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Results for “RAMAN SPECTROSCOPY”

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 1,243 records · Page 69
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Raman Microscopy Investigation of GLP-1 Peptide Association with Supported Phospholipid Bilayers

A wide range of important biological processes occur at phospholipid membranes including cell signaling, where a peptide or small molecule targets a membrane-localized receptor protein. In this work, we report the adaptation of confocal-Raman microscopy to quantify populations of unlabeled glucagon-like peptide-1 (GLP-1), a membrane-active 30-residue incretin peptide, in supported phospholipid bilayers deposited on the interior surfaces of wide-pore porous silica particles. Quantification of lipid bilayer-associated peptide is achieved by measuring the Raman scattering intensity of the peptide relative to that of the supported-lipid bilayer, which serves as an internal standard. The dependence of the bilayer-associated GLP-1 population on the solution-concentration of GLP-1 produces an isotherm used to determine the equilibrium constant for peptide-bilayer association and the maximum peptide surface coverage. The maximum coverage of GLP-1 in the lipid bilayer was found to be only 1/5th of a full monolayer based on its hydrodynamic radius. The saturation coverage, therefore, is not limited by the size of GLP-1 but by the ability of the bilayer to accommodate the peptide at high concentrations within the bilayer. Raman spectra show that GLP-1 association with the supported bilayer is accompanied by structural changes consistent with the intercalation of the peptide into bilayer, where the observed increase in acyl-chain order would increase the lipid density and provide free volume needed to accommodate the peptide. Furthermore, these results were compared with previous measurements of the association of fluorescently-labeled GLP-1 with a planar-supported bilayer; the unlabeled peptide exhibits a 3-fold greater affinity for the lipid-bilayer on the porous-silica support suggesting that the fluorescent label alters GLP-1 lipid-bilayer association.

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

Inter-Leaflet Phospholipid Exchange Impacts the Ligand Density Available for Protein Binding at Supported Lipid Bilayers

Phospholipid bilayers formed at solid-liquid interfaces have garnered interest as mimics of cell-membranes to model association reactions of proteins with lipid-bilayer-tethered ligands. Despite the importance of understanding how ligand density in a lipid bilayer impacts the protein-ligand association response, relating the ligand-modified lipid fraction to the absolute density of solution-accessible ligands in a lipid bilayer remains a challenge in interfacial quantitative analysis. In this work, confocal-Raman microscopy is employed to quantify the association of anti-biotin IgG with a small fraction of biotinylated lipids dispersed in either gel-phase or liquid-crystalline supported lipid bilayers, deposited on the interior surfaces of wide-pore silica surfaces. We examine the question whether inter-leaflet lipid translocation contributes to the population of solution-accessible biotin ligands on the distal leaflet of a supported lipid bilayer by comparing their protein accumulation response with ligands dispersed in lipid monolayers on nitrile-derivatized silica surfaces. The binding of antibody to biotin ligands dispersed in gel-phase bilayers exhibited an equivalent biotin-coverage response as the accumulation of IgG onto gel-phase monolayers, indicating that gel-phase bilayer symmetry was preserved. This result contrasts with the ~60% greater anti-biotin capture observed at fluid-phase bilayers compared to fluid-phase monolayers prepared at equivalent biotin fractions. This enhanced protein capture is attributed to biotin-capped lipids being transferred from the surface-associated proximal leaflet of the bilayer to the solution-exposed distal leaflet by the inter-leaflet exchange or lipid flip-flop, a facile process in fluid-phase supported lipid bilayers. Here, the results suggest caution in interpreting the results of quantitative studies of protein binding to lipid-tethered ligands dispersed in fluid-phase phospholipid bilayers.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Excitations of Intercalated Metal Monolayers in Transition Metal Dichalcogenides

We combine Raman scattering spectroscopy and lattice dynamics calculations to reveal the fundamental excitations of the intercalated metal monolayers in the Fe x TaS 2 (x = 1/4, 1/3) family of materials. Both in- and out-of-plane modes are identified, each of which has trends that depend upon the metal–metal distance, the size of the van der Waals gap, and the metal-to-chalcogenide slab mass ratio. We test these trends against the response of similar systems, including Cr-intercalated NbS 2 and RbFe(SO 4 ) 2 , and demonstrate that the metal monolayer excitations are both coherent and tunable. Here, we discuss the consequences of intercalated metal monolayer excitations for material properties and developing applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Electron–Phonon and Spin–Lattice Coupling in Atomically Thin Layers of MnBi 2 Te 4

MnBi 2 Te 4 represents a new class of magnetic topological insulators in which novel quantum phases emerge at temperatures higher than those found in magnetically doped thin films. Here in this paper, we investigate how couplings between electron, spin, and lattice are manifested in the phonon spectra of few-septuple-layer thick MnBi 2 Te 4 . After categorizing phonon modes by their symmetries, we study the systematic changes in frequency, line width, and line shape of a spectrally isolated A1g mode. The electron–phonon coupling increases in thinner flakes as manifested in a broader phonon line width, which is likely due to changes of the electron density of states. In 4- and 5-septuple thick samples, the onset of magnetic order below the Néel temperature is concurrent with a transition to an insulating state. We observe signatures of a reduced electron–phonon scattering across this transition as reflected in the reduced Fano parameter. Finally, spin–lattice coupling is measured and modeled from temperature-dependent phonon frequency.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Spin–Phonon Coupling and Magnetic Transition in an Organic Molecule Intercalated Cr 2 Ge 2 Te 6

The manipulation of spin–phonon coupling in both formations and explorations of magnetism in two-dimensional van der Waals ferromagnetic semiconductors facilitates unprecedented prospects for spintronic devices. The interlayer engineering with spin–phonon coupling promises controllable magnetism via organic cation intercalation. Here, in this study, spectroscopic evidence reveals the intercalation effect on the intrinsic magnetic and electronic transitions in quasi-two-dimensional Cr 2 Ge 2 Te 6 using tetrabutyl ammonium (TBA + ) as the intercalant. The temperature evolution of Raman modes, E g 3 and A g 1 , along with the magnetization measurements, unambiguously captures the enhancement of the ferromagnetic Curie temperature in the intercalated heterostructure. Moreover, the E g 4 mode highlights the increased effect of spin–phonon interaction in magnetic-order-induced lattice distortion. Combined with the first-principle calculations, we observed a substantial number of electrons transferred from TBA + to Cr through the interface. The interplay between spin–phonon coupling and magnetic ordering in van der Waals magnets appeals for further understanding of the manipulation of magnetism in layered heterostructures.

2D magnet↗
DOE OSTI2024

Vibrational Fermi Resonance in Atomically Thin Black Phosphorus

Fermi resonance is a phenomenon involving the hybridization of two coincidentally quasi-degenerate states that is observed in the vibrational or electronic spectra of molecules. Despite numerous examples in molecular systems, vibrational Fermi resonances in dispersive semiconducting systems remain largely unexplored due to the rarity of occurrence. Here we report a vibrational Fermi resonance in atomically thin black phosphorus. The Fermi resonance arises via anharmonic mixing of a fundamental Raman mode and a Davydov component of an infrared mode, leading to a doublet with mixed character. The extent of Fermi coupling can be modulated by the application of external biaxial strain. The consequences of Fermi hybridization are revealed by electronic resonance effects in the thickness-dependent and excitation-wavelength-dependent Raman spectrum, which is predicted by ab initio hybrid functional simulations including excitonic interactions. This work reveals new insight into electron–phonon coupling in black phosphorus and demonstrates a novel method for modulating Fermi resonances in 2D semiconductors.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

In Situ Raman Mapping of Si Island Electrodes and Stress Modeling as a Function of Lithiation and Size

Si is known for cracking and delamination during electrochemical cycling of a battery due to the large volume change associated with Li insertion and extraction. However, it has been found experimentally that patterned Si island electrodes that are 200 nm thick and less than 7 μm wide can deform in a purely elastic manner. Inspired by this, we performed in situ Raman stress characterization of model poly-crystalline Si island electrodes using an electrochemical cell coupled with an immersion objective lens and designed for a short working distance. A 5 μm wide Si island electrode showed a parabolic stress profile during lithiation, while for a 15 μm Si island electrode, a stress plateau in the center of the electrode was observed. A continuum model with coupled electro-chemo-mechanical (ECM) physics was established to understand the stress measurement. A qualitative agreement was reached between modeling and experimental data, and the critical size effect could be explained by the Li diffusive flux as governed by competition between the Li concentration and hydrostatic stress gradients. Below the critical size, the stress gradient drives Li toward the edges, where the electrode volume is free to expand, while above the critical size, the stress plateau inhibits Li diffusion to the edge and forces destructive stress relief by cracking. Furthermore, this work represents a promising methodology for in situ characterization of ECM coupling in battery electrodes, with suggestions provided for further improvement.

25 ENERGY STORAGE↗
DOE OSTI2025

Ultrastable Gold Nanostars via Bottlebrush-like Block Copolymers

Gold (Au) nanostars are plasmonic nanostructures possessing potentials for small molecule detection, photocatalytic activities, and photothermal therapy. However, Au nanostars synthesized in the traditional way are often plagued by poor photo, thermal, and chemical stabilities. Here, we report an unconventional route to the synthesis of ultrastable colloidal Au nanostars enabled by bottlebrush-like block copolymers (BBCPs), dispensing with the need for Au seeds. Crafting of Au nanostars using BBCPs is rendered by bridging the latter with Au 3+ ions as cross-linkers that have multiple coordination sites. Notably, the presence of a covalently tethered polymer shell on the surface of Au nanostars (i.e., polymer-ligated Au nanostars) imparts remarkably high stability under high temperature and laser excitation over conventional cetyltrimethylammonium bromide (CTAB)-mediated Au nanostars. Due to enhanced laser stability, plasmonic fields near Au nanostars can be visualized under high laser fluence by ultrafast electron microscopy (UEM) without morphological degradation. Notably, the presence of insulating polystyrene chains does not compromise the plasmonic field distribution, with the highest field intensity observed along the star arms. In conclusion, the greatly improved long-term photo, thermal, and chemical stabilities make Au nanostars a prospective noble metal nanomaterial for a range of sensing applications.

Cellulose↗
DOE OSTI2020

Crowd-Sourced Data and Analysis Tools for Advancing the Chemical Vapor Deposition of Graphene: Implications for Manufacturing

Industrial production of graphene by chemical vapor deposition (CVD) requires more than the ability to synthesize large domain, high-quality graphene in a lab reactor. The integration of graphene in the fabrication process of electronic devices requires the cost-effective and environmentally friendly production of graphene on dielectric substrates, but current approaches can only produce graphene on metal catalysts. Sustainable manufacturing of graphene should also conserve the catalyst and reaction gases, but today the metal catalysts are typically dissolved after synthesis. Progress toward these objectives is hindered by the hundreds of coupled synthesis parameters that can strongly affect CVD of low-dimensional materials and poor communication in the published literature of the rich experimental data that exists in individual laboratories. We report here on a platform, "graphene recipes for synthesis of high quality material" (Gr-ResQ: pronounced graphene rescue), which includes powerful new tools for data-driven graphene synthesis. At the core of Gr-ResQ is a crowd-sourced database of CVD synthesis recipes and associated experimental results. The database captures similar to 300 parameters ranging from synthesis conditions such as a catalyst material and preparation steps, to ambient lab temperature and reactor details, as well as resulting Raman spectra and microscopy images. These parameters are carefully selected to unlock the potential of machine-learning models to advance synthesis. A suite of associated tools enable fast, automated, and standardized processing of Raman spectra and scanning electron microscopy images. To facilitate community-based efforts, Gr-ResQ provides tools for cyber-physical collaborations among research groups, allowing experiments to be designed, executed, and analyzed by different teams. Gr-ResQ also allows publication and discovery of recipes via the Materials Data Facility, which assigns each recipe a unique identifier when published and collects parameters in a search index. We envision that this holistic approach to data-driven synthesis can accelerate CVD recipe discovery and production control and open opportunities for advancing not only graphene but also many other 1D and 2D materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Molecular Design of Supported MoO x Catalysts with Surface TaO x Promotion for Olefin Metathesis

A series of supported 3% MoOx catalysts were synthesized by incipient-wetness impregnation of 5%-15% TaO x surface modified γ-Al 2 O 3 support. The catalysts were characterized by in situ spectroscopies (DRIFTS, Raman, UV-vis, XAS) and multiple chemical probes (C 2 H 4 /C 4 H 8 titration, C 3 H 6 -TPSR, steady state propylene metathesis, NH 3 -IR adsorption). The supported tantalum oxide phase was present as surface TaO x sites on the γ-Al 2 O 3 support that capped that Al 2 O 3 surface hydroxyls. The change in available surface hydroxyls caused the subsequent anchoring of MoOx species to occur at different surface hydroxyls. This shifted the anchoring of MoO x species from basic (Al-OH) to neutral (Al 2 -OH) to more acidic (Al 3 -OH) surface hydroxyls as well as perturbation of the remaining alumina surface hydroxyls by the surface TaO x sites. The TaO x surface modified γ-Al 2 O 3 support increased the number of activated surface MoO x sites (Ns) by ~6x and the TOF by ~10x resulting in an increased activity of ~60x. In conclusion, It was found that the specific anchoring surface hydroxyls rather than the extent of oligomerization of the surface MoO x sites control the number of activated MoO x sites and TOF for propylene metathesis. No relationship between the nature of the surface Lewis/Brønsted acid sites and Ns and TOF were found to be present.

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

Atom Efficiency of Pd Sites for Methane Combustion: Single Atom Catalysts Versus Nanocatalysts

Methane combustion is an important reaction for energy production and methane removal from the atmosphere. This reaction highly relies on the use of noble metal Pd-based catalysts, which therefore drives the pursuit of catalysts with high atomic dispersion and activity. In this work, Pd/ceria catalysts dominated with Pd single atoms or nanosized Pd clusters (∼1 nm) are prepared and characterized by combining high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS), and Raman and X-ray absorption spectroscopy (XAS) techniques. By comparing the turnover frequencies (TOF; per every Pd atom) of Pd/ceria single atom catalysts and nanocatalysts, it is found that the atom efficiency of Pd is increased by 10 ∼30 times from single atom catalysts to nanocatalysts. For Pd single atom catalysts, although their activity can be tuned by changing the local structures, the intrinsic activity and number of active sites need to be further improved by engineering the surfaces of supports. For nanosized Pd species, despite the high TOF, the Pd atoms in the bulk structure are not directly participating in the catalytic reaction. Furthermore, this work highlights the importance of increasing the intrinsic activity of individual noble atoms, as well as the homogeneity of their local structures. For Pd/ceria systems reported in this work, our results indicate that from the application point of view, at the current stage, it is not practical to replace Pd nanocatalysts with single atom catalysts for methane combustion.

Pd↗
DOE OSTI2020

Flash Graphene Morphologies

Flash Joule heating (FJH) can convert almost any carbon-based precursor into bulk quantities of graphene. This work explores the morphologies and properties of flash graphene (FG) generated from carbon black. It is shown that FG is partially comprised of sheets of turbostratic FG (tFG) that have a rotational mismatch between neighboring layers. The remainder of the FG is wrinkled graphene sheets that resemble non-graphitizing carbon. To generate high quality tFG sheets, a FJH duration of 30 – 100 ms is employed. Beyond 100 ms, the turbostratic sheets have time to AB-stack and form bulk graphite. Atomistic simulations reveal that generic thermal annealing yields predominantly wrinkled graphene which displays minimal to no alignment of graphitic planes, as opposed to the high-quality tFG that might be formed under the direct influence of current conducted through the material. As a result, the tFG was easily exfoliated via shear, hence the FJH process has the potential for bulk production of tFG without the need for pre-exfoliation using chemicals or high energy mechanical shear.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Direct Optoelectronic Imaging of 2D Semiconductor–3D Metal Buried Interfaces

The semiconductor-metal junction is one of the most critical factors for high performance electronic devices. In two-dimensional (2D) semiconductor devices, minimizing voltage drop at this junction is of particularly challenging and important. Despite numerous studies on contact resistance in 2D semiconductors, the exact nature of the buried interface under a 3D metal remains elusive and unclear. Herein, we report the direct observation of 2D semiconductor-metal buried interface using recently developed metal-assisted transfer technique to expose the buried interface which is then directly investigated using scanning probe techniques. We characterize the spatially varying electronic and optical properties of this buried interface with < 20 nm resolution. To be specific, potential, conductance and photoluminescence at the buried metal/MoS 2 interface are correlated under variety of metal deposition conditions as well as type of metal contacts. We observe that direct evaporation of Au on MoS 2 induces large strain of ~5% in the MoS 2 which coupled with charge transfer leads to degenerate doping of the MoS 2 underneath the contact. These factors lead to improvement of contact resistance to record values of 138 kΩ μm measured using local conductance probes. This approach was adopted to investigate MoS 2 -In/Au alloy interface, which records lowest contact resistance of 63 kΩ μm. Overall, our results highlight that the MoS 2 /Metal interface is very sensitive to method of contact making and provides a universal strategy to characterize buried contact interfaces involving 2D semiconductors.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Unequal {110} Facets: The Potential Role of Intraparticle Heterogeneity and Facet Termination in Photoelectrochemical Activity of Single BiVO 4 Particles

BiVO 4 photoanodes are promising for solar water splitting, with photogenerated electrons and holes preferentially reacting at top {010} and lateral {110} facets, respectively. However, the mechanisms driving this facet-dependent reactivity remain unclear. Here, in this study, we investigate facet-dependent photocurrent and material heterogeneity using correlative scanning photoelectrochemical microscopy (SPCM), electron beam induced current (EBIC) mapping, and mid-IR scattering scanning near-field optical microscopy (s-SNOM). SPCM measurements of 62 BiVO 4 particles confirmed higher photocurrents at lateral {110} facets compared to top {010} facets, but unexpectedly revealed variations in photocurrent among lateral facets within the same particle. Variations in lateral facet surface termination could explain the intraparticle-level reactivity heterogeneity, consistent with theoretical predictions. Nano-FTIR spectroscopy and Raman microspectroscopy indicated significant materials chemistry heterogeneity within individual particles and facets that could be attributed to variations in lattice vibration distortions that enhance the overlap between Bi 6s and O 2p orbitals. The increased orbital overlap is significant as it potentially increases hole mobility in the valence band and potentially explains the lateral facet-dependent charge separation efficiency observed in photocurrent maps. Facet-dependent electrical and EBIC measurements showed no space charge regions at interfacet junctions or metal-BiVO 4 contacts under vacuum, suggesting that photogenerated holes beneath top {010} facets are unlikely to transport to lateral {110} facets to drive water/sulfite oxidation. These findings indicate the potential influence of distinct bulk properties and surface termination chemistries across different particles and facets, highlighting the importance of carefully controlling defects and surface chemistry during sample growth to optimize photocatalytic performance.

BiVO4↗