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At least 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Controlling Bond Scission Pathways of Isopropanol on Fe- and Pt-Modified Mo 2 N Model Surfaces and Powder Catalysts

Biomass valorization can be used to produce value-added chemicals and fuels from renewable biomass resources by upgrading them via selective bond scission while retaining certain functional groups. Specifically, upgrading biomass through the dehydrogenation of alcohols to carbonyl compounds has gained interest as a method of utilizing biomass-derived alcohols while additionally producing H 2 . In this work, isopropanol was used as a probe molecule to control bond scission selectivity over Fe- and Pt-modified molybdenum nitride (Mo 2 N) model surfaces and powder catalysts. Trends in the selectivity toward dehydration and dehydrogenation were dependent on both the type and coverage of the metal overlayer on model surfaces. These results were then extended to the corresponding powder catalysts to demonstrate how model surface studies can inform the design of supported catalysts. Density functional theory calculations provided insights into controlling the dehydration and dehydrogenation pathways. In conclusion, this work shows that a fundamental understanding of the reactivity and intermediates on Mo 2 N-based model surfaces can be applied to understand the catalytic performance of metal-modified Mo 2 N powder catalysts, and also demonstrates that Mo 2 N-based catalysts are potentially promising materials for upgrading biomass-derived oxygenates.

09 BIOMASS FUELS↗
DOE OSTI2024

Practical Considerations for Understanding Surface Reaction Mechanisms Involved in Heterogeneous Catalysis

Acquiring useful knowledge about the active site(s) of a catalyst, nature of reactant–catalyst interactions, nature of reactive intermediates, rate-determining step, reaction rate orders that affect various process parameters, and reaction mechanism as a whole is exceedingly challenging. This is especially true in the case of heterogeneous catalysts due to the complexity of the nature of surface active sites and their nonstatic behavior. Here, we present our perspective on differentiating between various surface reaction mechanisms in light of pioneering studies by leaders in the field, with the aim of clarifying some of the confusion associated with these complex mechanisms, especially the Eley–Rideal mechanism. Using bibliometric analysis, we identify and discuss the following four reactions that most commonly invoke the Eley– Rideal mechanism: H 2 activation, CO oxidation, esterification of alcohols by acids, and selective catalytic reduction (SCR) of NO x with NH 3 . Our analysis of studies utilizing well-suited experimental and computational methodologies for differentiating surface reaction mechanisms suggests that the above-mentioned four reactions do not occur via the Eley–Rideal mechanism. Instead, each reaction occurs via the Langmuir–Hinshelwood mechanism with nonidealities present. Lastly, we highlight practical considerations regarding select experimental (characterization methods and differential kinetics) and computational modeling that we believe can provide useful insights to accurately discern between the various possible reaction mechanisms in heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Controlling Selective C–O and C–H Bond Scission of Methanol by Supporting Pt on TiN and Mo 2 N Model Surfaces and Powder Catalysts

Transition metal nitrides (TMNs) have been explored as effective supports for Pt due to their Pt-like electronic properties. However, there is a lack of fundamental understanding regarding the behavior of Pt on different TMNs (Pt/TMN). Herein two TMNs, Mo 2 N and TiN, were modified with Pt and compared using methanol decomposition as a probe reaction via both ultrahigh vacuum (UHV) studies on thin films and ambient-pressure batch reactor studies of powder catalysts. Temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) measurements were conducted under UHV conditions with Mo 2 N and TiN thin films. Mo 2 N was shown to favor C–H bond scission to form CO with a 56.2% selectivity, while TiN favored C–O bond scission to form CH 4 with a 74.5% selectivity. The addition of 0.9 monolayers (MLs) of Pt increased C–H bond scission selectivity to 89.7% and 49.2% for Mo 2 N and TiN respectively. Density functional theory (DFT) calculations on model surfaces revealed that the binding energy of O (BE *O ) was significantly reduced on Pt/TMNs, from −4.02 eV on Mo 2 N to −1.31 eV on Pt/Mo 2 N and −4.74 eV on TiN to −1.37 eV on Pt/TiN. As a result, C–O bond scission pathways were suppressed, leading to the preferential C–H bond scission that was observed experimentally. The C–O and C–H bond scission trends observed on thin films were then extended to powder catalysts, which demonstrated similar trends toward methanol decomposition. In conclusion, results from the current study establish that by combining UHV studies and DFT calculations over model surfaces, one can effectively predict the catalytic behavior of realistic TMN powder catalysts.

08 HYDROGEN↗
DOE OSTI2026

Elucidating Lithium Transport Mechanisms in Disordered LiF from Machine-Learning Molecular Dynamics Simulations

Lithium fluoride (LiF) is a ubiquitous component of solid- and cathode–electrolyte interphases, yet its functional role remains unclear under the structural and chemical heterogeneity typical of cycling batteries. Here, we systematically quantify how structural disorder, off-stoichiometry, and strain govern Li-ion transport in LiF. Using a machine-learning potential to enable extensive molecular-dynamics sampling, we compare crystalline and amorphous LiF, Li 0.95 F, and LiF 0.95 , and evaluate the impact of small homogeneous deformations. Defect-free crystalline LiF is effectively ion-blocking at 300−500 K, whereas amorphization generates free-volume–assisted percolation pathways that facilitates Li-ion diffusion. At elevated temperatures, thermodynamically driven crystallization disrupts these pathways, leading to non-Arrhenius behavior. In crystalline phases, Li deficiency activates vacancy-mediated diffusion, while in amorphous LiF, transport is governed primarily by network connectivity. Strain is found to have only a marginal effect on Li mobility in both crystalline and amorphous structures.

Batteries↗
DOE OSTI2020

Concurrence of quantum anomalous Hall and topological Hall effects in magnetic topological insulator sandwich heterostructures

The quantum anomalous Hall (QAH) effect is a consequence of non-zero Berry curvature in momentum space. The QAH insulator harbours dissipation-free chiral edge states in the absence of an external magnetic field. Yet, the topological Hall (TH) effect, a hallmark of chiral spin textures, is a consequence of real-space Berry curvature. Herein, by inserting a topological insulator (TI) layer between two magnetic TI layers, we realized the concurrence of the TH effect and the QAH effect through electric-field gating. The TH effect is probed by bulk carriers, whereas the QAH effect is characterized by chiral edge states. The appearance of the TH effect in the QAH insulating regime is a consequence of chiral magnetic domain walls that result from the gate-induced Dzyaloshinskii–Moriya interaction and occurs during the magnetization reversal process in the magnetic TI sandwich samples. The coexistence of chiral edge states and chiral spin textures provides a platform for proof-of-concept dis- sipationless spin-textured spintronic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Interfacial stabilization for epitaxial CuCrO 2 delafossites

AB O 2 delafossites are fascinating materials that exhibit a wide range of physical properties, including giant Rashba spin splitting and anomalous Hall effects, because of their characteristic layered structures composed of noble metal A and strongly correlated B O 2 sublayers. However, thin film synthesis is known to be extremely challenging owing to their low symmetry rhombohedral structures, which limit the selection of substrates for thin film epitaxy. Hexagonal lattices, such as those provided by Al 2 O 3 (0001) and (111) oriented cubic perovskites, are promising candidates for epitaxy of delafossites. However, the formation of twin domains and impurity phases is hard to suppress, and the nucleation and growth mechanisms thereon have not been studied for the growth of epitaxial delafossites. In this study, we report the epitaxial stabilization of a new interfacial phase formed during pulsed-laser epitaxy of (0001)-oriented CuCrO 2 epitaxial thin films on Al 2 O 3 substrates. Through a combined study using scanning transmission electron microscopy/electron-energy loss spectroscopy and density functional theory calculations, we report that the nucleation of a thermodynamically stable, atomically thick CuCr 1-x Al x O 2 interfacial layer is the critical element for the epitaxy of CuCrO 2 delafossites on Al 2 O 3 substrates. This finding provides key insights into the thermodynamic mechanism for the nucleation of intermixing-induced buffer layers that can be used for the growth of other noble-metal-based delafossites, which are known to be challenging due to the difficulty in initial nucleation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Metal–insulator transition tuned by oxygen vacancy migration across TiO2/VO2 interface

Abstract Oxygen defects are essential building blocks for designing functional oxides with remarkable properties, ranging from electrical and ionic conductivity to magnetism and ferroelectricity. Oxygen defects, despite being spatially localized, can profoundly alter global properties such as the crystal symmetry and electronic structure, thereby enabling emergent phenomena. In this work, we achieved tunable metal–insulator transitions (MIT) in oxide heterostructures by inducing interfacial oxygen vacancy migration. We chose the non-stoichiometric VO 2-δ as a model system due to its near room temperature MIT temperature. We found that depositing a TiO 2 capping layer on an epitaxial VO 2 thin film can effectively reduce the resistance of the insulating phase in VO 2 , yielding a significantly reduced R OFF /R ON ratio. We systematically studied the TiO 2 /VO 2 heterostructures by structural and transport measurements, X-ray photoelectron spectroscopy, and ab initio calculations and found that oxygen vacancy migration from TiO 2 to VO 2 is responsible for the suppression of the MIT. Our findings underscore the importance of the interfacial oxygen vacancy migration and redistribution in controlling the electronic structure and emergent functionality of the heterostructure, thereby providing a new approach to designing oxide heterostructures for novel ionotronics and neuromorphic-computing devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Crystallographic analysis of nano-tendril bundle vs fuzz growth on tungsten exposed to helicon wave-coupled helium plasma

The propensity for nano-tendril bundle (NTB) vs widespread nano-tendril growth (i.e., fuzz) on polycrystalline W under varying ion energy modulation conditions, from DC to peak-to-peak energy modulation of 42 eV at 13.56 MHz, is correlated with the crystal orientation of the underlying grains. Grains that are vicinal to crystal orientations with high surface diffusivity (e.g., {101} for a body centered cubic crystal structure) exhibit NTB growth at lower ion energy modulation amplitude than grains that are vicinal to low surface diffusivity orientations, such as {100}. Adatom mobility considerations are presented to describe the experimental observations. These results support that surface diffusion or W adatom mobility enhanced by ion bombardment plays a key role in the surface morphology evolution of W under He irradiation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Accuracy of XAS theory for unraveling structural changes of adsorbates: CO on Ni(100)

Studying surface reactions using ultrafast optical pump and X-ray probe experiments relies on accurate calculations of X-ray spectra of adsorbates for correct identification of the spectral signatures and their dynamical evolution. We show that experimental XAS can be well reproduced for the different binding sites in a static prototype system CO/Ni(100) at a standard DFT (GGA) level of theory, using a plane-wave basis and pseudopotentials. This validates its utility in analyzing ultrafast X-ray probe experiments. The accuracy of computed relative core level binding energies is about 0.2 eV, representing a lower limit for which spectral features can be resolved with this method. We also show that the commonly used Z +1 approximation gives very good core binding energy shifts overall. However, we find a discrepancy for CO adsorbed in the hollow site, which we assign to the significantly stronger hybridization in hollow bonding than in on-top.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Enhanced electro-osmosis in propylene carbonate salt solutions

Properties of solid–liquid interfaces and surface charge characteristics mediate ionic and molecular transport through porous systems, affecting many processes such as separations. Herein, we report experiments designed to probe the electrochemical properties of solid–liquid interfaces using a model system of a single polyethylene terephthalate (PET) pore in contact with aqueous and propylene carbonate solutions of LiClO 4 . First, the existence and polarity of surface charges were inferred from current–voltage curves recorded when a pore was placed in contact with a LiClO4 concentration gradient. Second, the electro-osmotic transport of uncharged polystyrene particles through the PET pore provided information on the polarity and the magnitude of the pore walls’ zeta potential. Our experiments show that the PET pores become effectively positively charged when in contact with LiClO 4 solutions in propylene carbonate, even though in aqueous LiClO 4 , the same pores are negatively charged. Additionally, the electro-osmotic velocity of the particles revealed a significantly higher magnitude of the positive zeta potential of the pores in propylene carbonate compared to the magnitude of the negative zeta potential in water. The presented methods of probing the properties of solid–liquid interfaces are expected to be applicable to a wide variety of solid and liquid systems.

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

The role of surfaces in flexoelectricity

We develop the relationship between the strain derivative of the mean-inner potential and surface contributions to flexoelectricity, identifying the true surface-specific component of the flexoelectric response of finite samples. Density functional theory calculations on a range of experimentally observed, low energy SrTiO 3 , MgO, and Si surfaces demonstrate that the mean-inner potential and its contributions to flexoelectricity are sensitive to small differences in surface structure, chemistry, and adsorbates. We also introduce a method to estimate mean-inner potential contributions to flexoelectricity using electron scattering factors and use this approximation to predict total flexoelectric responses for a variety of insulators. Strategies to experimentally disentangle bulk and surface flexoelectric terms are also discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

RF sheath induced sputtering on Proto-MPEX part 2: Impurity transport modeling and experimental comparison

The Prototype Material Plasma Exposure eXperiment (Proto-MPEX) is a pulsed linear plasma device that uses a radio frequency (RF) helicon antenna and a helicon ceramic window as the plasma ionization source. Modeling performed within this work on the helicon operations predicts hot spots on the helicon ceramic window due to an RF-induced sheath. The RF sheath potential leads to physical sputtering of the ceramic window predominantly where the helicon antenna sits around the helicon window. The role of oxygen in sputtering within Proto-MPEX is also investigated and is needed to match the experimental data. Experiments on Proto-MPEX show reasonable agreement with the modeled erosion/redeposition pattern on the helicon window, and the modeled impurity flux to the target shows radial transport within the device as expected from classical collisional impurity transport. Temperature screening of impurities is shown to be needed for Proto-MPEX to reduce impurity flux to the target. The modeling approach used in this work can be applied to other plasma RF applications for the determination of impurity production and transport.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Elucidating the water–anatase TiO 2 (101) interface structure using infrared signatures and molecular dynamics

The structure and dynamics of water on solid surfaces critically affect the chemistry of materials in ambient and aqueous environments. Here, we investigate the hydrogen bonding network of water adsorbed on the majority (101) surface of anatase TiO 2 , a widely used photocatalyst, using polarization- and azimuth-resolved infrared spectroscopy combined with neural network potential molecular dynamics simulations. Our results show that one monolayer of water saturates the undercoordinated titanium (Ti 5c ) sites, forming one-dimensional chains of molecule hydrogen bonded to surface undercoordinated bridging oxygen (O 2c ) atoms. As the coverage increases, water adsorption on O 2c sites leads to significant restructuring of the water monolayer and the formation of a two-dimensional hydrogen bond network characterized by tightly bound pairs of water molecules on adjacent Ti 5c and O 2c sites. This structural motif likely persists at ambient conditions, influencing the reactions occurring there. In conclusion, the results reported here provide critical details of the structure of the water–anatase (101) interface that were previously hypothesized but unconfirmed experimentally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Development of an atomic layer deposition system for deposition of alumina as a hydrogen permeation barrier

Tritium permeation into and through materials poses a critical challenge for the development of nuclear fusion reactors. Minimizing tritium permeation is essential for the safe and efficient use of available fuel supplies. In this work, we present the design, construction, and validation of custom atomic layer deposition (ALD) and deuterium permeation measurement systems aimed at developing thin-film hydrogen permeation barriers. Using the ALD system, we deposited conformal $\mathrm{Al}_{2}\mathrm{O}_{3}$ films on copper foil substrates and characterized their growth behavior, morphology, and composition. ALD growth rates of ∼1.1 Å/cycle were achieved for temperatures between 100 ∘ C and 210 ∘ C. Permeation measurements on bare and alumina coated copper foils revealed a significant reduction in deuterium flux with the addition of a ∼10 nm $\mathrm{Al}_{2}\mathrm{O}_{3}$ layer. While bare copper followed diffusion-limited transport consistent with Sievert’s law, the alumina-coated samples exhibited surface-limited, pore-mediated transport with linear pressure dependence. Arrhenius analysis showed distinct differences in activation energy for the two transport regimes, and permeation reduction factors exceeding an order of magnitude were observed. These results demonstrate the potential of ALD-grown $\mathrm{Al}_{2}\mathrm{O}_{3}$ films as effective hydrogen isotope barriers and provide a foundation for future studies on film optimization and integration into fusion-relevant components.

atomic layer deposition↗
DOE OSTI2021

Dependence of the electronic structure of the EuS/InAs interface on the bonding configuration

The EuS/InAs interface has recently attracted attention for the possibility of inducing magnetic exchange correlations in a strong spin-orbit semiconductor, which could be useful for topological quantum devices. We use density functional theory with a machine-learned Hubbard U correction [Yu et al., npj Comput. Mater. 6, 180 (2020)] to elucidate the effect of the bonding configuration at the interface on the electronic structure. For all interface configurations considered here, we find that the EuS valence band maximum (VBM) lies below the InAs VBM. In addition, dispersed states emerge at the top of the InAs VBM at the interface, which do not exist in either material separately. These states are contributed mainly by the InAs layer adjacent to the interface. They are localized at the interface and may be attributed to charge transfer from the EuS to the InAs. The interface configuration affects the position of the EuS VBM with respect to the InAs VBM, as well as the dispersion of the interface states. For all interface configurations studied here, the induced magnetic moment in the InAs is small. Our results suggest that this interface, in its coherent form studied here, may not be promising for inducing equilibrium magnetic properties in InAs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Observation of gapless nodal-line states in NdSbTe

Lanthanide (Ln)-based systems in ZrSiS-type nodal-line semimetals have been subjects of research investigations as grounds for studying the interplay of topology with possible magnetic ordering and electronic correlations that may originate from the presence of Ln4f electrons. In this study, we carried out a thorough study of a LnSbTe system, NdSbTe, by using angle-resolved photoemission spectroscopy along with first-principles calculations and thermodynamic measurements. We experimentally detect the presence of multiple gapless nodal-line states, which is well supported by first-principles calculations. A dispersive and an almost nondispersive nodal line exist along the bulk X–R direction. Another nodal line is present well below the Fermi level across the Γ–M direction, which is formed by bands with high Fermi velocity that seem to be sensitive to light polarization. Finally, our study provides insight into the electronic structure of an alternative Ln⁢SbTe material system that will aid towards understanding the connection of Ln elements with topological electronic structures in these systems.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Opportunities and new developments for the study of surfaces and interfaces in soft condensed matter at the SIRIUS beamline of Synchrotron SOLEIL

The SIRIUS beamline of Synchrotron SOLEIL is dedicated to X-ray scattering and spectroscopy of surfaces and interfaces, covering the tender to mid-hard X-ray range (1.1–13 keV). The beamline has hosted a wide range of experiments in the field of soft interfaces and beyond, providing various grazing-incidence techniques such as diffraction and wide-angle scattering (GIXD/GIWAXS), small-angle scattering (GISAXS) and X-ray fluorescence in total reflection (TXRF). SIRIUS also offers specific sample environments tailored for in situ complementary experiments on solid and liquid surfaces. Recently, the beamline has added compound refractive lenses associated with a transfocator, allowing for the X-ray beam to be focused down to 10 µm × 10 µm while maintaining a reasonable flux on the sample. This new feature opens up new possibilities for faster GIXD measurements at the liquid–air interface and for measurements on samples with narrow geometries.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Superconducting platinum silicide analyzed by x-ray photoelectron spectroscopy

Platinum silicide has garnered increased attention due to its potential applications as a superconductor within silicon technology. In this work, we characterize a superconducting PtSi film using x-ray photoelectron spectroscopy with an Al K α excitation source. Survey spectra, Pt 5s, Pt 4f, Pt 4d, Pt 4p, Pt 4s, Si 2p, Si 2s, O 1s core levels, and the valence band spectrum were measured. In conclusion, this collection of high-quality core level spectra of a superconducting PtSi film provide reference data for this material, which often has a minimal native silicon oxide layer and overlapping Si and Pt core level peaks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗