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At least 1,297 records · Page 72
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Bulk‐Boundary Correspondence of Semimetal Ru 3 Sn 7 and Topological Surface States on Chemically Realistic Terminations

Ru 3 Sn 7 is experimentally demonstrated as an efficient catalyst, with potential utilization of topological surface states for hydrogen evolution reaction. Despite its promising catalytic performance, the topological nature of Ru 3 Sn 7 remains uncertain. Particularly, the bulk-boundary correspondence has not yet been established, hence hindering a rigorous justification of its topologically-protected surface states. In this work, the bulk topology of Ru 3 Sn 7 is detailed using first-principles calculations and the topological quantum chemistry formalism. Ru3Sn7 turns out to be an enforced semimetal possessing symmetry-protected crossings within a set of bands near the Fermi level, which are enforced and prescribed by the violations of symmetry-prescribed compatibility relations. Moreover, the surface states and the associated origin from the same set of entangled bands are identified, thereby establishing the bulk-boundary correspondence. To evaluate the effects of chemical modifications, the response of topological surface states to various surface terminations, stoichiometry, and oxidation is examined. The surface structures are globally optimized, and the phase diagrams for various experimental conditions are built. It is shown that, due to changes in the local chemical environment, the original surface states are significantly altered. Modified surface bands can be observed near the Fermi level on surface terminations that preserve the C 4v symmetry.

36 MATERIALS SCIENCE↗
NASA NTRS1984

The breakdown of fibrous structures in directionally grown monotectic alloys

The breakdown of aligned steady-state metallic growth products from the reversible monotectic reaction liquid (L1) yields solid (S1) + liquid (L2) is analyzed experimentally. Consideration is given to the temperatures of the monotectic horizontal, to upper consolute temperature of the liquid miscibility gap which through the relative liquid and solid surface energies determines whether the reaction is capable of steady-state growth; the growth characteristics of the solid (faceted or nonfaceted); and the relative whetting characteristics of parent and product phases with the glass cell walls. Schematic drawings and composite photographs are provided which illustrate the development of steady-state growth and the related changes in phase sickness of the reaction product.

Grugel, R. N.↗
DOE OSTI2026

Surface Charge Predicts the Presence of Cation Effects in Electrocatalysis

The identity of electrolyte cations has an important influence on the rates of many electrocatalytic reactions, but these effects are not always observed. Recently, we found that the surface charge of the catalyst, quantified by the potential of zero total charge (PZTC), is a useful heuristic for predicting when cation effects will be observed for the oxygen reduction reaction (ORR). Here, we demonstrate that this descriptor allows us to rationalize the observation or absence of cation effects across a range of conditions, reactions (the hydrogen evolution reaction, the ORR, methanol oxidation, ethylene glycol oxidation, glycerol oxidation, and glucose reduction) and metal surfaces (Pt, Pd, Ag, and Au). These results suggest that when the reaction’s operating potential is negative of the metal’s PZTC, electrolyte cations accumulate at the catalyst surface and influence reaction rates. As a result, when reactions occur positive of the PZTC, cation effects are not observed.

Cations↗
DOE OSTI2024

Interpretable Machine Learning Models for Practical Antimonate Electrocatalyst Performance

Computationally predicting the performance of catalysts under reaction conditions is a challenging task due to the complexity of catalytic surfaces and their evolution in situ, different reaction paths, and the presence of solid-liquid interfaces in the case of electrochemistry. We demonstrate here how relatively simple machine learning models can be found that enable prediction of experimentally observed onset potentials. Inputs to our model are comprised of data from the oxygen reduction reaction on non-precious transition-metal antimony oxide nanoparticulate catalysts with a combination of experimental conditions and computationally affordable bulk atomic and electronic structural descriptors from density functional theory simulations. From human-interpretable genetic programming models, we identify key experimental descriptors and key supplemental bulk electronic and atomic structural descriptors that govern trends in onset potentials for these oxides and deduce how these descriptors should be tuned to increase onset potentials. Here, we finally validate these machine learning predictions by experimentally confirming that scandium as a dopant in nickel antimony oxide leads to a desired onset potential increase. Macroscopic experimental factors are found to be crucially important descriptors to be considered for models of catalytic performance, highlighting the important role machine learning can play here even in the presence of small datasets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

Texture etching of (100) silicon for solar cells

A chemical means of creating the proper kind of light collection texture on (100) silicon slices is discussed. Texturing of (100) silicon surfaces in sodium or potassium hydroxides occurs by the growth of a reaction product in a random array of surface sites, which leads to pyramids remaining at the sites after other parts of the surface dissolve away. A new texture-promoting influence, a proximity effect, was discovered in this work. An attempt was made to quantify the various promotional effects. The purpose of the present paper is to: (1) explain in detail the attempt at understanding and quantifying texturing; (2) give an experimental description with observations on the proximity effect and the effect of additions of water glass that were discovered during this work; and (3) show that the precipitate or growth models account for almost all of the known promotional effects.

Dyer, L. D.↗
NASA NTRS1973

Volatile element chemistry of selected lunar, meteoritic, and terrestrial samples

Using vacuum pyrolysis and high resolution mass spectrometry, a study is made of the gas release patterns of representative lunar samples, meteorites, terrestrial samples, and synthetic samples doped with various sources of carbon and nitrogen. The pyrolytic gas evolution patterns were intercorrelated, allowing an assessment of the possible sources of the volatilizable material in the lunar samples to be made. Lightly surface adsorbed species and more strongly chemisorbed species are released from ambient to 300 C and from 300 to 500 C, respectively. The low-temperature volatiles (less than 500 C) derived from various chondrites correlate well with the gas evolution patterns of volatile-rich samples, as for example 74220 and 61221. Solar wind entrapped species and molecules derived from reactions probably in the grain surfaces are evolved from about 500 to 700 C, respectively. Solar wind implanted C, N, and S species are generated from 750 to 1150 C, probably by reaction with the mineral matrix during the annealing process. Possible indigenous and/or refractory carbide, nitride, and sulfide C, N, and S are released in the region from 1200 C to fusion.

Simoneit, B. R.↗
DOE OSTI2022

Time-resolved 3D characterisation of early-age microstructural development of Portland cement

Abstract Time-resolved in-situ synchrotron X-ray microtomography reveals new levels of detail about the chemical and physical processes that take place as Portland cement hardens. The conversion of a fluid paste into a hardened product can be monitored on a sub-minute time-scale, and with sample movement/settlement corrections applied to enable individual particles to be tracked as they react, hydrate, and become interconnected into a single strong monolith. The growth of the strength-giving hydrate phases surrounding cement grains, and of the fluid-filled pore network that surrounds them, is able to be directly viewed at the level of individual cement particles through the application of this tracking protocol. When cement is brought into contact with water, a layer which differs in density from the bulk of the cement grains becomes observable on the grain surfaces during the induction period (during which time the heat evolution from the paste is relatively low). As hydration continues, reaction products grow both from particle surfaces into the initially fluid-filled region, and also into the space originally occupied by the cement particles, forming a density gradient within the microstructure. As the reaction accelerates and larger volumes of solid phases precipitate, the newly-formed solid structure percolates via interconnection of agglomerated low-density outer hydrates, which then densify as hydration continues. This eventually leads to solidification of the structure into a hardened porous matrix. Graphical abstract

36 MATERIALS SCIENCE↗
NASA NTRS1973

Wear: Corrosion and erosion

The various forms of corrosion are discussed and the role of localized electrochemical reactions in the wear of sliding surfaces are considered. It is stated that there is evidence that fretting corrosion, stress corrosion cracking, corrosion fatigue, and erosion corrosion have as a common basis the localized electrochemical reactions caused by a combination of the induced homogeneity of the surfaces and the corrosive environment. Several processes leading to erosive wear are discussed.

Rowe, C. N.↗
DOE OSTI2024

Light-Induced Transformation of Virus-Like Particles on TiO 2

Titanium dioxide (TiO 2 ) shows significant potential as a self-cleaning material to inactivate severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and prevent virus transmission. This study provides insights into the impact of UV-A light on the photocatalytic inactivation of adsorbed SARS-CoV-2 virus-like particles (VLPs) on a TiO 2 surface at the molecular and atomic levels. X-ray photoelectron spectroscopy, combined with density functional theory calculations, reveals that spike proteins can adsorb on TiO 2 predominantly via their amine and amide functional groups in their amino acids blocks. We employ atomic force microscopy and grazing-incidence small-angle X-ray scattering (GISAXS) to investigate the molecular-scale morphological changes during the inactivation of VLPs on TiO 2 under light irradiation. Notably, in situ measurements reveal photoinduced morphological changes of VLPs, resulting in increased particle diameters. These results suggest that the denaturation of structural proteins induced by UV irradiation and oxidation of the virus structure through photocatalytic reactions can take place on the TiO 2 surface. The in situ GISAXS measurements under an N 2 atmosphere reveal that the virus morphology remains intact under UV light. This provides evidence that the presence of both oxygen and UV light is necessary to initiate photocatalytic reactions on the surface and subsequently inactivate the adsorbed viruses. The chemical insights into the virus inactivation process obtained in this study contribute significantly to the development of solid materials for the inactivation of enveloped viruses.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Representing Soil Microbial Dynamics and Organo‐Mineral Interactions in the E3SM Land Model (ELM‐ReSOM)

Explicit representation of soil microbial processes and interactions with biotic and abiotic processes in Earth System Models (ESMs) remains limited, despite their importance in biogeochemical cycles. To address this gap, which hinders prediction of global biogeochemial cycling and responses to atmospheric conditions, we integrated a microbe- and mineral-surface-explicit model, the Reaction-network-based model of soil organic matter and Microbes (ReSOM), into the Energy Exascale ESM (E3SM) land model (ELM). Here, we describe ELM-ReSOM and show a case study at a conifer forest in California. ELM-ReSOM accurately simulated surface CO 2 fluxes and SOM stocks, demonstrating improved representations of microbial and mineral interactions compared to the default ELM. We examined ELM-ReSOM sensitivity to microbial traits, enzyme properties, and organo-mineral interactions. Microbial traits such as the maximum mortality rate, transporter-density scaling factor, and maximum monomer assimilation rate were strong controllers of heterotrophic respiration, while these microbial traits and enzyme-related properties collectively influenced SOM stocks. Mineral surfaces primarily affected SOM stocks by adsorbing enzymes, thereby limiting depolymerization. Synergies among processes led to stronger impacts of parameters when evaluated together versus separately (i.e., most parameters had greater indirect than direct effects). For example, due to interactions of microbial necromass with mineral surface adsorption, the indirect effect of the maximum microbial mortality rate was 33% larger than its direct effect on SOM stock. Thus, microbial and enzyme dynamics and their interactions with mineral surfaces play critical roles in SOM cycling. Tackling the challenges of microbe-explicit models will advance understanding and modeling of SOM dynamics.

Tao, Jing [Lawrence Berkeley National Laboratory (↗
NASA NTRS1974

Interaction of gases with lunar materials

Quantitative efforts to assess the surface properties of lunar fines, particularly water induced porosity are discussed. Data show that: (1) changes induced in lunar fines are not visible in high energy electron micrographs, (2) scanning micrographs show no change in particle size distribution as a result of reaction with water, (3) water induced changes are internal to the particles themselves, (4) normal laboratory atmosphere blocks alteration reaction with water, and (5) surface properties of mature lunar soils appear to be almost independent of chemical composition and mineralogy, but there are some variations in their reactivity toward water.

Holmes, H. F.↗
DOE OSTI2020

Mechanism of the Accelerated Water Formation Reaction under Interfacial Confinement

Subnanoscale spaces at the interface between weakly coupled thin films and their metal supports offer exciting opportunities for studying chemical reactions under confinement. Here, we investigated the kinetics of water formation (from hydrogen and chemisorbed oxygen) in the confined space at the interface between bilayer (BL) silica and a Ru(0001) support, compared to the reaction on the bare Ru(0001) surface. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) experiments were carried out at different temperatures at elevated pressures of H 2 to follow the reaction kinetics. The apparent activation energy at the BL-silica/Ru(0001) interface was found to be 0.38 eV lower than that on bare Ru(0001), consistent with a recent report by Prieto et al. (Angew. Chem., Int. Ed.2018, 57(28), 8749–8753) carried out at lower H 2 pressures using low-energy electron microscopy. Density functional theory calculations revealed that the rate-limiting step in the direct hydrogenation pathway on the Ru(0001) surface is the first hydrogen addition step (*H + *O ↔ *OH). The confinement at the BL-silica/Ru(0001) interface only marginally affects the energy barrier of the first hydrogen addition. Instead, it activates an alternative disproportionation reaction pathway (*H 2 O + *O ↔ 2*OH). On the bare Ru(0001) surface, the disproportionation pathway can only occur at cryogenic temperatures or under high water vapor pressures. However, the presence of the BL-silica increases the desorption barrier for water molecules at the interface. The increased residence time allows trapped water molecules to react with chemisorbed oxygen to produce two *OH per H 2 O with an activation energy 0.25 eV lower than that of the first hydrogen addition step. Finally, this work reveals the origin of the observed accelerated water formation reaction at the BL-silica/Ru(0001) interface in the low-temperature regime (T < 350 K) and points to a route to engineer chemical reaction pathways by leveraging subnanoscale confined spaces at metal–oxide interfaces.

36 MATERIALS SCIENCE↗
NASA NTRS2001

Contact Angles and Surface Tension of Germanium-Silicon Melts

Precise knowledge of material parameters is more and more important for improving crystal growth processes. Two important parameters are the contact (wetting) angle and the surface tension, determining meniscus shapes and surface-tension driven flows in a variety of methods (Czochralski, EFG, floating-zone, detached Bridgman growth). The sessile drop technique allows the measurement of both parameters simultaneously and has been used to measure the contact angles and the surface tension of Ge(1-x)Si(x) (0 less than or equal to x less than or equal to 1.3) alloys on various substrate materials. Fused quartz, Sapphire, glassy carbon, graphite, SiC, carbon-based aerogel, pyrolytic boron nitride (pBN), AIN, Si3N4, and polycrystalline CVD diamond were used as substrate materials. In addition, the effect of different cleaning procedures and surface treatments on the wetting behavior were investigated. Measurements were performed both under dynamic vacuum and gas atmospheres (argon or forming gas), with temperatures up to 1100 C. In some experiments, the sample was processed for longer times, up to a week, to investigate any changes of the contact angle and/or surface tension due to slow reactions with the substrate. For pure Ge, stable contact angles were found for carbon-based substrates and for pBN, for Ge(1-x)Si(x) only for pBN. The highest wetting angles were found for pBN substrates with angles around 170deg. For the surface tension of Ge, the most reliable values resulted in gamma(T) = (591- 0.077 (T-T(sub m)) 10(exp -3)N/m. The temperature dependence of the surface tension showed similar values for Ge(1-x)Si(x), around -0.08 x 10(exp -3)N/m K, and a compositional dependence of 2.2 x 10(exp -3)N/m at%Si.

Croell, A.↗
DOE OSTI2025

A Combined Crossed Molecular Beam and Theoretical Investigation of the Elementary Reaction of Tricarbon (C 3 (X 1 Σ g + )) with Diacetylene (C 4 H 2 (X 1 Σ g + )): Gas Phase Formation of the Heptatriynylidyne Radical ( l -C 7 H(X 2 Π))

An elucidation of the underlying formation pathways to acyclic hydrocarbons such as polyynes (C n H 2 ), cumulenes (C n H 2 ), and linear resonantly stabilized linear radicals (l-C n H) is indispensable to understand the hydrocarbon chemistry in extreme low and high temperature environments. In this study, we exploited the crossed molecular beam technique to investigate the reaction of tricarbon C 3 (X 1 Σ g + ) with diacetylene (butadiyne; HCCCCH; X 1 Σ g + ) at a collision energy of 47 ± 1 kJ mol ⁻1 . The experimental data were merged with ab initio calculations of the singlet C 7 H 2 potential energy surface (PES) revealing that the reaction is initiated via the formation of an initial van der Waals reactant complex in the entrance channel. Subsequent rearrangements lead to various carbene-type and cyclic intermediates via ring-opening, ring-closure, and hydrogen migration processes eventually forming acyclic C 7 H 2 isomers prior to their barrierless unimolecular decomposition to the most stable linear isomer, heptatriynylidyne (C 7 H, X 2 Π) in an overall endoergic reaction (+57 kJ mol ⁻1 ). The reaction exhibits strong similarities to the tricarbon – acetylene (C 3 – C 2 H 2 ). Furthermore, the significant energy threshold suggests that the tricarbon reaction with (poly)acetylenes forming resonantly stabilized linear radicals are open in high-temperature environments such as combustion flames and circumstellar envelopes of carbon stars and planetary nebulae as their descendants; however, these reactions are closed in low-temperature environments as in cold molecular clouds and hydrocarbon-rich atmospheres of planets and their moons such as in Titan.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1979

Analysis and interpretation of Viking labeled release experimental results

The Viking Labeled Release (LR) life detection experiment on the surface of Mars produced data consistent with a biological interpretation. In considering the plausibility of this interpretation, terrestrial life forms were identified which could serve as models for Martian microbial life. Prominent among these models are lichens which are known to survive for years in a state of cryptobiosis, to grow in hostile polar environments, to exist on atmospheric nitrogen as sole nitrogen source, and to survive without liquid water by absorbing water directly from the atmosphere. Another model is derived from the endolithic bacteria found in the dry Antarctic valleys; preliminary experiments conducted with samples of these bacteria indicate that they produce positive LR responses approximating the Mars results. However, because of the hositility of the Martian environment to life, and the failure to find organics on the surface of Mars, a number of nonbiological explanations were advanced to account for the Viking LR data. A reaction of the LR nutrient with putative surface hydrogen peroxide is the leading candidate. Other possibilities raised include reactions caused by or with ultraviolet irradiation, gamma-Fe2O3, metalloperoxides or superoxides.

Levin, G. V.↗
DOE OSTI2021

Proton-Coupled Defects Impact O–H Bond Dissociation Free Energies on Metal Oxide Surfaces

Proton-coupled electron transfer (PCET) reactions on metal oxides require coupling between proton transfer at the solid-liquid interface and electron transfer involving defects at or near the band edge. Herein, hybrid functional periodic density functional theory is used to elucidate the impact of proton-coupled defects on the bond dissociation free energies (BDFEs) of O-H bonds on anatase TiO 2 surfaces. These O-H BDFEs are directly related to interfacial PCET thermochemistry. Comparison between geometrically similar O-H bonds associated with different defect types, namely conduction d-band electrons or valence p-band holes, reveals that the BDFEs differ by ~81 kcal/mol (3.50 eV), comparable to the wide TiO 2 band gap. These differences are shown to be determined primarily by differences in electron transfer driving forces, which are analyzed by using band energies and inner-sphere reorganization energies within a Marcus theory framework. Furthermore, these fundamental insights about the impact of proton-coupled defects on PCET thermochemistry at semiconductor surfaces have broad implications for electrocatalysis.

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

Nonequilibrium Solvent Effects during Photodissociation in Liquids: Dynamical Energy Surfaces, Caging and Chemical Identity

In the gas phase, potential energy surfaces can be used to provide insight into the details of photochemical reaction dynamics. In solution, however, it is unclear what potential energy surfaces, if any, can be used to describe even simple chemical reactions such as the photodissociation of a diatomic solute. In this paper, we use mixed quantum/classical (MQC) molecular dynamics (MD) to study the photodissociation of $Na$ $^+_2$ in both liquid Ar and liquid tetrahydrofuran (THF). We examine both the gas-phase potential surfaces and potentials of mean force (PMF), which assume that the solvent remains at equilibrium with the solute throughout the photodissociation process and show that neither resemble a nonequilibrium dynamical energy surface that is generated by taking the time integral of work. For the photodissociation of $Na$ $^+_2$ in liquid Ar, the dynamical energy surface shows clear signatures of solvent caging, and the degree of caging is directly related to the mass of the solvent atoms. For $Na$ $^+_2$ in liquid THF, local specific interactions between the solute and solvent lead to changes in chemical identity that create a kinetic trap that effectively prevents the molecule from dissociating. Here, the results show that nonequilibrium effects play an important role even in simple solution-phase reactions, requiring the use of dynamical energy surface to understand such chemical events.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

Atomic Oxygen Effects on Materials

One objective of this investigation has been to offer recommendations on the selection of metal samples to be exposed to ambient atomic oxygen on the STS-8 flight presently scheduled for August 30, 1983. (These samples constitute a small subgroup of a very large group of test specimens prepared by A. Whitaker and other members of the Physical Sciences Branch for this mission.) The metals selected and prepared for STS-8 are silver, lead, copper, nickel, tungsten, molybdenum, magnesium, platinum, and alloys of FeCrAl and NiCr. Literature data are reviewed concerning the oxidation properties of these materials with a view towards understanding which oxides might be formed, the state of the oxide (surface film or volatile form), and the reaction rate. In addition, various techniques for characterizing the parent metals and the surface oxides are reviewed.

Fromhold, A. T.↗