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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Electrocatalytic water oxidation performance in an extended porous organic framework with a covalent alliance of distinct Ru sites

The rational synthesis of durable, earth-abundant efficient electrocatalysts for the oxygen evolution reaction (OER) from water is one of the most important routes for storing renewable energy and minimizing fossil fuel combustion. The prime hurdles for effectively utilizing commercial RuO 2 as (OER) electrocatalysts are its very low stability, catalyst deactivation, and high cost. In this work, we explored a Ru-integrated porous organic polymer (Ru@Bpy-POP) by a facile one-pot Friedel–Crafts alkylation strategy between redox-active (Ru(demob) 3 Cl 2 ) and a carbazole unit, which is composed of unique features including an extended framework unit, isolated active sites, and tunable electrode kinetics. Ru@Bpy-POP can serve as a bridge between a Metal–Organic Framework (MOF) and POP-based catalytic systems with a balanced combination of covalent bonds (structural stability) and open metal sites (single site catalysis). Ru@Bpy-POP, deposited on a three-dimensional nickel foam electrode support, exhibits a promising electrocatalytic OER activity with an ultra-low ruthenium loading compared to a benchmark RuO 2 catalyst, providing an overpotential of about 270 mV to reach 10 mA cm –2 in an alkaline medium. Moreover, a high current density of 248 mA cm –2 was achieved for the Ru@Bpy-POP catalyst at only 1.6 V (vs. RHE), which is much higher than 91 mA cm –2 for commercial RuO 2 . The robust, albeit highly conjugated, POP framework not only triggered facile electro-kinetics but also suppressed aggregation and metallic corrosion during electrolysis. In particular, the benefits of covalent integration of distinct Ru sites into the framework can modulate intermediate adsorption and charge density, which contributes to its exceptional OER activity. All of the critical steps involved in OER are complemented by Density Functional Theory (DFT) calculations, which suggest that electrocatalytic water oxidation proceeds from a closed-shell configuration to open-shell electronic configurations with high-spin states. Finally, these open-shell configurations are more stable than their closed-shell counterparts by 1 eV, improving the overall catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Atomically Precise Single Metal Oxide Cluster Catalyst with Oxygen–Controlled Activity

Single cluster catalysts (SCCs) consisting of atomically precise metal nanoclusters dispersed on supports represent a new frontier of heterogeneous catalysis. However, the ability to synthesize SCCs with high loading and to precisely introduce non-metal atoms to further tune their catalytic activity and reaction scope of SCCs have been longstanding challenges. In this work, a new interface confinement strategy is developed for the synthesis of a high density of atomically precise Ru oxide nanoclusters (Ru 3 O 2 ) on reduced graphene oxide (rGO), attributed to the suppression of diffusion-induced metal cluster aggregation. Ru 3 O 2 /rGO exhibits a significantly enhanced activity for oxidative dehydrogenation of 1,2,3,4-tetrahydroquinoline (THQ) to quinoline with a high yield (≈86%) and selectivity (≈99%), superior to Ru and RuO 2 nanoparticles, and homogeneous single/multiple-site Ru catalysts. In addition, Ru 3 O 2 /rGO is also capable of efficiently catalyzing more complex oxidative reactions involving three reactants. The theoretical calculations reveal that the presence of two oxygen atoms in the Ru 3 O 2 motif not only leads to a weak hydrogen bonding interaction between the THQ reactant and the active site, but also dramatically depletes the density of states near the Fermi level, which is attributed to the increased positive valence state of Ru and the enhanced oxidative activity of the Ru 3 O 2 cluster for hydrogen abstraction.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Palladium Single-Atom (In)Stability Under Aqueous Reductive Conditions

Here, we investigate the stability and performance of single-atom Pd on TiO 2 for the selective dechlorination of 4-chlorophenol. A challenge inherent to single atoms is their high surface free energy, which results in a tendency for the surface migration and aggregation of metal atoms. This work evaluates various factors affecting the stability of Pd single-atoms, including atomic dispersion, coordination environment, and substrate properties, under reductive aqueous conditions. The transition from single atoms to clusters vastly enhanced dechlorination kinetics without diminishing carbon–chlorine bond selectivity. X-ray absorption spectroscopy analysis using both in situ and ex situ conditions followed the dynamic transformation of single atoms into amorphous clusters, which consist of a unique unsaturated coordination environment and few nanometer diameter. Importantly, the intricate relationship between stability and performance underscores the vital role of detailed characterization to properly determine the true active species for dehalogenation reactions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Migration and aggregation of Pt atoms on metal oxide-supported ceria nanodomes control reverse water gas shift reaction activity

Abstract Single-atom catalysts (SACs) are particularly sensitive to external conditions, complicating the identification of catalytically active species and active sites under in situ or operando conditions. We developed a methodology for tracing the structural evolution of SACs to nanoparticles, identifying the active species and their link to the catalytic activity for the reverse water gas shift (RWGS) reaction. The new method is illustrated by studying structure-activity relationships in two materials containing Pt SACs on ceria nanodomes, supported on either ceria or titania. These materials exhibited distinctly different activities for CO production. Multimodal operando characterization attributed the enhanced activity of the titania-supported catalysts at temperatures below 320 ˚C to the formation of unique Pt sites at the ceria-titania interface capable of forming Pt nanoparticles, the active species for the RWGS reaction. Migration of Pt nanoparticles to titania support was found to be responsible for the deactivation of titania-supported catalysts at elevated temperatures. Tracking the migration of Pt atoms provides a new opportunity to investigate the activation and deactivation of Pt SACs for the RWGS reaction.

36 MATERIALS SCIENCE↗
NASA NTRS2010

Preliminary Geological Findings on the BP-1 Simulant

The following is a summation of information and discussion between Doug Stoeser of the USGS and Doug Rickman of NASA in February and March, 2010 pertaining to the BP-1 simulant. The analytical results and the bulk of the text are from communications from Dr. Stoeser. The BP-1 simulant is made from Black Point Basalt Flow, San Francisco Volcanic Field, northern Arizona. There is an aggregate (road metal) quarry on the northern margin of the flow towards the west end that was used as a Desert Research and Technology Studies (Desert RATS) analog test site. Silty material from this site was also used in laboratory tests and found to have geotechnical properties similar to the LHT-2M and Chenobi regolith simulants and is being proposed as a possible simulant for geotechnical use. It currently has the designation of BP-1 (Black Point 1). Figure

Rickman, D. L.↗
DOE OSTI2023

ATCUN-like Copper Site in βB2-Crystallin Plays a Protective Role in Cataract-Associated Aggregation

Cataract is the leading cause of blindness worldwide, and it is caused by crystallin damage and aggregation. Senile cataractous lenses have relatively high levels of metals, while some metal ions can directly induce the aggregation of human γ-crystallins. Here, for this work, we evaluated the impact of divalent metal ions in the aggregation of human βB2-crystallin, one of the most abundant crystallins in the lens. Turbidity assays showed that Pb 2+ , Hg 2+ , Cu 2+ , and Zn 2+ ions induce the aggregation of βB2-crystallin. Metal-induced aggregation is partially reverted by a chelating agent, indicating the formation of metal-bridged species. Our study focused on the mechanism of copper-induced aggregation of βB2-crystallin, finding that it involves metal-bridging, disulfide-bridging, and loss of protein stability. Circular dichroism and electron paramagnetic resonance (EPR) revealed the presence of at least three Cu 2+ binding sites in βB2-crystallin, one of them with spectroscopic features typical for Cu 2+ bound to an amino-terminal copper and nickel (ATCUN) binding motif, which is found in Cu transport proteins. The ATCUN-like Cu binding site is located at the unstructured N-terminus of βB2-crystallin, and it could be modeled by a peptide with the first six residues in the protein sequence (NH 2 -ASDHQF-). Isothermal titration calorimetry indicates a nanomolar Cu 2+ binding affinity for the ATCUN-like site. An N-truncated form of βB2-crystallin is more susceptible to Cu-induced aggregation and is less thermally stable, indicating a protective role for the ATCUN-like site. EPR and X-ray absorption spectroscopy studies reveal the presence of a copper redox active site in βB2-crystallin that is associated with metal-induced aggregation and formation of disulfide-bridged oligomers. Our study demonstrates metal-induced aggregation of βB2-crystallin and the presence of putative copper binding sites in the protein. Whether the copper-transport ATCUN-like site in βB2-crystallin plays a functional/protective role or constitutes a vestige from its evolution as a lens structural protein remains to be elucidated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

High efficiency active environmental sampling of chemical traces

A method of sample collection includes collecting an analyte from a sampling surface using a rapidly curable liquid gel comprising one or more metal particles; co-aggregating the one or more metal particles from the rapidly curable liquid gel and the analyte from the sampling surface; and rapidly curing the rapidly curable liquid gel. The composition and sample preparation conditions may facilitate improved collection efficiency of analytes during environmental and forensic evidence sampling. In addition, the composition and sample preparation conditions may facilitate enhanced detection and identification of the analyte using e.g., Surface Enhanced Raman Spectrometry (SERS).

Junghans, Ann↗
NASA NTRS2017

Systems and Methods for Fabricating Objects Including Amorphous Metal Using Techniques Akin to Additive Manufacturing

Systems and methods in accordance with embodiments of the invention fabricate objects including amorphous metals using techniques akin to additive manufacturing. In one embodiment, a method of fabricating an object that includes an amorphous metal includes: applying a first layer of molten metallic alloy to a surface; cooling the first layer of molten metallic alloy such that it solidifies and thereby forms a first layer including amorphous metal; subsequently applying at least one layer of molten metallic alloy onto a layer including amorphous metal; cooling each subsequently applied layer of molten metallic alloy such that it solidifies and thereby forms a layer including amorphous metal prior to the application of any adjacent layer of molten metallic alloy; where the aggregate of the solidified layers including amorphous metal forms a desired shape in the object to be fabricated; and removing at least the first layer including amorphous metal from the surface.

Hofmann, Douglas↗
DOE OSTI2022

Influence of substrate composition on size and chemical state of ion beam synthesised Co nanoparticles – Towards fabrication of electrodes for energy devices

A one-step approach to synthesize ultrafine transition metal particles (size < 5 nm) in carbon substrates is highly desirable for fabricating electrodes for energy devices. Herein, cobalt ion implantation into amorphous carbon films (a:C) and hydrogenated amorphous carbon films (a:CH) was explored, with the aim of synthesizing ultrafine metallic cobalt nanoparticles at room temperature. Co ions of 30 keV energy were implanted into the carbon films to achieve a Co areal density of 1.0 ± 0.1 × 10 17 atoms cm -2 . Rutherford backscattering measurements revealed that hydrogenated amorphous carbon films gave a broader Co depth distribution compared to the amorphous carbon films. Further, cross-sectional TEM analysis revealed that hydrogenated carbon films suppressed metallic Co nanoparticle aggregation, leading to the creation of ultrafine Co nanoparticles (size < 5 nm). Co L-edge X-ray absorption spectroscopy measurements confirmed the formation of predominantly metallic Co nanoparticles by ion implantation. Results conclusively demonstrate that the presence of hydrogen (~ 28 at%) in the carbon matrix facilitates the synthesis of ultrafine metallic Co nanoparticles during Co ion implantation.

36 MATERIALS SCIENCE↗
NASA NTRS2001

Reflective and Electrically Conductive Surface Silvered Polyimide Films and Coatings Prepared via Unusual Single-Stage Self-Metallization Techniques

Highly reflective and/or surface conductive flexible polyimide films can be prepared by the incorporation of positive valent silver compounds into solutions of poly(amic acid)s formed from a variety of dianhydrides and diamines. Thermal curing of selected silver(I)-containing poly(amic acid)s leads to cycloimidization of the polyimide precursor with concomitant silver(I) reduction and surface aggregation of the metal yielding a reflective and/or conductive silver surface similar to that of the native metal. However, not all silver(I) precursors are effective surface metallization agents and not all poly(amic acid)s metallize with equal facility. Ligand/anion and polyimide structural effects on film metallization efficacy and on physical properties on metallized films are reviewed.

Southward, Robin E.↗
DOE OSTI2021

Origins of Clustering of Metalate–Extractant Complexes in Liquid–Liquid Extraction

Effective and energy-efficient separation of precious and rare metals is very important for a variety of advanced technologies. Liquid-liquid extraction (LLE) is a relatively less energy intensive separation technique, widely used in separation of lanthanides, actinides, and platinum group metals (PGMs). In LLE, the distribution of an ion between an aqueous phase and an organic phase is determined by enthalpic (coordination interactions) and entropic (fluid reorganization) contributions. The molecular scale details of these contributions are not well understood. Preferential extraction of an ion from the aqueous phase is usually correlated with the resulting fluid organization in the organic phase, as the longer-range organization increases with metal loading. However, it is difficult to determine the extent to which organic phase fluid organization causes, or is caused by, metal loading. In this study, we demonstrate that two systems with the same metal loading may impart very different organic phase organizations and investigate the underlying molecular scale mechanism. Small-angle X-ray scattering shows that the structure of a quaternary ammonium extractant solution in toluene is affected differently by the extraction of two metalates (octahedral PtCl 6 2- and square-planar PtCl 6 2- ), although both are completely transferred into the organic phase. The aggregates formed by the metalate-extractant complexes (approximated as reverse micelles) exhibit a more long-range order (clustering) with PtCl 6 2- compared to that with PtCl 6 2- . Vibrational sum frequency generation spectroscopy and complementary atomistic molecular dynamics simulations on model Langmuir monolayers indicate that the two metalates affect the interfacial hydration structures differently. Furthermore, the interfacial hydration is correlated with water extraction into the organic phase. Overall, these results support a strong relationship between the organic phase organizational structure and the different local hydration present within the aggregates of metalate-extractant complexes, which is independent of metalate concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Understanding the dynamic evolution of atomically dispersed Cu catalyst for CO 2 electrochemical conversion using integrated XANES analysis and mechanistic studies

Direct electrochemical conversion of CO 2 to ethanol (CH 3 CH 2 OH) offers a promising strategy to lower CO 2 emission while storing energy from renewable electricity. Our recent study reported a carbon-supported atomically dispersed Cu catalyst that achieved the highest reported selectivity for CH 3 CH 2 OH formation (91%) at a relatively low potential (-0.6 V), however, the active site structure that is responsible for such high activity and selectivity has yet to be understood. Here, in this paper, we demonstrate a computational investigation combining X-ray absorption near edge structure (XANES) simulations and a mechanistic study via density functional theory (DFT) to understand the catalyst structures of this Cu catalyst during electrocatalysis and the corresponding reaction mechanisms of the key products. An integrated computational and experimental XANES analysis depicted the dynamic evolution of the catalytic site during electrocatalysis. The as-prepared, atomically dispersed Cu catalyst aggregates and forms metallic clusters/nanoparticles under electrochemical condition, which then break down to smaller oxidized clusters after electrocatalysis. The formed Cu clusters/nanoparticles showed distinct catalytic activity and selectivity as a function of particle size based on the mechanistic investigation using DFT, which is consistent with experimental observations for catalyst samples with different Cu loadings. This comprehensive study which combines experimental and computational XANES investigation, mechanistic study via DFT calculations, and experimental performance of the catalysts, provides unprecedented dynamic and mechanistic insights into the supported atomically dispersed metal catalysts for CO 2 reduction. Such strategy and details gained can further guide discovery of novel catalyst materials for CO 2 electrochemical reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1995

Mineralogic variations in fluvial sediments contaminated by mine tailings as determined from AVIRIS data, Coeur D'Alene River Valley, Idaho

The success of imaging spectrometry in mineralogic mapping of natural terrains indicates that the technology can also be used to assess the environmental impact of human activities in certain instances. Specifically, this paper describes an investigation into the use of data from the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) for mapping the spread of, and assessing changes in, the mineralogic character of tailings from a major silver and base metal mining district. The area under investigation is the Coeur d'Alene River Valley in northern Idaho. Mining has been going on in and around the towns of Kellogg and Wallace, Idaho since the 1880's. In the Kellogg-Smelterville Flats area, west of Kellogg, mine tailings were piled alongside the South Fork of the Coeur d'Alene River. Until the construction of tailings ponds in 1968 much of these waste materials were washed directly into the South Fork. The Kellogg-Smelterville area was declared an Environmental Protection Agency (EPA) Superfund site in 1983 and remediation efforts are currently underway. Recent studies have demonstrated that sediments in the Coeur d'Alene River and in the northern part of Lake Coeur d'Alene, into which the river flows, are highly enriched in Ag, Cu, Pb, Zn, Cd, Hg, As, and Sb. These trace metals have become aggregated in iron oxide and oxyhydroxide minerals and/or mineraloids. Reflectance spectra of iron-rich tailing materials are shown. Also shown are spectra of hematite and goethite. The broad bandwidth and long band center (near 1 micron) of the Fe(3+) crystal-field band of the iron-rich sediment samples combined with the lack of features on the Fe(3+) -O(2-) charge transfer absorption edge indicates that the ferric oxide and/or oxyhydroxide in these sediments is poorly crystalline to amorphous in character. Similar features are seen in poorly crystalline basaltic weathering products (e.g., palagonites). The problem of mapping and analyzing the downriver occurrences of iron rich tailings in the Coeur d'Alene (CDA) River Valley using remotely sensed data is complicated by the full vegetation cover present in the area. Because exposures of rock and soil were sparse, the data processing techniques used in this study were sensitive to detecting materials at subpixel scales. The methods used included spectral mixture analysis and a constrained energy minimization technique.

Farrand, W. H.↗
DOE OSTI2020

Self-regenerative noble metal catalysts supported on high-entropy oxides

Discovery of anti-sintering noble metal catalysts is challenging, as supported noble metal species tend to aggregate at high temperatures, leading to severely deteriorated catalytic performances. Here we show that 1 wt% of noble metal species including Au, Pd and Ru can be incorporated into high-entropy oxides (HEOs) through entropy stabilization at 900 °C in air. A reversible temperature-dependent dissolution–exsolution process is observed for Au-HEO. Further correlation with distinct CO oxidation capabilities demonstrates the potential to utilize the entropy effect to access self-regenerative catalysts for catalytic reactions.

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

Strong Fermi-level pinning at metal contacts to halide perovskites

The performance of halide perovskite-based electronic and optoelectronic devices is often related to interfacial charge transport. To shed light on the underlying physical and chemical properties of CH 3 NH 3 PbI 3 (MAPbI 3 ) in direct contact with common electrodes Al, Ti, Cr, Ag, and Au, the evolution of interfacial properties and Fermi level pinning is systematically studied. Given a unique experimental facility, pristine interfaces without any exposure to ambient air were prepared. We observe aggregation of substantial amounts of metallic lead (Pb 0 ) at the metal/MAPbI 3 interface, resulting from the interfacial reaction between the deposited metal and iodine ions from MAPbI 3 . It is found that the Schottky barrier height at the metal/MAPbI 3 interface is independent of the metal work function due to strong Fermi level pinning, possibly due to the metallic Pb 0 aggregates, which act as interfacial trap sites. The charge neutrality level of MAPbI 3 is consistent with the energy level of Pb 0 -related defects, indicating that Pb 0 interfacial trap states can be nonradiative recombination sites. Here this work underlines that control of chemical bonding at interfaces is a key factor for designing future halide perovskite-based devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Tuning the Product Distribution of Acetylene Dimerization through Bimetallic Metal–Organic Framework-Supported Nanoporous Systems

Metal-organic frameworks (MOFs) are receiving increased attention due to their well-defined structures that allow the determination of structure-property relationships. MOFs have been used as heterogeneous catalyst supports in a variety of fashions including for confinement of metal nanoparticles, which have demonstrated enhanced resistance to aggregation, a common issue in amorphous metal oxide supports. Cu and In catalysts were installed in the Zr-based MOF NU-907, being confined within the nanoporous structure. The Cu catalyst is known to, under various conditions, either selectively hydrogenate acetylene to ethylene or generate C4 products such as butenes and 1,3-butadiene, an important feedstock for rubber and adhesives. The addition of indium to the Cu catalyst is intended to serve as a promoter to produce C4 products by decreasing the surface coverage of copper while still allowing for C-C coupling. When employed for acetylene dimerization, InCu-NU-907 shows slightly decreased C4 production overall but enhanced 1,3-butadiene production compared to all other catalysts studied herein. These catalysts were thoroughly characterized by a range of techniques to confirm structural integrity and porosity and probe the nature of the interactions of indium with the Cu nanoparticle active site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Formation of iron metal and grain coagulation in the solar nebula

The interstellar grain population in the giant molecular cloud from which the sun formed contained little or no iron metal. However, thermal processing of individual interstellar silicates in the solar nebula is likely to result in the formation of a population of very small iron metal grains. If such grains are exposed to even transient magnetic fields, each will become a tiny dipole magnet capable of interacting with other such dipoles over spatial scale orders of magnitude larger than the radii of individual grains. Such interactions will greatly increase the coagulation cross-section for this grain population. Furthermore, the magnetic attraction between two iron dipoles will significantly increase both the collisional sticking coefficient and the strength of the interparticle binding energy for iron aggregates. Formation of iron metal may therefore be a key step in the aggregation of planetesimals in a protoplanetary nebula. Such aggregates may have already been observed in protoplanetary systems. The enhancement in the effective interaction distance between two magnetic dipoles is directly proportional to the strength of the magnetic dipoles and inversely proportional to the relative velocity. It is less sensitive to the reduced mass of the interacting particles (alpha M(exp -1/2)) and almost insensitive to the initial number density of magnetic dipoles (alpha n(sub o)(exp 1/6)). We are in the process of measuring the degree of coagulation in our condensation flow apparatus as a function of applied magnetic field and correlating these results by means of magnetic remanance acquisition measurements on our iron grains with the strength of the magnetic field to which the grains are exposed. Results of our magnetic remanance acquisition measurements and the magnetic-induced coagulation study will be presented as well as an estimate of the importance of such processes near the nebular midplane.

Nuth, Joseph A., III↗
DOE OSTI2021

Efficient diffusion of superdense lithium via atomic channels for dendrite-free lithium–metal batteries

The non-uniform aggregation of fast-diffused Li on an anode surface would aggravate its tip-effect-induced nucleation/growth, leading to the notorious dendrite growth in Li metal batteries (LMBs). Tuning the Li diffusion on the anode surface has been regarded previously as a mainstream method to induce its uniform deposition, while the diffusion of Li in the anode bulk is usually ignored. In this study, conceptually different from the classic surface modification, we propose a molecular tunnelling strategy to construct atomic channels in graphite bulk, which enables the fast diffusion of superdense Li. Density functional theory calculations and ab initio molecular dynamics simulations prove that the bulk diffusion through atomic channels could become a new and dominating path. Its reversible and efficient diffusion has been further visualized by in situ transmission electron microscopy. As a result, when coupled with high-loading LiFePO 4 cathodes (20 mg cm –2 ), a high areal capacity and 100% capacity retention are achieved over 370 cycles. Through this work a new strategy is developed based on the bulk-diffusion of superdense Li for dendrite-free LMBs, which can be pervasive in other high-performance energy storage systems.

25 ENERGY STORAGE↗