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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 901 records · Page 50
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

Although well known in the material science field, surface reconstruction of perovskites has not been implemented in heterogeneous catalysis. In this work, we employ multiple surface sensitive techniques to characterize the surface reconstruction of SrTiO3 (STO) after thermal pretreatment (Sr-enrichment) and chemical etching (Ti-enrichment). We show, using the conversion of 2-propanol as a probe reaction, that the surface reconstruction of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivities in a wide range, which are inaccessible using single metal oxides, either SrO or TiO2. Density functional theory (DFT) calculations well explain the selectivity tuning and reaction mechanism on differently reconstructed surfaces of STO. Similar catalytic tunability is also observed on BaZrO3, highlighting the generality of the finding from this work.

Polo-Garzon, Felipe↗
DOE OSTI2019

Testing Hopkins’ Bioclimatic Law with PhenoCam data

We investigated the spatial and temporal patterns of vegetation phenology with phenometrics derived from PhenoCam imagery. Specifically, we evaluated the Bioclimatic Law proposed by Hopkins, which relates phenological transitions to latitude, longitude, and elevation. “Green-up” and “green-down” dates—representing the start and end of the annual cycles of vegetation activity—were estimated from measures of canopy greenness calculated from digital repeat photography. We used data from 65 deciduous broadleaf (DB) forest sites, 18 evergreen needleleaf (EN) forest sites, and 21 grassland (GR) sites. DB green-up dates were well correlated with mean annual temperature and varied along spatial gradients consistent with the Bioclimatic Law. Interannual variation in DB phenology was most strongly associated with temperature anomalies during a relatively narrow window of time. EN phenology was not well correlated with either climatic factors or spatial gradients, but similar to DB phenology, interannual variation was most closely associated with temperature anomalies. For GR sites, mean annual precipitation explained most of the spatial variation in the duration of vegetation activity, whereas both temperature and precipitation anomalies explained interannual variation in phenology. PhenoCam data provide an objective and consistent means by which spatial and temporal patterns in vegetation phenology can be investigated.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Kinetic modeling of microbial growth, enzyme activity, and gene deletions: An integrated model of β-glucosidase function in Cellvibrio japonicus

Understanding the complex growth and metabolic dynamics in microorganisms requires advanced kinetic models containing both metabolic reactions and enzymatic regulation to predict phenotypic behaviors under different conditions and perturbations. Most current kinetic models lack gene expression dynamics and are separately calibrated to distinct media, which consequently makes them unable to account for genetic perturbations or multiple substrates. This challenge limits our ability to gain a comprehensive understanding of microbial processes towards advanced metabolic optimizations that are desired for many biotechnology applications. Here, we present an integrated computational and experimental approach for the development and optimization of mechanistic kinetic models for microbial growth and metabolic and enzymatic dynamics. Our approach integrates growth dynamics, gene expression, protein secretion, and gene-deletion phenotypes. We applied this methodology to build a dynamic model of the growth kinetics in batch culture of the bacterium Cellvibrio japonicus grown using either cellobiose or glucose media. The model parameters were inferred from an experimental data set using an evolutionary computation method. The resulting model was able to explain the growth dynamics of C. japonicus using either cellobiose or glucose media and was also able to accurately predict the metabolite concentrations in the wild-type strain as well as in β-glucosidase gene deletion mutant strains. We validated the model by correctly predicting the non-diauxic growth and metabolite consumptions of the wild-type strain in a mixed medium containing both cellobiose and glucose, made further predictions of mutant strains growth phenotypes when using cellobiose and glucose media, and demonstrated the utility of the model for designing industrially-useful strains. Importantly, the model is able to explain the role of the different β-glucosidases and their behavior under genetic perturbations. Here, this integrated approach can be extended to other metabolic pathways to produce mechanistic models for the comprehensive understanding of enzymatic functions in multiple substrates.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Molecular Origin of the Selectivity Differences between Palladium and Gold-Palladium in Benzyl Alcohol Oxidation: Different Oxygen Adsorption Properties

The same mechanism and microkinetic model used for benzyl alcohol oxidation over Pd/C was shown to apply to benzyl alcohol oxidation over AuPd/C. Almost all of the selectivity differences could be explained by a decrease in oxygen adsorption on AuPd. After isolating oxygen adsorption as being the origin of the selectivity differences, density functional theory was used to investigate the oxygen adsorption properties of a pure Pd surface, a pure Au surface, and an alloyed AuPd surface. Finally, the calculations showed that Au–Pd alloying decreased the oxygen adsorption properties relative to pure Pd, which explained the selectivity differences, consistent with the microkinetic modeling.

36 MATERIALS SCIENCE↗
DOE OSTI2019

How Outer Coordination Sphere Modifications Can Impact Metal Structures in Proteins: A Crystallographic Evaluation

A challenging objective of de novo metalloprotein design is to control of the outer coordination spheres of an active site to fine tune metal properties. The well-defined three stranded coiled coils, TRI and CoilSer peptides, are used to address this question. Substitution of Cys for Leu yields a thiophilic site within the core. Metals such as Hg II , Pb II , and AsIII result in trigonal planar or trigonal pyramidal geometries; however, spectroscopic studies have shown that Cd II forms three-, four- or five-coordinate Cd II S 3 (OH 2 ) x (in which x=0–2) when the outer coordination spheres are perturbed. Unfortunately, there has been little crystallographic examination of these proteins to explain the observations. Here, the high-resolution X-ray structures of apo- and mercurated proteins are compared to explain the modifications that lead to metal coordination number and geometry variation. It reveals that Ala substitution for Leu opens a cavity above the Cys site allowing for water excess, facilitating Cd II S 3 (OH 2 ). Replacement of Cys by Pen restricts thiol rotation, causing a shift in the metal-binding plane, which displaces water, forming CdIIS 3 . Residue d-Leu, above the Cys site, reorients the side chain towards the Cys layer, diminishing the space for water accommodation yielding Cd II S 3 , whereas d-Leu below opens more space, allowing for equal Cd II S 3 (OH 2 ) and Cd II S 3 (OH 2 ) 2 . These studies provide insights into how to control desired metal geometries in metalloproteins by using coded and non-coded amino acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Ionic and Optical Properties of Methylammonium Lead Iodide Perovskite across the Tetragonal–Cubic Structural Phase Transition

Abstract Practical hybrid perovskite solar cells (PSCs) must endure temperatures above the tetragonal–cubic structural phase transition of methylammonium lead iodide (MAPbI 3 ). However, the ionic and optical properties of MAPbI 3 in such a temperature range, and particularly, dramatic changes in these properties resulting from a structural phase transition, are not well studied. Herein, we report a striking contrast at approximately 45 °C in the ionic/electrical properties of MAPbI 3 owing to a change of the ion activation energy from 0.7 to 0.5 eV, whereas the optical properties exhibit no particular transition except for the steady increase of the bandgap with temperature. These observations can be explained by the “continuous” nature of perovskite phase transition. We speculate that the critical temperature at which the ionic/electrical properties change, although related to crystal symmetry variation, is not necessarily the same temperature as when tetragonal–cubic structural phase transition occurs.

Hoque, Md Nadim Ferdous↗
DOE OSTI2022

Mechanistic Differences between Electrochemical Hydrogenation and Hydrogenolysis of 5‐Hydroxymethylfurfural and Their pH Dependence

Abstract Hydrogenation and hydrogenolysis are two important reactions for electrochemical reductive valorization of biomass‐derived oxygenates such as 5‐hydroxymethylfurfural (HMF). In general, hydrogenolysis (which combines hydrogenation and deoxygenation) is more challenging than hydrogenation (which does not involve the cleavage of carbon–oxygen bonds). Thus, identifying factors and conditions that can promote hydrogenolysis is of great interest for reductive valorization of biomass‐derived oxygenates. For the electrochemical reduction of HMF and its derivatives, it is known that aldehyde hydrogenation is not a part of aldehyde hydrogenolysis but rather a competing reaction; however, no atomic‐level understanding is currently available to explain their electrochemical mechanistic differences. In this study, combined experimental and computational investigations were performed using Cu electrodes to elucidate the key mechanistic differences between electrochemical hydrogenation and hydrogenolysis of HMF. The results revealed that hydrogenation and hydrogenolysis of HMF involve the formation of different surface‐adsorbed intermediates via different reduction mechanisms and that lowering the pH promoted the formation of the intermediates required for aldehyde and alcohol hydrogenolysis. This study for the first time explains the origins of the experimentally observed pH‐dependent selectivities for hydrogenation and hydrogenolysis and offers a new mechanistic foundation upon which rational strategies to control electrochemical hydrogenation and hydrogenolysis can be developed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Potential and limitations of inferring ecosystem photosynthetic capacity from leaf functional traits

Abstract The aim of this study was to systematically analyze the potential and limitations of using plant functional trait observations from global databases versus in situ data to improve our understanding of vegetation impacts on ecosystem functional properties ( EFP s). Using ecosystem photosynthetic capacity as an example, we first provide an objective approach to derive robust EFP estimates from gross primary productivity ( GPP ) obtained from eddy covariance flux measurements. Second, we investigate the impact of synchronizing EFP s and plant functional traits in time and space to evaluate their relationships, and the extent to which we can benefit from global plant trait databases to explain the variability of ecosystem photosynthetic capacity. Finally, we identify a set of plant functional traits controlling ecosystem photosynthetic capacity at selected sites. Suitable estimates of the ecosystem photosynthetic capacity can be derived from light response curve of GPP responding to radiation (photosynthetically active radiation or absorbed photosynthetically active radiation). Although the effect of climate is minimized in these calculations, the estimates indicate substantial interannual variation of the photosynthetic capacity, even after removing site‐years with confounding factors like disturbance such as fire events. The relationships between foliar nitrogen concentration and ecosystem photosynthetic capacity are tighter when both of the measurements are synchronized in space and time. When using multiple plant traits simultaneously as predictors for ecosystem photosynthetic capacity variation, the combination of leaf carbon to nitrogen ratio with leaf phosphorus content explains the variance of ecosystem photosynthetic capacity best (adjusted R 2 = 0.55). Overall, this study provides an objective approach to identify links between leaf level traits and canopy level processes and highlights the relevance of the dynamic nature of ecosystems. Synchronizing measurements of eddy covariance fluxes and plant traits in time and space is shown to be highly relevant to better understand the importance of intra‐ and interspecific trait variation on ecosystem functioning.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Associations among hydrologic classifications and fish traits to support environmental flow standards

Classification systems are valuable to ecological management in that they organize information into consolidated units thereby providing efficient means to achieve conservation objectives. Of the many ways classifications benefit management, hypothesis generation has been discussed as the most important. However, in order to provide templates for developing and testing ecologically relevant hypotheses, classifications created using environmental variables must be linked to ecological patterns. Herein, we develop associations between a recent US hydrologic classification and fish traits in order to form a template for generating flow ecology hypotheses and supporting environmental flow standard development. Tradeoffs in adaptive strategies for fish were observed across a spectrum of stable, perennial flow to unstable intermittent flow. In accordance with theory, periodic strategists were associated with stable, predictable flow, whereas opportunistic strategists were more affiliated with intermittent, variable flows. We developed linkages between the uniqueness of hydrologic character and ecological distinction among classes, which may translate into predictions between losses in hydrologic uniqueness and ecological community response. Comparisons of classification strength between hydrologic classifications and other frameworks suggested that spatially contiguous classifications with higher regionalization will tend to explain more variation in ecological patterns. Despite explaining less ecological variation than other frameworks, we contend that hydrologic classifications are still useful because they provide a conceptual linkage between hydrologic variation and ecological communities to support flow ecology relationships. Mechanistic associations among fish traits and hydrologic classes support the presumption that environmental flow standards should be developed uniquely for stream classes and ecological communities, therein.

aquatic conservation↗
DOE OSTI2014

Spatiotemporal patterns of evapotranspiration along the North American east coast as influenced by multiple environmental changes

The North American east coast has experienced significant land-use and climate changes since the beginning of the 20th century. In this study, using the Dynamic Land Ecosystem Model 2.0 driven by time-series input data of land use, climate and atmospheric CO 2 , we examined how these driving forces have affected the spatiotemporal trends and variability of evapotranspiration (ET) in this region during 1901–2008. Annual ET in the North American east coast during this period was 648.3 ± 38.6 mm/year and demonstrated an increasing trend. Factorial model simulations indicated that climate variability explained 76% of the inter-annual ET variability. Although land-use change only explained 16% of the ET temporal variability, afforestation induced the upward trend of ET and increased annual ET by 12.8 mm/year. Elevated atmospheric CO 2 reduced annual ET by 0.84 mm, and its potential impacts under future atmospheric CO 2 levels could be much larger than estimates for the historical 1901–2008 period. Climate change determined the spatial pattern of ET changes across the entire study area, whereas land-use changes dramatically affected ET in watersheds with significant land conversions. In spite of the multiple benefits from afforestation, its impacts on water resources should be considered in future land-use policy making. As a result, elevated ET may also affect fresh water availability for the increasing social and economic water demands.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Temporal patterns of fine‐root dynamics have little influence on seasonal soil CO 2 efflux in a mixed, mesic forest

Among the contributors to soil CO 2 efflux, there remains uncertainty about the contribution of root activity to the overall soil efflux. Soil water and temperature frequently have been used to predict a large portion of the variation in soil CO 2 efflux. We hypothesized that fine-root dynamics explain most of the remaining variability in soil CO 2 efflux that cannot be explained by soil temperature and water content. We anticipated that seasonal increases in root production, mortality via decomposition, and standing crop would result in corresponding increases in soil CO 2 efflux. We tested our hypotheses by collecting and analyzing two years of minirhizotron and soil chamber CO 2 flux data from plots distributed throughout the Shale Hills Catchment of the Susquehanna-Shale Hills Critical Zone Observatory in Central Pennsylvania, USA. Here we showed that: (1) seasonal fluctuations in fine-root dynamics yielded only a very small increase in the predictability of soil CO 2 efflux; (2) fine-root mortality effects on soil CO 2 efflux were strongly tied to soil temperature; (3) fluctuations in fine-root presence or standing mass independent of temperature and moisture had little effect on soil CO 2 efflux; and (4) new fine-root length and root length mortality had limited impacts on soil CO 2 efflux rates. We conclude that, at least in temperate forests on rocky soils, characterizing fine-root dynamics may provide only limited improvement in the estimation of soil CO 2 efflux.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects: Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects

Having the ability to tune the oxidation state of Cu nanoparticles is essential for their utility as catalysts. The degree of oxidation that maximizes product yield and selectivity is known to vary, depending on the particular reaction. Using first principles calculations and XANES measurements, we show that for subnanometer sizes in the gas phase, smaller Cu clusters are more resistant to oxidation. However, this trend is reversed upon deposition on an alumina support. We are able to explain this result in terms of strong cluster-support interactions, which differ significantly for the oxidized and elemental clusters. The stable cluster phases also feature novel oxygen stoichiometries. Our results suggest that one can tune the degree of oxidation of Cu catalysts by optimizing not just their size, but also the support they are deposited on.

ab initio calculations↗
DOE OSTI2016

Understanding Water Transport in Polymer Electrolyte Fuel Cells Using Coupled Continuum and Pore-Network Models

Water management remains a critical issue for polymer electrolyte fuel cell performance and durability, especially at lower temperatures and with ultrathin electrodes. To understand and explain experimental observations better, water transport in gas diffusion layers (GDLs) with macroscopically heterogeneous morphologies was simulated using a novel coupling of continuum and pore-network models. X-ray computed tomography was used to extract GDL material parameters for use in the pore-network model. The simulations were conducted to explain experimental observations associated with stacking of anode GDLs, where stacking of the anode GDLs increased the limiting current density. Through imaging, it is shown that the stacked anode GDL exhibited an interfacial region of high porosity. The coupled model shows that this morphology allowed more efficient water movement through the anode and higher temperatures at the cathode compared to the single GDL case. As a result, the cathode exhibited less flooding and hence better low temperature performance with the stacked anode GDL.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2023

Structural Determinants of the Binding and Activation of Estrogen Receptor α by Phenolic Thieno[2,3- d ]pyrimidines

Synthetic, structural, and computational approaches were used to solve the puzzle as to how a phenolic nonsteroidal estrogen 1 with only a single H-bond to its receptor was more potent than an isomer 2 which formed an intricate network of H-bonds. Synthesis of a series of substituted phenols revealed that pK a was not a determinant of estrogenic activity. First-principles calculation also failed to explain the difference in activity of 1 and 2. Molecular dynamics revealed that 1 formed a more stable receptor complex compared to 2, which may explain its increased activity despite forming fewer apparent H-bonds with the protein.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Tidal frequencies and quasiperiodic subsurface water level variations dominate redox dynamics in a salt marsh system

Salt marshes are hotspots of nutrient processing en route to sensitive coastal environments. Whilst our understanding of these systems has improved over the years, we still have limited knowledge of the spatiotemporal variability of critical biogeochemical drivers within salt marshes. Sea-level rise will continue to force change on salt marsh functioning, highlighting the urgency of filling this knowledge gap. Our study was conducted in a central California estuary experiencing extensive marsh drowning and relative sea-level rise, making it a model system for such an investigation. Here we instrumented three marsh positions subjected to different degrees of tidal inundation (6.7%, 8.9%, and 11.2% of the time for the upper, middle, and lower marsh positions, respectively), providing locations with varied biogeochemical characteristics and hydrological interactions at the site. We continuously monitored redox potential (Eh) at depths of 0.1, 0.3, and 0.5 m, subsurface water levels (WL), and temperature at 0.7 m depth at each marsh position. To understand how drivers of subsurface biogeochemical processes fluctuate across tidal cycles, we used wavelet analyses to explain the interactions between Eh and WL. We found that tidal forcing significantly affects key drivers of biogeochemical processes by imparting controls on Eh variability, likely driving subsurface hydro-biogeochemistry of the salt marsh. Wavelet coherence showed that the Eh-WL relationship is nonlinear, and their lead–lag relationship is variable. We found that precipitation events perturb Eh at depth over timescales of hours, even though WL shows relatively minimal change during events. Furthermore, this work highlights the importance of high frequency in situ measurements, such as Eh, to help explain factors that govern subsurface biogeochemistry and hydrological processes in salt marshes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2013

The Mechanism of First Raindrops Formation in Deep Convective Clouds

The formation of first raindrops in deep convective clouds is investigated. A combination of observational data analysis and 2-D and 3-D numerical bin microphysical simulations of deep convective clouds suggests that the first raindrops form at the top of undiluted or slightly diluted cores. It is shown that droplet size distributions in these regions are wider and contain more large droplets than in diluted volumes. The results of the study indicate that the initial raindrop formation is determined by the basic microphysical processes within ascending adiabatic volumes. It allows one to predict the height of the formation of first raindrops considering the processes of nucleation, diffusion growth and collisions. The results obtained in the study explain observational results reported by Freud and Rosenfeld (2012) according to which the height of first raindrop formation depends linearly on the droplet number concentration at cloud base. The results also explain why a simple adiabatic parcel model can reproduce this dependence. The present study provides a physical basis for retrieval algorithms of cloud microphysical properties and aerosol properties using satellites proposed by Rosenfeld et al. ( 2012). The study indicates that the role of mixing and entrainment in the formation of the first raindrops is not of crucial importance. It is also shown that low variability of effective and mean volume radii along horizontal traverses, as regularly observed by in situ measurements, can be simulated by high-resolution cloud models, in which mixing is parameterized by a traditional 1.5 order turbulence closure scheme.

clouds↗
DOE OSTI2016

High‐frequency daily temperature variability in China and its relationship to large‐scale circulation

ABSTRACT Two measures of intra‐seasonal variability, indicated respectively by standard deviations ( SD ) and day‐to‐day ( DTD ) fluctuations denoted by absolute differences between adjacent 2‐day periods, as well as their relationships with large‐scale circulation patterns were investigated in China during 1962–2008 on the basis of homogenized daily temperature records from 549 local stations and reanalysis data. Our results show that both the SD and DTD of daily minimum temperatures ( T min ) in summer as well as the minimum and maximum temperatures in winter have been decreasing, while the daily maximum temperature ( T max ) variability in summer is fluctuating more, especially over southern China. In summer, an attribution analysis indicates that the intensity of the Western Pacific Subtropical High ( WPSH ) and high‐level East Asian Subtropical Jet stream ( EASJ ) are positively correlated with both SD and DTD , but the correlation coefficients are generally greater with the SD than with the DTD of the daily maximum temperature, T max . In contrast, the location of the EASJ shows the opposite correlation pattern, with intensity regarding the correlation with both SD and DTD . In winter, the Arctic Oscillation ( AO ) is negatively correlated with both the SD and DTD of the daily minimum temperature, but its intra‐seasonal variability exhibits good agreement with the SD of the T min . The Siberian High acts differently with respect to the SD and DTD of the T min , demonstrating a regionally consistent positive correlation with the SD . Overall, the large‐scale circulation can well explain the intra‐seasonal SD, but DTD fluctuations may be more local and impacted by local conditions, such as changes in the temperature itself, the land surface, and so on.

Wu, Fu‐Ting↗
DOE OSTI2021

Oxidation and pyrolysis of methyl propyl ether

The ignition, oxidation, and pyrolysis chemistry of methyl propyl ether (MPE) was probed experimentally at several different conditions, and a comprehensive chemical kinetic model was constructed to help understand the observations, with many of the key parameters computed using quantum chemistry and transition state theory. Experiments were carried out in a shock tube measuring time variation of CO concentrations, in a flow tube measuring product concentrations, and in a rapid compression machine (RCM) measuring ignition delay times. The detailed reaction mechanism was constructed using the Reaction Mechanism Generator software. Sensitivity and flux analyses were used to identify key rate and thermochemical parameters, which were then computed using quantum chemistry to improve the mechanism. Validation of the final model against the 1-20 bar 600-1500 K experimental data is presented with a discussion of the kinetics. The model is in excellent agreement with most of the shock tube and RCM data. Strong non-monotonic variation in conversion and product distribution is observed in the flow-tube experiments as the temperature is increased, and unusually strong pressure dependence and significant heat release during the compression stroke is observed in the RCM experiments. These observations are largely explained by a close competition between radical decomposition and addition to O2 at different sites in MPE; this causes small shifts in conditions to lead to big shifts in the dominant reaction pathways. The validated mechanism was used to study the chemistry occurring during ignition in a diesel engine, simulated using Ignition Quality Test (IQT) conditions. At the IQT conditions, where the MPE concentration is higher, bimolecular reactions of peroxy radicals are much more important than in the RCM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗