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At least 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Assessing factors that determine adatom migration and clustering on a thin film oxide; Pt 1 and Rh 1 on the “29” Cu x O/Cu(1 1 1) surface

The dynamical nature of single-site catalysts under non-equilibrium conditions poses significant challenges in the full characterization of their active sites. The “29” oxide is a thin Cu x O film grown on Cu(111) which provides a well-defined surface on which to study the structure and chemistry of atomically dispersed precious metals. A combination of experimental and first-principles approaches is used to investigate the factors that influence the mobility of metal adatoms and their clustering tendencies. Our work elucidates how a homogenous coordination environment of neutral single-atoms can be obtained when its tendency to break oxide bonds within its vicinity is low. Herein we demonstrate that this in turn affects the chemical atomically dispersed species on thin-film oxides, as defects on the oxide would in fact allow such species to be more accessible to CO. We thus highlight the importance of understanding the relationship between defects and atomically dispersed active sites upon designing single-site catalysts.

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

Atomic Layer-Deposited TiO{sub 2} Coatings on NiTi Surface

NiTi shape-memory alloys may release poisonous Ni ions at the alloys’ surface. In an attempt to prepare a well-performing surface layer on an NiTi sample, the thermally grown TiO{sub 2} layer, which formed during the heat treatment of NiTi, was removed and replaced with a new TiO{sub 2} layer prepared using the atomic layer deposition (ALD) method. Using x-ray photoelectron spectroscopy, it was found that the ALD layer prepared at as low a temperature as 100 °C contained Ti in oxidation states + 4 and + 3. As for static corrosion properties of the ALD-coated NiTi samples, they further improved compared to those covered by thermally grown oxide. The corrosion rate of samples with thermally grown oxide was 1.05 × 10{sup −5} mm/year, whereas the corrosion rate of the ALD-coated samples turned out to be about five times lower. However, cracking of the ALD coating occurred at about 1.5% strain during the superelastic mechanical loading in tension taking place via the propagation of a localized martensite band.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Impact of vegetation physiology and phenology on watershed hydrology in a semiarid watershed in the Pacific Northwest in a changing climate

Concurrent with changes in climate conditions, increases in atmospheric composition and transport can affect land surface processes by regulating physiological and phenological responses of plants, and consequently perturb water, carbon, and nitrogen (N) dynamics at multiple scales. Howerver, the relationships bwtween plants physiological and phenological and land surface processes in a changing climate are less well known due to the limitation of representing palnts properties in traditional hydrological models. In this study, we use the Community Land Model version 5 (CLM5) to investigate how projected changes in large scale atmospheric conditions can affect hydrologic and biogeochemical dynamics in the Upper Columbia-Priest Rapids (UCPR) watershed, a typical semi-arid watershed located in the north-western United States dominated by croplands. Six numerical experiments considering climate change, CO2 concentration, and N deposition consistent with the Representative Concentration Pathways (RCPs) 4.5 and 8.5 are performed at 1-km resolution over the period of 2015-2099. Our results show that, compared with historical results (1985-2014), the elevated CO2 directly increases plants N uptake rates that provide additional leaf N to enhance photosynthesis by the end of 21st century (2070-2099). The higher GPP leads to changes in stomatal resistance and increased leaf area index (LAI) that affect evaporatranspiration (ET) and its components. As a result of stomatal responses to a higher CO2 concentration, ET over corn fields declines by 24.6 mm yr-1 under RCP4.5, and by 64.0 mm yr-1 under RCP8.5, respectively by the end of the century from its historical mean of 428 mm yr-1. Meanwhile, ET over soybean fields increases by 27.7 mm yr-1 under RCP4.5 and 9.98 mm yr-1 under RCP8.5 from its historical mean of 507 mm yr-1 as a result of CO2 fertilization as soybeans are able to uptake more N to increase LAI significantly. Furtherfore, the changes in physiological and phenological in corn and soybean can strongly modulate water budget terms over the watershed in response to expected changes in greenhouse gas concentrations and atmospheric composition. Additionally, increases in CO2 concentration and N deposition are beneficial for improving water use efficiency of corn and soybean, therefore lead to less water consumption per unit gram of carbon produced from these crops. Our study elucidates the need to jointly consider effects of surface climate and atmospheric composition and transport in understanding and predicting watershed hydrologic and biogeochemical responses, especially for an agricultural watershed.

Zhu, Bowen↗
DOE OSTI2023

Calorimetric Energies and Chemical Potentials of Metal Atoms in Catalytic Nanoparticles on Oxide and Carbon Supports: Improved Size Dependencies and Adhesion Energies

The chemical potential of metal atoms, μM, in supported metal nanoparticles is an important descriptor related to both the catalytic activity and the stability of the nanoparticles. Here, we derive an expression relating μM to the radius of the particle’s contact area with the support and the adhesion energy at the metal/support interface (E adh ) that assumes the particles have the shape of spherical caps but of arbitrary contact angle with the support (θ c ) and includes an empirical correction for the increase in metal surface energy and adhesion energy with decreasing radius of curvature. We then show that, at any assumed contact angle, we can simultaneously fit previously reported measurements of both calorimetric μ M (from heats of metal vapor adsorption during nanoparticle growth by vapor deposition) versus metal coverage data and the He + low-energy ion scattering (LEIS) intensities for the metal and/or support versus metal coverage (using our recently developed spherical cap model for quantitative LEIS intensities), to determine the particle size versus coverage and E adh . Only one choice of contact angle gives a pair of values for contact angle and E adh , which is consistent with the Young–Dupré equation for the equilibrium shape of a spherical particle. At this equilibrium shape, we then applied this spherical cap model (SCM) to reanalyze microcalorimetric metal chemical potentials and LEIS signals versus coverage data for nine metal/support combinations that were previously analyzed by assuming that the particles had the shape of hemispherical caps, i.e., with a contact angle of 90°. We show that this revised approach gives close agreement with the calorimetric and LEIS data; the best-fit contact angles vary from 64 to 84°, correcting the earlier assumption of 90°. Furthermore, these results provide significant accuracy improvements in particle size versus coverage, metal chemical potential versus size and coverage, metal/support adhesion energies and contact angles for Cu, Ag and Au on CeO 2 (111), Ni on MgO(100), Ag on Fe 3 O 4 (111) and TiO 2 (100), and Ag, Ni and Pd on Ni-supported graphene. This revised approach is much more broadly applicable than the earlier hemispherical cap model (HCM).

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2023

Understanding the Effect of Single Atom Cationic Defect Sites in an Al 2 O 3 (012) Surface on Altering Selenate and Sulfate Adsorption: An Ab Initio Study

Adsorption is a promising under-the-sink selenate remediation technique for distributed water systems. Recently it was shown that adsorption induced water network rearrangement control adsorption energetics on the α-Al 2 O 3 (012) surface. Here, we aim to elucidate the relative importance of the water network effects and surface cation identity on controlling selenate and sulfate adsorption energy using density functional theory calculations. Density functional theory (DFT) calculations predicted the adsorption energies of selenate and sulfate on nine transition metal cations (Sc–Cu) and two alkali metal cations (Ga and In) in the α-Al 2 O 3 (012) surface under simulated acidic and neutral pH conditions. We find that the water network effects had a larger impact on the adsorption energy than the cationic identity. However, cation identity secondarily controlled adsorption. Most cations decreased the adsorption energy, weakening the overall performance, the larger Sc and In cations enabled inner-sphere adsorption in acidic conditions because they relaxed outward from the surface, providing more space for adsorption. Additionally, only Ti induced Se selectivity over S by reducing the adsorbing selenate to selenite but not reducing the sulfate. Altogether, this study indicates that tuning water network structure will likely have a larger impact than tuning cation–selenate interactions for increasing adsorbate effectiveness.

Adsorption↗
DOE OSTI2022

Vapor–Fed Electrolyzers for Carbon Dioxide Reduction Using Tandem Electrocatalysts: Cuprous Oxide Coupled with Nickel–Coordinated Nitrogen–Doped Carbon

We report ethylene is particularly attractive due to its major importance as a feedstock for various applications including the polymer industry. As such, catalyst and electrolyzer developments are crucial to achieve industrially relevant ethylene production and efficiency levels. In this work, a tandem electrocatalyst composed of copper nanocubes and nickel-coordinated nitrogen-doped carbon (NiNC) is presented, which is integrated into gas diffusion electrodes (GDEs) for direct conversion of vapor-fed CO 2 into ethylene. Evaluation of tandem GDEs in the vapor-fed flow electrolyzer shows significantly increased ethylene selectivity in terms of faradaic efficiency and C 2 H 4 /CO ratio compared to a non-tandem copper GDE. The enhancements are attributed to the increased local CO availability near the copper surface via effective CO 2 to CO conversion on neighboring NiNC. The experimental results are validated by 3D resolved continuum simulations, which show increased flux of higher-order prod-ucts with the added CO flux from NiNC. The practical viability of Cu/NiNC catalyst is further evaluated in a membrane electrode assembly electrolyzer, achieving 40% FE toward ethylene at 150 mA cm -2 and 3.2 V. These find-ings highlight the high selectivity and formation rate of ethylene achieved by successful device integration of the Cu/NiNC catalyst, demonstrating the potential for implementation in large-scale sustainable CO 2 electrolyzers.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Fermi Surface Nesting and Anomalous Hall Effect in Magnetically Frustrated Mn 2 PdIn

Noncollinear magnets with near-zero net magnetization and nontrivial bulk electronic topology hold significant promise for spintronic applications, though their scarcity necessitates deliberate design strategies. In this work, a topologically nontrivial electronic structure is reported in metallic Mn 2 PdIn, which crystallizes in the inverse Heusler structure and exhibits a spin-glassy ground state with quenched magnetization. The system features Weyl-type band crossings near the Fermi level and reveals a novel interplay among momentum-space nesting, orbital hybridization, and spin-orbit coupling. Comprehensive magnetotransport measurements reveal a pronounced anomalous Hall effect (AHE) in Mn 2 PdIn. The observed quadratic relationship between the longitudinal and anomalous Hall resistivities highlights the dominance of the intrinsic Berry curvature contribution to the AHE. These findings establish inverse Heusler alloys as compelling platforms for realizing noncollinear magnets that host Weyl-type semimetallic or metallic phases-combining suppressed magnetization with robust electronic transport-thereby offering a promising route toward their seamless integration into next-generation spintronic devices.

Ahmed, Afsar [Saha Institute of Nuclear Physics, K↗
DOE OSTI2017

Graphene‐Assisted Antioxidation of Tungsten Disulfide Monolayers: Substrate and Electric‐Field Effect

Transition metal dichalcogenides (TMDs) have emerged as promising materials to complement graphene for advanced optoelectronics. However, irreversible degradation of chemical vapor deposition‐grown monolayer TMDs via oxidation under ambient conditions limits applications of TMD‐based devices. Here, the growth of oxidation‐resistant tungsten disulfide (WS 2 ) monolayers on graphene is demonstrated, and the mechanism of oxidation of WS 2 on SiO 2 , graphene/SiO 2 , and on graphene suspended in air is elucidated. While WS 2 on a SiO 2 substrate begins oxidation within weeks, epitaxially grown WS 2 on suspended graphene does not show any sign of oxidation, attributed to the screening effect of surface electric field caused by the substrate. The control of a local oxidation of WS 2 on a SiO 2 substrate by a local electric field created using an atomic force microscope tip is also demonstrated.

Kang, Kyungnam↗
DOE OSTI2017

Giant Ferroelectric Polarization in Ultrathin Ferroelectrics via Boundary-Condition Engineering

Tailoring and enhancing the functional properties of materials at reduced dimension is critical for continuous advancement of modern electronic devices. Here, the discovery of local surface induced giant spontaneous polarization in ultrathin BiFeO 3 ferroelectric films is reported. Using aberration-corrected scanning transmission electron microscopy, it is found that the spontaneous polarization in a 2 nm-thick ultrathin BiFeO 3 film is abnormally increased up to ≈90–100 µC cm -2 in the out-of-plane direction and a peculiar rumpled nanodomain structure with very large variation in c/a ratios, which is analogous to morphotropic phase boundaries (MPBs), is formed. By a combination of density functional theory and phase-field calculations, it is shown that it is the unique single atomic Bi 2 O 3-x layer at the surface that leads to the enhanced polarization and appearance of the MPB-like nanodomain structure. This finding clearly demonstrates a novel route to the enhanced functional properties in the material system with reduced dimension via engineering the surface boundary conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Dynamic Motions of Topological Defects in Nematic Liquid Crystals under Spatial Confinement

Abstract Topological defects (TDs) have become a sensational topic due to their significant influence on the unusual optical and physiochemical characteristics of the material. To facilitate their application across a wide range of disciplines it is desirable to analyze and gain fundamental understanding of TDs in both equilibrium and nonequilibrium systems. Liquid crystals (LCs) are considered an ideal system for study given the direct visualization of TDs and a straightforward analyzation process. In addition to the equilibrium morphology of LC TDs, it is also of great interest to track and control the formation and annihilation of defects during thermodynamic processes. However, controlling the dynamic behavior of formed defects remains a challenge. Here, nematic LCs confined in a cell exhibiting surfaces with periodic anchoring conditions containing surface topography are relied on. The effects of patterned surface characteristics such as width, periodicity, and degree of curvature on defects dynamic motion, stabilization, and annihilation are explored. The computational experiments recapitulate the TDs transition path and provide free energy‐based predictions of critical distances for defect annihilation. Taken together, this simple approach offers a promising opportunity to control the dynamics of TDs in LCs through chemical patterned surfaces with topography.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Near–Band–Edge Enhancement in Perovskite Solar Cells via Tunable Surface Plasmons

Plasmonic perovskite solar cells (PSCs) using core-shell type plasmonic particles are designed, which possess the plasmon resonance in the near-infrared range. This can selectively strengthen the interaction of the perovskite layer with low-energy photons. The mesoporous PSCs employing the plasmonic particles have delivered a 10%-15% enhancement of external quantum efficiency in the plasmonic resonance range. This surface-plasmonic effect has been analyzed using complementary techniques, including selective wavelength excitation and time-dependent photoluminescence. Here it is shown that the metal-based core-shell-type plasmonic structures in PSCs optimize the scattering and absorption of incident light and the dynamics of photogenerated carriers. Furthermore, both optical and electronic effects increase the power conversion efficiency of PSCs from 17.49% to 19.88%, paving a way toward controlling the thickness of the photoactive layer for advanced devices such as tandem solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Addressing Inherent Challenges to Chemical Relithiation of Cycled End‐of‐Life Cathode Materials

Recycling end‐of‐life (EOL) lithium‐ion batteries (LIBs) is important to retain valuable resources from critical materials present in EOL battery waste. Direct recycling methods offer an opportunity to recover intact valuable cathode materials with minimal re‐processing. An important step of the direct recycling process is relithiation which is used to restore lithium content to EOL cathode materials. However, little has been done to study how preprocessing steps such as washing or binder removal may affect relithiation methods in the direct recycling process. Here, the evolution of fluorine byproducts left over from preprocessing steps during a low‐temperature chemical redox mediator relithiation process is tracked. A facile washing step is presented as a solution for mediating adverse effects of surface contamination on the chemical relithiation performance. The structure, lithium content, and electrochemical performance of relithiated EOL NMC 622 material that underwent a pre‐relithiation washing step to remove fluorine byproducts is shown to match that of pristine NMC 622. In this work, it is showed that redox mediator relithiation as a part of a direct recycling process is a promising low energy method that can be applied to EOL material with inherent surface impurities if the proper pre‐relithiation processing steps are implemented.

25 ENERGY STORAGE↗
DOE OSTI2024

Formulation, Implementation and Validation of a 1D Boundary Layer Inflow Scheme for the QUIC Modeling System

Recent studies have highlighted the importance of accurate meteorological conditions for urban transport and dispersion calculations. In this work, we present a novel scheme to compute the meteorological input in the Quick Urban & Industrial Complex () diagnostic urban wind solver to improve the characterization of upstream wind veer and shear in the Atmospheric Boundary Layer (ABL). The new formulation is based on a coupled set of Ordinary Differential Equations (ODEs) derived from the Reynolds Averaged Navier–Stokes (RANS) equations, and is fast to compute. Building upon recent progress in modeling the idealized ABL, we include effects from surface roughness, turbulent stress, Coriolis force, buoyancy and baroclinicity. We verify the performance of the new scheme with canonical Large Eddy Simulation (LES) tests with the GPU-accelerated FastEddy"Equation missing" solver in neutral, stable, unstable and baroclinic conditions with different surface roughness. Furthermore, we evaluate QUIC calculations with and without the new inflow scheme with real data from the Urban Threat Dispersion (UTD) field experiment, which includes Lidar-based wind measurements as well as concentration observations from multiple outdoor releases of a non-reactive tracer in downtown New York City. Compared to previous inflow capabilities that were limited to a constant wind direction with height, we show that the new scheme can model wind veer in the ABL and enhance the prediction of the surface cross-isobaric angle, improving evaluation statistics of simulated concentrations paired in time and space with UTD measurements.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Theoretical Insights to Bulk Activity Towards Oxygen Evolution in Oxyhydroxides

The nature of the electrochemical water splitting activity of layered pure and Fe-doped NiOOH is investigated using density functional theory calculations. We find similar thermodynamics for the oxygen evolution reaction (OER) intermediates between the layers of oxyhydroxides, that is, in the bulk of the materials as on the (001) surface. The effect of interlayer spacing on adsorption energy is affected by both the crystal structure and the level of hydrogenation of the active sites. For the Fe-doped NiOOH, we observe general weakening of binding between the different OER intermediates and the catalyst material. The calculated OER activity depends both on doping and interlayer spacing, and our results are generally congruent with available experimental data. In conclusion, these results suggest that such interlayer “bulk” sites may contribute to measured OER activity for both the pure and Fe-doped NiOOH catalysts.

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

Effects of UV/Photo-Initiator Treatments on Enhancement of Crystallinity of Polylactide Films and Their Physicochemical Properties

Effects of UV/photo-initiator treatments on crystal formation and properties of polylactide (PLLA) films are investigated. Camphorquinone and riboflavin photo-initiator solutions in methanol are employed in the treatment of amorphous quenched PLLA films. Results from FTIR, ATR-FTIR, DSC, XRD, and SEM show evidence of crystalline domain formation dispersed throughout the film. {sup 1}H NMR and GPC results suggest that the molecular weights of the polymer slightly decrease after the treatment. This indicates that the treatment leads to a diffusion of the photo-initiators molecules through the film matrix, resulting in a low degree of PLLA chain scissions, and formation of carboxylic acid and hydroxyl polar end groups. This, in turn, induces PLLA crystallization, which imposes profound effects on surface wettability and physical and mechanical properties of the samples. The process can be applied in optimizing properties of PLLA films with shorter treatment times, compared to other methods, which is suitable for use in various fields; especially those that require specific characteristics like biomedical, packaging and environmental applications.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Impedance Spectroscopy, Magnetic and Optical Analysis of Cadmium Tungstate Nanoparticles from Influence of Capping Agent Additives

Nano crystals of cadmium tungstate (CdWO{sub 4}) were obtained by facile precipitation route by using cadmium sulfate octahydrate and sodium tungstate dihydrate. These nanoparticles were then coated using different capping agents such as glucose, polyvinyl alcohol (PVA), and valine and their effects on the particle size, band gap, morphology, and magnetic character were investigated by powder X-ray diffraction, UV-Visible, FESEM, TEM, and VSM analysis. Capping agents are used in the synthesis of nanoparticles since they facilitate the growth and aggregation of particles in a precise manner, by usually acting as a physical barrier which controls the flow of free electron to the catalyst, so that they can be utilized by the catalyst and sensors of nanoparticle. Impedance spectroscopic technique was carried out, which was very useful in separating the grain boundary resistance and grain boundary capacitance contributions. We discuss the utilization of capping agents and their effects, including surface, optical and intergranular potential barriers in this work.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Phase Diagrams in Graphene-like Ising Nanoparticles

The phase diagrams of four graphene-like nanoparticles described by the Ising model are investigated by the use of the effective-field theory with correlations. The particle is represented by a two-dimensional array of spin-1/2 atoms with two types of exchange interactions, J and J{sub S}. The effects of surface exchange interaction J{sub S} on the phase diagrams are examined. We have found some characteristic behaviours.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Evaporation of Cu, Sn, and S from Fe-C-Cu-Sn-S Liquid Alloys in the Temperature Range from 1513 K to 1873 K (1240 °C to 1600 °C)

Evaporation of Cu or Sn from liquid iron alloys containing C and S was experimentally investigated. The initial C concentration, [pct C] 0 , in the liquid alloy was varied from zero to C saturation, and the evaporation temperature was varied from 1513 K to 1773 K (1240 °C to 1500 °C). Along with the report by one of the present authors, the evaporation mechanism of Cu and Sn from liquid Fe-C-S alloy is proposed, after a modification from the previous mechanism. It was proposed that Cu and Sn evaporate as Cu(g) and Sn(g) and also evaporate as CuS(g) and SnS(g), which are more volatile species. Therefore, availability of S in the alloy affects the overall evaporation rate of Cu and Sn. At the same time, C in the alloy also forms volatile carbosulfides CS(g) and CS 2 (g), thereby competing with Cu and Sn. Moreover, C increases the activity coefficients of Cu, Sn, and S. This increases the thermodynamic driving force for the formation of CuS(g) and SnS(g). Therefore, increasing [pct C] partly accelerates the evaporation rate of Cu and Sn by increasing the activity coefficient but partly decelerates the evaporation rate by lowering the available S content. S partly accelerates the evaporation rate by increasing the available S for the sulfide gas species but partly decelerates the evaporation rate due to the surface poisoning effect. Increasing the reaction temperature increases the overall evaporation rate. All these facts were taken into account in order to develop an evaporation rate model. This model was extended from the present authors’ previous one by taking into account (1) CS(g), S(g), and CS{ 2 (g) (therefore, the following species were considered as dominant evaporating species: Cu(g), CuS(g), Sn(g), SnS(g), S(g), CS(g), and CS 2 (g)); (2) the effect of C and temperature on the activity coefficients of Cu, Sn, and S; (3) the effect of C and temperature on the density of the liquid alloy; and (4) the effect of temperature on the S adsorption coefficient. This revised evaporation model was used in order to explain the experimental data, and it showed good agreement. In particular, it was found that the temperature showed a significant effect on the evaporation rate, and the effect of temperature and C content on the activity coefficients of Cu, Sn, and S also significantly affected the evaporation rate. The chemical reaction rate constant of the individual evaporation reaction (k i } R ) and residual rate constant (k i r ) could be obtained as a function of temperature. The activation energy of each evaporation reaction was derived and discussed. The evaporation rate model can be applied in order to predict the content of Cu and Sn remaining in liquid iron under various conditions of temperature and [pct C].

36 MATERIALS SCIENCE↗