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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 595 records · Page 33
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Plasmonic hybrid core-shell (HyCoS) AgPt NP template hybridized with GQDs for SERS enhancement of 4-MBA and BT

Surface-enhanced Raman spectroscopy (SERS) is an attractive vibrational spectroscopic technique that can enable a non-destructive and ultra-sensitive detection down to the single-molecule level. Herein, a novel hybrid SERS platform is developed based on hybrid core-shell (HyCoS) AgPt nanoparticles (NPs) and graphene quantum dots (GQDs) for the enhancement of Raman vibration of 4-mercaptobenzoic acid (4-MBA) and benzenethiol (BT). The unique design of HyCoS AgPt NPs induces strong electromagnetic mechanism (EM) enhancement through the amplification of electromagnetic fields by the excitation of high-density surface plasmons and hot spots. Superior localized surface plasmon resonance (LSPR) is generated by the AgPt core-shell and background Ag NP coupling, which is systematically investigated by the optical properties and FDTD simulations. The background Ag NPs can further increase the coverage of metallic NPs, leading to higher-density hot spots and enhanced SERS response. At the same time, GQDs can provide plentiful accessible edges for the charge transfer to the HOMO and LUMO of 4-MBA and BT based on the chemical mechanism (CM) enhancement. The mixing approach of GQDs and target molecules on the HyCoS AgPt NPs can significantly amplify the Raman signals via the strong adsorption of probe molecules by the π – π interaction. The enhancement factors of proposed SERS platform can reach ~107 and ~105 for the 4-MBA and BT respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Plasmonic hybrid core-shell (HyCoS) AgPt NP template hybridized with GQDs for SERS enhancement of 4-MBA and BT

Surface-enhanced Raman spectroscopy (SERS) is an attractive vibrational spectroscopic technique that can enable a non-destructive and ultra-sensitive detection down to the single-molecule level. Herein, a novel hybrid SERS platform is developed based on hybrid core-shell (HyCoS) AgPt nanoparticles (NPs) and graphene quantum dots (GQDs) for the enhancement of Raman vibration of 4-mercaptobenzoic acid (4-MBA) and benzenethiol (BT). The unique design of HyCoS AgPt NPs induces strong electromagnetic mechanism (EM) enhancement through the amplification of electromagnetic fields by the excitation of high-density surface plasmons and hot spots. Superior localized surface plasmon resonance (LSPR) is generated by the AgPt core-shell and background Ag NP coupling, which is systematically investigated by the optical properties and FDTD simulations. The background Ag NPs can further increase the coverage of metallic NPs, leading to higher-density hot spots and enhanced SERS response. At the same time, GQDs can provide plentiful accessible edges for the charge transfer to the HOMO and LUMO of 4-MBA and BT based on the chemical mechanism (CM) enhancement. The mixing approach of GQDs and target molecules on the HyCoS AgPt NPs can significantly amplify the Raman signals via the strong adsorption of probe molecules by the π–π interaction. The enhancement factors of proposed SERS platform can reach ~10 7 and ~10 5 for the 4-MBA and BT respectively.

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

Efficient up-conversion in CsPbBr 3 nanocrystals via phonon-driven exciton-polaron formation

Lead halide perovskite nanocrystals demonstrate efficient up-conversion, although the precise mechanism remains a subject of active research. This study utilizes steady-state and time-resolved spectroscopy methods to unravel the mechanism driving the up-conversion process in CsPbBr 3 nanocrystals. Employing above- and below-gap photoluminescence measurements, we extract a distinct phonon mode with an energy of ~7 meV and identify the Pb-Br-Pb bending mode as the phonon involved in the up-conversion process. This result was corroborated by Raman spectroscopy. We confirm an up-conversion efficiency reaching up to 75%. Transient absorption measurements under conditions of sub-gap excitation also unexpectedly reveal coherent phonons for the subset of nanocrystals undergoing up-conversion. This coherence implies that the up-conversion and subsequent relaxation is accompanied by a synchronized and phased lattice motion. This study reveals that efficient up-conversion in CsPbBr 3 nanocrystals is powered by a unique interplay between the soft lattice structure, phonons, and excited states dynamics.

Anti-Stokes Photoluminescence↗
DOE OSTI2025

Operando probing dynamic migration of copper carbonyl during electrocatalytic CO2 reduction

Single crystals and shape-controlled nanocrystals are well known to exhibit facet-dependent catalytic properties. However, few studies have investigated how those nanocrystals evolve and (de)activate during reactions, calling for the development of nanoscale time-resolved operando methods. In this context, we have designed Cu nanocubes as a model system to elucidate the underlying driving force of dynamic nanocatalyst reconstruction during the CO2 reduction reaction (CO2RR). Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) and synchrotron-based X-ray spectroscopy reveal the size- and potential-dependent complete transformation from (100)-oriented Cu@Cu2O nanocubes to polycrystalline metallic Cu nanograins under CO2RR conditions. In addition, machine learning-assisted operando four-dimensional STEM reveals that large Cu nanograins derived from nanocubes form mainly crystalline domains, while their smaller counterparts are more amorphous due to faster evolution kinetics. In situ Raman spectroscopy and density functional theory calculations suggest that CO drives the ejection of single Cu atoms, resulting in few-nanometre Cu clusters and the surface migration of highly mobile copper carbonyl (Cu–CO) species. Combined, these multimodal operando methods and theoretical approaches pave the way for understanding the complex structural evolution of energy-related nanocatalysts under electrochemical conditions.

Yang, Yao↗
DOE OSTI2020

Direct Evidence of Graphene-Induced Molecular Reorientation in Polymer Films

For the first time, direct evidence of graphene-induced molecular reorientation in polymer films using polarization modulated infrared reflection absorption spectroscopy (PMIRRAS) are presented. By creating favorable electrostatic interactions, graphene-polymer interfaces can be controlled by varying polymer and solvent composition. After trans of unmodified graphene from copper onto a polymer substrate, polymer chain rearrangement relative to the orientation at the polymer-copper interface is observed using PM-IRRAS. Transfer success is characterized using both optical transmission measurements and Raman spectroscopy to quantify the transfer fidelity, i.e. graphene coverage fraction. Taken together, oxygencontaining poly(ethylene-co-vinyl acetate) shows more polymer chain rearrangement and better graphene coverage compared to oxygen-free polyethylene. Polymer composition seems to dominate graphene-polymer interactions while solvent choice has a smaller effect on transfer quality. These results are the first direct measurement of this effect and point towards the possibility of engineering graphene-polymer interactions for specific applications.

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

Thermal decomposition of neptunyl ammonium nitrate: mechanistic insights and structural characterization of the Np 2 O 5 intermediate phase

Neptunium (Np) possesses a rich and unique chemistry that often diverges from other actinide elements yet remains relatively underexplored compared with the other light actinides. A resurgence of interest in Np has been spurred by the application of 237 Np for plutonium-238 ( 238 Pu) production for use in radioisotope thermoelectric generators (RTGs), necessitating evaluation of Np chemical reactions and materials. The work presented here studied the thermal decomposition of neptunyl ammonium nitrate (NH 4 Np VI O 2 (NO 3 ) 3 ) for synthesis of neptunium dioxide (NpO 2 ), which is the target material used for production of 238 Pu. Additionally, structural characterization of the intermediate solid Np pentoxide (Np 2 O 5 ) was performed. Advanced solid-state characterization techniques, including simultaneous thermal analysis (STA), powder X-ray diffraction (pXRD), Raman spectroscopy, and density functional theory (DFT) modeling have been combined to study the reaction pathways. Analysis revealed that NH 4 Np VI O 2 (NO 3 ) 3 thermally decomposes to a proposed neptunyl nitrate intermediate, followed by Np 2 O 5 and finally NpO 2 , all within the temperature range of 150 °C–600 °C. Further characterization of the pentoxide intermediate provided the first Raman spectra of pure-phase Np 2 O 5 and associated DFT modeling confirmed Raman peak assignments for this phase. These findings provide mechanistic information to advance production of the critical radioisotope 238 Pu and advance the state of knowledge on Np materials chemistry using modern characterization techniques.

Lawson, Kathryn M. [Oak Ridge National Laboratory ↗
DOE OSTI2025

Characterizing sample degradation from synchrotron based X-ray measurements of ultra-thin exfoliated flakes

It is undeniable that novel 2D devices and heterostructures will have a lasting impact on the advancement of future technologies. However, the inherent instability of many exfoliated van der Waals (vdW) materials is a well-known hurdle yet to be overcome. Thus, the sustained interest in exfoliated vdW materials underscores the importance of understanding the mechanisms of sample degradation to establish proactive protective measures. Here, the impact of prolonged synchrotron-based X-ray beam exposure on exfoliated flakes of two contemporary vdW materials, NiPS 3 and α-RuCl 3 , is explored using resonant inelastic X-ray scattering (RIXS) and total fluorescence yield X-ray absorption spectroscopy (XAS). In NiPS 3 , the resulting RIXS and XAS spectra show a suppression, then vanishing, of NiS 6 multiplet excitations coupled with an upward shift of the peak energy of the XAS as a function of X-ray dose. In α-RuCl 3 , the signs of beam damage from the RIXS spectra are less evident. However, the post-experiment characterization of both materials using Raman spectroscopy exhibits signals of an amorphous and disordered system compared to pristine flakes; in addition, energy-dispersive X-ray spectroscopy of NiPS 3 shows evidence of ligand vacancies. As synchrotron radiation is fast becoming a required probe to study 2D vdW materials, these findings lay the groundwork for the development of future protective measures for synchrotron-based prolonged X-ray beam exposure, as well as for X-ray free electron laser.

2D magnetism↗
DOE OSTI2021

Importance of multimodal characterization and influence of residual Li 2 S impurity in amorphous Li 3 PS 4 inorganic electrolytes

Amorphous Li 3 PS 4 (LPS) solid-state electrolytes are promising for energy-dense lithium metal batteries. LPS glass, synthesized from a 3:1 mol ratio of Li 2 S and P 2 S 5 , has high ionic conductivity and can be synthesized by ball milling or solution processing. Ball milling has been attractive because it provides the easiest route to access amorphous LPS with a conductivity of 3.5 × 10 –4 S cm –1 (20 °C). However, achieving the complete reaction of precursors via ball milling can be difficult, and most literature reports use X-ray diffraction (XRD) or Raman spectroscopy to confirm sample purity, both of which have limitations. Furthermore, the effect of residual precursors on ionic conductivity and lithium metal cycling is unknown. In this work, we illustrate the importance of multimodal characterization to determine LPS phase and chemical purity. To determine the residual Li 2 S content in LPS, we show that (1) XRD and 31 P solid state nuclear magnetic resonance (ssNMR) are insufficient and (2) Raman loses sensitivity at concentrations below 12 mol% Li 2 S. Most importantly, we show that 7 Li ssNMR is highly sensitive. Using 7 Li ssNMR, we investigate the effect of ball milling parameters and develop a robust and highly reproducible procedure for pure LPS synthesis. We find that as the residual Li 2 S precursor content increases, LPS conductivity decreases and lithium metal batteries exhibit higher overpotentials and poor cycle life. Furthermore, our work reveals the importance of multimodal characterization techniques for amorphous solid-state electrolyte characterization and will enable better synthetic strategies for highly conductive electrolytes for efficient energy-dense solid-state lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Calibration of Raman Spectrometer for Gas Phase Measurements

Raman spectroscopy is currently used at SRNL to measure the concentration of gaseous species evolved from chemical reactions. This report documents the methods used to calibrate the spectroscopic systems in both frequency and intensity spaces.

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

Pressure-driven symmetry transitions in dense H 2 O ice

X-ray diffraction and Raman spectroscopy of H 2 O (ice) structures are measured under static compression in combination with grain normalizing heat treatment via direct laser heating. Here, we report the transition from cubic ice-VII to a structure of tetragonal symmetry, ice-VII t at 5.1 ± 0.5 GPa. This is succeeded by the H-bond symmetrization transition occurring at a pressure of 30.9 ± 3 GPa. Both experimental observations are supported by simulated Raman spectra from density-functional theory quantum calculations. The transition to H-bond symmetrization is evidenced by the reversible emergence of its characteristic Raman mode and a 2.5-fold increase in bulk modulus, implying a significant increase in bonding strength.

58 GEOSCIENCES↗
DOE OSTI2025

Cavity-Assisted Coherent Phonon Generation and Control in a WSe 2 /Au Structure

Coherent phonons in the Terahertz (THz) regime have gained attention as potential candidates for next-generation high-speed, low-energy information carriers in atomically thin phononic or phonon-integrated on-chip devices. Nevertheless, achieving efficient control over THz coherent phonons continues to pose a considerable challenge. In this work, we explore THz coherent phonon generation in exfoliated van der Waals (vdW) flakes of WSe 2 on Au (WSe 2 /Au) and Si (WSe 2 /Si) using time-resolved pump-probe spectroscopy. The generation of THz coherent phonons was studied as a function of WSe 2 layer thickness and laser wavelength. Notably, a significant enhancement in THz coherent phonon generation was observed in the WSe 2 /Au structure, but only within specific ranges of WSe 2 thickness and laser wavelength. Further, the results from numerical simulations, which consider a self-hybridized optical cavity depending on WSe 2 thickness, along with optical reflectance and Raman spectroscopy measurements, aligned well with the time-domain observations of THz coherent phonon generation. We propose that the observed enhancement in THz coherent phonon generation is strongly influenced by light-matter interaction in the WSe 2 cavity, a mechanism that may be applicable to a broader range of vdW materials. These findings offer promising insights for the development of THz phononic or phonon-integrated devices.

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

Characterization of thermally heat-treated polyacrylonitrile carbon fibers

This study investigates the graphitization process of polyacrylonitrile (PAN) carbon fibers by subjecting commercial fibers to thermal heat treatment at temperatures ranging from 1400 to 2100 °C in 100 °C increments, using either argon or nitrogen gas atmospheres. Changes in crystallinity, surface morphology, and lattice parameters were analyzed for two commercial carbon fibers using X-ray diffraction, scanning electron microscopy, and Raman spectroscopy. Results indicated minimal changes in surface morphology with increasing heat-treatment temperature; however, crystallinity significantly increased. Crystallinity changes were more strongly dependent on temperature rather than gas atmosphere or fiber type. At intermediate heat-treatment temperatures (1600–1800 °C), fibers treated in argon showed a slight preference for graphitization. The highest level of graphitization was measured at 2100 °C. Crystallite size increased as the intensity ratio of the D1 to G Raman peaks increased, reaching a peak around ~1800 °C, after which the ratio started to decrease. This behavior aligns with Ferrari's three-stage model of carbon crystallization and is consistent with both the Marie-Mering degree of graphitization and Brubaker's Integrated Absolute Differential models, all of which describe the transformation from an amorphous to a more graphitic structure. At the higher heat-treatment temperatures, the changes between atmospheres and fiber types were measured to converge to similar levels of graphitization. In conclusion, this study evaluates the progressive change in commercial grade carbon fibers when heat-treated.

Characterization↗
DOE OSTI2021

A comparison of strategies for state-selective coherent Raman excitation

Here we report on the theoretical and experimental evaluation of state-selective bond activation for coherent Raman spectroscopy and control of chemical reactivity. We compare six different strategies for state-selective activation using shaped broadband femtosecond laser pulses. Results for a pair of long pulses with different wavelengths are also considered. For each of these approaches, we report on their theoretical and experimental ability to excite a desired vibrational mode while minimizing excitation of other modes including harmonics. We find that the double parabola spectral phase function gives the most intense Raman excitation with 10 cm -1 selectivity with the lowest background. The sinusoidal phase function produces intense Raman excitation with high selectivity but gives a series of harmonic excitations which could hinder selectivity. Implications of this study on several fields ranging from sensing, to controlling chemical reactions, and selective excited state excitation by X-ray pulses are discussed.

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

The S solubility of Cr and Al containing simulated low-activity waste glass

Here, the presence of sulfur-containing molten salt phases during vitrification is a particular problem which can be detrimental to the melter. Borosilicate compositions were designed to explore both the effects of a fixed amount of Cr, as Cr 2 O 3 or Na 2 CrO 4 , and the impact of Al 2 O 3 , on sulfur solubility as determined by progressively adding elemental S. The NABS series (with Al 2 O 3 ) has a higher SO 3 solubility of ~3.5 mol% while the NBS series (without Al 2 O 3 ) has a SO 3 solubility of ~2 mol%. Crystalline Cr 2 O 3 formed in the NABS series upon the addition of S but is not present in the NBS series. At the highest S addition, a separate salt phase always forms, and was identified as Na 2 (S,Cr)O 4 via electron dispersive spectroscopy, ultraviolet-visible spectroscopy, x-ray diffraction, and thermal analysis. Magic angle spinning nuclear magnetic resonance identified no change in the B coordination in either series as S is added, suggesting that the Na is scavenged from other locations, such as the Si sites, to charge compensate sulfate, whether in the glass or in the salt. The Cr precursor identity did not affect the observed overall behavior regarding sulfur, but did impact Cr redox as identified with Raman spectroscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Regioisomer-Specific Crystallization of Diglycidyl Ether of Bisphenol F Epoxy Resin

Diglycidyl ether of bisphenol F (DGEBF) is a common industrial epoxy resin, desired for its possible replacement of the bisphenol A (BPA) analogue DGEBA due to potential health hazards of BPA. During curing, crystallization of the DGEBF resin can cause inaccurate resin-to-hardener ratios, resulting in incomplete crosslinking; therefore, understanding the crystallization of DGEBF is important for proper industrial control of the material. Here, in this work, we utilized a combination of single-crystal x-ray diffraction, Raman spectroscopy, and 1 H-NMR to investigate the crystallization of DGEBF. We observed crystallization of two DGEBF regioisomers: ortho-ortho’-DGEBF and ortho-para’-DGEBF, and report their crystal structures. Notably, para-para’-DGEBF crystallization is not observed, indicating crystallization of this regioisomer does not occur under ambient conditions. Density functional theory calculations were performed to describe the phonon modes of the ortho-ortho’- and ortho-para’-DGEBF structures, corroborating Raman signatures for the respective isomers. Using a phonon mode analysis, we identify the presence of three specific optical vibrational modes at 631.3, 344.1, and 345.6 cm -1 that are unique to the para monomer. This work offers insights into the crystallization behavior of DGEBF resins under ambient conditions and may inform potential industrial application of this material.

Neu, Jennifer [Oak Ridge National Laboratory (ORNL↗
DOE OSTI2023

Observation of flat and weakly dispersing bands in the van der Waals semiconductor Nb 3 Br 8 with breathing kagome lattice

Niobium halides, Nb 3 ⁢X 8 (X=Cl,Br,I), which are predicted two-dimensional magnets, have recently gotten attention due to their breathing kagome geometry. Here we have studied the electronic structure of Nb 3⁢ Br 8 by using angle-resolved photoemission spectroscopy (ARPES) and first-principles calculations. ARPES results depict the presence of multiple flat and weakly dispersing bands. These bands are well explained by the theoretical calculations, which show they have Nbd character indicating their origination from the Nb atoms forming the breathing kagome plane. This van der Waals material can be easily thinned down via mechanical exfoliation to the ultrathin limit and such ultrathin samples are stable as depicted from the time-dependent Raman spectroscopy measurements at room temperature. Finally, these results demonstrate that Nb 3 ⁢Br 8 is an excellent material not only for studying breathing kagome induced flat band physics and its connection with magnetism but also for heterostructure fabrication and for practical application.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Magnetic-Core/Gold-Shell Nanoparticles for the Detection of Hydrophobic Chemical Contaminants

Magnetic-core/gold-shell nanoparticles (MAuNPs) are of interest for enabling rapid and portable detection of trace adulterants in complex media. Gold coating provides biocompatibility and facile functionalization, and a magnetic core affords analyte concentration and controlled deposition onto substrates for surface-enhanced Raman spectroscopy. Iron oxide cores were synthesized and coated with gold by reduction of HAuCl4 by NH2OH. MAuNPs were grafted with polyethylene glycol (PEG) and/or functionalized with 4-mercaptobenzoic acid (4-MBA) and examined using a variety of microscopic, spectroscopic, magnetometric, and scattering techniques. For MAuNPs grafted with both PEG and 4-MBA, the order in which they were grafted impacted not only the graft density of the individual ligands, but also the overall graft density. Significant Raman signal enhancement of the model analyte, 4-MBA, was observed. This enhancement demonstrates the functionality of MAuNPs in direct detection of trace contaminants. The magnetic deposition rate of MAuNPs in chloroform and water was explored. The presence of 4-MBA slowed the mass deposition rate, and it was postulated that the rate disparity originated from differing NP-substrate surface interactions. These findings emphasize the importance of ligand choice in reference to the medium, target analyte, and substrate material, as well as functionalization procedure in the design of similar sensing platforms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Direct observation of two-dimensional magnons in atomically thin CrI 3

Magnons are collective spin excitations in crystals with long-range magnetic order. The emergent van der Waals magnets provide a highly tunable platform to explore magnetic excitations in the two-dimensional limit with intriguing properties, manifesting from their honeycomb lattice structure and switchable magnetic configurations. Here, we report the direct observation of two-dimensional magnons through magneto-Raman spectroscopy with optical selection rules determined by the interplay between crystal symmetry, layer number and magnetic states in atomically thin CrI 3 . In monolayers, we observe an acoustic magnon mode at ~0.3 meV. It has strict cross-circularly polarized selection rules locked to the magnetization direction that originates from the conservation of angular momentum of photons and magnons dictated by three-fold rotational symmetry. Additionally, we reveal optical magnon modes at ~17 meV. This mode is Raman silent in monolayers, but optically active in bilayers and bulk due to a relaxation of the parity criterion resulting from the layer index. In the layered antiferromagnetic states, we directly resolve two degenerate optical magnon modes with opposite angular momentum and conjugate optical selection rules. From these measurements, we quantitatively extract the spin-wave gap, magnetic anisotropy and intralayer and interlayer exchange constants, and establish two-dimensional magnets as a new platform for exploring magnon physics.

36 MATERIALS SCIENCE↗