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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Desorption of Ag from Grain Boundaries in Ag Film on Br and H-Passivated Si(111) Surfaces

Growth of Ag film on Br- and H-passivated Si(111) surfaces was examined by Rutherford backscattering spectrometry (RBS), scanning electron microscopy (SEM) and photoemission electron microscopy (PEEM) techniques. The phenomenon of thermal grooving was observed after annealing at higher temperatures. Hierarchical desorption of Ag from the grain boundaries produce a fractal structure of Ag-depleted regions. Hierarchical desorption may be used for nanopatterning of the layer.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Angular distributions of surface produced H{sup −} ions for reflection and desorption processes

A numerical simulation code, Atomic Collision in Amorphous Target, has been run to clarify the effects due to the incident angle of hydrogen flux onto surface collision cascade in the subsurface region of a Cs covered Mo plasma grid. The code has taken into account the threshold energy for negative hydrogen (H{sup −}) ions to leave the surface. This modification has caused the shift of energy distribution functions of H{sup −} from that of hydrogen atoms leaving the surface. The results have shown that large incident angle of hydrogen particle tilt the angular distribution of reflection component, while it caused a small effect onto the angular distribution of desorption component. The reflection coefficient has increased, while the desorption yield has decreased for increased angle of incidence measured from the surface normal.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2014

On factors controlling activity of submonolayer bimetallic catalysts: Nitrogen desorption

We model N{sub 2} desorption on submonolayer bimetallic surfaces consisting of Co clusters on Pt(111) via first-principles density functional theory-based kinetic Monte Carlo simulations. We find that submonolayer structures are essential to rationalize the high activity of these bimetallics in ammonia decomposition. We show that the N{sub 2} desorption temperature on Co/Pt(111) is about 100 K higher than that on Ni/Pt(111), despite Co/Pt(111) binding N weaker at low N coverages. Co/Pt(111) has substantially different lateral interactions than single metals and Ni/Pt. The lateral interactions are rationalized with the d-band center theory. The activity of bimetallic catalysts is the result of heterogeneity of binding energies and reaction barriers among sites, and the most active site can differ on various bimetallics. Our results are in excellent agreement with experimental data and demonstrate for the first time that the zero-coverage descriptor, used until now, for catalyst activity is inadequate due not only to lacking lateral interactions but importantly to presence of multiple sites and a complex interplay of thermodynamics (binding energies, occupation) and kinetics (association barriers) on those sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

REACTIVE DESORPTION AND RADIATIVE ASSOCIATION AS POSSIBLE DRIVERS OF COMPLEX MOLECULE FORMATION IN THE COLD INTERSTELLAR MEDIUM

The recent discovery of terrestrial-type organic species such as methyl formate and dimethyl ether in the cold interstellar gas has proved that the formation of organic matter in the Galaxy begins at a much earlier stage of star formation than was previously thought. This discovery represents a challenge for astrochemical modelers. The abundances of these molecules cannot be explained by the previously developed ''warm-up'' scenario, in which organic molecules are formed via diffusive chemistry on surfaces of interstellar grains starting at 30 K, and then released to the gas at higher temperatures during later stages of star formation. In this article, we investigate an alternative scenario in which complex organic species are formed via a sequence of gas-phase reactions between precursor species formed on grain surfaces and then ejected into the gas via efficient reactive desorption, a process in which non-thermal desorption occurs as a result of conversion of the exothermicity of chemical reactions into the ejection of products from the surface. The proposed scenario leads to reasonable if somewhat mixed results at temperatures as low as 10 K and may be considered as a step toward the explanation of abundances of terrestrial-like organic species observed during the earliest stages of star formation.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Swift heavy ion irradiation of Pt nanocrystals: II. Structural changes and H desorption

The structural properties and H desorption from embedded Pt nanocrystals (NCs) following irradiation with swift heavy ions were investigated as a function of energy and fluence. From x-ray absorption near-edge spectroscopy analysis, Pt-H bonding was identified in NCs annealed in a forming gas (95% N{sub 2} + 5% H{sub 2}) ambient. The H content decreased upon irradiation and the desorption process was NC-size dependent such that larger NCs required a higher fluence to achieve a H-free state. Pt-H bonding and NC dissolution both perturbed the NC structural parameters (coordination number, bond-length and mean-square relative displacement) as determined with extended x-ray absorption fine structure measurements.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2012

IN-SITU PROBING OF RADIATION-INDUCED PROCESSING OF ORGANICS IN ASTROPHYSICAL ICE ANALOGS-NOVEL LASER DESORPTION LASER IONIZATION TIME-OF-FLIGHT MASS SPECTROSCOPIC STUDIES

Understanding the evolution of organic molecules in ice grains in the interstellar medium (ISM) under cosmic rays, stellar radiation, and local electrons and ions is critical to our understanding of the connection between ISM and solar systems. Our study is aimed at reaching this goal of looking directly into radiation-induced processing in these ice grains. We developed a two-color laser-desorption laser-ionization time-of-flight mass spectroscopic method (2C-MALDI-TOF), similar to matrix-assisted laser desorption and ionization time-of-flight (MALDI-TOF) mass spectroscopy. Results presented here with polycyclic aromatic hydrocarbon (PAH) probe molecules embedded in water-ice at 5 K show for the first time that hydrogenation and oxygenation are the primary chemical reactions that occur in astrophysical ice analogs when subjected to Ly{alpha} radiation. We found that hydrogenation can occur over several unsaturated bonds and the product distribution corresponds to their stabilities. Multiple hydrogenation efficiency is found to be higher at higher temperatures (100 K) compared to 5 K-close to the interstellar ice temperatures. Hydroxylation is shown to have similar efficiencies at 5 K or 100 K, indicating that addition of O atoms or OH radicals to pre-ionized PAHs is a barrierless process. These studies-the first glimpses into interstellar ice chemistry through analog studies-show that once accreted onto ice grains PAHs lose their PAH spectroscopic signatures through radiation chemistry, which could be one of the reason for the lack of PAH detection in interstellar ice grains, particularly the outer regions of cold, dense clouds or the upper molecular layers of protoplanetary disks.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2013

On gas desorption from the tokamak first wall during edge localized modes

The effect of gas desorption from the tokamak first wall on the pedestal recovery in the H-mode after an edge-localized-mode burst is considered. Results of FACE code simulations of hydrogen desorption from a beryllium wall are presented. It is found that the wall has a significant effect on plasma processes only at sufficiently low temperatures (of about 400 K), which agrees with qualitative estimates obtained earlier in the zero-dimensional approximation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Electron-Stimulated Desorption of Cesium Atoms from Graphene to Iridium Intercalated and not Intercalated with Cesium

The processes of electron-stimulated desorption of neutral cesium atoms from graphene to iridium are studied in the cases in which the graphene layer is or is not intercalated with cesium. It was found that there are two peaks in the kinetic energy distributions of desorbed neutral cesium atoms: a high-energy peak at 0.36 eV and a low-energy one at 0.13 eV. The high-energy peak is observed in both cases and is associated with the excitation of the 2s core levels of carbon. The low-energy peak is observed only in the absence of intercalation and is associated with the excitation of the 4f and 5p core levels of iridium. A model describing the processes of electron-stimulated desorption of cesium atoms from a graphene surface on iridium is proposed, and a conclusion is made that graphene on iridium behaves in these processes as a dielectric.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

UV PHOTODESORPTION OF METHANOL IN PURE AND CO-RICH ICES: DESORPTION RATES OF THE INTACT MOLECULE AND OF THE PHOTOFRAGMENTS

Wavelength-dependent photodesorption rates have been determined using synchrotron radiation for condensed pure and mixed methanol ice in the 7–14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10{sup −5} molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower (<10{sup −6} molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH{sub 3}OH ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH{sub 3}, OH, H{sub 2}CO, and CH{sub 3}O/CH{sub 2}OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH{sub 3}O, therefore, opening new gas phase chemical routes for the formation of complex molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Water and Ammonia Desorption from 5A Zeolite

The objective of this project is to demonstrate the adsorption and desorption characteristics of water and ammonia on 5A zeolite during regeneration conditions. As discussed in literature, zeolite material is a crystalline hydrated aluminosilicate material. Zeolites have high cation exchange ability and are commonly used as adsorbents in separation and purification processes. The property of uniformly sized pores allows zeolites to selectively separate gases. Because they have varying ion selectivity, there is competitive adsorption in a multicomponent mixture. 5A zeolite has a uniform pore diameter of 5 Angstroms. Water and ammonia are miscible components with similar molecular weights and size. This makes distinguishing the two compounds difficult using mass spectrometry. In a previous study, it was shown that water tends to desorb from 5A zeolite from 40 deg. C to 353 deg. C with peaks at 177 deg. C and 244 deg. C, while ammonia tends to desorb from 300 deg. C to 580 deg. C with a peak at 436 deg. C as determined using a Micromeritics AutoChem 2920 Instrument. The one drawback of using a Micromeritics Instrument is that only a few milligrams of sample material can be used. Bench scale tests can better demonstrate desorption characteristics of water and ammonia during regeneration from 5A zeolite material. Water in argon carrier gas and ammonia in hydrogen carrier gas will be tested separately, then a mixture of the two will be tested. Initial bake-out conditions: hydrogen carrier gas, slowly raise temp to approximately 450 deg. C until desired moisture content <100 ppm is achieved. Water loading: argon carrier gas through bubbler until breach is observed using the residual gas analyzer (RGA). Ammonia loading: hydrogen carrier gas through system until breach is observed using RGA. Regeneration conditions: hydrogen carrier gas, raise temp to approximately 300 deg. C, then slowly to 450 deg. C. Observe signals on RGA. Weigh samples between tests and integrate RGA signals. Accomplishments: Developed work control documentation and completed safety related requirements; Flow sheet and test system development; Initial bake-out of first sample. Testing will determine if regenerating zeolite material can be safely accomplished by high-temperature bake-out to remove ammonia. If unsuccessful, ammonia would only be removed at the end of life.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Water and Ammonia Desorption from 5A Zeolite

Demonstrate adsorption and desorption characteristics of water and ammonia on 5A zeolite during regeneration conditions using a Thermogravimetric analyzer (TGA) on samples previously evaluated by residual gas analyzer (RGA)/mass balance. Molecular sieve (zeolite) adsorbents have the following characteristics: Crystalline alumino-silicates containing pores or 'cages' that adsorb water or other molecules. Polar compound are adsorbed with high loading even at very low concentrations of the fluid. A 5A molecular sieve was chosen for its ability to adsorb both water and ammonia (NH{sub 3}) from a carrier gas stream. Preliminary RGA/mass balance testing indicated: 5A zeolite captured both NH{sub 3} and water as anticipated based on molecular size; Reloading showed limited success after zeolite heated beyond manufacturer recommended operating conditions: Steam dealumination theorized cause; Tests were reprioritized to focus on NH{sub 3} removal and end of life potential holdup of NH{sub 3} and water on 5A zeolite material. TGA measures a sample's weight and volatile composition as it is heated or cooled in a furnace. TGA heats sample to release volatile materials, (change in mass is measured). MS detects/measures low levels of impurities. Perform TGA desorption of zeolite samples taken at the following conditions tested with RGA (RGA results not shown here): Initial Bakeout conditions: hydrogen carrier gas, slowly raise temp to approximately 300 deg. C until desired moisture content <<100 ppm is achieved. Water loading (re-loading): argon carrier gas through bubbler until breach is observed. Ammonia loading (re-loading): hydrogen carrier gas through system. Regenerations/End of life conditions: hydrogen carrier gas, raise temp to approximately 300 deg. C, then slowly to 450 deg. C (end of life). After end of life testing less than 4% of the total mass was residual ammonia or water at bakeout conditions. Peak water and ammonia removal occurred around 275 deg. C and 150 deg. C respectively.

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

Mass Spectrometry Imaging of Bio‐oligomer Polydispersity in Plant Tissues by Laser Desorption Ionization from Silicon Nanopost Arrays

Abstract Mass spectrometry imaging (MSI) enables simultaneous spatial mapping for diverse molecules in biological tissues. Matrix‐assisted laser desorption ionization (MALDI) mass spectrometry (MS) has been a mainstream MSI method for a wide range of biomolecules. However, MALDI‐MSI of biological homopolymers used for energy storage and molecular feedstock is limited by, e.g., preferential ionization for certain molecular classes. Matrix‐free nanophotonic ionization from silicon nanopost arrays (NAPAs) is an emerging laser desorption ionization (LDI) platform with ultra‐trace sensitivity and molecular imaging capabilities. Here, we show complementary analysis and MSI of polyhydroxybutyric acid (PHB), polyglutamic acid (PGA), and polysaccharide oligomers in soybean root nodule sections by NAPA‐LDI and MALDI. For PHB, number and weight average molar mass, polydispersity, and oligomer size distributions across the tissue section and in regions of interest were characterized by NAPA‐LDI‐MSI.

Samarah, Laith Z.↗
DOE OSTI2020

A comparative study of silver- and palladium-exchanged zeolites in propylene and nitrogen oxide adsorption and desorption for cold-start applications

Here, silver and palladium ion-exchanged BEA zeolites (Si/Al = 12.5) and silver ion-exchanged ZSM-5 zeolites (Si/Al = 15) were studied for their ability to adsorb and desorb propylene and NO under simulated diesel exhaust conditions. The adsorption experiment results demonstrated the excellent ability of bare BEA zeolites to adsorb propylene, but only a small amount of NO. The presence of H 2 O inhibited the adsorption of both C 3 H 6 and NO. Ion-exchanging BEA zeolites with Ag (1.2 and 5.1 wt.% Ag/BEA) attenuated the inhibiting effect of H 2 O on C 3 H 6 adsorption, while NO storage remained inhibited. Adsorption experiments indicated that C 3 H 6 and NO competed with each other for Pd sites with C 3 H 6 showing stronger adsorption compared to NO, whereas Ag sites preferentially adsorbed C 3 H 6 . DRIFTS data indicated the formation of nitrate, formate and acetate species on Ag and Pd, while C 3 H 6 and NO adsorption was also observed on the zeolite hydroxyl groups in the absence of H 2 O. However, the C 3 H 6 and NO adsorption on the zeolite hydroxyl groups was significantly inhibited in the presence of H 2 O. Additionally, nitrosyl, acrolein and carbonate species were formed over 1.0 wt.% Pd/BEA. The effluent analysis during the temperature-programmed desorption in the DRIFTS reactor revealed that adsorbed C 3 H 6 and NO reacted during the release to form oxidation reaction byproducts. The 1.0 wt.% Pd/BEA zeolite showed the greatest oxidation ability during desorption with the majority of stored C 3 H 6 converted to CO 2 .

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

Zinc speciation and desorption kinetics in a mining waste impacted tropical soil amended with phosphate

Mining is an important component of the Brazilian economy. However, it may also contribute to environmental problems such as the pollution of soils with zinc and other potentially toxic metals. Our objective was to evaluate changes in the chemical speciation and mobility of Zn in a soil amended with phosphate. Soil samples were collected from a deactivated mining area in the state of Minas Gerais, Brazil, and amended with NH 4 H 2 PO 4 saturated with deionized water to 70 % of maximum water retention and incubated at 25 ± 2 °C in open containers for 60 days. The soil was chemically and mineralogically characterized, and sequential extraction, desorption kinetics, and speciation were carried out using synchrotron bulk-sample and micro–X-ray Absorption Near-Edge Structure (XANES/μ-XANES) spectroscopy at the Zn K-edge, and X-ray fluorescence microprobe analysis (μ-XRF). The combination of μ-XRF and μ-XANES techniques made it possible to identify Zn hotspots in the main species formed after phosphate remediation. The best fit combination for bulk XANES and μ-XANES was observed in Zn-montmorillonite, Zn-kerolite, Zn-ferrihydrite, and gahnite. In the course of phosphate treatment, gahnite, Zn layered double hydroxides (Zn-LDH), Zn3(PO4), and ZnO were identified by bulk XANES, while Zn-ferrihydrite, Zn-montmorillonite, and scholzite were identified by μ-XANES. Zinc in the phosphate-amended soil had the strongest partial correlations (r' > 0.05) with Ni, Co, Fe, Cr, Mn, Si, P, Cd, Pb, and Cd, while the unamended soil showed the strongest correlation with Cu, Pb, Fe, and Si. The application of NH 4 H 2 PO 4 altered Zn speciation and favored an increase in Zn desorption. Here, the most available Zn contents after phosphate amendment were correlated with the release of exchangeable Zn fractions, associated with carbonate and organic matter.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Large scale nanoparticle screening for small molecule analysis in laser desorption ionization mass spectrometry

Nanoparticles (NPs) have been suggested as efficient matrixes for small molecule profiling and imaging by laser-desorption ionization mass spectrometry (LDI-MS), but so far there has been no systematic study comparing different NPs in the analysis of various classes of small molecules. Here, we present a large scale screening of 13 NPs for the analysis of two dozen small metabolite molecules. Many NPs showed much higher LDI efficiency than organic matrixes in positive mode and some NPs showed comparable efficiencies for selected analytes in negative mode. Our results suggest that a thermally driven desorption process is a key factor for metal oxide NPs, but chemical interactions are also very important, especially for other NPs. Furthermore, the screening results provide a useful guideline for the selection of NPs in the LDI-MS analysis of small molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Diffusion and photon-stimulated desorption of CO on TiO2(110)

Thermal diffusion of CO adsorbed on rutile TiO2(110) was studied in the 20 - 110 K range using photon-stimulated desorption (PSD), temperature programmed desorption (TPD) and scanning tunneling microscopy. During UV irradiation, CO desorbs from certain photoactive sites (e.g. oxygen vacancies). This phenomenon was exploited to study CO thermal diffusion in three steps: first empty these sites during a first irradiation cycle, then replenish them with CO during annealing, and finally probe the active site occupancy in the second PSD cycle. The PSD and TPD experiments show that the CO diffusion rate correlates with the CO adsorption energy – stronger binding corresponds to slower diffusion. Increasing the CO coverage or hydroxylation of the surface decreases the CO binding and increases the CO diffusion rate. Relative to the reduced surface, the CO adsorption energy increases and the diffusion decreases on the oxidized surface. The CO diffusion kinetics can be modeled satisfactorily as an Arrhenius process with a “normal” prefactor (i.e. = 1012 s 1) and a Gaussian distribution of activation energies where the peak of the distribution is ~0.28 eV and the full width at half maximum (FWHM) is 0.1 eV at the lowest coverages. The observations are consistent with a significant electrostatic component of the CO binding energy on the TiO2(110) surface which is affected by changes in the surface dipole and dipole-dipole interactions.

Petrik, Nikolay G.↗
DOE OSTI2026

Understanding Solvent-Induced Glass Transition in Polymer Thin Films Using Absorption–Desorption Isotherms

The fundamental thermodynamic and mechanical underpinnings of polymer thin films exposed to solvent vapor are critical for the development of advanced nanolithography and high-performance coatings. This work investigates the solvent− polymer interactions of glassy thin films by using the solvent absorption−desorption isotherms. An analogous relationship to the Flory−Fox equation was observed between solvent−induced glass transition, swelling, Flory−Huggins interaction parameter, and molecular weight. Isothermal swelling measurements revealed that the glass transition trends are more robust in the absorption curve compared to desorption, contrary to previous reports. Excess osmotic pressure analysis of the isotherm provides a measure of the degree of physical aging in thin films annealed below the glass transition. This is further validated in the ordering of block copolymer (BCP) films annealed at low solvent activity. In agreement with the thermal analysis, free-surface plasticization effects become the most prominent below 100 nm. However, solvent annealing is largely dependent on solvent mass transport, as made evident by the strong dependence on solvent viscosity. From these observations, four general types of isotherms are identified that graphically capture distinct solvent−polymer interaction regimes. More broadly, these results inform solvent vapor annealing-induced self-assembly, sequential infiltration synthesis, membrane-based separations, adsorptive processes, and swelling-based responsive materials design.

Hendeniya, Nayanathara [Iowa State Univ., Ames, IA↗
DOE OSTI2026

Desorption Electrospray Ionization–Mass Spectrometry Imaging Provides Spatiochemical Information on Potential Biocontrol Agents against Phytophthora capsici Infection in Tomato Plants

Biological control agents can offer an eco-friendly and more sustainable alternative to conventional chemical pesticides, providing protection against destructive pathogens, such as Phytophthora capsici, while reducing potential environmental harm associated with synthetic pesticide use in agricultural systems. This work evaluates the biocontrol effectiveness of Bacillus vallismortis, Bacillus amyloliquefaciens, Bacillus thuringiensis, and Bacillus subtilis, against the widespread plant pathogen Phytophthora capsici. Our studies showed that Bacillus thuringiensis and Bacillus subtilis promote plant growth and provide protection against Phytophthora capsici in both in vitro and in vivo greenhouse studies, while Bacillus vallismortis and Bacillus amyloliquefaciens were effective in vitro but not in vivo. Specifically, Bacillus thuringiensis was observed to both hinder the growth of Phytophthora capsici and enhance plant resilience to this pathogen, with B. thuringiensis-treated, pathogen-exposed plants displaying a 94.4% increase in root length and a 74.0% increase in shoot height compared to plants with only oomycete exposure. To probe the molecular interactions between the biocontrol agent and pathogen, a dual culture of Bacillus thuringiensis and Phytophthora capsici was analyzed in situ using a desorption electrospray ionization–mass spectrometry imaging (DESI-MSI) workflow. This approach interrogated the spatially oriented biochemical interactions that may serve as the molecular foundation for the effectiveness of these biological control agents in crop protection, identifying seven unique phenotypic regions within the dual culture. Herein, we demonstrate the benefits of biological control agent application in tomato cultivation and showcase the strengths of desorption electrospray ionization–mass spectrometry imaging when applied to the spatially resolved molecular characterization of agriculturally relevant microorganisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗