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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Bond Selective Photochemistry at Metal Nanoparticle Surfaces: CO Desorption from Pt and Pd

The use of visible photon fluxes to influence catalytic reactions on metal nanoparticle surfaces has attracted attention based on observations of reaction mechanisms and selectivity not observed under equilibrium heating. These observations suggest that photon fluxes can selectively impact the rates of certain elementary steps, creating nonequilibrium energy distributions among various reaction pathways. However, quantitative studies validating these hypotheses on metal nanoparticle surfaces are lacking. Here, we examine the influence of continuous wave visible photon fluxes on the CO desorption rates from 1 to 2 nm diameter Pt and Pd nanoparticle surfaces supported on γ-Al 2 O 3 . Temperature-programmed desorption measurements quantified via diffuse reflectance infrared Fourier transform spectroscopy demonstrate that visible photon fluxes significantly enhanced the rate of CO desorption from Pt nanoparticles in a wavelength-dependent manner. 440 nm photons most efficiently promoted CO desorption from Pt nanoparticle surfaces, aligning with the excitation energy for the interfacial electronic transition within the Pt–CO bond. Conversely, visible photon fluxes had no measurable influence on CO desorption rates from Pd nanoparticle surfaces after accounting for photon-induced heating. Density functional theory calculations demonstrate that the Pt–CO bond exhibits a narrower LUMO resonance, stronger coupling between the photoexcitation and forces induced on the metal–C bond, and vibrational energy dissipation that more effectively couples to desorption as compared to Pd–CO. These results demonstrate the specificity photons provide in facilitating chemical reactions on metal nanoparticle surfaces and substantiate the idea that photon fluxes can steer processes and outcomes of catalytic reactions in ways not achievable by equilibrium heating.

desorption↗
DOE OSTI2015

Hydrogen adsorption and desorption with 3D silicon nanotube-network and film-network structures: Monte Carlo simulations

Hydrogen is clean, sustainable, and renewable, thus is viewed as promising energy carrier. However, its industrial utilization is greatly hampered by the lack of effective hydrogen storage and release method. Carbon nanotubes (CNTs) were viewed as one of the potential hydrogen containers, but it has been proved that pure CNTs cannot attain the desired target capacity of hydrogen storage. In this paper, we present a numerical study on the material-driven and structure-driven hydrogen adsorption of 3D silicon networks and propose a deformation-driven hydrogen desorption approach based on molecular simulations. Two types of 3D nanostructures, silicon nanotube-network (Si-NN) and silicon film-network (Si-FN), are first investigated in terms of hydrogen adsorption and desorption capacity with grand canonical Monte Carlo simulations. It is revealed that the hydrogen storage capacity is determined by the lithium doping ratio and geometrical parameters, and the maximum hydrogen uptake can be achieved by a 3D nanostructure with optimal configuration and doping ratio obtained through design optimization technique. For hydrogen desorption, a mechanical-deformation-driven-hydrogen-release approach is proposed. Compared with temperature/pressure change-induced hydrogen desorption method, the proposed approach is so effective that nearly complete hydrogen desorption can be achieved by Si-FN nanostructures under sufficient compression but without structural failure observed. The approach is also reversible since the mechanical deformation in Si-FN nanostructures can be elastically recovered, which suggests a good reusability. This study may shed light on the mechanism of hydrogen adsorption and desorption and thus provide useful guidance toward engineering design of microstructural hydrogen (or other gas) adsorption materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Dynamics of deuterium retention and desorption from plasma-facing materials in fusion reactor-relevant conditions

Hydrogen isotopes retention and desorption during and after discharges in fusion devices are still not well understood due to the complex device conditions and limitations of in-situ diagnostics and measurements. Here, we simulated well-diagnosed recent experiments at the DIII-D facility to benchmark our ITMC-DYN integrated package of modeling deuterium diffusion, retention, and desorption during and after D discharge irradiation. Modeling results were compared with detail experimental data of D desorption fluxes for various irradiation conditions. We predicted the temporal evolution of free and trapped D distribution in tungsten (W) plasma-facing material (PFM). Effects of key parameters namely diffusion coefficient, recombination rate, trapping energies against different defect types, were examined in these simulations. Existing experimental data of these parameters in literature varies significantly which makes it harder to identify key mechanisms and physics responsible for hydrogen isotope retention and desorption. The purpose of this work is to accurately simulate recent well-diagnosed reactor experiments given the uncertainties in such parameters and identify mechanisms responsible for the retention and desorption. We implemented the best identified diffusion, recombination, and trapping parameters in ITMC-DYN package that integrate both various collisional and thermal processes. We predicted, for example, that sample cooling between discharges in DIII-D operations can significantly affect the spatial distribution of trapped D in W under reactor irradiation conditions. Correct prediction of desorption spectra from samples irradiated during 10 DIII-D discharges showed that up to 35% of D can be retained in high binding energy defects such as vacancy clusters or voids.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Effect of Temperature on the Desorption of Lithium from Molybdenum(110) Surfaces: Implications for Fusion Reactor First Wall Materials

Determining the strength of Li binding to Mo is critical to assessing the survivability of Li as a potential first wall material in fusion reactors. Here, we present the results of a joint experimental and theoretical investigation into how Li desorbs from Mo(110) surfaces, based on what can be deduced from temperature-programmed desorption measurements and density functional theory (DFT). Li desorption peaks measured at temperatures ranging from 711 K (1 monolayer, ML) to 1030 K (0.04 ML), with corresponding desorption onsets from 489 to 878 K, follow a trend similar to predicted Gibbs free energies for Li adsorption. Bader charge analysis of DFT densities reveals that repulsive forces between neighboring positively charged Li atoms increase with coverage and thus reduce the bond strength between Mo and Li, thereby lowering the desorption temperature as the coverage increases. In addition, DFT predicts that Li desorbs at higher temperatures from a surface with vacancies than from a perfect surface, offering an explanation for the anomalously high desorption temperatures for the last Li to desorb from Mo(110). Analysis of simulated local densities of states indicates that the stronger binding to the defective surface is correlated with enhanced interaction between Li and Mo, involving the Li 2s electrons and not only the Mo 4d electrons as in the case of the pristine surface, but also the Mo 5s electrons in the case with surface vacancies. We suggest that steps and kinks present on the Mo(110) surface behave similarly and contribute to the high desorption temperatures. These findings imply that roughened Mo surfaces may strengthen Li film adhesion at higher temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Effect of Subgrid Heterogeneity on Scaling Geochemical and Biogeochemical Reactions: A Case of U(VI) Desorption

The effect of subgrid heterogeneity in sediment properties on the rate of uranyl[U(VI)] desorption was investigated using a sediment collected from the US Department of Energy Hanford site. The sediment was sieved into 7 grain size fractions that each exhibited different U(VI) desorption properties. Six columns were assembled using the sediment with its grain size fractions arranged in different spatial configurations to mimic subgrid heterogeneity in reactive transport properties. The apparent rate of U(VI) desorption varied significantly in the columns. Those columns with sediment structures leading to preferential transport had much lower rates of U(VI) desorption than those with relatively homogeneous transport. Modeling analysis indicated that the U(VI) desorption model and parameters characterized from well-mixed reactors significantly over-predicted the measured U(VI) desorption in the columns with preferential transport. A dual domain model, which operationally separates reactive transport properties into two subgrid domains improved the predictions significantly. A similar effect of subgrid heterogeneity, albeit at a less degree, was observed for denitrification, which also occurred in the columns. The results imply that subgrid heterogeneity is an important consideration in extrapolating reaction rates from the laboratory to field.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2012

Surface and Particle-Size Effects on Hydrogen Desorption from Catalyst-Doped MgH2

With their high capacity, light-metal hydrides like MgH2 remain under scrutiny as reversible H-storage materials, especially to develop control of H-desorption properties by decreasing size (ball-milling) and/or adding catalysts. By employing density functional theory and simulated annealing, we study initial H2 desorption from semi-infinite stepped rutile (110) surface and Mg31H62 nanoclusters, with(out) transition-metal catalyst dopants (Ti or Fe). While Mg31H62 structures are disordered (amorphous), the semi-infinite surfaces and nanoclusters have similar single, double, and triple H-to-metal bond configurations that yield similar H-desorption energies. Hence, there is no size effect on desorption energetics with reduction in sample size, but dopants do reduce the H-desorption energy. All desorption energies are endothermic, in contrast to a recent report.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces

Here, we report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H 2 peak is seen from planar Ir(210) at all coverages whereas a single H 2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H 2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity in recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H 2 from faceted Ir(210): F1 from desorption of H 2 on {311} facets while F2 from desorption of H 2 on (110) facets.

1st-principles↗
DOE OSTI2017

Preliminary Desorption studies for HZ-PAN and AgZ-PAN

Adsorption of Kr and Xe on HZ-PAN and AgZ-PAN has been the studied extensively. Prior research focused on sorbent capacity and breakthrough of Kr and Xe, with desorption cycles completed in order to close material balances and prepare sorbents for further adsorption testing. This series of tests was designed to determine preliminary information about desorption to guide further research to optimize desorption cycles for each sorbent. A series of desorption tests were run using thermal and pressure swing operations. For AgZ-PAN, these tests indicated that both heat and carrier gas are likely necessary to removed adsorbed gases. However, vacuum pressure and heat may be sufficient to desorb gases from HZ-PAN, which should result in a cleaner Kr stream during desorption. Desorption optimization for both sorbents merits further study in order to make final waste form volume as small as possible.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS2003

Electron- and Photon-stimulated Desorption of Alkali Atoms from Lunar Sample and a Model Mineral Surface

We report recent results on an investigation of source mechanisms for the origin of alkali atoms in the tenuous planetary atmospheres, with focus on non-thermal processes (photon stimulated desorption (PSD), electron stimulated desorption (ESD), and ion sputtering). Whereas alkaline earth oxides (MgO, CaO) are far more abundant in lunar samples than alkali oxides (Na2O, K2O), the atmosphere of the Moon contains easily measurable concentrations of Na and K, while Ca and Mg are undetected there; traces of Ca have recently been seen in the Moon's atmosphere (10-3 of Na). The experiments have included ESD, PSD and ion sputtering of alkali atoms from model mineral surface (amorphous SiO2) and from a lunar basalt sample obtained from NASA. The comparison is made between ESD and PSD efficiency of monovalent alkalis (Na, K) and divalent alkaline earths (Ba, Ca).The ultrahigh vacuum measurement scheme for ESD and PSD of Na atoms includes a highly sensitive alkali metal detector based on surface ionization, and a time-of-flight technique. For PSD measurements, a mercury arc light source (filtered and chopped) is used. We find that bombardment of the alkali covered surfaces by ultraviolet photons or by low energy electrons (E>4 eV) causes desorption of hot alkali atoms. This results are consistent with the model developed to explain our previous measurements of sodium desorption from a silica surface and from water ice: electron- or photon-induced charge transfer from the substrate to the ionic adsorbate causes formation of a neutral alkali atom in a repulsive configuration, from which desorption occurs. The two-electron charge transfer to cause desorption of divalent alkaline eath ions is a less likely process.The data support the suggestion that PSD by UV solar photons is a dominant source process for alkalis in the tenuous lunar atmosphere.

Yakshinskiy, B. V.↗
DOE OSTI2021

Time-dependent water vapor desorption isotherm model of hardened cement paste

Highlights: • Short-term and long-term desorption isotherms of hardened cement paste are reviewed. • Water content at RH depends on both thermodynamic and microstructural equilibria. • An extended GAB equation is proposed to fit the cavitation drop during desorption. • A dynamic time-dependent sorption isotherm model is shown and used for simulations. • Numerical results capture anomalous drying in the same RH as seen experimentally. This study aims to enhance moisture transport modeling by elucidating the so-called anomalous water diffusion in cementitious materials. Water desorption isotherms are measured from samples at various drying stages using techniques with different durations to quantify the impact of the drying duration on the water sorption ability. A single water sorption isotherm does not solely give a relationship between the water content and relative humidity but also represents the state of microstructure. The continuous evolution of a desorption isotherm due to drying-induced microstructural rearrangement is demonstrated. For numerical modeling, the microstructural alteration can be explicitly considered through a dynamic desorption isotherm model, which governs the local thermodynamic equilibrium at the capillary meniscus. This approach is implemented into a multiphase transport code, whose ability to predict drying is validated using literature data. Finally, the effect of prolonged drying on the colloidal nature of the calcium-silicate-hydrate gel is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Desorption of plutonium from montmorillonite: An experimental and modeling study

Desorption of plutonium (Pu) will likely control the extent to which it is transported by mineral colloids. In this article, we evaluated the adsorption/desorption behavior of Pu on SWy-1 montmorillonite colloids at pH 4, pH 6, and pH 8 using batch adsorption and flow cell desorption experiments. After 21 days adsorption, Pu(IV) affinity for montmorillonite displayed a pH dependency, with K d values highest at pH 4 and lowest at pH 8. The pH 8 experiment was further allowed to equilibrate for 6 months and showed an increase in K d , indicating that true sorption equilibrium was not achieved within the first 21 days. For the desorption experiments, aliquots of the sorption suspensions were placed in a flow cell, and Pu-free solutions were then pumped through the cell for a period of 12 days. Changes in influent solution flow rate were used to investigate the kinetics of Pu desorption and demonstrated that it was rate-limited over the experimental timescales. At the end of the 12-day flow cell experiments, the extent of desorption was again pH dependent, with pH 8 > pH 6 > pH 4. Further, at pH 8, less Pu was desorbed after an adsorption contact time of 6 months than after a contact time of 21 days, consistent with an aging of Pu on the clay surface. In addition, a conceptual model for Pu adsorption/desorption that incorporated known surface-mediated Pu redox reactions was used to fit the experimental data. The resulting rate constants indicated processes occurring on timescales of months and even years which may, in part, explain observations of clay colloid-facilitated Pu transport on decadal timescales. Importantly, however, our results also imply that migration of Pu adsorbed to montmorillonite colloids at long (50–100 year) timescales under oxic conditions may not be possible without considering additional phenomena, such as co-precipitation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

A thermal desorption spectroscopy study of hydrogen trapping in polycrystalline α-uranium

The kinetics of hydrogen desorption from polycrystalline α-uranium (α-U) was examined using thermal desorption spectroscopy (TDS). The goal was to identify the major trap sites for hydrogen and their associated trap energies. In polycrystalline α-U six TDS adsorption peaks were observed at temperatures of 521 K, 556 K, 607 K, 681 K, 793 K and 905 K. In addition, the desorption was determined to be second order based on peak shape. The position of the first three peaks was consistent with desorption from UH3. To identify the trap site corresponding to the high temperature peaks the data were compared to a plastically deformed sample and a high purity single crystal sample. The plastically deformed sample allowed the identification of trapping at dislocations while the single crystal sample allow for the identification of high angle boundaries and impurities. Thus, with respect to the desorption energy associated with each peak, values between 12.9 and 26.5 kJ/mole were measured.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Deuterium desorption from tungsten using laser heating

Retention and desorption of hydrogenic species need to be accurately modeled to predict the tritium inventory of next generation fusion devices, which is needed both for tritium fuel recovery and for tritium safety concerns. In this paper, experiments on thermal desorption of deuterium from intrinsic polycrystalline tungsten defects using laser heating are compared to TMAP-7 modeling. The samples during deuterium plasma exposure were at a temperature of 373 K for this benchmark study with ion fluence of 0.7–1.0 × 10 24 Dm -2 . Following plasma exposure, a fiber laser (λ = 1100 nm) heated the samples to peak surface temperatures ranging from ~500 to 1400 K with pulse widths from 10 ms to 1 s, and 1 to 10 pulses applied to each sample. The remaining deuterium retention was measured using temperature programmed desorption (TPD). Results show that > 95% of deuterium is desorbed when the peak surface temperature reached ~950 K for > 1 s. TMAP-7 is used to predict deuterium desorption from tungsten for a range of surface temperatures and heating durations, and is compared to previous work on desorption from beryllium codeposits.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Influence of surface coverage on the chemical desorption process

In cold astrophysical environments, some molecules are observed in the gas phase whereas they should have been depleted, frozen on dust grains. In order to solve this problem, astrochemists have proposed that a fraction of molecules synthesized on the surface of dust grains could desorb just after their formation. Recently the chemical desorption process has been demonstrated experimentally, but the key parameters at play have not yet been fully understood. In this article, we propose a new procedure to analyze the ratio of di-oxygen and ozone synthesized after O atoms adsorption on oxidized graphite. We demonstrate that the chemical desorption efficiency of the two reaction paths (O+O and O+O{sub 2}) is different by one order of magnitude. We show the importance of the surface coverage: for the O+O reaction, the chemical desorption efficiency is close to 80% at zero coverage and tends to zero at one monolayer coverage. The coverage dependence of O+O chemical desorption is proved by varying the amount of pre-adsorbed N{sub 2} on the substrate from 0 to 1.5 ML. Finally, we discuss the relevance of the different physical parameters that could play a role in the chemical desorption process: binding energy, enthalpy of formation, and energy transfer from the new molecule to the surface or to other adsorbates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Field-Induced Desorption of Cesium from Rhenium

Desorption of cesium atoms from a rhenium point emitter in an electric field has been studied by method of field-desorption microscopy (FDM). Dependence of the desorbing field on degree of emitter surface coverage with Cs atoms is established. The heat of Cs-atom adsorption, which is dependent on the surface concentration of adsorbate and work function of the surface, is estimated in the framework of the model of mirror-image forces for field-induced desorption. Saturation of the rhenium emitter with carbon leads to changes in the character of desorption and in the distribution of desorption zones on the emitter surface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Isotope effects on desorption kinetics of hydrogen isotopes implanted into stainless steel by glow discharge

In a fusion device the control of fuel particles implies to know the desorption rate of hydrogen isotopes by the plasma-facing materials. In this paper desorption kinetics of hydrogen isotopes implanted into type 316L stainless steel by glow discharge have been studied by experiment and numerical calculation. The temperature of a maximum desorption rate depends on glow discharge time and heating rate. Desorption spectra observed under various experimental conditions have been successfully reproduced by numerical simulations that are based on a diffusion-limited process. It is suggested, therefore, that desorption rate of a hydrogen isotope implanted into the stainless steel is limited by a diffusion process of hydrogen isotope atoms in bulk. Furthermore, small isotope effects were observed for the diffusion process of hydrogen isotope atoms. (authors)

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Tritium species diffusion on and desorption from γ-LiAlO 2 (100) surface: A first-principles investigation

γ-LiAlO 2 enriched in the 6 Li isotope is a good candidate for tritium (T, 3 H) production in nuclear reactor. In this work, to better understand its 3 H production performance, first-principles calculations are performed to study the 3 H-related species diffusion on and desorption from the γ-LiAlO 2 (100) surface. For the diffusion process, we investigate the pathways and energy barriers for the T and OT diffusion on the pristine and defective γ-LiAlO 2 (100) surfaces. Our results reveal that the O and Li/Al atoms of the surface layer play important roles for T and OT diffusion, respectively. By comparing with its diffusion barrier in bulk γ-LiAlO 2 , the order of energy barrier for T diffusion is: bulk < surface < defective surface, which is reversed for OT diffusion. Space is the prime factor for OT diffusion, while diffusion-mediating atom instead of space becomes the key factor for T diffusion. For the desorption process, we investigate the 3 H-related species (T, OT, T 2 , and T 2 O) desorption from the γ-LiAlO 2 (100) surface. The desorption energies we obtained are so high that the desorption behavior of all the 3 H-related species is nearly prohibited. We expect the possible T 2 or T 2 O release from the large accumulation of 3 H atoms on the surface.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

In situ observation of irradiation-induced enhancement to the desorption pressure of zirconium hydride in a nuclear reactor

We quantify the effect of a nuclear-reactor environment on the hydrogen isotope equilibrium vapor pressure over pure zirconium and zirconium hydride. A vacuum-sealed capsule containing a zirconium foil with 6 atom% deuterium was irradiated at a neutron flux of ~10 14 cm -2 s -1 at the University of Missouri Research Reactor (MURR). The internal stainless-steel (SS) sample holder acted as the heat source via gamma absorption. To measure low desorption pressures in a high-flux environment, we developed a method to transduce pressure from the measured sample temperature during irradiation, calibrating with known deuterium pressures in unirradiated capsules at various heating powers using an internal filament-heated system designed to mimic irradiation-induced heating. Our temperature-pressure transduction method operates similarly to a Pirani or thermocouple pressure gauge. The in-reactor measurements revealed a roughly 4-fold enhancement in desorption pressure after only 6 h of irradiation (~2 × 10 18 cm -2 neutron fluence) compared to thermal desorption in control experiments, indicating a nonthermal contribution from neutron irradiation. The slower temperature/pressure stabilization rate in the reactor suggests that desorption pressure enhancement increases with neutron fluence. Further, this enhancement signifies increased solubility of hydrogen isotopes in zirconium during irradiation. We propose that high-energy neutron collisions with hydrogen isotopes in hydrides lead to their decomposition at lower temperatures, supersaturating the surrounding αZr lattice and resulting in higher desorption pressure, which continues to rise as more hydrides dissolve with increasing neutron fluence.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗