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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 1,387 records · Page 77
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts

Atomically dispersed supported metal catalysts offer new properties and the benefits of maximized metal accessibility and utilization. The characterization of these materials, however, remains challenging. Using atomically dispersed platinum supported on crystalline MgO (chosen for its well-defined bonding sites) as a prototypical example, we demonstrate in this work how systematic density functional theory calculations for assessing all the potentially stable platinum sites, combined with automated analysis of extended X-ray absorption fine structure (EXAFS) spectra, leads to unbiased identification of isolated, surface-enveloped platinum cations as the catalytic species for CO oxidation. The catalyst has been characterized by atomic-resolution imaging and EXAFS and high-energy resolution fluorescence detection X-ray absorption near edge spectroscopy. The proposed platinum sites are in agreement with experiment. This theory-guided workflow leads to rigorously determined structural models and provides a more detailed picture of the structure of the catalytically active site than what is currently possible with conventional EXAFS analyses. As this approach is efficient and agnostic to the metal, support, and catalytic reaction, we posit that it will be of broad interest to the materials characterization and catalysis communities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Identifying the Active Surfaces of Electrochemically Tuned LiCoO 2 for Oxygen Evolution Reaction

Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2 ) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Biophysical Characterization of a Disabled Double Mutant of Soybean Lipoxygenase: The “Undoing” of Precise Substrate Positioning Relative to Metal Cofactor and an Identified Dynamical Network

Soybean lipoxygenase (SLO) has served as a prototype for understanding the molecular origin of enzymatic rate accelerations. The double mutant (DM) L546A/L754A is considered a dramatic outlier, due to the unprecedented size and near temperature-independence of its primary kinetic isotope effect, low catalytic efficiency, and elevated enthalpy of activation. To uncover the physical basis of these features, we herein apply three structural probes: hydrogen–deuterium exchange mass spectrometry, room-temperature X-ray crystallography and EPR spectroscopy on four SLO variants (wild-type (WT) enzyme, DM, and the two parental single mutants, L546A and L754A). DM is found to incorporate features of each parent, with the perturbation at position 546 predominantly influencing thermally activated motions that connect the active site to a protein–solvent interface, while mutation at position 754 disrupts the ligand field and solvation near the cofactor iron. However, the expanded active site in DM leads to more active site water molecules and their associated hydrogen bond network, and the individual features from L546A and L754A alone cannot explain the aggregate kinetic properties for DM. Lastly, using recently published QM/MM-derived ground-state SLO-substrate complexes for WT and DM, together with the thorough structural analyses presented herein, we propose that the impairment of DM is the combined result of a repositioning of the reactive carbon of linoleic acid substrate with regard to both the iron cofactor and a catalytically linked dynamic region of protein.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Identifying Key Drivers of Wildfires in the Contiguous US Using Machine Learning and Game Theory Interpretation

Abstract Understanding the complex interrelationships between wildfire and its environmental and anthropogenic controls is crucial for wildfire modeling and management. Although machine learning (ML) models have yielded significant improvements in wildfire predictions, their limited interpretability has been an obstacle for their use in advancing understanding of wildfires. This study builds an ML model incorporating predictors of local meteorology, land‐surface characteristics, and socioeconomic variables to predict monthly burned area at grid cells of 0.25° × 0.25° resolution over the contiguous United States. Besides these predictors, we construct and include predictors representing the large‐scale circulation patterns conducive to wildfires, which largely improves the temporal correlations in several regions by 14%–44%. The Shapley additive explanation is introduced to quantify the contributions of the predictors to burned area. Results show a key role of longitude and latitude in delineating fire regimes with different temporal patterns of burned area. The model captures the physical relationship between burned area and vapor pressure deficit, relative humidity (RH), and energy release component (ERC), in agreement with the prior findings. Aggregating the contribution of predictor variables of all the grids by region, analyses show that ERC is the major contributor accounting for 14%–27% to large burned areas in the western US. In contrast, there is no leading factor contributing to large burned areas in the eastern US, although large‐scale circulation patterns featuring less active upper‐level ridge‐trough and low RH two months earlier in winter contribute relatively more to large burned areas in spring in the southeastern US.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Using Large Ensembles to Identify Regions of Systematic Biases in Moderate-to-Heavy Daily Precipitation

Because of internal variability in both the real-world and global climate models, it is unclear whether disagreement between models and observations reflects true systematic differences, or different phasing of internal variability in the short observational period. Here, we address this issue through an examination of moderate-to-heavy precipitation in large ensembles of global climate models. We find that model inconsistency with a global observational product is lowest for extratropical precipitation in northern hemisphere winter. The inconsistency is systematically greater for the southern hemisphere winter, but the difference between hemispheres could be due to observational quality. Moderate-to-heavy extratropical winter precipitation is less inconsistent than moderate-to-heavy tropical precipitation in most models. Within the tropics, moderate-to-heavy precipitation is particularly inconsistent with the reference in regions including the Caribbean (especially during JJA), the northern and southern flanks of the Pacific and Atlantic ITCZ, and the Indian Ocean.

58 GEOSCIENCES↗
DOE OSTI2021

Identifying Key Environmental Factors Explaining Temporal Patterns of DOC Export From Watersheds in the Conterminous United States

The export of dissolved organic carbon (DOC) from a watershed is a key component of the terrestrial biosphere carbon cycle. There is a need to improve our understanding of how and by how much various environmental factors are driving the temporal patterns of DOC export in order to accurately model and evaluate terrestrial carbon storage and fluxes. In this synthesis, we compiled observational data sets from 14 watersheds in the conterminous United States spanning the time period from 1981 to 2017. We used these data sets to examine the relative impacts of various climate, atmospheric deposition, and land cover factors on the temporal patterns of DOC export across watersheds of different sizes and landscape conditions, as well as the time-series autocorrelation of DOC export. Overall, our results suggest that the dominant factor on an annual scale was the amount of precipitation, which had a positive correlation with DOC export from a watershed. Overall increasing nitrogen deposition was coincident with increasing DOC export, and increasing sulfur deposition was coincident with declining DOC export. The seasonal pattern of DOC export was strongly regulated by air temperature, the long-term trend was negatively influenced by increasing sulfur deposition, and no obvious autocorrelation was detected in DOC export. In addition, higher rates of DOC export were positively correlated with greater area of wetlands within a watershed, but was not found to be strongly related to any of the other land cover types.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

A GeoHealth Call to Action: Moving Beyond Identifying Environmental Injustices to Co-Creating Solutions

As marginalized communities continue to bear disproportionate impacts from environmental hazards, we urgently call for researchers and institutions to elevate the principles of Environmental Justice. The American Geophysical Union (AGU) GeoHealth section supports members' engagement in health-related community-engaged and community-led transdisciplinary research. We highlight intersectional research that provides examples and actions for both individuals and organizations on community science and trust building, removing barriers created by scientific agency priorities and career expectations, and opportunities in education and policy. Justice does not start or end at one meeting; this is ongoing work that is active, evolving, and an ethical responsibility of AGU's membership.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Applying Magnetic Curvature to MMS Data to Identify Thin Current Sheets Relative to Tail Reconnection

Thin current sheets (TCSs) have been postulated to be a necessary precondition for reconnection onset. Magnetic reconnection X-lines in the magnetotail have been observed to be more common duskward of midnight. We take advantage of the MMS tetrahedral formation during the 2017–2020 MMS tail seasons to calculate the thickness of the cross-tail neutral sheet relative to ion gyroradius. While a similar technique was applied to Cluster data, current sheet thickness over a broader range of radial distances has not been robustly explored before this study. We compare our analysis to recent theories regarding mechanisms of tail current sheet thinning and to recent simulations. We find MMS spent more than twice as long in ion-scale TCSs in the pre-midnight sector than post-midnight, despite nearly even plasma sheet dwell time. The dawn-dusk asymmetry in the distribution of Ion Diffusion Regions, as previously reported in relation to regions of TCSs, is also analyzed.

79 ASTRONOMY AND ASTROPHYSICS↗