat Capacity Mapping Mission data

Four dates of Heat Capacity Mapping Mission (HCMM) data were analyzed in order to evaluate HCMM thermal data use in estimating near-surface soil moisture in a complex agricultural landscape. Because of large spatial and temporal ground cover variations, HCMM radiometric temperatures alone did not correlate with soil water content. The radiometric temperatures consisted of radiance contributions from different canopies and their respective soil backgrounds. However, when surface soil temperatures were empirically estimated from HCMM temperatures and percent cover of each pixel, a highly significant correlation was obtained between the estimated soil temperatures and near-surface soil water content.

Heilman, J. L.↗
NASA NTRS2018

Dragonfly: Investigating the Surface Composition of Titan

Dragonfly is a rotorcraft lander mission, selected as a finalist in NASA's New Frontiers Program, that is designed to sample materials and determine the surface composition in different geologic settings on Titan. This revolutionary mission concept would explore diverse locations to characterize the habitability of Titan's environment, to investigate how far prebiotic chemistry has progressed, and to search for chemical signatures that could be indicative of water-based and/or hydrocarbon-based life. Here we describe Dragonfly's capabilities to determine the composition of a variety of surface units on Titan, from elemental components to complex organic molecules. The compositional investigation ncludes characterization of local surface environments and finely sampled materials. The Dragonfly flexible sampling approach can robustly accommodate materials from Titan's most intriguing surface environments.

Trainer, M. G.↗
DOE OSTI2018

Natural Attenuation Progress, Plume Movement, and Source Reduction for the SRS CMP Pits VOC Plume - 18384

Monitoring the effectiveness of natural attenuation for remediating the Savannah River Site (SRS) Chemical, Metals, and Pesticides (CMP) Pits plume fringe has focused intensive sampling of shallow groundwater for different reaches of Pen Branch from 2005 to 2017. Volatile organic compounds (VOCs) were analyzed for the critical hyporheic zone beneath Pen Branch and adjacent floodplain. These sampling efforts assisted larger-scale compliance monitoring in accordance with US Environmental Protection Agency (EPA) guidelines. When applicable, EPA has found natural attenuation to be an acceptable mode of achieving regulatory compliance. While natural attenuation can include any ecosystem function that reduces contaminant loads, it is focused on microbial biochemical pathways. The study plume originated from CMP Pits, a waste disposal area in operation from 1971 to 1979, when the pits were closed and backfilled. In 1984, excavations of source material and contaminated soils were removed up to a depth of 7.6 m below the trenches. However, monitoring well data indicated that perchloroethylene (PCE) and trichloroethylene (TCE) had seeped beneath the vadose zone and formed groundwater plumes reaching the Pen Branch valley below. Although 'hot spots' of TCE were found within the Pen Branch floodplain, it was unknown just how the flow pattern was entering Pen Branch and to what degree natural attenuation was reducing the contaminant load. For this reason, our stations were located along the Pen Branch reach bordering the modelled plume fringe. In general, VOCs were highest at station piezometer holes in the middle study zone. Moderate VOC levels were detected at upstream stations and lowest VOC levels were found at downstream stations. Electrical resistance heating (ERH) with soil vapor extraction (SVE) conducted by Savannah River Nuclear Solutions (SRNS) from 2008 to 2009 at the filled CMP Pits helped to remove contaminants trapped in clay horizons beneath the CMP Pits and to reduce overall new plume concentrations. Collectively PCE, TCE, and their degradation products displayed a favorable yearly trend of contaminant natural attenuation. Additionally, phytoremediation actions by native bamboo, Arundinaria gigantea, added to VOC removal from wetlands soils. Total VOC concentrations at some stations declined by >25% and concentrations of vinyl chloride (VC), a nearly-final stage degradation product increased from 0.0 ppb to >20 ppb. Temporal patterns displayed a continued reduction of VOCs, while spatial patterns indicated a possible slow progression of the plume downstream along Pen Branch. Conclusions about plume export into surface waters must address the seasonal and geological complexities of this system. Hydrological patterns are complex and plumes do not directly outcrop into Pen Branch surface waters, but emerge into the stream through pathways in the porous hyporheic zone. For this reason, continued sampling must identify critical depths and downstream locations where plume flows may be more intense. During drought periods with no surface flow in Pen Branch, subsurface plume flows may be flowing downslope in the hyporheic zone. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Enhanced rare earth element recovery with cross-linked glutaraldehyde-lanthanide binding peptides in foam-based separations

Lanthanide Binding Tag (LBT) peptides that coordinate selectively with lanthanide ions can be used to replace the energy intensive processes used for the separation of rare earth elements (REEs). These surface-active biomolecules, once selectively complexed with the trivalent REE cations, can adsorb to air/aqueous interfaces of bubbles for foam-based REEs recovery. Glutaraldehyde, an organic compound that is a homobifunctional crosslinker for proteins and peptides, can be used to enhance the adsorption and interfacial stabilization of lanthanide-bound peptides films. The stability of the interfacial cross-linked films was tested by measuring their dilational and shear surface rheological properties. Surface activity of the adsorbed species was analyzed using pendant drop tensiometry, while surface density and molecular arrangement were determined using x-ray reflectivity and x-ray fluorescence near total reflection. Glutaraldehyde cross-linked REE-peptide complexes enhance the adsorption of lanthanides to air-water interfaces, resulting in thicker interfacial structures. Subsequently, these thicker layers enhance the dilational and shear interfacial rheological properties. The interfacial film stabilization and REEs extraction promoted by the cross-linker presented in this work provides an approach to integrate glutaraldehyde as a substitute of common foam stabilizers such as polymers, surfactants, and particles to optimize the recovery of REEs when using biomolecules as extractants.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Intersystem crossing in the exit channel

We report that intersystem crossing (ISC), plays an important role in photochemistry. It is understood to be efficient when heavy atoms are present due to strong spin–orbit coupling, or when strongly bound long-lived complexes are formed that increase the chance of finding the singlet–triplet intersection seam. Here we present evidence for a different ISC mechanism in the bimolecular reaction of O( 3 P) with alkylamines. In crossed-beam experiments, product velocity-flux maps are measured for aminoalkyl radicals produced from H-abstraction from the methyl group, which also gives OH radicals as co-fragments. The low translational-energy release and isotropic angular distributions of the products indicate that such reactions undergo the formation of a complex before OH and aminoalkyl are produced. However, there is no well on the triplet potential-energy-surface that could support such a complex. Multireference ab initio calculations suggest, instead, that ISC occurs in the exit-channel region due to the long-range dipole–dipole interaction between the nascent radical product pair coupled with the vanishing singlet–triplet splitting at long range. Finally, ISC then leads to a deep hydroxylamine well before OH elimination.

74 ATOMIC AND MOLECULAR PHYSICS↗