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All sources NASA NTRS DOE OSTI

DOE OSTI2022

Atomic-scale characterization of (electro-)catalysts and battery materials by atom probe tomography

To optimise the performance of heterogeneous (electro-)catalysts and battery electrodes, it is essential to establish the structure-property relationships. This can only be achieved by obtaining a full three-dimensional (3D) characterisation of atomic-scale structure and chemistry of these advanced materials. Atom probe tomography (APT) can provide unique insights into 3D elemental distribution, including low atomic mass elements, with sub-nanometer spatial resolution. Despite its superior chemical analytical capability and spatial resolution, APT has limited applications for sustainable energy materials due to technical and analytical challenges. The recent developments in experimental setups, sample preparation methods and data analysis algorithms have opened the door to the possibility of analysing heterogeneous (electro-)catalysts and battery electrodes. This perspective provides an overview of these developments, exemplified by recent achievements of analyzing model heterogeneous model (electro-)catalysts, nanoparticles, zeolites, MOFs and Li-ion battery electrodes, followed by a discussion of limitations, opportunities, and potentials of APT for future scientific exploration.

atom probe tomography↗

DOE OSTI2024

Coupling Microdroplet-Based Sample Preparation, Multiplexed Isobaric Labeling, and Nanoflow Peptide Fractionation for Deep Proteome Profiling of the Tissue Microenvironment

There is increasing interest in developing in-depth proteomic approaches for mapping tissue heterogeneity in a cell-type-specific manner to better understand and predict the function of complex biological systems such as human organs. Existing spatially resolved proteomics technologies cannot provide deep proteome coverage due to limited sensitivity and poor sample recovery. Herein, we seamlessly combined laser capture microdissection with a low-volume sample processing technology that includes a microfluidic device named microPOTS (microdroplet processing in one pot for trace samples), multiplexed isobaric labeling, and a nanoflow peptide fractionation approach. The integrated workflow allowed us to maximize proteome coverage of laser-isolated tissue samples containing nanogram levels of proteins. We demonstrated that the deep spatial proteomics platform can quantify more than 5000 unique proteins from a small-sized human pancreatic tissue pixel (∼60,000 μm2) and differentiate unique protein abundance patterns in pancreas. Furthermore, the use of the microPOTS chip eliminated the requirement for advanced microfabrication capabilities and specialized nanoliter liquid handling equipment, making it more accessible to proteomic laboratories.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Cross Section Generation Capability in Griffin

The Griffin code is a Multiphysics Object-Oriented Simulation Environment (MOOSE) based reactor multiphysics analysis application jointly developed by Idaho National Laboratory and Argonne National Laboratory. The code includes a variety of steady-state solvers for fixed-source, k-eigenvalue, adjoint, and subcritical multiplication, as well as transient solvers for point-kinetics, improved quasi-static, and spatial dynamics. The code reads multigroup cross sections in the ISOXML format generated from external deterministic or Monte Carlo cross section generation codes. The implementation of the cross section generation capability in Griffin was initiated last year by plugging in the cross section application programming interface (CSAPI) and reviewing the methodologies for treating particulate fuels. The focus this year was on improving the CSAPI integration and implementing advanced self-shielding methods for applications to advanced reactor problems with TRISO fuels. First, the process for cross section library generation was updated to accurately and rigorously produce isotopic cross section data. Second, the equivalent Dancoff factor cell method performing slowing down calculations on the fly for the resonance treatment was implemented in CSAPI to improve the accuracy of effective multigroup cross sections in the resonance energy range. Third, the iterative local spatial self-shielding method was implemented under the calculation framework of the equivalent Dancoff factor cell method to accurately deal with the double heterogeneity effect of particulate fuel. The updated CSAPI with the advanced self-shielding methods, together with the cross section libraries generated based on the improved process, were tested for pin-cell, unit-cell, and fuel assembly problems with various resonance self-shielding conditions based on very high temperature reactor, high temperature test reactor, and Empire benchmark cores, indicating that the updated CSAPI in Griffin is able to produce multigroup cross sections accurately and efficiently. We also showed that the methodology worked well for pebble bed fuel from HTR-10, but the capability still needs to be fully integrated into CSAPI. In the future, further benchmark tests will be performed for various thermal reactor core problems, including particulate fuel-based pebble bed reactors.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2021

Cross Section Generation Capability in Griffin

The Griffin code is a Multiphysics Object-Oriented Simulation Environment (MOOSE) based reactor multiphysics analysis application jointly developed by Idaho National Laboratory and Argonne National Laboratory. The code includes a variety of steady-state solvers for fixed-source, k-eigenvalue, adjoint, and subcritical multiplication, as well as transient solvers for point-kinetics, improved quasi-static, and spatial dynamics. The code reads multigroup cross sections in the ISOXML format generated from external deterministic or Monte Carlo cross section generation codes. The implementation of the cross section generation capability in Griffin was initiated last year by plugging in the cross section application programming interface (CSAPI) and reviewing the methodologies for treating particulate fuels. The focus this year was on improving the CSAPI integration and implementing advanced self-shielding methods for applications to advanced reactor problems with TRISO fuels. First, the process for cross section library generation was updated to accurately and rigorously produce isotopic cross section data. Second, the on-the-fly slowing down method for the resonance treatment was implemented in CSAPI to improve the accuracy of effective multigroup cross sections in the resonance energy range. Among various on-the-fly slowing down methods, the equivalent Dancoff factor cell method was employed. Third, the iterative local spatial self-shielding method was implemented under the calculation framework of the equivalent Dancoff factor cell method to accurately deal with the double heterogeneity effect of particulate fuel. The updated CSAPI with the advanced self-shielding methods, together with the cross section libraries generated based on the improved process, were tested for the very high temperature reactor (VHTR), high temperature test reactor (HTTR), and Empire benchmark problems with various resonance self-shielding conditions, indicating that the updated CSAPI in Griffin is able to produce multigroup cross sections accurately and efficiently. We also show that the methodology works well for pebble bed fuel from HTR-10, but the capability still needs to be fully integrated into CSAPI. In the future, further benchmark tests will be performed for various thermal reactor core problems, including particulate fuel-based pebble bed reactors.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗

NASA NTRS1991

Aerosol backscatter measurements at 10.6 microns with airborne and ground-based CO2 Doppler lidars over the Colorado High Plains. I - Lidar intercomparison

An airborne continuous-wave (CW) focused CO2 Doppler lidar and a ground-based pulsed CO2 Doppler lidar were to obtain seven pairs of comparative measurements of tropospheric aerosol backscatter profiles at 10.6-micron wavelength, near Denver, Colorado, during a 20-day period in July 1982. In regions of uniform backscatter, the two lidars show good agreement, with differences usually less than about 50 percent near 8-km altitude and less than a factor of 2 or 3 elsewhere but with the pulsed lidar often lower than the CW lidar. Near sharp backscatter gradients, the two lidars show poorer agreement, with the pulsed lidar usually higher than the CW lidar. Most discrepancies arise from a combination of atmospheric factors and instrument factors, particularly small-scale areal and temporal backscatter heterogeneity above the planetary boundary layer, unusual large-scale vertical backscatter structure in the upper troposphere and lower stratosphere, and differences in the spatial resolution, detection threshold, and noise estimation for the two lidars.

Bowdle, David A.↗

NASA NTRS1994

Landscape dynamics of northeastern forests

This project involves collaborative research with Stephen W. Pacala and Simon A. Levin of Princeton University to calibrate, test, and analyze models of heterogeneous forested landscapes containing a diverse array of habitats. The project is an extension of previous, NASA-supported research to develop a spatially-explicit model of forest dynamics at the scale of an individual forest stand (hectares to square kilometer spatial scales). That model (SORTIE) has been thoroughly parameterized from field studies in the modal upland environment of western Connecticut. Under our current funding, we are scaling-up the model and parameterizing it for the broad range of upland environments in the region. Our most basic goal is to understand the linkages between stand-level dynamics (as revealed in our previous research) and landscape-level dynamics of forest composition and structure.

Canham, Charles D.↗

NASA NTRS2008

Titan's Winter Polar Vortex

Titan's atmosphere has provided an interesting study in contrasts and similarities with Earth's. While both have N$_2$ as the dominant constituent and comparable surface pressures $\sim1$ bar, Titan's next most abundant molecule is CH$_4$, not O$_2$, and the dissociative breakup of CH$_4$ and N$_2$ by sunlight and electron impact leads to a suite of hydrocarbons and nitriles, and ultimately the photochemical smog that enshrouds the moon. In addition, with a 15.95-day period, Titan is a slow rotator compared to Earth. While the mean zonal terrestrial winds are geostrophic, Titan's are mostly cyclostrophic, whipping around the moon in as little as 1 day. Despite the different dynamical regime, Titan's winter stratosphere exhibits several characteristics that should be familiar to terrestrial meteorologists. The cold winter pole near the 1 -mbar level is circumscribed by strong winds (up to 190 m/s) that act as a barrier to mixing with airmasses at lower latitudes. There is evidence of enhancement of several organic species over the winter pole, indicating subsidence. The adiabatic heating associated with this subsidence gives rise to a warm anomaly at the 0.01-mbar level, raising the stratopause two scale heights above its location at equatorial latitudes. Condensate ices have been detected in Titan's lower stratosphere within the winter polar vortex from infrared spectra. Although not always unambiguously identified, their spatial distribution exhibits a sharp gradient, decreasing precipitously across the vortex away from the winter pole. The interesting question of whether there is important heterogeneous chemistry occurring within the polar vortex, analogous to that occurring in the terrestrial polar stratospheric clouds in the ozone holes, has not been addressed. The breakup of Titan's winter polar vortex has not yet been observed. On Earth, the polar vortex is nonlinearly disrupted by interaction with large-amplitude planetary waves. Large-scale waves have not been identified in Titan's atmosphere, so the decay of its polar vortex may be more gradual than on Earth. Observations from an extended Cassini mission into late northern spring should provide critical data indicating whether the vortex goes away with a bang or just fades away.

Flasar, F.M.↗

NASA NTRS2012

Evaluation of Moderate-Resolution Imaging Spectroradiometer (MODIS) Snow Albedo Product (MCD43A) over Tundra

This study assesses the MODIS standard Bidirectional Reflectance Distribution Function (BRDF)/Albedo product, and the daily Direct Broadcast BRDF/Albedo algorithm at tundra locations under large solar zenith angles and high anisotropic diffuse illumination and multiple scattering conditions. These products generally agree with ground-based albedo measurements during the snow cover period when the Solar Zenith Angle (SZA) is less than 70deg. An integrated validation strategy, including analysis of the representativeness of the surface heterogeneity, is performed to decide whether direct comparisons between field measurements and 500- m satellite products were appropriate or if the scaling of finer spatial resolution airborne or spaceborne data was necessary. Results indicate that the Root Mean Square Errors (RMSEs) are less than 0.047 during the snow covered periods for all MCD43 albedo products at several Alaskan tundra areas. The MCD43 1- day daily albedo product is particularly well suited to capture the rapidly changing surface conditions during the spring snow melt. Results also show that a full expression of the blue sky albedo is necessary at these large SZA snow covered areas because of the effects of anisotropic diffuse illumination and multiple scattering. In tundra locations with dark residue as a result of fire, the MODIS albedo values are lower than those at the unburned site from the start of snowmelt.

Wang, Zhuosen↗

NASA NTRS2012

Intercomparison of Desert Dust Optical Depth from Satellite Measurements

This work provides a comparison of satellite retrievals of Saharan desert dust aerosol optical depth (AOD) during a strong dust event through March 2006. In this event, a large dust plume was transported over desert, vegetated, and ocean surfaces. The aim is to identify the differences between current datasets. The satellite instruments considered are AATSR, AIRS, MERIS, MISR, MODIS, OMI, POLDER, and SEVIRI. An interesting aspect is that the different algorithms make use of different instrument characteristics to obtain retrievals over bright surfaces. These include multi-angle approaches (MISR, AATSR), polarisation measurements (POLDER), single-view approaches using solar wavelengths (OMI, MODIS), and the thermal infrared spectral region (SEVIRI, AIRS). Differences between instruments, together with the comparison of different retrieval algorithms applied to measurements from the same instrument, provide a unique insight into the performance and characteristics of the various techniques employed. As well as the intercomparison between different satellite products, the AODs have also been compared to co-located AERONET data. Despite the fact that the agreement between satellite and AERONET AODs is reasonably good for all of the datasets, there are significant differences between them when compared to each other, especially over land. These differences are partially due to differences in the algorithms, such as assumptions about aerosol model and surface properties. However, in this comparison of spatially and temporally averaged data, it is important to note that differences in sampling, related to the actual footprint of each instrument on the heterogeneous aerosol field, cloud identification and the quality control flags of each dataset can be an important issue.

desert dust↗

NASA NTRS2017

Assessment of Satellite-Derived Surface Reflectances by NASA's CAR Airborne Radiometer over Railroad Valley, Nevada

CAR (Cloud Absorption Radiometer) is a multi-angular and multi-spectral airborne radiometer instrument, whose radiometric and geometric characteristics are well calibrated and adjusted before and after each flight campaign. CAR was built by NASA (National Aeronautics and Space Administration) in 1984. On 16 May 2008, a CAR flight campaign took place over the well-known calibration and validation site of Railroad Valley in Nevada (38.504 deg N, 115.692 deg W).The campaign coincided with the overpasses of several key EO (Earth Observation) satellites such as Landsat-7, Envisat and Terra. Thus, there are nearly simultaneous measurements from these satellites and the CAR airborne sensor over the same calibration site. The CAR spectral bands are close to those of most EO satellites. CAR has the ability to cover the whole range of azimuth view angles and a variety of zenith angles depending on altitude and, as a consequence, the biases seen between satellite and CAR measurements due to both unmatched spectral bands and unmatched angles can be significantly reduced. A comparison is presented here between CARs land surface reflectance (BRF or Bidirectional Reflectance Factor) with those derived from Terra/MODIS (MOD09 and MAIAC), Terra/MISR, Envisat/MERIS and Landsat-7. In this study, we utilized CAR data from low altitude flights (approx. 180 m above the surface) in order to minimize the effects of the atmosphere on these measurements and then obtain a valuable ground-truth data set of surface reflectance. Furthermore, this study shows that differences between measurements caused by surface heterogeneity can be tolerated, thanks to the high homogeneity of the study site on the one hand, and on the other hand, to the spatial sampling and the large number of CAR samples. These results demonstrate that satellite BRF measurements over this site are in good agreement with CAR with variable biases across different spectral bands. This is most likely due to residual aerosol effects in the EO derived reflectances.

calibration↗

DOE OSTI2020

Predicting mesoscale spectral thermal conductivity using advanced deterministic phonon transport techniques

We present a review, demonstration and simulation of phonon transport for the purposes of predicting materials performance at the mesoscale. We focus primarily on the development and implementation of a unified methodology to enable predictive heat transport. We report on the current state of the art as it pertains to deterministic phonon transport methodologies, discussing various topics concerning phonons. In application, we focus on the Self-Adjoint Angular Flux (SAAF) formulation of the Boltzmann transport equation for phonons, and develop the spatial, angular, and material property discretization required to accurately simulate the predictive physics of heat transport in dielectrics. We discuss thermal interfacial resistance and present our formulation of the diffuse mismatch model for simulating phonon interactions at internal boundaries. We have recently developed a deterministic, spectral phonon transport method for predicting effective thermal conductivity ($\kappa_{\textrm{eff}}$), using Bose-Einstein source terms coupled through an average material temperature. In this method, we introduce a closure term to the phonon transport system which acts as a redistribution function for the total energy of the system, and serves as a guide for the amount of non-equilibrium behavior occurring in the system. This method predicts thermal conductivity and equilibrium temperature distributions in homogeneous and heterogeneous materials using data generated by ab initio density functional theory methods. We employ polarization, density of states and full dispersion spectra to resolve thermal conductivity with numerous angular and spatial discretizations. Our implementation utilizes a Richardson iteration on a modified version of the phonon scattering source. The equations associated with this method are solved via a modification of traditional source iteration. We compare the performance of source iteration applied to an existing uncoupled, traditional SAAF method to our new method and comment on the iterative performance of each. We observe ballistic and diffusive phonon scattering as acoustic thickness of the domain changes, and are able to make comparisons between the accuracy and efficiency of both methods.

36 MATERIALS SCIENCE↗

NASA NTRS1997

Laser-Induced Incandescence in Microgravity

Knowledge of soot concentration is important due to its presence and impact upon a wide range of combustion processes ranging from diffusion to premixed flames, laminar to turbulent processes and homogeneous to heterogeneous combustion. Measurement of soot volume fraction (f(sub v)) is essential to discerning its formation and growth. The presence of soot also affects other physical and chemical properties of combustion thereby affecting studies not directly concerned with either its formation or growth, such as radiative heat transfer, CO oxidation and fuel vaporization or pyrolysis rates. Microgravity offers unique opportunities for studying both soot growth and the effect of soot radiation upon flame structure and spread. Spatial scales and residence time scales are greatly extended in 0-g facilitating soot growth studies. With the varied geometries, short duration microgravity test times and time-varying processes there is a demand for measurement of f(sub v) with high spatial and temporal resolution. Laser-induced incandescence (LII) has advanced f(sub v) measurements in many 1-g combustion processes. To create laser-induced incandescence, a pulsed high intensity laser heats soot to incandescence temperatures. Using appropriate spectral and temporal detection conditions, the resulting incandescence can be selectively detected apart from the non-laser-heated soot and flame gases. Theoretical modelling and experiments have shown that the resulting incandescence is representative of f(sub v). Using an intensified array camera and a laser sheet for excitation, one- and two-dimensionally resolved LII images of f(sub v) have been obtained in 1-g. LII has been characterized and developed at NASA-Lewis for soot volume fraction determination in a wide range of 1-g combustion applications. Broadly grouped, the characterization work has included studies of excitation intensity, excitation wavelength and the optimum temporal and spectral detection conditions to enable an accurate representation of soot volume fraction by LII. Tests for special requirements imposed by different combustion processes have been performed in laminar and turbulent diffusion flames, rich sooting premixed flames, single droplet combustion, and other heterogeneous combustion. These studies demonstrated LII's high sensitivity, temporal and spatial capabilities and its geometric versatility. In contrast to the advantages offered to combustion studies by a microgravity environment, advanced diagnostics, specifically those requiring pulsed laser diagnostics have been limited due to the size, weight and power limitations in a low-gravity environment. Reported here are the first demonstrations of LII performed in a microgravity environment. Examples are shown for laminar and turbulent gas-jet diffusion flames in 0-g.

VanderWal, Randy L.↗

NASA NTRS1994

Structural analysis of airborne flux estimates over a region

Aircraft-based observations of turbulence fields of velocity, moisture, and temperature are used to study coherent turbulent structures that dominate turbulent transfer of moisture and heat above three different eco-systems. Flux traces are defragmented, to reconstruct the presumed full size (along the sampled transect) of these structures, and flux traces are simplified by elimination of those that contribute negligibly to the flux estimate. Structures are analyzed in terms of size, spatial distribution, and contribution to the flux, in the four 'quadrant' modes of eddy-covariance transfer (excess up/down and deficit up/down). The effect of nonlinear detrending of moisture and temperature data on this 'structural analysis,' over surfaces with heterogeneous surface wetness, is also examined. Results over grassland, wetland, and moist and dry agricultural land, show that nonlinear detrending may provide a more physically realistic description of structures. Significant differences are observed between structure size and associated relative flux contribution, between moist and dry areas, with smaller structures playing a more important role over the moist areas. Structure size generally increases with height, as spatial reorganization from smaller structures into larger ones takes place. This coincides with a gradual loss of surface 'signature' (position and clustering of plumes above localized source areas). The data are expected to provide a basis for an eventual statistical description of boundary-layer transfer events , and help to interpret the link between boundary-layer transfer and hydrological surface conditions.

Caramori, Paulo↗

NASA NTRS2022

Spatial Downscaling of GOES-R Land Surface Temperature over Urban Regions: A Case Study for New York City

The surface urban heat island (SUHI) effect is among the major environmental issues encountered in urban regions. To better predict the dynamics of the SUHI and its impacts on extreme heat events, an accurate characterization of the surface energy balance in urban regions is needed. However, the ability to improve understanding of the surface energy balance is limited by the heterogeneity of surfaces in urban areas. This study aims to enhance the understanding of the urban surface energy budget through an innovation in the use of land surface temperature (LST) observations from remote sensing satellites. A LST database with 5–min temporal and 30–m spatial resolution is developed by spatial downscaling of the Geostationary Operational Environmental Satellites—R (GOES–R) series LST product over New York City (NYC). The new downscaling method, known as the Spatial Downscaling Method (SDM), benefits from the fine spatial resolution of Landsat–8 and high temporal resolution of GOES–R, and considers the temporal variation in LST for each land cover type separately. Preliminary results show that the SDM can reproduce the temporal and spatial variability of LST over NYC reasonably well and the downscaled LST has a spatial root mean square error (RMSE) of the order of 2 K as compared to the independent Landsat–8 observations. The SDM shows smaller RMSE of 1.93 K over the tree canopy land cover, whereas RMSE is 2.19 K for built–up areas. The overall results indicate that the SDM has potential to estimate LST at finer spatial and temporal scales over urban regions.

land surface temperature↗

DOE OSTI2020

High-speed x-ray phase contrast imaging and digital image correlation analysis of microscale shock response of an additively manufactured energetic material simulant

The performance of energetic materials subjected to dynamic loading significantly depends on their micro- and meso-scale structural morphology. The geometric versatility offered by additive manufacturing opens new pathways to tailor the performance of these materials. Additively manufactured energetic materials (AMEMs) have a wide range of structural characteristics with a hierarchy of length scales and process-inherent heterogeneities, which are hitherto difficult to precisely control. It is important to understand how these features affect AMEMs’ response under dynamic/shock loading. Therefore, temporally and spatially resolved measurements of both macroscopic behavior and micro- and meso-level processes influencing macroscopic behavior are required. In this paper, we analyze the shock compression response of an AMEM simulant loaded under several impact conditions and orientations. Furthermore, x-ray phase contrast imaging (PCI) is used to track features across the observed shock front and determine the linear shock velocity vs particle velocity equation of state, as well as to quantify the interior deformation fields via digital image correlation (DIC) analyses. Photon Doppler velocimetry is simultaneously used to measure the particle velocities of the specimens, which are consistent with those obtained from x-ray PCI. The DIC analyses provide an assessment of the average strain fields inside the material, showing that the average axial strain depends on the loading intensity and reaches as high as 0.23 for impact velocities up to 1.5 km/s. The overall results demonstrate the utility of x-ray PCI for probing “in-material” equation of state and interior strains associated with dynamic shock compression behavior of the AMEM simulant.

3D printing↗

DOE OSTI2023

Fe 3+ /Fe T ratios of amphiboles determined by high spatial resolution single-crystal synchrotron Mössbauer spectroscopy

The Fe 3+ /Fe T ratios (Fe 3+ /[Fe 2+ +Fe 3+ ]) in minerals can be used to understand their crystallization and post-crystallization conditions. However, as natural minerals are often zoned and contain inclusions, bulk techniques, e.g., wet chemistry, may not provide accurate Fe 3+ /Fe T values for a single phase of interest. We determined Fe 3+ /Fe T ratios of amphiboles in different crystallographic orientations by single-crystal synchrotron Mössbauer spectroscopy (SMS) in energy and time domain modes from four volcanic localities (Long Valley Caldera, Mount St. Helens, Lassen Volcanic Center, U.S.A., and Mt. Pinatubo, Philippines). The high spatial resolution (as low as 12 × 12 μm spot size) and standard-free nature of SMS allow the detection of intra-grain compositional heterogeneities in Fe 3+ /Fe T with relatively low uncertainties. Here, we combine SMS with major element compositions, water contents, and hydrogen isotope compositions to document the Fe 3+ /Fe T ratios as a function of mineral composition and post-crystallization dehydrogenation. Spectra were fitted with up to five distinct sites: ferrous iron on M(1), M(2), M(3), and ferric iron on M(2) and M(3), consistent with X-ray diffraction studies on single crystals of amphibole. The Fe 3+ /Fe T ratios range from 0.14 ± 0.03 (Long Valley Caldera), 0.51 to 0.63 ± 0.02 (representing intra-grain heterogeneities, Mount St. Helens) to 0.86 ± 0.03 (Lassen Volcanic Center). The latter grain experienced post-crystallization dehydrogenation, shown by its low water content (0.6 ± 0.05 wt%) and its elevated hydrogen isotope composition (δD = +25 ± 3‰ relative to SMOW). The Fe 3+ /Fe T ratios of 0.62 ± 0.01 and 0.20 ± 0.01 of two Mt. Pinatubo grains correlate with high-Al 2 O 3 cores and low-Al 2 O 3 rims and smaller phenocrysts in the sample, respectively. This study shows that SMS is capable of distinguishing two different domains with dissimilar Fe 3+ /Fe T values formed under different crystallization conditions, demonstrating that SMS in combination with major element, water, and hydrogen isotope compositions allows the interpretation of amphibole Fe 3+ /Fe T ratios in the context of crystallization and post-crystallization processes.

47 OTHER INSTRUMENTATION↗

DOE OSTI2023

Probing the Structure and Dynamics of Fluid Mixtures in Porous Materials Through Ultrafast Vibrational Spectro-Microscopy and Many-Body Molecular Dynamics

This research program focused on the characterization of both molecular structure and dynamics of aqueous solutions in various metal-organic frameworks (MOFs) and organic polymers that have recently been proposed for applications in water treatment technologies. This was accomplished by integrating ultrafast vibrational spectroscopy and microscopy, which are sensitive to local environments, molecular orientation, and dynamical couplings, with many-body molecular dynamics (MB-MD) simulations, which enable realistic modeling of aqueous systems and porous materials under different thermodynamic conditions. Our studies allowed for identifying the physical mechanisms and characterizing the underlying molecular interactions between water and host materials that determine the adsorption and transport processes of water in various MOFs and β-cyclodextrin polymers – prototypical examples of porous materials and polymers, that have recently been proposed for technological applications in water purification. By combining bulk- and surface-sensitive, spatially resolved ultrafast vibrational spectroscopy with MB-MD simulations, it was possible to gain broad insight into the structure and mobility of water under heterogeneous confinement at various length scales. In particular, measurements of surface- and bulk-sensitive vibrational spectra at single crystal level, integrated with MB-MD simulations were used to characterize domain-specific, structure–binding affinity relationships. Besides providing specific information about the behavior of aqueous solutions in prototypical MOFs and organic polymers for potential applications in water treatment technologies, our studies also provided fundamental insights into the properties of aqueous solutions in confined heterogeneous environments, which have broad implications in many areas, ranging from heterogeneous catalysis to oil recovery, ion transport processes, and reaction-diffusion processes in crowded systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1990

In situ analysis of CO during chemisorption and oxidation on graphite: Supported Pt by FTIR-microspectrometry

For chemisorption and oxidation on Pt/HOPG (highly-orientated pyrolytic) graphite, reflectance Fourier Transform Infrared (FTIR)-microspectrometry reveals a variable state and reactivity for CO. Even for model surface science systems, where surface heterogeneity is minimal, surface diffusion may be too slow relative to the reaction rate to avoid segregation of reactants into surface islands under steady-state conditions. Thus in CO oxidation on Pt (where the relevant surface diffusion coefficients are such that D sub O less than D sub CO) then reactant CO islands exists at the perimeters of which the surface reaction is thought to occur. Furthermore CO can chemisorb on metals in linear and bridge forms to extents which vary with precise faces predominantly exposed coverage, etc. Infrared has long been used to probe the nature of adsorbed CO on model film and heterogeneous surfaces, but it may now be that FTIR-microspectrometry will allow the state of this adsorbate and reactant to be investigated with a spatial resolution of 4.4 microns on model (and real) catalytic surfaces.

Self, Valerie A.↗