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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Enhanced Interfacial Electron Transfer in Photocatalyst-Natural Enzyme Coupled Artificial Photosynthesis System: Tuning Strategies and Molecular Simulations

Laccase is capable of catalyzing a vast array of reactions, but its low redox potential limits its potential applications. The use of photocatalytic materials offers a solution to this problem by converting absorbed visible light into electrons to facilitate enzyme catalysis. Herein, MIL-53(Fe) and NH 2 -MIL-53(Fe) serve as both light absorbers and enzyme immobilization carriers, and laccase is employed for solar-driven chemical conversion. Electron spin resonance spectroscopy results confirm that visible light irradiation causes rapid transfer of photogenerated electrons from MOF excitation to T1 Cu(II) of laccase, significantly increasing the degradation rate constant of tetracycline (TC) from 0.0062 to 0.0127 min -1 . Conversely, there is only minimal or no electron transfer between MOF and laccase in the physical mixture state. Theoretical calculations demonstrate that the immobilization of laccase's active site and its covalent binding to the metal-organic framework surface augment the coupled system's activity, reducing the active site accessible from 27.8 to 18.1 Å. In conclusion, the constructed photo-enzyme coupled system successfully combines enzyme catalysis’ selectivity with photocatalysis's high reactivity, providing a promising solution for solar energy use.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Development of an Attenuated Total Reflectance–Ultraviolet–Visible Probe for the Online Monitoring of Dark Solutions

Optical spectroscopy is a valuable tool for on-line monitoring of a variety of processes. Ultraviolet-visible (UV-vis) spectroscopy in particular, can monitor the concentration of analytes as well as identify speciation and oxidation state. However, it can be difficult to impossible to employ UV-vis based sensors on chemical systems that are very dark (i.e., high optical density) as exceedingly short pathlengths are required (for transmission approaches) or effective means of backscattering are needed (for reflectance approaches). Examples of processes that would benefit significantly from the use of optical sensors and encounter these challenges include used nuclear fuel recycling and molten salts with high concentrations of dissolved uranium. Utilizing an attenuated total reflectance (ATR) UV-vis approach can overcome these challenges and allow for the measurement of solutions orders of magnitude more concentrated than transmission UV-vis. However, determining ideal sensor specifications for varied processes can be time consuming and expensive. Here, in this study, we evaluate the ability for a novel ATR-UV-vis probe to measure very concentrated solutions of Co(II) and Ni(II) nitrate as well as organic dyes (methylene blue, acid red 1, and crystal violet). This sensor design provides a modular method for exploring possible “pathlengths” by altering the exposed ATR fiber length. Also studied were approaches to loading and measuring the sensor cell. These results are compared to a traditional 1 cm cuvette measured by transmission UV-vis. It was found that the ATR-UV-vis probe was capable of measuring solutions 600 times more concentrated than the 1 cm cuvette. Advanced data analysis in the form of multivariate curve resolution (MCR) was used to analyze the speciation of methylene blue over a large concentration range. The application of this novel ATR-UV-vis probe to the interrogation of dark solutions is a promising avenue for use in on-line monitoring of nuclear processes.

47 OTHER INSTRUMENTATION↗
NASA NTRSDate not supplied

Stratigraphy of the Apollo 17 Landslide Core 73002 From FMR Maturity and VNIR and Mössbauer Spectroscopy

A suite of samples from the Apollo missions to the Moon (1969-1973) were set aside and stored under controlled conditions to have unexamined lunar samples available decades later for analyses that take advantage of evolved sample handling techniques, maturation of then existing instrumentation, and development of new analytical techniques and instrumentation [e.g., 1]. One preserved sample is the Apollo 17 double drive tube core (73001/2) that was driven into the lunar surface on the landslide deposit at Station 3 on the South Massif in the Taurus-Littrow valley [2]. The deeper section (73001) was stored frozen in a Core Sample Vacuum Container (CSVC) to maximize preservation of lunar volatiles. We report here, as a part of the Apollo Next Generation Sample Analysis (ANGSA) Initiative [1,3], stratigraphy for the upper core section (73002) with respect to maturity (ferromagnetic resonance (FMR) maturity index Is/FeO [4-6]), visible-near-IR (VNIR) spectroscopy, and, for representative samples, grain-size analysis and Mössbauer spectroscopy. Stratigraphy provides data to model the dynamics of lunar landslide deposits and their post-emplacement evolution in comparison to impact-driven mixing on an airless body and stratigraphic context for volatile and (if any) organic behavior. Reported by [7] are preliminary results for multispectral imaging and hyperspectral scanning of the first dissection pass of 73002.

R. V. Morris↗
DOE OSTI2022

Proton damage in (Y,Lu,Gd) 3 (Al,Ga) 5 O 12 :Ce mixed garnet scintillators

Scintillators are vital components for nuclear instrumentation and its applications, including plasma diagnostics and imaging. As yields in controlled fusion experiments increase, the radiation tolerance of scintillator candidates for use in instrumentation is of particular importance. High radiation exposure can damage scintillating materials and alter the optical properties. The effects of radiation damage in Ce-doped mixed garnet ceramics over the compositional range (Y,Gd,Lu) 3 (Al,Ga) 5 O 12 are investigated using optical techniques. The samples were exposed to 200 keV protons to an accumulated fluence of 10 16 protons per square centimeter, then characterized using diffuse reflectance spectroscopy (DRS). DRS with visible light can assess the radiation tolerance of opaque poly-crystalline samples, which can be easily sintered from powders and thus offer distinct advantages in characterization compared to single crystals. Qualitative trends in induced absorption are presented as a function of composition, and the ideal cerium dopant concentration for Y 2 LuAl 5 O 12 is determined to be 0.60–0.75 mol.%.

47 OTHER INSTRUMENTATION↗
NASA NTRS2015

Characterization of Synthetic and Natural Manganese Oxides as Martian Analogues

Recent discoveries of highly concentrated manganese oxides in Gale Crater and on the rim of Endeavour Crater by the Mars Science Laboratory Curiosity and Mars Exploration Rover Opportunity, respectively, imply more highly oxidizing aqueous conditions than previously recognized. Manganese oxides are a significant environmental indicator about ancient aqueous conditions, provided the phases can be characterized reliably. Manganese oxides are typically fine-grained and poorly crystalline, making the mineral structures difficult to determine, and they generally have very low visible reflectance with few distinctive spectral features in the visible to near infrared, making them a challenge for interpretation from remote sensing data. Therefore, these recent discoveries motivate better characterization using methods available on Mars, particularly visible to near infrared (VNIR) spectroscopy, X-ray diffractometry (XRD), and compositional measurements. Both rovers have complementary instruments in this regard. Opportunity is equipped with its multispectral visible imager, Pancam, and an Alpha Particle X-ray Spectrometer (APXS), and Curiosity has the multispectral Mastcam, ChemCam (laser-induced breakdown spectroscopy and passive spectroscopy), and APXS for in situ characterization, and ChemMin (XRD) for collected samples.

Fox, V. K.↗
DOE OSTI2026

SULI Report - Development of a Molten Salt Circulation Loop for in-situ Spectroscopy

This project supports the development of real time optical monitoring capabilities for molten salt reactor (MSR) environments by designing, testing, and refining a molten salt circulation loop suitable for combined laser induced breakdown spectroscopy (LIBS) and ultraviolet visible (UV Vis) absorption measurements. Online spectroscopic monitoring is increasingly important for nuclear safeguards, corrosion tracking, and material accountancy, yet MSR process fluids present substantial challenges due to their chemical complexity and hazards such as high temperatures and radiation. To address these needs, this work focuses on Phase I, the development of a room temperature aqueous circulation loop that serves as a surrogate platform for evaluating flow behavior, optical access, and component performance prior to high temperature salt operation. Initial testing identified several practical issues—including leaks, obstructions, and two-phase flow through the absorption cell—that were systematically resolved through hardware replacement, flow path redesign, and venturi pressure optimization. Relocating the flow cell upstream of the primary venturi enabled periods of stable single-phase flow, demonstrating the feasibility of integrating optical diagnostics into a circulation system. The results of Phase I provide essential design insight for Phase II, which will incorporate furnace compatible materials and LiCl KCl eutectic salt. Completion of the molten salt system will deliver a reusable testbed for evaluating multimodal spectroscopic techniques, advancing nondestructive, real time monitoring tools for future MSR and nuclear fuel cycle applications.

98 - NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL↗
DOE OSTI2026

Near-Real-Time Material Tracking: Combining Vis–NIR Spectroscopy with Flow Sensing for Accurate Nd(III) Quantification

A fiber-optic visible–near-infrared (vis–NIR) absorption spectroscopy and flow sensor system has been developed for near-real-time tracking of Nd mass in the effluent stream from a column in a fume hood. The approach leverages two unique data streams and a partial least-squares regression (PLSR) model trained on vis–NIR absorption spectra of Nd(III) (0–1.5 M) in 1 M HNO 3 . In-line volumetric flow rate and vis–NIR spectra are measured in sequence after a chromatography column. The time stamps from each data stream are then synchronized, which allows integrated volumes to be combined with Nd(III) molarities predicted by a PLSR model to accurately calculate the Nd mass flowing through the column. This integrated measurement provides instantaneous mass flow and accumulates these data over time to obtain the total mass processed. The methodology developed in this study contributes critical technical infrastructure to improve monitoring capabilities to support chemical separations and the production of strategic materials and isotopes.

Irvine, Sawyer B. [Oak Ridge National Laboratory (↗
NASA NTRS1987

High performance visible and near-infrared charge-coupled-device array for spectroscopy applications

This paper describes the design and performance of a scientific CCD array for use in NASA's Shuttle Image Spectrometer Experiment. The device is a four-phase, buried-channel CCD structure that operates in the frame-transfer mode. The sensor consists of 64 x 404 pixels, has a 100 percent fill factor, and operates in the visible and near-infrared spectral regions. In operation, the 404 horizontal elements provide spatial information, while the 64 vertical elements give spectral information covering the wavelength range of 400 to 1000 nm in 10 nm increments. The high full-well capacity of each pixel and low noise floor yield a dynamic range of more than 95 dB. In addition, the device has been designed to have good linearity characteristics. The unique dual-output structure allows a horizontal row to be read out to the right or to the left, or it can be split from the middle to both right and left output circuits simultaneously for high speed applications. The power dissipation of the device is about 60 mW.

Wang, Weng-Lyang↗
DOE OSTI2025

Using Neural Networks to Identify Mixture Components in Hyperspectral Reflectance Data

Neural networks have been employed to identify materials of interest from hyperspectral data (generally imagery) based on their unique spectral signatures. This approach assumes that there is a single material that is standing out from the rest of the spectrum to be identified. However, pixels often contain more than one material, or a material of interest may itself be a mixture of multiple materials. Neural networks are only as good as the data used to train them, and it takes a great deal of work in the laboratory to identify, make, and measure all potential mixtures of interest. Thus, researchers often calculate synthetic spectra using algorithms with varying degrees of fidelity to the physics that govern the interactions between light and multiple materials. In this work, we have (1) adapted a neural network designed to identify mixture components from Raman spectroscopy to work with visible to near‐infrared reflectance data and (2) tested three common mixture algorithms to determine the most accurate and least computationally expensive method to build synthetic training datasets. With our initial test dataset, we have achieved accuracies of > 90% and found that the synthetic training dataset produced using the Hapke mixture model provides the best results.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2021

Determination of affinities of lanthanide-binding proteins using chelator-buffered titrations

The recent discoveries of the first proteins that bind lanthanides as part of their biological function not only are relevant to the emerging field of lanthanide-dependent biology, but also hold promise to revolutionize the technologically critical rare earths industry. Although protocols to assess the thermodynamics of metal–protein interactions are well established for “traditional” metal ions in biology, the characterization of lanthanide-binding proteins presents a challenge to biochemists due to the lanthanides' Lewis acidity, propensity for hydrolysis, and high-affinity complexes with biological ligands. These properties necessitate the preparation of metal stock solutions with very low buffered “free” metal concentrations (e.g., femtomolar to nanomolar) for such determinations. Here in this paper we describe several protocols to overcome these challenges. First, we present standardization methods for the preparation of chelator-buffered solutions of lanthanide ions with easily calculated free metal concentrations. We also describe how these solutions can be used in concert with analytical methods including UV–visible spectrophotometry, circular dichroism spectroscopy, Förster resonance energy transfer (FRET), and sensitized terbium luminescence, in order to accurately determine dissociation constants (K d s) of lanthanide–protein complexes. Finally, we highlight how application of these methods to lanthanide-binding proteins, such as lanmodulin, has yielded insights into selective recognition of lanthanides in biology. We anticipate that these protocols will facilitate discovery and characterization of additional native lanthanide-binding proteins, will motivate the understanding of their biological context, and will prompt their applications in biotechnology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Elucidating the speciation of extracted lanthanides by diglycolamides

Many studies over the past few decades have been devoted to addressing the application of diglycolamides (DGAs) for hydrometallurgical-based, f-element separations. Work to date has shown the molecular structure of a DGA derivative can have a significant impact on intra-lanthanide partitioning patterns. More recent studies have pushed towards probing the structure function relationship of the lanthanide-DGA complex to enable the design of more efficient lanthanide separation systems. Spectroscopic techniques, such as UV–Visible, Fourier Transformed Infrared Spectroscopy (FT-IR), Nuclear Magnetic Resonance (NMR), and Extended X-ray Absorption Fine Structure (EXAFS), provide information regarding the inner-sphere coordination of a given lanthanide-DGA complex. Scattering techniques, such as Dynamic Light Scattering (DLS), Small-Angle X-ray Scattering (SAXS), and Small-Angle Neutron Scattering (SANS), address nanoscale structures including aggregate sizes and morphology. Here, this review assesses the current state-of-knowledge regarding lanthanide-DGA hydrometallurgical (i.e., solvent extraction systems) interrogated using spectroscopic and scattering techniques to characterize the extracted Ln 3+ DGA species. Of particular interest to this review is the impact of varied diluents, inclusion and variation of phase modifiers, and DGA derivatization on system characteristics. While there has been extensive literature on the application of DGAs for f-element separations, the literature lacks a collective assessment of the speciation of Ln 3+ in the organic phase. This review provides new insights into the field of DGA separations, explicitly with an application to intra-lanthanide separations. Specifically, this review illustrates the importance of both the co-extraction anion (Cl - , NO 3 - , or ClO 4 - ) as it pertains to both the aggregate size and Ln 3+ distribution coefficient. It is evident the ability of the anion to disrupt the hydrogen bonding network limits both aggregate size and distribution coefficients according to the Hoffmeister series. This suggests the importance of the large, softer anions with a low charge-to-surface area ratio on encouraging hydrogen bond interactions. In addition, the co-extracted cation (H + vs Na + ) is important for mitigating transfer of Ln 3+ from the aqueous to the organic phase through extensive hydrogen bonding networks. These networks are responsible for forming supramolecular aggregates where a change in morphology is observed with increasing concentrations of H + and/or Ln 3+ in the organic phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Exploring the Complex Chemistry of Uranium within Molten Chloride Salts

Harsh environments represent a unique opportunity to explore new frontiers in chemistry while developing novel tools to meet global needs. Exploring the chemistry of uranium within molten salts is a key example. Actinide chemistry within the highly ionic environment of a molten salt is poorly understood, particularly in the presence of common salt impurities or without active oxidation state control. Delving into this chemistry can provide new insight into actinide and f-electron interactions. Furthermore, expanding our chemical knowledge can also enable advances in and deployment of molten salt reactors or molten salt recycle schemes. Both molten salt applications aim towards providing green, reliable, and equitable energy as well as critical materials for the world. Here the utilization of visible absorbance and Raman spectroscopies to understand and quantify U within chloride-based salt eutectics is discussed. Furthermore, machine learning techniques in the form of chemometric modelling are developed and described, providing advanced analytical tools to quantify and characterize the U present. In conclusion, these tools are then leveraged to monitor and explore the dynamic fundamental chemistry of U within chloride-based salt melts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

The Photoactive Excited State of the B 12 -Based Photoreceptor CarH

In this study we have used transient absorption spectroscopy in the UV–visible and X-ray regions to characterize the excited state of CarH, a protein photoreceptor that uses a form of B 12 , adenosylcobalamin (AdoCbl), to sense light. With visible excitation, a nanosecond-lifetime photoactive excited state is formed with unit quantum yield. The time-resolved X-ray absorption near edge structure difference spectrum of this state demonstrates that the excited state of AdoCbl in CarH undergoes only modest structural expansion around the central cobalt, a behavior similar to that observed for methylcobalamin rather than for AdoCbl free in solution. We propose a new mechanism for CarH photoreactivity involving formation of a triplet excited state. This allows the sensor to operate with high quantum efficiency and without formation of potentially dangerous side products. By stabilizing the excited electronic state, CarH controls reactivity of AdoCbl and enables slow reactions that yield nonreactive products and bypass bond homolysis and reactive radical species formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Elemental zoning enhances mass transport in zeolite catalysts for methanol to hydrocarbons

Mass transport limitations in zeolite catalysts pose major hurdles for their optimal performance in diverse chemical reactions. Most approaches to reduce these restrictions focus on the synthesis of either hierarchical or nanosized zeolites. Here we demonstrate that the existence of a siliceous, catalytically inactive exterior rim on ZSM-5 particles dramatically reduces the diffusion limitations, which leads to an enhanced catalyst lifetime for the methanol-to-hydrocarbon reaction. In this study, our findings reveal that binary inorganic and organic structure-directing agents enable a one-pot synthesis of Si-zoned ZSM-5 catalysts with diffusion properties that are characteristic of particles with a much smaller size. Operando ultraviolet–visible light diffuse reflectance spectroscopy reveals a marked reduction in external coking among Si-zoned samples. Molecular dynamics simulations to assess the diffusion of methanol and benzene in siliceous pores and in those with Brønsted acids reveal substantially reduced transport limitations in zoned regions, consistent with the improved catalyst activity of Si-zoned zeolites relative to that of ZSM-5 with a homogeneous acid-site distribution.

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

Evaluating Np(v) disproportionation: effect of Np concentration

The role of Np(V) concentration as a potential chemical driver of Np(V) disproportionation was investigated by probing Np redox chemistry in two different acid media using visible-near-infrared absorbance spectroscopy. In situ spectroscopy of chemically and electrochemically manipulated Np oxidation states at molar concentrations of Np underscores the difficulty in stabilizing pure Np(V), even in dilute acid. A Np(VI) component coexisting with the majority Np(V) component was observed in both HNO 3 and HCl. Electrochemical tuning and subsequent spectroscopic analysis of the Np(VI/V) ratio revealed neptunyl self-complexation as a key mechanism occurring in both acid media. Chemical reduction of the Np(VI) component and stabilization of a minor Np(IV) component in HNO 3 were observed; however, spectral data indicated that these two oxidation states were not observed to coexist, and pure Np(V) was stabilized only briefly. These findings demonstrate that high Np concentrations significantly affect the redox chemistry of Np in acidic solutions. Finally, the occurrence of Np(V) disproportionation could not be definitely determined by spectral data, but other mechanisms such as self-complexation and radiolysis, which potentially compete with disproportionation, must be considered.

Gilson, Sara E. [Oak Ridge National Laboratory (OR↗
DOE OSTI2022

Probing f-orbital covalency through the fold angles of transuranium dithiolene complexes

The ability of the actinide elements to covalently bond to ligands is not well understood. A computational effort for compounds of the formula [Cp 2 AnS 2 C 2 H 2 ] -1,0,+1 where An = U, Np, or Pu has shown that the angle between the plane formed by the two sulfurs and the plane formed by the two sulfur atoms and the two carbons converges to 70 – 75° when the ligand is in the dithiolate state (-2 charge on the ligand). Upon oxidation of [Cp 2 NpS 2 C 2 H 2 ] 0 or [Cp 2 PuS 2 C 2 H 2 ] 0 the electron is removed from the dithiolate rather than the actinide and the dihedral angle is reduced to planarity. The reaction of NpCl 4 DME 2 with deprotonated benzene dithiol shows an intense color change suggestive of a charge transfer complex. The binding of the benzene dithiol as the dithiolate to the neptunium metal center is supported by visible, infrared and NMR spectroscopies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The Effect of Intensity Fluctuations on Sequential X-ray Photon Correlation Spectroscopy at the X-ray Free Electron Laser Facilities

How materials evolve at thermal equilibrium and under external excitations at small length and time scales is crucial to the understanding and control of material properties. X-ray photon correlation spectroscopy (XPCS) at X-ray free electron laser (XFEL) facilities can in principle capture dynamics of materials that are substantially faster than a millisecond. However, the analysis and interpretation of XPCS data is hindered by the strongly fluctuating X-ray intensity from XFELs. Here we examine the impact of pulse-to-pulse intensity fluctuations on sequential XPCS analysis. We show that the conventional XPCS analysis can still faithfully capture the characteristic time scales, but with substantial decrease in the signal-to-noise ratio of the g2 function and increase in the uncertainties of the extracted time constants. We also demonstrate protocols for improving the signal-to-noise ratio and reducing the uncertainties.

36 MATERIALS SCIENCE↗