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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,099 records · Page 61
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Electrolyte Solvation Structure at Solid/Liquid Interface Probed by Nanogap Surface-Enhanced Raman Spectroscopy

Understanding the fundamental factors that drive ion solvation structure and transport is key to design high performance, stable battery electrolytes. Reversible ion solvation and desolvation are critical to the interfacial charge transfer process across the solid-liquid interface as well as the resulting stability of the solid electrolyte interphase (SEI). Here in this paper, we report the first study of Li+ salt solvation structure in aprotic solution in the immediate vicinity (~ 20 nm) of the solid electrode-liquid interface using surface-enhanced Raman spectroscopy (SERS) from a gold nanoparticle (Au NP) monolayer. The plasmonic coupling between Au NPs produces strong electromagnetic field enhancement in the gap region, leading to 5 orders of magnitude increase in Raman intensity for electrolyte components and their mixtures namely, lithium hexafluorophosphate (LiPF6), fluoroethylene carbonate (FEC), ethylene carbonate (EC) and diethyl carbonate (DEC). Further, we estimate and compare the lithium-ion solvation number derived from SERS and Infra-Red (FTIR) spectroscopy experiments to monitor and ascertain the changes in the solvation shell diameter in the confined nanogap region where there is maximum enhancement of the electric field. Our findings provide a new multi-modal spectroscopic approach to gain fundamental insights into the molecular structure of the electrolyte at the solid-liquid interface.

25 ENERGY STORAGE↗
DOE OSTI2020

Probing Heterogeneous Charge Distributions at the α-Al 2 O 3 (0001)/H 2 O Interface

Unlike metal or semiconductor electrodes, the surface charge resulting from the protonation or deprotonation of insulating mineral oxides is highly localized and heterogeneous in nature. In this work the Stark active C≡N stretch of potassium thiocyanate is used as a molecular probe of the heterogeneity of the interfacial electrostatic potential at the α-Al 2 O 3 (0001)/H 2 O interface. Vibrational sum frequency generation (vSFG) measurements performed in the OH stretching region suggest that thiocyanate species organize interfacial water similarly to halide ions. Changes in the electrostatic potential are then tracked via Stark shifts of the vibrational frequency of the thiocyanate stretch. Our vSFG measurements show that we can simultaneously measure the vSFG response of SCN – ions experiencing charged and neutral surface sites. We assign local potentials of +308 and -154 mV to positively and negatively charged aluminol groups that are present at pH = 4 and pH = 10, respectively. Thiocyanate anions at positively charged surface sites and negatively charged surface sites and those participating in contact ion pairing adopt similar orientations and are oppositely oriented relative to thiocyanate ions near neutral surface sites. All four species followed Langmuir adsorption isotherms. Density functional theory–molecular dynamics (DFT-MD) simulations of SCN – near the neutral α-Al 2 O 3 (0001)/H 2 O interface show that the vSFG response in the C≡N stretch region originates from a SCN–H–O–Al complex, suggesting the surface site specificity of these experiments. To our knowledge this is the first spectroscopic measurement of local potentials associated with a heterogeneously charged surface. The ability to probe the evolution of local charges in situ could provide vital insight into many industrial, electrochemical, and geochemically relevant interfaces.

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

Electron Inversion and Tunneling at Silicon Thermal Oxide Interfaces for Solar-Driven Molecular Catalysis to Syngas

Semiconductor photoelectrodes are regularly coupled to solid-state heterogeneous catalysts to perform solar-driven reduction of CO 2 . Less frequently, molecular catalysts are employed to better control the reactivity toward desired products, yet the development of robust semiconductor/molecule interfaces has proven challenging. Here, we demonstrate that a 2–3 nm thermal oxide layer on Si exhibits stability in aqueous solution, high photovoltage, and a photocurrent density of ∼10 mA/cm 2 for the solar-driven photoelectrochemical reduction of a homogeneous molecular catalyst, producing syngas with an ∼2:1 H 2 to CO ratio. Because of a low defect density, the oxide interface forms an electron inversion layer with metal-like electron density at cathodic potentials. This inversion layer facilitates electron transfer to redox-active molecules via tunneling even if the molecule’s reduction potential is beyond the semiconductor’s conduction band edge. Using an electrolyte solution composed of a homogeneous cobalt bis(terpyridine) catalyst in a water/organic solvent mixture, stable photoelectrochemistry was observed under 1-sun illumination, exhibiting an ∼30% Faradaic efficiency for CO that was similar to a glassy carbon electrode under comparable conditions. Furthermore, the results demonstrate that an ultrathin thermal oxide interface is a robust platform for development of aqueous-stable, molecule-driven photoelectrocatalysis.

Catalysts↗
DOE OSTI2026

pH-Driven Restructuring of Hydration Layers and Cation Adsorption at the Alumina–Water Interface

Oxide−water interfaces underpin ion separations, catalysis, and electrochemical energy technologies, where the electrical double layer (EDL) controls adsorption, transport, and reactivity. However, the molecular-scale links between pHdependent surface protonation, hydration-layer structure, and counterion adsorption remain poorly defined. Here, we combine in situ crystal truncation rod (CTR) and resonant anomalous X-ray reflectivity (RAXR) with streaming potential measurements and ab initio molecular dynamics (AIMD) simulations to resolve the chemical and structural evolution of the EDL at the single-crystal alumina (012)−water interface in 10 mM Rb + over pH 3−12. CTR measurements reveal two distinct adsorbed water layers at ∼2.2 and ∼3.5 Å above the surface. Each water layer shifts toward the substrate at transition pHs near 6.5 and 10.6, respectively, reflecting changes in primary hydration layer structure in response to the deprotonation of bridging and terminal aluminol groups. RAXR shows a 10-fold increase in Rb + coverage and a decrease in mean adsorption height from ∼3.5 to ∼2.7 Å with increasing pH, indicating enhanced counterion binding accompanied by Stern layer contraction. Streaming potential measurements demonstrate that the zeta potential, i.e., the potential at the hydrodynamic shear plane, is positive at pH 3 and becomes negative at pH ≥ 3.5. The negative charge magnitude increases with increasing pH, consistent with progressive surface deprotonation at higher pH. AIMD identifies inner- and outer-sphere Rb+ complexes whose adsorption heights and coordination geometries depend sensitively on the protonation state of surface oxygens, providing atomistic support for the experimentally inferred trends. These measurements establish two discrete, site-specific pH transitions in hydration-layer structure that track aluminol (de)protonation and quantitatively link them to a pH-driven contraction of the Stern layer (increasing Rb + coverage and decreasing adsorption height). This provides a direct structural basis for connecting surface acid−base chemistry to ion binding distances at an oxide−water interface.

Adsorption↗
DOE OSTI2020

Design and Evaluation of a Tethered, Open Port Sampling Interface for Liquid Extraction-Mass Spectrometry Chemical Analysis

Presented in this work is a tethered, liquid-extraction-sampling interface designed for the mass spectrometric surface sampling/analysis of 3D objects. The tethered, open port sampling interface (TOPSI) incorporates a vacuum line between the sampling probe and ionization source, which enables the ability for an extended, tethered sample transfer line. Herein, several designs of the hand-held TOPSI are presented and evaluated on the basis of the analytical metrics of analyte transport time, peak width, and analyte sensitivity. The best analytical metrics were obtained with capillary flow resistances arranged in a particular order and the vacuum region set at 6.2 kPa. This TOPSI design incorporated a transfer capillary 1 m in length, while retaining a fast analyte transport time (12 s), short signal peak width (5 s baseline-to-baseline), and high analyte signal at 90% of that obtained with a regular open port sampling interface (OPSI). The hand-held TOPSI was demonstrated for the characterization of extracted small molecules and metabolites from the surface of mint and rosemary leaves.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Tough and circular glass fiber composites via a tailored dynamic boronic ester interface

Glass fiber reinforced polymer (GFRP) composites are valued for their strength and cost-effectiveness. However, traditional GFRPs often face challenges for end-of-life recycling due to their non-depolymerizable thermoset matrices, and long-term performance due to inadequate interfacial adhesion, which can lead to fiber–matrix delamination. Here, in this work, we have designed dynamic fiber–matrix interfaces to allow tough and closed-loop recyclable GFRPs by utilizing a vitrimer, derived from upcycled polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) with boronic ester (S-Bpin) and amine-based diol crosslinker. The boronic ester groups in S-Bpin form dynamic covalent bonds with the naturally present hydroxyl groups on the unsized GF surface, which eliminates the need for fiber sizing and enables facile closed-loop recyclability of both the fibers and the vitrimer matrix. The resulting strong fiber–matrix interface, depicted by the Raman mapping, leads to a 552% increase in-plane shear toughness (6.2 ± 0.3 MJ m -3 ) and 27% ultimate tensile strength (361 ± 89.2 MPa) compared to those of the conventional epoxy-based matrix (0.95 ± 0.05 MJ m -3 and 264 ± 59.7 MPa, respectively). The network rearrangement through dynamic boronic ester exchange enables fast thermoformability and repairability of micro-cracks at elevated temperatures. Additionally, both the matrix and composite demonstrate strong adhesion to various surfaces including steel and glasses exhibiting ≥6 MPa lap shear strength, which expands their suitability for diverse industrial applications. The readily created dynamic interface between boronic ester functionalized vitrimer and neat GFs presents a promising strategy for developing closed-loop recyclable, multifunctional structural materials, offering a sustainable alternative to non-recyclable thermoset GFRPs and contributes to a circular economy in composite materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Thermal interfaces in dynamic compression experiments

Temperature is a difficult thermodynamic variable to measure in dynamic compression experiments. Optical pyrometry is a general-purpose technique for measuring temperature from a radiant surface, but that surface is often the interface between distinct materials with temperatures that vary spatially along the loading direction. This leads to a fundamental problem: how does the measured interface temperature relate to this temperature profile along the compression axis? Numerical analysis of loading history and thermal diffusion at these interfaces shows that seemingly subtle changes in experiment geometry can lead to very different temperature profiles. We compare these results to laboratory temperature measurements of shock-compressed tin.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Interface learning in fluid dynamics: Statistical inference of closures within micro–macro-coupling models

Many complex multiphysics systems in fluid dynamics involve using solvers with varied levels of approximations in different regions of the computational domain to resolve multiple spatiotemporal scales present in the flow. The accuracy of the solution is governed by how the information is exchanged between these solvers at the interface and several methods have been devised for such coupling problems. In this article, we construct a data-driven model by spatially coupling a microscale lattice Boltzmann method (LBM) solver and macroscale finite difference method (FDM) solver for reaction-diffusion systems. The coupling between the micro-macro solvers has one to many mapping at the interface leading to the interface closure problem, and we propose a statistical inference method based on neural networks to learn this closure relation. The performance of the proposed framework in a bifidelity setting partitioned between the FDM and LBM domain shows its promise for complex systems where analytical relations between micro-macro solvers are not available.

42 ENGINEERING↗
DOE OSTI2026

Hidden features in the OH-stretching spectra of amino acid decorated air–water interfaces

Chemical reactivity at the air–water interface is governed by the interfacial solvation of reactive species. For instance, during aqueous amino acid-based CO 2 absorption, water reorganizes around the reactive sites and couples dynamically with reaction pathways, facilitating the reaction. In this context, surface-sensitive vibrational sum-frequency generation (vSFG) spectroscopy can probe the OH stretch vibrations of interfacial water and determine the solvation structures around reactants and products, thereby furthering our understanding of the role of interfacial solvation. However, vSFG spectra of the air–water interface in the presence of charged species can be remarkably complex; key species-bound local water structures with distinct orientations may be hidden beneath prominent vSFG peaks arising from water–water hydrogen bonds and remain difficult to resolve. Here, we measure and compute vSFG spectra of the water OH stretch at air–water interfaces decorated with amino acids in their zwitterionic and anionic forms, as well as equimolar mixtures of these forms with bicarbonate. The latter represents post-CO 2 -absorption conditions. We find that computing depth- and frequency-dependent spectral densities—decomposed into contributions from water molecules hydrogen-bonded exclusively to other water molecules, exclusively to amines, exclusively to carboxylates, or shared between these polar/charged groups—is indispensable for accurate interpretation of the vSFG spectra. Key findings include orientational flip-flop in water sub-layers, strong carboxylate-water H-bonding, and water orientational ordering extending into the bulk aqueous phase induced by anionic amino acids. Here, this study provides a computational spectroscopic platform for improved understanding of interfacial solvation relevant to interfacial reactivity.

Air-water interface↗
DOE OSTI2025

Strong adsorption of guanidinium cations to the air–water interface

Combining Deep-UV second harmonic generation spectroscopy with molecular simulations, we confirm and quantify the specific adsorption of guanidinium cations to the air–water interface. Using a Langmuir analysis of measurements at multiple concentrations, we extract the Gibbs free energy of adsorption, finding it larger than typical thermal energies. Molecular simulations clarify the role of polarizability in tuning the thermodynamics of adsorption, and establish the preferential parallel alignment of guanidinium at the air–water interface. As a polyatomic cation, guanidinium represents one of the few examples of a positively charged species to exhibit a propensity for the air-water interface. As such, these results expand on the growing body of work on specific ion adsorption.

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

Molecular dynamics simulation of zirconium tungstate amorphization and the amorphous-crystalline interface

Classical molecular dynamics (MD) simulations were performed to provide a conceptual understanding of the amorphous-crystalline interface for a candidate negative thermal expansion (NTE) material, ZrW 2 O 8 . Simulations of pressure-induced amorphization at 300 K indicate that an amorphous phase forms at pressures of 10 GPa and greater, and this phase persists when the pressure is subsequently decreased to 1 bar. However, the crystalline phase is recovered when the slightly distorted 5 GPa phase is relaxed to 1 bar. Simulations were also performed on a two-phase model consisting of the high-pressure amorphous phase in direct contact with the crystalline phase. Upon equilibration at 300 K and 1 bar, the crystalline phase remains unchanged beyond a thin layer of disrupted structure at the crystalline-amorphous interface. In conclusion, the differences in local atomic structure at the interface are quantified from the simulation trajectories.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Detection of uncompensated magnetization at the interface of an epitaxial antiferromagnetic insulator

We have probed directly the temperature and magnetic field dependence of pinned uncompensated magnetization at the interface of antiferromagnetic FeF 2 with Cu, using FeF 2 -Cu-Co spin valves. Electrons polarized by the Co layer are scattered by the pinned uncompensated moments at the FeF 2 -Cu interface giving rise to giant magnetoresistance. We determined the direction and magnitude of the pinned uncompensated magnetization at different magnetic fields and temperatures using the angular dependencies of resistance. The strong FeF 2 anisotropy pins the uncompensated magnetization along the easy axis independent of the cooling field orientation. Most interestingly, magnetic fields as high as 90 kOe cannot break the pinning at the FeF 2 -Cu interface. This proves that the pinned interfacial magnetization is strongly coupled to the antiferromagnetic order inside the bulk FeF 2 layer. Studies as a function of FeF2 crystalline orientation show that uncompensated spins are only detected in a spin valve with (110) crystal orientation, but not in valves containing FeF 2 (100) and FeF 2 (001). This observation is in agreement with symmetry-related considerations which predict the equilibrium boundary magnetization for the FeF 2 (110) layer.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Emergence of topological and trivial interface states in VSe 2 films coupled to Bi 2 Se 3

Coupling ordinary metals with topological Bi 2 Se 3 can instigate the long-range migration of the spin-polarized Dirac states. Instead, for trivial metallic VSe 2 films on Bi 2 Se 3 , topological and trivial Rashba-type interface states emerge, each strongly localized at the VSe 2 /Bi 2 Se 3 interface. Their rapidly decaying spectral weights are uncovered by thickness-dependent band mappings of VSe 2 films and replicated by a phenomenological first-principles model of the spectral function. In this work, the results are pertinent to spintronic devices requiring spin transmission across metal/topological insulator interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Antiferromagnetic Fe Te 2 1 T - phase formation at the Sb 2 Te 3 / Ni 80 Fe 20 interface

Bilayer topological insulator/ferromagnet (TI/FM) heterostructures are promising for spintronic applications due to their low switching energy and therefore power efficiency. Until recently, the reactivity of TI with FM films was overlooked in the spin orbit-torque literature, even though there are reports that it is energetically favorable for TIs to react with transition metals and form interfacial layers. Here, in this study we fabricated a TI/FM heterostructure comprised of molecular beam epitaxy grown Sb 2 Te 3 and DC sputtered Ni 80 Fe 20 . Broadband ferromagnetic resonance revealed spin-pumping evident by the significant enhancement in Gilbert damping, which is likely a signature of the topological surface states or the presence of large spin-orbit-coupling in the adjacent Sb 2 Te 3 . With low-temperature magnetometry, an exchange bias is observed which indicates an exchange interaction between an antiferromagnet (AFM) and an adjacent FM. Cross-section high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) characterization of the Sb 2 Te 3 - Ni 80 Fe 20 bilayer revealed a complex interface showing diffusion of Fe and Ni into the Sb 2 Te 3 film yielding the formation of a FeTe 2 1T-type structural phase. Furthermore, density functional theory calculations revealed that the FeTe 2 1T-phase has an AFM ground state. Due to experimental limitations in the electron energy loss spectroscopy measurements precise chemistry of the interfacial phase could not be determined, therefore it is possible that the FeTe 2 1T and/or an intermixed (Fe 1-x Ni x )Te 2 1T is the AFM interfacial phase contributing to exchange bias in the system. This work emphasizes the chemical complexity of TI/FM interfaces that host novel, metastable magnetic topological phases and require more in-depth studies of other similar interfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

First Principles Predictions of SnO2/CdTe and SnO2/CdCl2/CdTe Interface Structures

Interfaces become increasingly the limiting factor of solar cell efficiency, raising the interest in computational models. However, explicit atomic structure models from microscopy are rare, and hypothetical assumptions about the atomic structure become ambiguous for incoherent or highly lattice mismatched interfaces. Adopting a bulk crystal structure prediction algorithm to interfacial systems enables explicit structure models for the bare and CdCl 2 treated SnO 2 /CdTe interface.

CdTe↗
DOE OSTI2021

An Energy Service Interface for Distributed Energy Resources

Renewable energy resources, particularly wind and solar photovoltaic, are becoming significant contributors to electric power generation. These re-sources will contribute towards achieving sustainable electric power systems. However, renewable resources will dramatically increase the demand for flexible power system operations. This paper proposes an energy service interface that will allow aggregated distributed energy resources, such as residential loads and inverter-based systems, to participate in NERC-defined smart energy reliability services. Such cyber-physical systems will increase system flexibility by ensuring match between energy supply and energy demand.Aggregation and coordinated dispatch of millions of distributed energy resources will require development of large-scale computing networks. Several smart grid interface-enabling technologies, including IEEE 2030.5, Common Smart Inverter Profile, SunSpec Modbus, and CTA 2045, are discussed. Residential loads are categorized by their static and dynamic energy characteristics to identify services in which they can participate. The business model for the energy services interface as well as probabilistic modeling for resource estimation are highlighted as future considerations.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2022

Proposed Application for an Entity Component System in an Energy Services Interface

An Entity Component System is a data-oriented architecture originally developed to streamline video game performance. Despite being quite new, Entity Component Systems are relatively well established within the video game industry due to the cutting edge nature of research into performance, especially around graphics. However, Entity Component Systems have not been widely examined or adopted outside of that industry. We propose adopting an Entity Component Systems framework to serve the needs of an Energy Service Interfaces. We examine the needs of an Energy Service Interface, give an overview of open-source Entity Component Systems (ECSs) libraries, examine some preliminary performance results for ECSs, and explore the traditional approach to fulfilling the needs of an Energy Service Interface (ESI) with database architectures.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Emergent phenomena at oxide interfaces studied with standing-wave photoelectron spectroscopy

Emergent phenomena at complex-oxide interfaces have become a vibrant field of study in the past two decades due to the rich physics and a wide range of possibilities for creating new states of matter and novel functionalities for potential devices. The electronic-structural characterization of such phenomena presents a unique challenge due to the lack of direct yet nondestructive techniques for probing buried layers and interfaces with the required Ångstrom-level resolution, as well as element and orbital specificity. In this Review, we survey several recent studies wherein soft x-ray standing-wave photoelectron spectroscopy—a relatively newly developed technique—is used to investigate buried oxide interfaces exhibiting emergent phenomena such as metal-insulator transition, interfacial ferromagnetism, and two-dimensional electron gas. The advantages, challenges, and future applications of this methodology are also discussed.

36 MATERIALS SCIENCE↗