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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Characterisation of nano-assemblies inside mesopores using neutron scattering

Adsorption of molecular and nanoscale matter in mesoporous materials is important in filtration and chromatography as well as membrane processes. However, the morphology and distribution of self-assembled structures of adsorbate formed within nanoconfined environments is largely unknown. Small Angle Neutron Scattering (SANS) with porous matrix matching the neutron scattering length density of the solvent has the potential to provide detailed information on the self-assemblies formed in pore spaces. However, analysis of such SANS profiles remains a challenge. In this study, we extend the SANS analysis method previously developed by Findenegg and co-workers to include interparticle correlations, providing a qualitative characterisation of the adsorption state of surfactants and nanoparticles in the cylindrical pores of silica nanomaterials. We find that the pore filling fraction and the self-assembled state of the adsorbate governs the scattering profile. We apply the model to two materials namely, triethyleneglycol monohexyl ether (C 6 E 3 ) surfactant and gold nanoparticles adsorbed in SBA-15 mesoporous silica. In contrast to the C 6 E 3 system, Bragg scattering dominates the diffuse scattering in gold nanoparticle system, which we attribute to the immobile internal structure of the nanoparticles. In conclusion, this new SANS analysis method has potential to elucidate structures of soft matter nanoassemblies inside mesopores.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1979

Bonding of nitrogen atoms on Cu/001/ surfaces - A cluster approach

A study of the chemisorption of nitrogen atoms on a copper surface has been performed, based on an analysis of the electronic structure of the Cu5N cluster obtained from self-consistent-field X-alpha scattered-wave calculations. Calculations show that the chemisorption of nitrogen on Cu(001) surfaces induces peaks below and above the Cu d-band region in the total density of states curve. The bonding orbitals formed between the N 2p and the Cu valence orbitals are generally found near the bottom of the Cu d-band region, while the antibonding orbitals formed between the N 2p and Cu orbitals are found to lie above the Cu d-band region. These hybridized orbitals involving the N 2p orbital gave a satisfactory interpretation of the adsorbate-induced structure reported in N/Cu(001) ultraviolet photoemission studies.

Yu, H. L.↗
DOE OSTI2022

Temperature Effects in Flexible Adsorption Processes for Amorphous Microporous Polymers

A collection of atomistic molecular simulations is reported that illustrate the impact of adsorption temperature on species uptake and adsorbate-induced structural rearrangement for amorphous polymers of intrinsic microporosity. Temperature-sensitive structural rearrangement is evaluated by contrasting two methods: standard grand canonical Monte Carlo simulations using a rigid framework approximation and a combined Monte Carlo/molecular dynamics approach that fully incorporates framework flexibility. We report single-component gas phase adsorption isotherms for CH 4 , C 2 H 4 , C 2 H 6 , C 3 H 6 , C 3 H 8 , and CO 2 across a temperature range of 250–400 K for models of an archetypal polymer of intrinsic microporosity, PIM-1. A quadratic model is presented that captures two main mechanisms of temperature-dependent adsorption-induced deformation of PIM-1 up to a relative swelling of 1.15: thermal expansion and an increased propensity to swell as a function of species uptake. Two case studies are reported that highlight the critical role of operating temperature in industrial storage and separation applications. The first study focuses on methane storage and delivery applications using a pressure–temperature swing adsorption application (PTSA). We demonstrate that larger working capacities are accompanied by increased volumetric strain between adsorption–desorption steps. The second case study considers PIM-1 as an adsorbent to separate an exemplar ternary syngas mixture at operating temperatures ranging 300–550 K. Here, a temperature threshold of ~400 K is identified, beyond which adsorption-induced PIM-1 swelling is negligible and the solubility selectivity-loading curve transitions to exhibiting a nearly linear relationship.

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

Observation of adsorbate-induced surface states by elastic electron tunneling spectroscopy

Electronic structure induced by adsorbates at the interface of Al/AlOx/Au tunnel junctions has been observed by elastic electron tunneling spectroscopy. Strong structures appearing in the tunneling spectra above approximately 1 eV after exposure to I, Hg, Bi, and organohalides, have been interpreted in terms of adsorbate-induced surface states. The spectroscopic capabilities of elastic electron tunneling spectroscopy may be useful in the area of chemical detection. In the broader sense, the observation of adsorbate-induced unoccupied electronic states below the vacuum energy, makes elastic electron tunneling spectroscopy a potentially useful technique for the study of surfaces.

Leduc, H. G.↗
DOE OSTI2023

Insights into Acetic Acid Binding and Ketene Formation on Anatase TiO 2 (101)

Understanding the adsorption and reactivity of carboxylic acids on oxide surfaces is of great interest in catalysis for biomass upgrading via ketonization, a carbon–carbon coupling reaction. Herein, we investigate the adsorption and reaction of acetic acid on anatase TiO 2 (101) using scanning tunneling microscopy, infrared spectroscopy, temperature programmed reaction, and density functional theory calculations. We demonstrate the adsorption of acetic acid can form two intermediates: (1) dissociated, bidentate acetate with an associated bridging hydroxyl, and (2) molecular, monodentate acetic acid. The coexistence of ordered phases with increasing monolayer (ML) saturation coverages consisting of (1) pure acetate (0.5 ML), (2) mixed acetate/acetic acid (0.67 ML), (3) mixed acetate/acetic acid (1.0 ML) and (4) pure acetic acid demonstrates similar energetics for both acetate and acetic acid species. Under ultra-high vacuum conditions, the presence of both monodentate acetic acid and bidentate acetate was observed below room temperature, while solely bidentate acetate was observed up to 575 K. The deprotonation of acetic acid produces water at 280 K, while the thermal decomposition of bidentate acetate produces ketene and acetic acid at 645 K. In conclusion, this model study provides detailed insight into the stability and reactivity of carboxylic acid surface-bound intermediates, which could participate during ketonization reactions for biomass upgrading.

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

Adsorption of Non-Ionic Surfactant and Monoclonal Antibody on Siliconized Surface Studied by Neutron Reflectometry

The adsorption of monoclonal antibodies (mAbs) on hydrophobic surfaces is known to cause protein aggregation and degradation. Therefore, surfactants, such as Poloxamer 188, are widely used in therapeutic formulations to stabilize mAbs and protect mAbs from interacting with liquid-solid interfaces. Here, the adsorption of Poloxamer 188, one mAb and their competitive adsorption on a model hydrophobic siliconized surface is investigated with neutron scattering coupled with contrast variation to determine the molecular structure of adsorbed layers for each case. Small angle neutron scattering measurements of the affinity of Poloxamer 188 to this mAb indicate that there is negligible binding at these solution conditions. Neutron reflectometry measurements of the mAb show irreversible adsorption on the siliconized surface, which cannot be washed off with neat buffer. Poloxamer 188 can be adsorbed on the surface already occupied by mAb, which enables partial removal of some adsorbed mAb by washing with buffer. The adsorption of the surfactant introduces significant conformational changes for mAb molecules that remain on the surface. In contrast, if the siliconized surface is first saturated with the surfactant, no adsorption of mAb is observed. Competitive adsorption of mAb and Poloxamer 188 from solution leads to a surface dominantly occupied with surfactant molecules, whereas only a minor amount of mAb absorbs. These findings clearly indicate that Poloxamer 188 can protect against mAb adsorption as well as modify the adsorbed conformation of previously adsorbed mAb.

36 MATERIALS SCIENCE↗
DOE OSTI2021

First-Principles Grand-Canonical Simulations of Water Adsorption in Proton-Exchanged Zeolites

Water appears by design or as impurities in many important reactive systems. For those catalyzed by porous solid acids, such as widely used zeolites, experimentally quantifying the amount or elucidating the structure of adsorbed water clusters at reaction conditions is challenging, while computational studies (e.g., first-principles molecular dynamics simulations) often need to assume the loading to examine solvation effects. Furthermore, we perform first-principles grand-canonical simulations to predict water adsorption to H-ZSM-5 zeolites under specified experimental conditions. Presampling with inexpensive force fields and a pool-based parallelization algorithm are used to improve simulation efficiency, while molecular dynamics is used to sample configurations involving hydronium species. We observe that H + exchange dramatically increases the hydrophilicity of zeolite MFI and an appreciable amount of water is present at very low relative humidities. At all conditions examined, the zeolitic protons are found to dissociate readily from the surface basic sites and become mobile by participating in the hydrogen-bonded chains of adsorbed water molecules.

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

Surface chemistry-mediated modulation of adsorbed albumin folding state specifies nanocarrier clearance by distinct macrophage subsets

Controlling nanocarrier interactions with the immune system requires a thorough understanding of the surface properties that modulate protein adsorption in biological fluids, since the resulting protein corona redefines cellular interactions with nanocarrier surfaces. Albumin is initially one of the dominant proteins to adsorb to nanocarrier surfaces, a process that is considered benign or beneficial by minimizing opsonization or inflammation. Here, we demonstrate the surface chemistry of a model nanocarrier can be engineered to stabilize or denature the three-dimensional conformation of adsorbed albumin, which respectively promotes evasion or non-specific clearance in vivo. Interestingly, certain common chemistries that have long been considered to convey stealth properties denature albumin to promote nanocarrier recognition by macrophage class A1 scavenger receptors, providing a means for their eventual removal from systemic circulation. We establish that the surface chemistry of nanocarriers can be specified to modulate adsorbed albumin structure and thereby tune clearance by macrophage scavenger receptors.

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

Molecular dynamics study on the interfacial properties of mixtures of monomers of polyvinylpyrrolidone (PVP)-based battery binders on graphene and graphite surfaces

This study investigates the behavior of two different mixtures of monomers of polyvinylpyrrolidone (PVP)-based battery binders, polyvinylpyrrolidone:polyvinylidene difluoride (PVP:PVDF) and polyvinylpyrrolidone:polyacrylic acid (PVP:PAA), at graphene and graphite interfaces using classical molecular dynamics simulations. The aim is to identify the best performing monomer binder blend and carbon-based material for the design of battery-optimized energy devices. The PVP:PAA monomer binder blend and graphite are found to have the best interaction energies, densification upon adsorption, and more ordered structure. The adsorption of both monomer binder blends is strongly guided by the higher affinity of PVP and PAA monomeric molecules for the surfaces compared to PVDF. The structure of adsorbed layers of PVP:PVDF monomer binder blend on graphene and graphite develops more quickly than PVP:PAA, indicating faster kinetics. This study complements a previous density functional theory study recently reported by our group and contributes to a better understanding of the nanoscopic features of relevant interfacial regions involving mixtures of monomers of PVP-based battery binders and different carbon-based materials. In conclusion, the effect of a blend of commonly used monomer binders on carbon-based materials is essential for obtaining tightly bound anode and cathode active materials in lithium-ion batteries, which is crucial for designing battery-optimized energy devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2016

Multispectral VNIR Observations by the Opportunity Rover Pancam of Multiple Episodes of Aqueous Alteration in Marathon Valley, Endeavour Crater, Mars

Since early 2015, the Mars Exploration Rover Opportunity has been exploring the break in the rim of Endeavour Crater dubbed Marathon Valley by the rover team. Marathon Valley was identified by orbital hyperspectral data from the MRO CRISM as having a relatively strong spectral feature in the 2.3 micrometer region indicative of an Mg or Fe-OH combination overtone absorption band indicative of smectite clay. Earlier in its mission, Opportunity examined the Matijevic Hill region on the more northerly Cape York crater rim segment and found evidence for smectite clays in a stratigraphically lower, pre-impact formed unit dubbed the Matijevic formation. However, the smectite exposures in Marathon Valley appear to be associated with the stratigraphically higher Shoemaker formation impact breccia. Evidence for alteration in this unit in Marathon Valley is provided by Pancam multispectral observations in the 430 to 1010 nm visible/near infrared (VNIR) spectral range. Sinuous troughs ("red zones") contain fragmented cobbles and pebbles displaying higher blue-to-red slopes, moderately higher 535 nm band depths, elevated 754 to 934 nm, and negative 934 to 1009 nm slopes. The lack of an absorption at 864 to 904 nm indicates the lack of crystalline red hematite in these red zones, but likely an enrichment in nanophase ferric oxides. The negative 934 to 1009 nm slope is potentially indicative of the presence of adsorbed or structurally bound water. A scuff in a red zone near the southern wall of Marathon Valley uncovered light-toned soils and a pebble with an 803 to 864 nm absorption resembling that of light-toned Fe-sulfate bearing soils uncovered by the Spirit rover in the Columbia Hills of Gusev crater. APXS chemical measurements indicated enrichments of Mg and S in the scuff soils and the pebble, Joseph Field, with the strongest 803 nm band- consistent with Mg and Fe sulfates. The presence of Fe and Mg sulfates can be interpreted as evidence of a potentially later episode of aqueous alteration with an earlier, neutral to alkaline pH episode forming the Fe/Mg smectites and a later acid pH episode forming the Fe and Mg sulfates.

Farrand, William H.↗
NASA NTRS2019

JSC-Rocknest: a Large-Scale Mojave Mars Simulant (MMS) Based Soil Simulant for In-Situ Resource Utilization Water-Extraction Studies

The Johnson Space Center Rocknest (JSC-RN) simulant was developed in response to a need by NASA's Advanced Exploration Systems (AES) In Situ Resource Utilization (ISRU) project for a simulant to be used in component and system testing for water extraction from Mars regolith. JSC-RN was de-signed to be chemically and mineralogically similar to material from the aeolian sand shadow named Rocknest in Gale Crater, particularly the 1-3 weight percentage water release as measured by the Sample Analysis at Mars (SAM) instrument. Rocknest material is a proxy for average martian soils, which are unconsolidated and could be easily scooped by rovers or landers in order to extract water. One way in which water can be extracted from aeolian material is through heating, where adsorbed and structural water is thermally removed from minerals. The water can then be condensed and used as drinking water or split and used as propellant for spacecraft or as a source of breathable O2. As such, it was essential that JSC-RN contained evolved gas profiles, especially low temperature water (less than 400 degrees Centigrade), that mimicked what is observed in martian soils. Because many of these ISRU tests require hundreds of kilograms of Mars soil simulant, it was essential that JSC-RN be cost-effective and based on com-ponents that could be purchased commercially (i.e., not synthesized in the lab). Here, we describe the JSC-RN martian soil simulant, which is ideal for large-scale production and use in ISRU water extraction studies.

Hogancamp, J. V.↗
NASA NTRS2020

Life-Limiting Factors of the CMTS for Precision Pointing Observatory Missions

Development of the next generation Colloid Micronewton Thruster System (CMTS) has focused on incorporation of complete redundancy, and extension of life beyond the 3,458 hrs previously demonstrated to the >40,000 hrs necessary for future missions. The present life- limiting factor of the CMTS is impingement of the electrospray beam onto the electrostatic grids, which is mitigated by the use of porous grid structures to adsorb and trap the small fraction (typically <0.5%) of the beam that intercepts the grids. A detailed alignment survey using a single emitter electrospray source has been performed in order to establish thruster production requirements and produce data necessary for lifetime model validation. Capillary emitter tilt (Θ), lateral displacement (X), and source spacing (Z), where independently assessed for their impact on changes in grid interception, as well as combined lateral and tilt displacement. Throughout testing, incremental improvements were made to reduce facility effects that impacted measured results. The data validate the alignment tolerances used in design and fabrication of the CMTS. Increased interception was not observed until emitter tilt exceeded 3X, lateral misalignment exceeded 5X, and emitter spacing >1.5X tolerance requirements. Results also indicate that, at target grid impingement levels <0.5%, facility effects begin to dominate measured grid currents and must be mitigated for more accurate assessments of thruster life.

Ziemer, John K.↗
DOE OSTI2022

Electronic structure factors and the importance of adsorbate effects in chemisorption on surface alloys

The chemisorption energy is an integral aspect of surface chemistry, central to numerous fields such as catalysis, corrosion, and nanotechnology. Electronic-structure-based methods such as the Newns-Anderson model are therefore of great importance in guiding the engineering of material surfaces with optimal properties. However, existing methods are inadequate for interpreting complex, multi-metallic systems. Herein, we introduce a physics-based chemisorption model for alloyed transition metal surfaces employing primarily metal d-band properties that accounts for perturbations in both the substrate and adsorbate electronic states upon interaction. Importantly, we show that adsorbate-induced changes in the adsorption site interact with its chemical environment leading to a second-order response in chemisorption energy with the d-filling of the neighboring atoms. We demonstrate the robustness of the model on a wide range of transition metal alloys with O, N, CH, and Li adsorbates yielding a mean absolute error of 0.13 eV versus density functional theory reference chemisorption energies.

36 MATERIALS SCIENCE↗