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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Trends in Carbon, Oxygen, and Nitrogen Core in the X-ray Absorption Spectroscopy of Carbon Nanomaterials: A Guide for the Perplexed

Successful deployment of carbon nanomaterials in many applications, such as sensing, energy storage, and catalysis, relies on the selection, synthesis, and tailoring of the surface properties. Predictive analysis of the behavior is difficult without detailed knowledge of the differences between various carbon nanomaterials and their surface functionalization, thus leaving the selection process to traditional trial-and-error work. The present characterization fills this knowledge gap for carbon nanomaterial surface properties with respect to chemical states and functionalization. We present an overview of the chemical trends that can be extracted from soft X-ray absorption spectroscopy (XAS) spectra on an extended set of nonideal carbon nanomaterials as a function of sp 2 bonded carbon and bond ordering. In particular, the surface chemical state, the presence of long-range order in the carbon matrix, and a qualitative estimation of the amount of oxygen and nitrogen and their respective functional group formation on the material surface, together with the detailed material fabrication parameters, are reported. The results expand our understanding of carbon nanomaterial functionalization, which can support material selection in practice, provided that the specifications of the application are known.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Hot Carrier Dynamics in the X Valley in Si and Ge Measured by Pump-IR-Probe Absorption Spectroscopy

Si is the semiconductor of choice for nanoelectronic roadmap into the next century for computer and other nanodevices. With growing interest in Si, Ge, and Si(sub m)Ge(sub n) strained superlattices, knowledge of the carrier relaxation processes in these materials and structures has become increasingly important. The limited time resolution for earlier studies of carrier dynamics in Ge and Si, performed using Nd:glass lasers, was not sufficient to observe the fast cooling processes. In this paper, we present a direct measurement of hot carrier dynamics in the satellite X valley in Si and Ge by time-resolved infrared(IR) absorption spectroscopy, and show the potential of our technique to identify whether the X valley is the lowest conduction valley in semiconductor materials and structures.

Wang, W. B.↗
DOE OSTI2021

Ab Initio Molecular Dynamics Simulations of Amorphous Calcium Carbonate: Interpretation of Pair Distribution Function and X-Ray Absorption Spectroscopy Data

The structure and transformation of hydrous amorphous calcium carbonate (ACC) are key to understanding biomineralization pathways and their relationship with the properties of the resulting material. Quantitative interpretation of scattering experiments aimed at elucidating the structure of ACC is challenging, due to the amorphous nature of this material, and, therefore, requires models for the structure and the scattering physics. Here, we generate physically realistic ensembles of hydrated ACC structures and their vibrational disorder from ab initio molecular dynamics (AIMD) simulations with an emphasis on enabling the consistent interpretation of the finer details of three complementary structural probes: neutron and x-ray pair distribution experiments and x-ray absorption spectroscopy (XAS). In each case, we simulate the signal directly in reciprocal space and then manipulate it into the real-space pair distribution function (PDF) or spectrum using the same procedures for the experimental and theoretical data. Good agreement with experiment was obtained across the three techniques with the simulations accounting well for all features in the spectra. Remaining small discrepancies pointed to differences between real samples and the idealized simulated systems such as deviations from the nominal CaCO3·nH2O stoichiometry. Additionally, the simulations offered a more accurate description of the local coordination environment of calcium than previous shell-by-shell fits to spectra of synthetic ACC and classical molecular dynamics simulations. This work demonstrates that AIMD is a powerful approach for extracting detailed structural information from neutron PDF, x-ray PDF, and XAS of amorphous carbonate phases.

Prange, Micah P.↗
DOE OSTI2023

X-ray Absorption Spectroscopy Illustrates the Participation of Oxygen in the Electrochemical Cycling of Li 4 Mn 2 O 5

A combination of oxygen redox and Mn-based oxides would be the best option for high-energy-density Li-ion batteries crucial for a sustainable society. The disordered rock-salt Li 4 Mn 2 O 5 was recently reported to display a very large capacity of 460 mAh/g with moderate reversibility. Previous studies proposed the involvement of lattice oxygen redox in such intriguing electrochemical performance, whereas no direct evidence was presented. To clarify the charge compensation mechanism, we systematically investigated the evolution of the electronic structure of both Mn and O upon cycling via Mn/OK-edge X-ray absorption spectroscopy (XAS). Mn K-edge XAS unequivocally demonstrates the participation of Mn redox upon the initial stages of charging, yet changes are arrested at the high potentials, while O continues to evolve according to O K-edge XAS. Upon discharging, both Mn and O are simultaneously reduced, but to states different from pristine. In conclusion, the results highlight the significance of a disordered structure in maintaining the reversible redox chemistry of both transition metals and oxygen to design cathode materials with high energy density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

New Constraints on the Melting Temperature and Phase Stability of Shocked Iron up to 270 GPa Probed by Ultrafast X-Ray Absorption Spectroscopy

Studying the properties and phase diagram of iron at high-pressure and high-temperature conditions has relevant implications for Earth’s inner structure and dynamics and the temperature of the inner core boundary (ICB) at 330 GPa. Also, a hexagonal-closed packed to body-centered cubic (bcc) phase transition has been predicted by many theoretical works but observed only in a few experiments. The recent coupling of high-power laser with advanced x-ray sources from synchrotrons allows for novel approaches to address these issues. Here, we present a study on shock compressed iron up to 270 GPa and 5800 K probed by single-pulse (100 ps FWHM) x-ray absorption spectroscopy (XAS). Based on the analysis of the XAS spectra, we provide structural identification and bulk temperature measurements along the Hugoniot up to the melting. These results rule out the predicted transition to a high-temperature bcc phase and allow one to discriminate among existing equations of state models and melting curves. In particular, we report the first bulk temperature measurement in shock compressed iron on the melting plateau at 240(20) GPa and 5345(600) K. The melting curve resulting from our work extrapolates to a temperature of 6202(514) K at 330 GPa and represents a refined upper bound for the ICB temperature. Published by the American Physical Society 2024

Balugani, S.↗
DOE OSTI2025

Illuminating the Role of Alcohol Substrate in Nickel Photoredox Catalysis via Ground State and Transient Absorption Spectroscopy

Direct excitation of nickel photocatalysts has gained popularity over the last several years following the successful activation of nickel by Ir and Ru photosensitizers. The ability to pair these photosensitizers with Ni catalysts facilitates the formation of crucial chemical bonds under relatively mild conditions. However, there are still gaps in our understanding of what influences the performance of these Ni photocatalysts. Previous work from our group identified a nickel photocatalyst supported by a tridentate pyridinophane ligand that undergoes wavelength-dependent cross-coupling reactivity. Herein, we report detailed studies of the wavelength dependence of the C–O cross-coupling reactivity, illustrating that the catalytic activity has an optimal wavelength, and excitation on both the blue and red sides of this optimal wavelength leads to a reduction in product yield. We also reveal a crucial catalyst-alcohol preirradiation interaction that drastically alters the catalyst’s optical properties. Furthermore, we investigate both wavelength dependency and alcohol dependency via optical transient absorption spectroscopy and reveal a substrate binding process responsible for the observed wavelength-dependent cross-coupling catalysis.

alcohol↗
DOE OSTI2021

Operando bulk and interfacial characterization for electrochemical energy storage: Case study employing isothermal microcalorimetry and X-ray absorption spectroscopy

Abstract The global shift to electricity as the main energy carrier will require innovation in electrochemical energy storage (EES). EES systems are the key to the “electron energy economy,” minimizing losses and increasing reliability between energy supply and demand. However, steep challenges such as cost, cycle/calendar life, energy density, material availability, and safety limit widespread adoption of batteries for large-scale grid and vehicle applications. Battery innovation that meets today’s challenges will require new chemistries, which can originate from understanding charge transport phenomena at multiple time and length scales. The advancement of operando characterization can expedite this progress as changes can be observed during battery function. This article highlights progress in bulk and interfacial operando characterization of batteries. Specifically, a case study involving Fe 3 O 4 is provided demonstrating that combining X-ray absorption spectroscopy and isothermal microcalorimetry can provide real-time characterization of productive faradaic redox processes and parasitic interfacial reactions during (de)lithiation. Graphic abstract

36 MATERIALS SCIENCE↗
DOE OSTI2023

Nature of S-States in the Oxygen-Evolving Complex Resolved by High-Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy

Photosystem II, the water splitting enzyme of photosynthesis, utilizes the energy of sunlight to drive the four-electron oxidation of water to dioxygen at the oxygen-evolving complex (OEC). The OEC harbors a Mn 4 CaO 5 cluster that cycles through five oxidation states S i (i = 0–4). The S 3 state is the last metastable state before the O 2 evolution. Its electronic structure and nature of the S 2 → S 3 transition are key topics of persisting controversy. Most spectroscopic studies suggest that the S 3 state consists of four Mn(IV) ions, compared to the Mn(III)Mn(IV) 3 of the S 2 state. However, recent crystallographic data have received conflicting interpretations, suggesting either metal- or ligand-based oxidation, the latter leading to an oxyl radical or a peroxo moiety in the S 3 state. Herein, we utilize high-energy resolution fluorescence detected (HERFD) X-ray absorption spectroscopy to obtain a highly resolved description of the Mn K pre-edge region for all S-states, paying special attention to use chemically unperturbed S 3 state samples. In combination with quantum chemical calculations, we achieve assignment of specific spectroscopic features to geometric and electronic structures for all S-states. These data are used to confidently discriminate between the various suggestions concerning the electronic structure and the nature of oxidation events in all observable catalytic intermediates of the OEC. Our results do not support the presence of either peroxo or oxyl in the active configuration of the S 3 state. This establishes Mn-centered storage of oxidative equivalents in all observable catalytic transitions and constrains the onset of the O–O bond formation until after the final light-driven oxidation event.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1987

Single-tone and two-tone AM-FM spectral calculations for tunable diode laser absorption spectroscopy

A generalized theory for optical heterodyne spectroscopy with phase modulated laser radiation is used which allows the calculation of signal line shapes for frequency modulation spectroscopy of Lorentzian gas absorption lines. In particular, synthetic spectral line shapes for both single-tone and two-tone modulation of lead-salt diode lasers are presented in which the contributions from both amplitude and frequency modulations are included.

Chou, Nee-Yin↗
DOE OSTI2021

Resolving the Evolution of Atomic Layer-Deposited Thin-Film Growth by Continuous In Situ X-Ray Absorption Spectroscopy

In situ synchrotron X-ray absorption near-edge structure characterization of thin-film titania growth by atomic layer deposition (ALD) over ZnO nanowires reveals persistent low-coordinated Ti motifs leading to a new picture of ALD growth. Through the design of growth and measurement cycles, Ti K-edge spectral data are continuously recorded so as to characterize the film evolution as a function of ALD cycle number and the surface changes within the time scale of the ALD cycle. A unified set of analysis tools is developed to interpret the time-series of spectral data. A prenucleation stage of growth, a transition region, and then a steady-state growth stage are observed with distinguishable features. Multivariate curve resolution analysis, that is physically constrained, demonstrates two specific spectral components with associated, time-dependent concentrations. The bulk-film component tracks the stages of growth. The surface and interface components, present throughout the stages of growth, reveal a significant coverage of relatively isolated or loosely networked tetrahedrally coordinated Ti atomic motifs. Lastly, spectral signatures for the intra-cycle growth kinetics are reconstructed at a time resolution of ~1 s and demonstrate that the transient Ti motifs on the growing surface stabilize within a few seconds of the Ti precursor pulse.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Carrier and Phonon Dynamics in Multilayer WSe 2 Captured by Extreme Ultraviolet Transient Absorption Spectroscopy

Carrier and phonon dynamics in a multilayer WSe2 film are captured by extreme ultraviolet (XUV) transient absorption (TA) spectroscopy at the W N 6,7 , W O 2,3 , and Se M 4,5 edges (30–60 eV). After the broadband optical pump pulse, the XUV probe directly reports on occupations of optically excited holes and phonon-induced band renormalizations. Here, when compared with density functional theory calculations, XUV transient absorption due to holes is identified below the W O 3 edge whereas signals at the Se M 4,5 edges are dominated by phonon dynamics. Therein, 0.4 ps hole relaxation time, 1.5 ps carrier recombination time, and 1.7 ps phonon heating time are extracted. The acquisition of hole and phonon-induced signals in a single experiment can facilitate the investigation of the correlations between electron and phonon dynamics. Furthermore, the simultaneous observation of signals from different elements can be further extended to explore photochemical processes in multilayers and alloys, thereby providing key information for their applications in electronics, photocatalysts, and spintronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

How Does Metal Spin State Affect Electronic Communication in Mixed-Valence Dimers? Insights from Ultrafast Near-Infrared and Soft X-ray Transient Absorption Spectroscopy

Recent advancements in photocatalysis, photovoltaics, and quantum information science take advantage of electron spin, and determining how spin multiplicity affects electron transfer is key to understanding these phenomena. Here, in this study, we examine how metal spin state affects electronic communication in an organometallic mixed-valence dimer, ferrocenyl cobaltocenium ([Fe II Cp 2 Co III Cp 2 ] + ). This complex can be photoexcited from its low-spin singlet Fe II ground state to form intermediate-spin triplet Fe II and high-spin quintet Fe II excited states. Using femtosecond optical transient absorption (OTA) spectroscopy with visible (vis), near-infrared (NIR), and short-wave IR (SWIR) probes, supported by time-dependent density functional theory (TD-DFT) calculations, we measure Fe II Co III →Fe III Co II intervalence charge transfer (IVCT) bands in each of the Fe II spin states. Mulliken–Hush analysis of the excited-state IVCT bands was used to compute the electronic coupling between the metal centers in all three spin states, which increased as quintet < triplet < singlet. Meanwhile, the peak energy of the bands, and thus the ΔG of the IVCT transition, increased as triplet < quintet < singlet. Then, to directly probe the electronic structure at each metal center, we employed picosecond soft X-ray transient absorption (XTA) spectroscopy at the Fe and Co L 3 edges. Our results show that the low-spin and high-spin states of [Fe II Cp 2 Co III Cp 2 ] + are valence-localized, while the intermediate-spin state is partially delocalized. The differences in charge delocalization are attributed to differences in orbital occupation and geometry that affect the free energy and superexchange coupling.

Burke, John H. [Univ. of Illinois at Urbana-Champa↗
DOE OSTI2023

Synchrotron based transient x-ray absorption spectroscopy for emerging solid-state energy materials

The rational design of cutting-edge materials for an efficient solar energy conversion process is a challenging task, which demands a fundamental understanding of the mechanisms operative during the photoinduced physical and chemical reactions. In response to these issues, progress in the field has steered attention toward the use of time-resolved spectroscopic techniques to resolve the multiple intermediate species involved in these photoinduced reactions. Thanks to the advent of pump–probe technique, which leads to the development of various time-resolved spectroscopic methods, significant progress has been made in understanding the photophysical and photochemical properties (e.g., excited state dynamics, charge transfer mechanism, charge separation dynamics, etc.) of energy materials. Synchrotron-based x-ray transient absorption (XTA) spectroscopy is one of the most important time-resolved techniques to unravel the direct correlation of the material structure with their photophysical properties owing to its unique capability in directly observing electronic and structural evolution simultaneously. As a result, the aim of this work is to provide a systematic overview of the recent progress in using XTA for capturing the structural dynamics associated with excited state and charge separation dynamics in emerging solid-state energy materials.

14 SOLAR ENERGY↗
DOE OSTI2026

X-ray Absorption Spectroscopy and Neutron Scattering Data, Mineral Incubation Experiment, Walker Branch Watershed, TN (2020 - 2021)

Iron (Fe) (oxyhydr)oxides are well-recognized contributors to soil carbon (C) storage, but the effects of manganese (Mn) oxides on carbon storage and transformation are relatively unexplored. Here, the relative capacities of Fe and Mn oxides to bind and stabilize soil organic C were directly compared using an in-situ incubation experiment. Quartz sands coated with either poorly crystalline Mn(III/IV) oxides or Fe(III) oxides, or left uncoated, were buried in a temperate forest soil for up to one year. This data package contains processed data outputs of carbon near edge x-ray absorption fine structure spectroscopy (C NEXAFS), iron and manganese x-ray absorption near edge structure spectroscopy (XANES), and small angle neutron scattering (SANS) data collected for initial oxide-coated and uncoated quartz sands and for those buried in the temperate forest soil for 365 days.

Energy (eV)↗
DOE OSTI2020

Temperature estimation in a spatially inhomogeneous flame by diode laser absorption spectroscopy

A two-temperature (2T) model is proposed for estimating the temperature of a spatially inhomogeneous hot zone using single-beam diode laser absorption spectrometry. The proposed algorithm is based on fitting experimental absorption spectra by a linear combination of two database-simulated single-temperature spectra with different temperatures. The model efficiency is experimentally demonstrated when determining the temperature in different flame zones of a Wolfgard – Parker slot burner. The proposed 2T algorithm is used to find the maximum and minimum temperatures in different flame sections, which are compared with local temperatures in the same flame zones measured by the method of coherent anti-Stokes Raman scattering (CARS). It is shown that the maximum temperatures determined by the proposed 2T algorithm are in good agreement with CARS data in flame zones where high-temperature regions prevail. A good agreement between the minimum temperatures obtained by these two methods is also observed for predominantly cold zones. (paper)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS1991

On the state of the emitter of the 3.3 micron unidentified infrared band - Absorption spectroscopy of polycyclic aromatic hydrocarbon species

Results of absorption measurements indicate that the PAH species responsible for the UIR (unidentified infrared) emission probably exist in a condensed form rather than as isolated molecules. It is shown that the peak absorption of the C-H stretch feature of vapor-phase PAHs occurs at a higher frequency than that of the condensed-phase PAHs and does not match the 3.289-micron interstellar feature. The vapor-phase experiments duplicate the phenomenon of the 3.3-micron profile simplification of PAH in KBr at elevated temperature. This confirms that the change of the profile with temperature is an intrinsic molecular effect, and is not a consequence of matrix (KBr) or condensed state interactions.

Flickinger, Gregory C.↗