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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 1,153 records · Page 64
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Biogeochemical dynamics and microbial community development under sulfate- and iron-reducing conditions based on electron shuttle amendment

Iron reduction and sulfate reduction are two of the major biogeochemical processes that occur in anoxic sediments. Microbes that catalyze these reactions are therefore some of the most abundant organisms in the subsurface, and some of the most important. Due to the variety of mechanisms that microbes employ to derive energy from these reactions, including the use of soluble electron shuttles, the dynamics between iron- and sulfate-reducing populations under changing biogeochemical conditions still elude complete characterization. Here, we amended experimental bioreactors comprised of freshwater aquifer sediment with ferric iron, sulfate, acetate, and the model electron shuttle AQDS (9,10-anthraquinone-2,6-disulfonate) and monitored both the changing redox conditions as well as changes in the microbial community over time. The addition of the electron shuttle AQDS did increase the initial rate of Fe III reduction; however, it had little effect on the composition of the microbial community. Our results show that in both AQDS- and AQDS+ systems there was an initial dominance of organisms classified as Geobacter (a genus of dissimilatory Fe III -reducing bacteria), after which sequences classified as Desulfosporosinus (a genus of dissimilatory sulfate-reducing bacteria) came to dominate both experimental systems. Furthermore, most of the ferric iron reduction occurred under this later, ostensibly “sulfate-reducing” phase of the experiment. This calls into question the usefulness of classifying subsurface sediments by the dominant microbial process alone because of their interrelated biogeochemical consequences. To better inform models of microbially-catalyzed subsurface processes, such interactions must be more thoroughly understood under a broad range of conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Co-precipitation induces changes to iron and carbon chemistry and spatial distribution at the nanometer scale

Association of organic matter (OM) with mineral phases via co-precipitation is expected to be a widespread process in environments with high OM input and frequent mineral dissolution and re-precipitation. In contrast to surface area-limited adsorption processes, co-precipitation may allow for greater carbon (C) accumulation. However, the potential sub-micrometer scale structural and compositional differences that affect the bioavailability of co-precipitated C are largely unknown. In this work, we used a combination of high-resolution analytical electron microscopy and bulk spectroscopy to probe interactions between a mineral phase (ferrihydrite, nominally Fe 2 O 3 •0.5H 2 O) and organic soil-derived water-extractable OM (WEOM). In co-precipitated WEOM-Fe, nanometer-scale scanning transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS) revealed increased Fe(II) and less Fe aggregation relative to adsorbed WEOM-Fe. Spatially distinct lower- and higher-energy C regions were detected in both adsorbed and co-precipitated WEOM-Fe. In co-precipitates, lower-energy aromatic and/or substituted aromatic C was spatially associated with reduced Fe(II), but higher-energy oxidized C was enriched at the oxidized Fe(III) interface. Therefore, we show that co-precipitation does not constitute a non-specific physical encapsulation of C that only affects Fe chemistry and spatial distribution, but may cause a bi-directional set of reactions that lead to spatial separation and transformation of both Fe and C forms. In particular, we propose that abiotic redox reactions between Fe and C via substituted aromatic groups (e.g., hydroquinones) play a role in creating distinct co-precipitate composition, with potential implications for its mineralization.

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

Kβ X-ray Emission Spectroscopy of Cu(I)-Lytic Polysaccharide Monooxygenase: Direct Observation of the Frontier Molecular Orbital for H 2 O 2 Activation

Lytic polysaccharide monooxygenases (LPMOs) catalyze the degradation of recalcitrant carbohydrate polysaccharide substrates. These enzymes are characterized by a mononuclear Cu(I) active site with a three-coordinate T-shaped “His-brace” configuration including the N-terminal histidine and its amine group as ligands. Here, this study explicitly investigates the electronic structure of the d 10 Cu(I) active site in a LPMO using Kβ X-ray emission spectroscopy (XES). The lack of inversion symmetry in the His-brace site enables the 3d/p mixing required for intensity in the Kβ valence-to-core (VtC) XES spectrum of Cu(I)-LPMO. These Kβ XES data are correlated to density functional theory (DFT) calculations to define the bonding, and in particular, the frontier molecular orbital (FMO) of the Cu(I) site. These experimentally validated DFT calculations are used to evaluate the reaction coordinate for homolytic cleavage of the H 2 O 2 O–O bond and understand the contribution of this FMO to the low barrier of this reaction and how the geometric and electronic structure of the Cu(I)-LPMO site is activated for rapid reactivity with H 2 O 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Influence of QD photosensitizers in the photocatalytic production of hydrogen with biomimetic [FeFe]-hydrogenase. Comparative performance of CdSe and CdTe

Photocatalytic systems comprising a hydrogenase-type catalyst and CdX (X = S, Se, Te) chalcogenide quantum dot (QD) photosensitizers show extraordinary hydrogen production rates under visible light excitation. What remains unknown is the mechanism of energy conversion in these systems. In this work, we have explored this question by comparing the performance of two QD sensitizers, CdSe and CdTe, in photocatalytic systems featuring aqueous suspensions of a [Fe 2 (μ-1,2-benzenedithiolate) CO 6 ] catalyst and an ascorbic acid sacrificial agent. Overall, the hydrogen production yield for CdSe-sensitized reactions QDs was found to be 13 times greater than that of CdTe counterparts. According to emission quenching experiments, an enhanced performance of CdSe sensitizers reflected a greater rate of electron transfer from the ascorbic acid (k Asc ). The observed difference in the QD-ascorbic acid charge transfer rates between the two QD materials was consistent with respective driving forces for these systems.

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

Direct Evidence of Visible Light-Induced Homolysis in Chlorobis(2,9-dimethyl-1,10-phenanthroline)copper(II)

Developments in the field of photoredox catalysis that leveraged the long-lived excited states of Ir(III) and Ru(II) photosensitizers to enable radical coupling processes paved the way for explorations of synthetic transformations that would otherwise remain unrealized. While first row transition metal photocatalysts have not been as extensively investigated, valuable synthetic transformations covering broad scopes of olefin functionalization have been recently reported featuring photoactivated chlorobis(phenanthroline) Cu(II) complexes. In this study, the photochemical processes underpinning the catalytic activity of [Cu(dmp) 2 Cl]Cl (dmp = 2,9-dimethyl-1,10-phenanthroline) were studied. The combined results from static spectroscopic measurements and conventional photochemistry, ultrafast transient absorption, and electron paramagnetic resonance spin trapping experiments strongly support blue light (λ ex = 427 or 470 nm)-induced Cu–Cl homolytic bond cleavage in [Cu(dmp) 2 Cl] + occurring in <100 fs. On the basis of electronic structure calculations, this bond-breaking photochemistry corresponds to the Cl → Cu(II) ligand-to-metal charge transfer transition, unmasking a Cu(I) species [Cu(dmp) 2 ] + and a Cl atom, thereby serving as a departure point for both Cu(I)- or Cu(II)-based photoredox transformations. No net photochemistry was observed through direct excitation of the ligand-field transitions in the red (λ ex = 785 or 800 nm), and all combined experiments indicated no evidence of Cu–Cl bond cleavage under these conditions. As a result, the underlying visible light-induced homolysis of a metal–ligand bond yielding a one-electron-reduced photosensitizer and a radical species may form the basis for novel transformations initiated by photoinduced homolysis featuring in situ-formed metal–substrate adducts utilizing first row transition metal complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Coherent-phase or random-phase acceleration of electron beams in solar flares

Time structures of electron beam signatures at radio wavelengths are investigated to probe correlated versus random behavior in solar flares. In particular we address the issue whether acceleration and injection of electron beams is coherently modulated by a single source, or whether the injection is driven by a stochastic (possibly spatially fragmented) process. We analyze a total of approximately = 6000 type III bursts observed by Ikarus (Zurich) in the frequency range of 100-500 MHz, during 359 solar flares with simultaneous greater than or = 25 keV hard X-ray emission, in the years 1890-1983. In 155 flares we find a total of 260 continuous type III groups, with an average number of 13 +/- 9 bursts per group, a mean duration of D = 12 +/- 14 s, a mean period of P = 2.0 +/- 1.2 s, with the highest burst rate at a frequency of nu = 310 +/- 120 MHz. Pulse periods have been measured between 0.5 and 10 s, and can be described by an exponential distribution, i.e., N(P) varies as e (exp -P/1.0s). The period shows a frequency dependence of P(nu)=46(exp-0.6)(sub MHz)s for different flares, but is invariant during a particular flare. We measure the mean period P and its standard deviation sigma (sub p) in each type III group, and quantify the degree of periodicity (or phase-coherence) by the dimensionless parameter sigma (sub p)P. The representative sample of 260 type III burst groups shows a mean periodicity of sigma (sub p/P) = 0.37 +/- 0.12, while Monte Carlo simulations of an equivalent set of truly random time series show a distinctly different value of sigma (sub p)P = 0.93 +/- 0.26. This result indicates that the injection of electron beams is coherently modulated by a particle acceleration source which is either compact or has a global organization on a timescale of seconds, in contrast to an incoherent acceleration source, which is stochastic either in time or space. We discuss the constraints on the size of the acceleration region resulting from electron beam propagation delays and from Alfvenic synchronization during a pulse period. We discuss two periodic preocesses in flares, which potentially control quasi-periodic particle acceleration: (1) MHD oscillations, and (2) current sheets with oscillatory dynamics.

Aschwanden, Markus J.↗
DOE OSTI2020

Metal-organic pulsed laser deposition for stoichiometric complex oxide thin films

Methods and systems for forming complex oxide films are provided. Also provided are complex oxide films and heterostructures made using the methods and electronic devices incorporating the complex oxide films and heterostructures. In the methods pulsed laser deposition is conducted in an atmosphere containing a metal-organic precursor to form highly stoichiometric complex oxides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Metal-organic pulsed laser deposition for stoichiometric complex oxide thin films

Methods and systems for forming complex oxide films are provided. Also provided are complex oxide films and heterostructures made using the methods and electronic devices incorporating the complex oxide films and heterostructures. In the methods pulsed laser deposition is conducted in an atmosphere containing a metal-organic precursor to form highly stoichiometric complex oxides.

Eom, Chang-Beom↗
DOE OSTI2023

Metal-organic pulsed laser deposition for stoichiometric complex oxide thin films

Methods and systems for forming complex oxide films are provided. Also provided are complex oxide films and heterostructures made using the methods and electronic devices incorporating the complex oxide films and heterostructures. In the methods pulsed laser deposition is conducted in an atmosphere containing a metal-organic precursor to form highly stoichiometric complex oxides.

Eom, Chang-Beom↗
DOE OSTI2024

Marine aerosol generation experiments in the High Arctic during summertime

The rapidly warming Arctic has transitioned to thinner sea ice which fractures, producing leads. Few studies have investigated Arctic sea spray aerosol (SSA) produced from open ocean, leads, and melt ponds, which vary in salinity and organic and microbial community composition. A marine aerosol reference tank was deployed aboard an icebreaker to the Arctic Ocean during August–September 2018 to study SSA generated from locally collected surface waters. Aerosol generation experiments were carried out using water collected from the marginal ice zone, a human-made hole in sea ice near the North Pole, and both lead and melt pond water during an ice floe drift period. Salinity, chlorophyll a, organic carbon, nitrogen, and microbial community composition were measured. Eukaryotic plankton and bacterial abundance were elevated in experimental water from the marginal ice zone, but the relative contributions from major eukaryotic taxonomic groups varied little across the experiments. The chemical composition of individual SSA particles was analyzed using Raman microspectroscopy and computer-controlled scanning electron microscopy with energy-dispersive X-ray spectroscopy. Individual sea salt aerosol, primary organic aerosol, and mineral dust particles were observed. Sea salt aerosol constituted 44–95% of individual submicrometer and 68–100% of supermicrometer particles, by number, generated during each experiment. Carbon was detected in 85%, by number, of the individual sea salt particles, with visible organic coatings. Carbohydrates were detected in 72% of particles, by number, with smaller contributions from long-chain fatty acids (13%) and siliceous material (15%). SSA generated from melt pond water contained only long-chain fatty acids and siliceous material. Quantification of the ice-nucleating activity showed that locally produced SSA may define the High Arctic background ice-nucleating particle population, but cannot account for the peak atmospheric concentrations observed. As the Arctic warms, the increasing SSA emissions have a complex dependence on changing biological and physical processes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Engineering Active Surface Oxygen Sites of Cubic Perovskite Cobalt Oxides toward Catalytic Oxidation Reactions

Unraveling the role of surface oxygen sites in transition metal oxides during catalytic reactions has always been the focus of environmental and energy chemistry research. For this work, active surface oxygen sites of cubic perovskite cobalt oxide were engineered to comprehend their crucial role and catalytic mechanism at the molecular level. By removing those inert Sr/La–O termination layers, active oxygen sites were exposed on the Co terminated surface of Sr 0.6 La 0.4 CoO 3–δ that furnished the dominant catalytic process of CO oxidation via the Mars–van Krevelen (MvK) mechanism. The fabrication of five-coordinate cobalt ions and the enhanced covalency of Co–O bonds not only optimize the surface electronic structure of Co 3d–O 2p, but also supply active surface oxygen sites, which effectively oxidizes CO to CO 2 with a significantly improved oxidation performance and stability as evidenced by soft/hard XAS, XPS, and O 2 -TPD. Furthermore, online isotopic 18 O 2 mass spectrometry, in situ DRIFTS, and theoretical simulation demonstrate that the activity of surface oxygen sites enhances the kinetics of the MvK reaction, while unsaturated coordination sites from five-coordinate cobalt ions primarily contribute to the activated oxygen molecules and the stable catalytic cycle. The results reported here provide a deep insight into the comprehension of the relationships among active oxygen sites, surface electronic structure, and the reaction mechanism of transition metal oxides necessary for catalytic oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electron beam treatment for the removal of 1,4-dioxane in water and wastewater

Electron beam (e-beam) treatment uses accelerated electrons to form oxidizing and reducing radicals when applied to water without the use of external chemicals. In this study, electron beam treatment was used to degrade 1,4-dioxane in several water matrices. Removal improved in the progressively cleaner water matrices and removals as high as 94% to 99% were observed at a dose of 2.3 kGy in secondary effluent. 1,4-dioxane removal was confirmed to be primarily through hydroxyl radical oxidation. The calculated electrical energy per order was found to be 0.53, 0.26, and 0.08 kWh/m 3 /order for secondary effluent (Avg. total organic carbon (TOC) 9.25 mg/L), granular activated carbon effluent (TOC 3.46 mg/L), and ultrapure water, respectively, with a 70% generation and transfer efficiency applied.

1,4-dioxane↗
DOE OSTI2020

Vibrational Spectroscopy Reveals Effects of Electron Push–Pull and Solvent Polarity on Electron Delocalization in Radical Anions of Donor–Acceptor Compounds

Herein, the nature of excess electrons has been studied in donor–acceptor (D–A) compounds based on substituted triarylamines and a nitrile-functionalized fluorene, by changing the substituents on the triarylamines and also the solvent polarity. We observed that both electron push-pull capability at the distant location in the amine donor unit and solvation in solvents of varying polarity significantly affect the nitrile $ν(C≡N)$ vibrations of the fluorene acceptor unit in radical anions of these D–A compounds. Quantum calculations show that the push-pull capability translates the position of an excess electron while keeping its width relatively constant. On the other hand, solvation changes both, making an electron more compact in polar media. The current study points to the idea that solvation plays a more significant role in controlling the nature of excess electrons, while synthetic modification that influences electron push-pull capability enables further tuning.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Precision Synthesis of Conjugated Polymer Films by Surface-Confined Stepwise Sonogashira Cross-Coupling

Thin films of poly(arylene ethynylene)-conjugated polymers, including low-energy-gap donor–acceptor polymers, can be prepared via stepwise polymerization utilizing surface-confined Sonogashira cross-coupling. This robust and efficient polymerization protocol yields conjugated polymers with a precise molecular structure and with nanometer-level control of the organization and the uniform alignment of the macromolecular chains in the densely packed film. In addition to high stability and predictable and well-defined molecular organization and morphology, the surface-confined conjugated polymer chains experience significant interchain electronic interactions, resulting in dominating intermolecular π-electron delocalization which is primarily responsible for the electronic and spectroscopic properties of polymer films. The fluorescent films demonstrate remarkable performance in chemosensing applications, showing a turn-off fluorescent response on the sub-ppt (part per trillion) level of nitroaromatic explosives in water. This unique sensitivity is likely related to the enhanced exciton mobility in the uniformly aligned and structurally monodisperse polymer films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1979

Light-dependent hydrogen production by C. reinhardi

The activity of hydrogenase in nonsynchronous, photoheterotrophically grown cells of C. reinhardi is a function of culture age. Rapidly growing cultures (exponential phase) exhibit lower hydrogenase activity than early stationary phase cultures. During prolonged dark anaerobic incubation the hydrogenase activity attains a maximal value in two to five hours. The activity declines rapidly after three to four hours of anaerobic incubation unless the pH of the suspending medium is maintained above 6.0. In C. reinhardi the source of electrons for hydrogen photoproduction appears to be derived mainly from water oxidation. However, when the water-splitting complex of photosystem II is impaired by a mutational block, the organism can utilize intracellular organic reductants as substrate for H2 production in a light-dependent reaction involving both PSII and PSI. When photosynthetic electron transport is uncoupled from phosphorylation, a rate of 174 micromoles of hydrogen evolved per mg cells per hour is observed. This rate of hydrogen photoproduction corresponds to 76% of the reductant generating capacity of PSII under steady-state photosynthesis.

Lien, S.↗
DOE OSTI2021

OrbNet Denali: A machine learning potential for biological and organic chemistry with semi-empirical cost and DFT accuracy

We present OrbNet Denali, a machine learning model for an electronic structure that is designed as a drop-in replacement for groundstate density functional theory (DFT) energy calculations. The model is a message-passing graph neural network that uses symmetryadapted atomic orbital features from a low-cost quantum calculation to predict the energy of a molecule. OrbNet Denali is trained on a vast dataset of 2.3 × 10 6 DFT calculations on molecules and geometries. This dataset covers the most common elements in biochemistry and organic chemistry (H, Li, B, C, N, O, F, Na, Mg, Si, P, S, Cl, K, Ca, Br, and I) and charged molecules. OrbNet Denali is demonstrated on several well-established benchmark datasets, and we find that it provides accuracy that is on par with modern DFT methods while offering a speedup of up to three orders of magnitude. For the GMTKN55 benchmark set, OrbNet Denali achieves WTMAD-1 and WTMAD-2 scores of 7.19 and 9.84, on par with modern DFT functionals. For several GMTKN55 subsets, which contain chemical problems that are not present in the training set, OrbNet Denali produces a mean absolute error comparable to those of DFT methods. For the Hutchison conformer benchmark set, OrbNet Denali has a median correlation coefficient of R 2 = 0.90 compared to the reference DLPNO-CCSD(T) calculation and R 2 = 0.97 compared to the method used to generate the training data (ωB97X-D3/def2- TZVP), exceeding the performance of any other method with a similar cost. Similarly, the model reaches chemical accuracy for noncovalent interactions in the S66x10 dataset. For torsional profiles, OrbNet Denali reproduces the torsion profiles of ωB97X-D3/def2-TZVP with an average mean absolute error of 0.12 kcal/mol for the potential energy surfaces of the diverse fragments in the TorsionNet500 dataset.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗