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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

Non-OH Chemistry in Oxidation Flow Reactors for the Study of Atmospheric Chemistry Systematically Examined by Modeling

Oxidation flow reactors (OFRs) using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D), O(3P), and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to relative humidity (RH) and external OH reactivity (OHRext), as both non-OH reactants and OH scale roughly proportional to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D), O(3P), and O3 have relative contributions to VOC consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. Under pathological OFR conditions of low RH and/or high OHRext, the importance of non-OH reactants is enhanced because OH is suppressed. Some biogenics can have substantial destructions by O3, and photolysis at non-tropospheric wavelengths (185 and 254 nm) may also play a significant role in the degradation of some aromatics under pathological conditions. Working under low O2 with the OFR185 mode allows OH to completely dominate over O3 reactions even for the biogenic species most reactive with O3. Non-tropospheric VOC photolysis may have been a problem in some laboratory and source studies, but can be avoided or lessened in future studies by diluting source emissions and working at lower precursor concentrations in lab studies, and by humidification. SOA photolysis is shown to be insignificant for most functional groups, except for nitrates and especially aromatics, which may be photolyzed at high UV flux settings. Our work further establishes the OFR's usefulness as a tool to study atmospheric chemistry and enables better experiment design and interpretation, as well as improved future reactor design.

Peng, Zhe↗
DOE OSTI2020

Open Chemistry, JupyterLab, REST, and quantum chemistry

Quantum chemistry must evolve if it wants to fully leverage the benefits of the internet age, where the worldwide web offers a vast tapestry of tools that enable users to communicate and interact with complex data at the speed and convenience of a button press. The Open Chemistry project has developed an open-source framework that offers an end-to-end solution for producing, sharing, and visualizing quantum chemical data interactively on the web using an array of modern tools and approaches. These tools build on some of the best open-source community projects such as Jupyter for interactive online notebooks, coupled with 3D accelerated visualization, state-of-the-art computational chemistry codes including NWChem and Psi4, and emerging machine learning and data mining tools such as ChemML and ANI. They offer flexible formats to import and export data, along with approaches to compare computational and experimental data.

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

The sensitive surface chemistry of Co-free, Ni-rich layered oxides: identifying experimental conditions that influence characterization results

Recent studies have suggested that Co-free, Ni-rich layered cathodes (e.g., doped LiNiO2) can provide promising battery performance for practical applications. However, these layered cathodes suffer from significant surface instability during various stages of the sample history, which generates inherent challenges for achieving stable battery performance and obtaining statistically representative characterization results. To reliably report the surface chemistry of these materials, delicate controls of stepwise sample preparation are required. In this study, we aim to reveal how the surface chemistry of LiNiO2 based materials changes with various environments, including human exhalation, sample storage, sample preparation, electrochemistry cycling, and surface doping. Our results demonstrate that the surface of these materials is highly reactive and prone to alter at various stages of sample handling and characterization. The sensitive surface could impact the interpretation of the surface chemical and structural information, including surface carbonate formation, transition metal reduction and dissolution, and surface reconstruction. Importantly, the heterogeneity of the surface degradation calls for a consolidation of nanoscale, high-resolution characterization, and ensemble-averaged methods in order to improve statistical representation. Furthermore, the doping chemistry can effectively mitigate the surface degradation and improve overall battery performance due to the enhanced surface oxygen retention. Our study highlights the necessity of strict measurements through complementary characterizations at multiple length scales to eliminate unintentional biased conclusions.

surface chemistry, Co-free Ni-rich cathodes, Istab↗
DOE OSTI2022

Reticular Chemistry for Highly Porous Metal–Organic Frameworks: The Chemistry and Applications

Current global crises related to clean energy and the environment entail the development of materials that are capable of addressing these challenges. Metal–organic frameworks (MOFs), a class of functional materials assembled from metal-containing nodes and organic ligands via coordination bonds, have been successfully developed for various applications, including catalysis, toxic chemical removal, and gas storage and separation, as a result of their highly tailorable nature and precisely engineered pore structures. In particular, the exceptionally high surface areas and porosities of MOFs are two of their most attractive characteristics and place them among the best porous materials for the storage of clean energy gases, such as hydrogen and methane. Reticular chemistry stands out as a prominent approach to the design of MOFs as this strategy allows for the rational top-down design of frameworks guided by topological nets to afford extended framework structures with precise architectural arrangements at the molecular level. Furthermore, bridging the gap between reticular chemistry design strategies and highly porous MOFs can facilitate the development of next-generation high-performance materials through state-of-the-art chemical design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Kinetic Modeling of Secondary Organic Aerosol in a Weather-Chemistry Model: Parameterizations, Processes, and Predictions for GOAmazon

Secondary organic aerosol (SOA) forms and evolves in the atmosphere through many pathways and processes, over diverse spatial and time scales. Hence, there is a need to represent these widely-varying kinetic processes in large-scale atmospheric models to allow for accurate predictions of the abundance, properties, and impacts of SOA. In this work, we integrated a kinetic, process-level model (simpleSOM-MOSAIC) into a weather-chemistry model (WRF-Chem) to simulate the oxidation chemistry and microphysics of atmospheric SOA. simpleSOM-MOSAIC simulates multigenerational gas-phase chemistry, autoxidation reactions, heterogeneous oxidation, oligomerization, and phase-state-influenced gas/particle partitioning of SOA. As a case study, the integrated WRF-Chem-simpleSOM-MOSAIC (WC-SSM) model was used to simulate the photochemical evolution downwind of a large city (Manaus, Brazil) in the Amazon and, in turn, study the anthropogenic and biogenic interactions in an otherwise pristine environment. Consistent with previous work, we found that OA was enhanced by up to a factor of four in the urban plume due to elevated hydroxyl radical (OH) concentrations, relative to the background, and that this OA was dominated by SOA from biogenic precursors (80%). Further, in addition to accurately simulating the OA enhancement in the urban plume, the model reproduced the magnitude of the OA oxygen-to-carbon (O:C) ratio and broadly tracked the evolution of the aerosol size distribution. Our work highlights the importance of including an integrated, kinetic representation of SOA processes in an atmospheric model

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1977

Comparison of orbital chemistry with crustal thickness and lunar sample chemistry

A correlation between orbital chemistry (FeO, Al2O3, Mg/Al, MgO/FeO, Th) and the lunar crustal thickness is examined. The correlation suggests either lack of complete homogenization by lateral or vertical mixing, or lateral variation in the differentiation process. In addition, links between orbital chemistry and lunar sample chemistry are investigated. In regions with crustal thickness between 100 and 110 km, gabbroic anorthosites are very abundant, while in regions with crustal thickness of about 80 km anorthositic gabbros are frequent. Special attention is given to the distribution of low-potassium Fra Mauro basalt, found in high concentrations in regions with 50 to 60 km crustal thickness.

Schonfeld, E.↗
DOE OSTI2022

Stability Analysis of Substituted Cobaltocenium [Bis(cyclopentadienyl)cobalt(III)] Employing Chemistry-Informed Neural Networks

Cobaltocenium derivatives are promising components of the anion exchange membranes due to their excellent thermal and alkaline stability under the operating conditions of a fuel cell. Here we present an efficient modeling approach of assessing the chemical stability of substituted cobaltocenium CoCp 2 + based on the computed electronic structure enhanced by machine learning techniques. Within the aqueous environment, the positive charge of the metal cation is balanced by the hydroxide anion through formation of the CoCp 2 + OH¯ complexes, whose dissociation is studied within the implicit solvent employing density functional theory. The data set of about 118 species based on 42 substituent groups characterized by a range of electron- donating (ED) and electron-withdrawing (EW) properties is constructed and analyzed. Given 12 carefully chosen chemistry-informed descriptors of the complexes and relevant fragments, the stability of the complexes is found to strongly correlate with the energies of the highest occupied and lowest unoccupied molecular orbitals, modulated by a switching function of the Hirshfeld charge. The latter is used as a measure of the electron withdrawing-donating character of the substituents. Based on this observation from the conventional regression analysis, two fully connected, feed-forward neural network (FNN) models with different unit structures, called the chemistry-informed (CINN) and the quadratic (QNN) neural networks, are developed. Both models predict the bond dissociation energies of the cobaltocenium complexes with mean relative errors less than 5.40% and average absolute errors less than 0.94 kcal/mol. The results show the potential of QNN to efficiently capture more complex relationships. Here, the concept of incorporating the domain (chemical) knowledge/insight into the neural network structure paves the way to applications of machine learning techniques with small data sets, ultimately leading to better predictive models compared to the conventional regression analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Accurate Compression of Tabulated Chemistry Models with Partition of Unity Networks

Tabulated chemistry models are widely used to simulate large-scale turbulent fires in applications including energy generation and fire safety. Tabulation via piecewise Cartesian interpolation suffers from the curse-of-dimensionality, leading to a prohibitive exponential growth in parameters and memory usage as more dimensions are considered. Artificial neural networks (ANNs) have attracted attention for constructing surrogates for chemistry models due to their ability to perform high-dimensional approximation. However, due to well-known pathologies regarding the realization of suboptimal local minima during training, in practice they do not converge and provide unreliable accuracy. Partition of unity networks (POUnets) are a recently introduced family of ANNs which preserve notions of convergence while performing high-dimensional approximation, discovering a mesh-free partition of space which may be used to perform optimal polynomial approximation. In this work, we assess their performance with respect to accuracy and model complexity in reconstructing unstructured flamelet data representative of nonadiabatic pool fire models. Our results show that POUnets can provide the desirable accuracy of classical spline-based interpolants with the low memory footprint of traditional ANNs while converging faster to significantly lower errors than ANNs. For example, we observe POUnets obtaining target accuracies in two dimensions with 40 to 50 times less memory and roughly double the compression in three dimensions. We also address the practical matter of efficiently training accurate POUnets by studying convergence over key hyperparameters, the impact of partition/basis formulation, and the sensitivity to initialization.

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

Polyoxometalate-based complexes as ligands for the study of actinide chemistry

The complexation of actinide cations by polyoxometalates (POMs) has been extensively studied over the past 50 years. In this perspective article, we present the rich structural diversity of actinide-POM complexes and their contribution to the extension of our knowledges of actinide chemistry, especially regarding aspect of their redox chemistry, as well as application for the capture and separation of these cations in the context of nuclear fuel remediation. Furthermore, these heterometallic assemblies have also proven highly valuable as model for heterogeneous systems based on actinides supported by metal oxide surfaces. In particular, activation of the An–O bond of actinyl fragments upon complexation with lacunary POMs has been reported, creating opportunities for future developments regarding the reactivity of these heterometallic assemblies.

Auvray, Thomas↗
NASA NTRS2017

Description and Evaluation of the Multiscale Online Nonhydrostatic AtmospheRe CHemistry Model (NMMB-MONARCH) Version 1.0: Gas-Phase Chemistry at Global Scale

This paper presents a comprehensive description and benchmark evaluation of the tropospheric gas-phase chemistry component of the Multiscale Online Nonhydrostatic AtmospheRe CHemistry model (NMMBMONARCH), formerly known as NMMB/BSC-CTM, that can be run on both regional and global domains. Here, we provide an extensive evaluation of a global annual cycle simulation using a variety of background surface stations (EMEP, WDCGG and CASTNET), ozonesondes (WOUDC, CMD and SHADOZ), aircraft data (MOZAIC and several campaigns), and satellite observations (SCIAMACHY and MOPITT).We also include an extensive discussion of our results in comparison to other state-of-the-art models. We note that in this study, we omitted aerosol processes and some natural emissions (lightning and volcano emissions). The model shows a realistic oxidative capacity across the globe. The seasonal cycle for CO is fairly well represented at different locations (correlations around 0.3-0.7 in surface concentrations), although concentrations are underestimated in spring and winter in the Northern Hemisphere, and are overestimated throughout the year at 800 and 500 hPa in the Southern Hemisphere. Nitrogen species are well represented in almost all locations, particularly NO2 in Europe (root mean square error - RMSE - below 5 ppb). The modeled vertical distributions of NOx and HNO3 are in excellent agreement with the observed values and the spatial and seasonal trends of tropospheric NO2 columns correspond well to observations from SCIAMACHY, capturing the highly polluted areas and the biomass burning cycle throughout the year. Over Asia, the model underestimates NOx from March to August, probably due to an underestimation of NOx emissions in the region. Overall, the comparison of the modeled CO and NO2 with MOPITT and SCIAMACHY observations emphasizes the need for more accurate emission rates from anthropogenic and biomass burning sources (i.e., specification of temporal variability).

atmospheric chemistry↗
DOE OSTI2021

Stabilizing Anionic Redox Chemistry in a Mn-Based Layered Oxide Cathode Constructed by Li-Deficient Pristine State

Li-rich cathode materials are of significant interest for coupling anionic redox with cationic redox chemistry to achieve high-energy-density batteries. However, lattice oxygen loss and derived structure distortion would induce serious capacity loss and voltage decay, further hindering its practical application. Herein, a novel Li-rich cathode material, O3-type Li 0.6 [Li 0.2 Mn 0.8 ]O 2 , is developed with the pristine state displaying both a Li excess in the transition metal layer and a deficiency in the alkali metal layer. Benefiting from stable structure evolution and Li migration processes, not only can high reversible capacity (≈329 mAh g -1 ) be harvested but also irreversible/reversible anionic/cationic redox reactions are comprehensively assigned via the combination of in/ex situ spectroscopies. Furthermore, irreversible lattice oxygen loss and structure distortion are effectively restrained, resulting in long-term cycle stability (capacity drop of 0.045% per cycle, 500 cycles). Altogether, tuning the Li state in the alkali metal layer presents a promising way for modification of high-capacity Li-rich cathode candidates.

anionic redox reactions↗
DOE OSTI2021

Interactions between microbial diversity and substrate chemistry determine the fate of carbon in soil.

Microbial decomposition drives the transformation of plant-derived substrates into microbial products that form stable soil organic matter (SOM). Recent theories have posited that decomposition depends on an interaction between SOM chemistry with microbial diversity and resulting function. Here, we explicitly test these theories by coupling quantitative stable isotope probing and metabolomics to track the fate of 13C enriched substrates that vary in chemical composition as they are assimilated by microbes and transformed into new metabolic products in soil. We found that mycorrhizal-driven differences in forest nutrient economies (e.g., nutrient cycling, microbial competition) led to arbuscular mycorrhizal (AM) soils harboring greater micro8ial diversity than ectomycorrhizal (ECM) soils. When incubated with 13C enriched substrates, substrate type drove shifts in the identity of active decomposers and their metabolic products in the highly diverse AM soils. The decomposition pathways were more static in the less diverse, ECM soil. Importantly, the majority of these shifts were driven by taxa only present in the AM soil suggesting a strong link between microbial identity and specialized function. Collectively, these results highlight an important interaction between ecosystem-level processes and microbial diversity; whereby the identity and function of active decomposers impacts the composition of decomposition products that can form stable SOM.

Raczka, Nanette↗
DOE OSTI2022

Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

Rechargeable aqueous Zn-MnO 2 technology combines one of the oldest battery chemistries with favourable sustainability characteristics, including safety, cost and environmental compatibility. However, the ambiguous charge storage mechanism presents a challenge to fulfil the great potential of this energy technology. In this work, we leverage on advanced electron microscopy, electrochemical analysis and theoretical calculations to look into the intercalation chemistry within the cathode material, or α-MnO 2 more specifically. We show that Zn 2+ insertion into the cathode is unlikely in the aqueous system; rather, the charge storage process is dominated by proton intercalation to form α-H x MnO 2 . We further reveal anisotropic lattice change as a result of entering protons proceeding from the surface into the bulk of α-MnO 2 , which accounts for the structural failure and capacity decay of the electrode upon cycling. Our work not only advances the fundamental understanding of rechargeable zinc batteries but also suggests the possibility to optimize proton intercalation kinetics for better-performing cell designs. A rechargeable aqueous Zn-MnO 2 battery features a combination of favourable sustainability characteristics from safety to cost. The authors deploy advanced characterizations and theoretical calculations to provide fresh insight into the charge storage mechanism, which not only closes an ongoing debate but suggests ways forward.

25 ENERGY STORAGE↗
DOE OSTI2021

Moving beyond the constraints of chemistry via crystal structure discovery with isotropic multiwell pair potentials

The rigid constraints of chemistry-dictated by quantum mechanics and the discrete nature of the atom-limit the set of observable atomic crystal structures. What structures are possible in the absence of these constraints? Here, we systematically crystallize one-component systems of particles interacting with isotropic multiwell pair potentials. We investigate two tunable families of pairwise interaction potentials. Our simulations self-assemble a multitude of crystal structures ranging from basic lattices to complex networks. Sixteen of the structures have natural analogs spanning all coordination numbers found in inorganic chemistry. Fifteen more are hitherto unknown and occupy the space between covalent and metallic coordination environments. The discovered crystal structures constitute targets for self-assembly and expand our understanding of what a crystal structure can look like.

crystal structures↗
NASA NTRS1992

Effect of finite-rate chemistry and unequal Schmidt numbers on turbulent non-premixed flames modeled with single-step chemistry

The interaction between a quasi-laminar flame and a turbulent flowfield is investigated through direct numerical simulations (DNS) of reacting flow in two- and three-dimensional domains. Effects due to finite-rate chemistry are studied using a single step global reaction A (fuel) + B (oxidizer) yields P (product), and by varying a global Damkoehler number, as a result of which the turbulence-chemistry interaction in the flame is found to generate a wide variety of conditions, ranging from near-equilibrium to near-extinction. Differential diffusion effects are studied by changing the Schmidt number of one reactive species to one-half. It is observed that laminar flamelet response is followed within the turbulent flowfield, except in regions where transient effects seem to dominate.

Chen, J. H.↗