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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Hydrogenation of organic matter as a terminal electron sink sustains high CO 2 :CH 4 production ratios during anaerobic decomposition

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO2 and CH4 for each molecule of organic matter degraded. However, CO2:CH4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO2 has an oxidation state of +4, if CH4 (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO2:CH4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. This mechanism for CO2 generation without concomitant CH4 production has the potential to regulate the global warming potential of peatlands by elevating CO2:CH4 production ratios.

58 GEOSCIENCES↗
DOE OSTI2024

Styrene Thermal Decomposition and Its Reaction with Acetylene under Shock Tube Pyrolysis Conditions: an Experimental and Kinetic Modeling Study

Styrene is an important compound for polymer production and a key intermediate in gas-phase kinetics of polycyclic aromatic hydrocarbons (PAHs). For the first time, the pyrolysis of styrene with and without the presence of acetylene is investigated in a single-pulse shock tube coupled to gas chromatography and mass spectrometry. For each reaction system, quantitative speciation profiles are probed within the temperature range of 1100-1730 K, nominal pressure of 20 bar, and reaction duration of similar to 4 ms. A kinetic model is built to simulate the results. The model explains how styrene is consumed under high-pressure pyrolytic conditions, how the secondary chemistry of intermediate products affect subsequent PAH formation, and how acetylene addition alters the reaction pathways. Throughout the temperature range, styrene breakdown is dominated by the bimolecular interaction between styrene and hydrogen atom, which produces benzene+vinyl or phenyl and ethylene through the stabilization of 2-phenylethyl and its subsequent dissociation. As a result, large amounts of phenyl accumulate, which react with styrene to form C14H12 species while simultaneously releasing H atoms through addition/elimination reactions. The reactivity of fuel consumption is preserved by the regeneration of H atoms as chain carriers. Several C14H10 compounds are formed as a result of the following breakdown of the C14H12 isomers, particularly stilbene, 1,1-diphenyl ethylene, and 9-methyl-9H-fluorene. The presence of acetylene as a co-reactant with styrene allows the Hydrogen-Abstraction-Acetylene-Addition (HACA) pathway to proceed from phenyl radical to enhance the production of phenylacetylene at very low temperatures and acenaphthylene. This hinders the formation of C14H12 isomers, exclusive products from pure styrene dissociation by competing with the styrene+phenyl routes.

Kinetic Modeling↗
DOE OSTI2024

In situ characterization of metastable Pb3O5 and Pb2O3 phases during thermal decomposition of PbO2 to PbO

Nonstoichiometric lead oxides play a key role in the formation and cycling of the positive electrodes in a lead acid battery. These phases have been linked to the underutilization of the positive active material but also play a key role in the battery’s cycle life, providing inter-particle adhesion and the connection to the underlying lead grid. Similar phases have previously been identified by mass loss or color change during thermal annealing of PbO2 to PbO, suggesting that at least two intermediate PbOx phases exist. Using multiple in situ analysis techniques (powder diffraction, x-ray absorption, x-ray photoelectron spectroscopy) and ex situ nuclear magnetic resonance measurements, the structural conversion and changes in the lead oxidation states were identified during this process. Isolation of the PbOx phases enabled confirmation of Pb3O5 and Pb2O3 by diffraction and the first 207Pb NMR measurement of these intermediates.

Kinnibrugh, Tiffany L.↗