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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH{sub 2} group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C{sub 2v} symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO{sub 2} + H{sub 2}O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358–366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory Study

We present a first-principles, self-consistent periodic density functional theory (PW91-GGA) study of formic acid (HCOOH) decomposition on model (111) and (100) facets of eight fcc metals (Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh) and (0001) facets of four hcp (Co, Os, Ru, and Re) metals. The calculated binding energies of key formic acid decomposition intermediates including formate (HCOO), carboxyl (COOH), carbon monoxide (CO), water (H2O), carbon dioxide (CO2), hydroxyl (OH), carbon (C), oxygen (O), and hydrogen (H; H2) are presented. Using these energetics, we develop thermochemical potential energy diagrams for both the carboxyl-mediated and the formate-mediated dehydrogenation mechanisms on each surface. We evaluate the relative stability of COOH, HCOO, and other isomeric intermediates (i.e., CO + OH, CO2 + H, CO + O + H) on these surfaces. These results provide insights into formic acid decomposition selectivity (dehydrogenation versus dehydration), and in conjunction with calculated vibrational frequency modes, the results can assist with the experimental search for the elusive carboxyl (COOH) surface intermediate. Results are compared against experimental reports in the literature.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2014

Formic Acid Decomposition on Au catalysts: DFT, Microkinetic Modeling, and Reaction Kinetics Experiments

A combined theoretical and experimental approach is presented that uses a comprehensive mean-field microkinetic model, reaction kinetics experiments, and scanning transmission electron microscopy imaging to unravel the reaction mechanism and provide insights into the nature of active sites for formic acid (HCOOH) decomposition on Au/SiC catalysts. All input parameters for the microkinetic model are derived from periodic, self-consistent, generalized gradient approximation (GGA-PW91) density functional theory calculations on the Au(111), Au(100), and Au(211) surfaces and are subsequently adjusted to describe the experimental HCOOH decomposition rate and selectivity data. It is shown that the HCOOH decomposition follows the formate (HCOO) mediated path, with 100% selectivity toward the dehydrogenation products (CO21H2) under all reaction conditions. An analysis of the kinetic parameters suggests that an Au surface in which the coordination number of surface Au atoms is 4 may provide a better model for the active site of HCOOH decomposition on these specific supported Au catalysts.

active sites↗
DOE OSTI2016

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

Cycloheptatrienyl (tropyl) radical, C{sub 7}H{sub 7}, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C{sub 7}H{sub 7} were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C{sub 7}H{sub 7} are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C{sub 7}H{sub 7}) radicals but rather only benzyl (C{sub 6}H{sub 5}CH{sub 2}). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C{sub 6}H{sub 5}CH{sub 2}, C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Investigation of the Decomposition Mechanism of Lithium Bis(oxalate)borate (LiBOB) Salt in the Electrolyte of an Aprotic Li-O 2 Battery

The stability of the lithium bis(oxalate) borate (LiBOB) salt against lithium peroxide (Li2O2) in an aprotic Li-O2 cell is investigated. From theoretical and experimental findings, we find that the chemical decomposition of LiBOB in electrolytes leads to the formation lithium oxalate during discharge of a Li-O2 cell. According to DFT calculations, the formation of lithium oxalate as the reaction product is exothermic, and therefore is thermodynamically feasible. This reaction seems to be independent of solvents used in the Li-O2 cell, and therefore LiBOB is probably not suitable to be used as the salt in Li-O2 cell electrolytes.

Lau, Kah Chun↗
DOE OSTI2018

Traits drive global wood decomposition rates more than climate

Wood decomposition is a major component of the global carbon cycle. Decomposition rates vary across climate gradients, which is thought to reflect the effects of temperature and moisture on the metabolic kinetics of decomposers. However, decomposition rates also vary with wood traits, which may reflect the influence of stoichiometry on decomposer metabolism as well as geometry relating the surface areas that decomposers colonize with the volumes they consume. In this paper, we combined metabolic and geometric scaling theories to formalize hypotheses regarding the drivers of wood decomposition rates, and assessed these hypotheses using a global compilation of data on climate, wood traits, and wood decomposition rates. Our results are consistent with predictions from both metabolic and geometric scaling theories. Approximately half of the global variation in decomposition rates was explained by wood traits (nitrogen content and diameter), whereas only a fifth was explained by climate variables (air temperature, precipitation, and relative humidity). These results indicate that global variation in wood decomposition rates is best explained by stoichiometric and geometric wood traits. Our findings suggest that inclusion of wood traits in global carbon cycle models can improve predictions of carbon fluxes from wood decomposition.

Hu, Zhenhong↗
DOE OSTI2014

Decomposition of Amino Diazeniumdiolates (NONOates): Molecular Mechanisms

Although diazeniumdiolates (X[N(O)NO]-) are extensively used in biochemical, physiological, and pharmacological studies due to their ability to slowly release NO and/or its congeneric nitroxyl, the mechanisms of these processes remain obscure. In this work, we used a combination of spectroscopic, kinetic, and computational techniques to arrive at a qualitatively consistent molecular mechanism for decomposition of amino diazeniumdiolates (amino NONOates: R2N[N(O)NO]-, where R = -N(C2H5)2 (1), -N(C3H4NH2)2 (2), or -N(C2H4NH2)2 (3)). Decomposition of these NONOates is triggered by protonation of their [NN(O)NO]- group with apparent pKa and decomposition rate constants of 4.6 and 1 s-1 for 1-H, 3.5 and 83 x 10-3 s-1 for 2-H, and 3.8 and 3.3 x 10-3 s-1 for 3-H. Although protonation occurs mainly on the O atoms of the functional group, only the minor R2N(H)N(O)NO tautomer (population ~0.01%, for 1) undergoes the N-N heterolytic bond cleavage (k ~102 s-1 for 1) leading to amine and NO. Decompositions of protonated amino NONOates are strongly temperature-dependent; activation enthalpies are 20.4 and 19.4 kcal/mol for 1 and 2, respectively, which includes contributions from both the tautomerization and bond cleavage. The bond cleavage rates exhibit exceptional sensitivity to the nature of R substituents which strongly modulate activation entropy. At pH < 2, decompositions of all these NONOates are subject to additional acid catalysis that occurs through di-protonation of the [NN(O)NO]- group.

amino↗
DOE OSTI2022

Microbe-iron interactions control lignin decomposition in soil

Lignin decomposition is critically linked to terrestrial carbon (C) cycle due to the enormous C mass of lignin and its importance in controlling overall rates of litter decomposition. Interactions between lignin and iron (Fe) minerals have been increasingly recognized as key mediators of lignin decomposition in experimental studies. However, we still lack a quantitative understanding of how Fe minerals interact with microbes to control lignin decomposition. Here, we leveraged experimental results from an incubation of Fe-rich soil, in which lignin decomposition rates were measured at aerobic conditions after four levels of pre-treated O2 availability, to examine microbe-Fe (MiFe) interactions in lignin decomposition with a MiFe model. We quantified how Fe redox cycling interacted with microbial activities to control lignin decomposition via data-model integration. Our results showed that the MiFe model with time-dependent growth and mortality functions better represented CO2 release from lignin decomposition (R2 ranging from 0.96 to 0.97) than models assuming either first-order or Michaelis-Menten kinetics. Reduction of Fe(III) to Fe(II) after pre-treatments with lower O2 availability stimu-lated the Fenton reaction to break down macro-molecular lignin into small molecules available to microbes. The small molecules of lignin and necromass bounded with oxidized Fe and were protected from decomposition. After 1-year incubation, the model implied that most of C stabilized with Fe minerals was derived from small molecular lignin C. Our quantitative analysis of microbe-Fe interactions sheds new light on lignin decomposition and preservation and helps improve model prediction of soil C persistence under global change.

Liao, Cuijuan↗
DOE OSTI2025

Arctic shrub expansion generates regional variation in litter decomposition by altering litter quality and the decomposition environment

Abstract The expansion of deciduous shrubs into the graminoid‐dominated arctic tundra is expected to alter litter decomposition by changing litter quality and local abiotic and biotic conditions. However, it remains unclear how shrub expansion will affect litter decomposition at regional scales, where macroclimate is expected to be the dominant regulator of decomposition. To determine the relative influence of macroclimate and local controls on regional patterns of litter mass loss and nitrogen release, we conducted two hierarchical litter decomposition experiments across spatial scales. We decomposed leaf and root litter from a prominent graminoid ( Eriophorum vaginatum ) and three genera of deciduous shrubs ( Betula , Alnus and Salix ) for 1 year within replicated plots at five sites spanning a 160 km latitudinal gradient in northern Alaska. Using Eriophorum litter as a substrate, we found that macroclimate was the primary regulator of mass loss but had opposing effects on leaf and root litter. As summer temperature increased along the latitudinal gradient (11.9 to 13.9°C), leaf litter mass loss increased by 20% whereas root litter mass loss decreased by 33%. Leaf nitrogen release also increased with summer temperature. Conversely, root nitrogen release was controlled by the vegetation type of the decomposition environment. Using different shrub litters as substrates, we found that litter quality and its interaction with soil microclimate and macroclimate controlled decomposition. Overall, shrub root litters decomposed faster than Eriophorum root litter, losing 53% more mass and 190% more nitrogen across all sites and decomposition environments. For leaf litter, however, patterns varied by litter genus, with Salix losing more mass and Betula and Alnus losing less mass than Eriophorum . Our findings demonstrate that shrub expansion in the Arctic can regulate leaf and root litter decomposition at the regional scale through its effects on local controls, primarily litter quality. Ongoing increases in shrub cover are likely to accelerate the turnover of root litter carbon and nitrogen pools in tundra ecosystems. Therefore, including shrub‐related processes in Earth system models will improve our ability to predict regional‐scale litter decomposition and its effects on carbon and nutrient cycling in a warming Arctic. Read the free Plain Language Summary for this article on the Journal blog.

Vozzo, Justin T. [Department of Natural Resources ↗
DOE OSTI2018

Temperature sensitivity of soil organic carbon decomposition increased with mean carbon residence time: Field incubation and data assimilation

Abstract Temperature sensitivity of soil organic carbon ( SOC ) decomposition is one of the major uncertainties in predicting climate‐carbon (C) cycle feedback. Results from previous studies are highly contradictory with old soil C decomposition being more, similarly, or less sensitive to temperature than decomposition of young fractions. The contradictory results are partly from difficulties in distinguishing old from young SOC and their changes over time in the experiments with or without isotopic techniques. In this study, we have conducted a long‐term field incubation experiment with deep soil collars (0–70 cm in depth, 10 cm in diameter of PVC tubes) for excluding root C input to examine apparent temperature sensitivity of SOC decomposition under ambient and warming treatments from 2002 to 2008. The data from the experiment were infused into a multi‐pool soil C model to estimate intrinsic temperature sensitivity of SOC decomposition and C residence times of three SOC fractions (i.e., active, slow, and passive) using a data assimilation ( DA ) technique. As active SOC with the short C residence time was progressively depleted in the deep soil collars under both ambient and warming treatments, the residences times of the whole SOC became longer over time. Concomitantly, the estimated apparent and intrinsic temperature sensitivity of SOC decomposition also became gradually higher over time as more than 50% of active SOC was depleted. Thus, the temperature sensitivity of soil C decomposition in deep soil collars was positively correlated with the mean C residence times. However, the regression slope of the temperature sensitivity against the residence time was lower under the warming treatment than under ambient temperature, indicating that other processes also regulated temperature sensitivity of SOC decomposition. These results indicate that old SOC decomposition is more sensitive to temperature than young components, making the old C more vulnerable to future warmer climate.

Zhou, Xuhui↗
DOE OSTI2014

Secondary channels in the thermal decomposition of monomethylhydrazine (CH 3 NHNH 2 )

Mass spectrometric observations in a very low pressure pyrolysis study of the decomposition of the prototypical rocket fuel monomethylhydrazine (MMH) indicated a dominant role for the molecular channels producing NH 3 and H 2 and their coproducts. In contrast, a recent ab initio transition state theory based master equation theoretical study indicated that simple N–N and C–N bond fissions dominate the kinetics. In this work, the possible role of molecular decomposition channels in MMH is explored further through additional investigations of the potential energy surface. These investigations consider the role of triplet channels, of roaming radical channels, and of some previously unexplored pathways for molecular decomposition. New ab initio transition state theory based master equation calculations provide revised predictions for the temperature and pressure dependence of the MMH decomposition kinetics that are in excellent agreement with recent shock tube measurements. These calculations continue to suggest only a very limited contribution from the molecular elimination channels. A roaming pathway is suggested to provide the dominant route for direct formation of ammonia. The possible role of secondary abstraction reactions in the very-low-pressure pyrolysis experiments is briefly discussed.

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

Effect of aging temperature on phase decomposition and mechanical properties in cast duplex stainless steels

The microstructure and mechanical properties in unaged and thermally aged (at 280 oC, 320 oC, 360 oC, and 400 oC to 4300 h) CF–3 and CF–8 cast duplex stainless steels (CDSS) are investigated. The unaged CF–8 steel has Cr-rich M23C6 carbides located at the δ–ferrite/γ– austenite heterophase interfaces that were not observed in the CF–3 steel and this corresponds to a difference in mechanical properties. Both unaged steels exhibit incipient spinodal decomposition into Fe-rich α–domains and Cr-rich α’–domains. During aging, spinodal decomposition progresses and the mean wavelength (MW) and mean amplitude (MA) of the compositional fluctuations increase as a function of aging temperature. Additionally, G–phase precipitates form between the spinodal decomposition domains in CF–3 at 360 oC and 400 oC and in CF–8 at 400 oC. The microstructural evolution is correlated to changes in mechanical properties.

atom probe tomography↗
DOE OSTI2023

Elevated temperature alters microbial communities, but not decomposition rates, during 3 years of in situ peat decomposition

ABSTRACT Peatlands are large carbon sinks with primary production outpacing decomposition of organic matter. Results from the S pruce and P eatland R esponses U nder C hanging E nvironments (SPRUCE) study show net losses of organic matter and increased greenhouse gas production from peatlands in response to whole-ecosystem warming. Here, we investigated how warming and elevated CO 2 impact peat microbial communities and peat soil decomposition rates and characterized microbial communities through amplicon sequencing and compositional changes across four depth increments. Microbial diversity and community composition were significantly impacted by soil depth, temperature, and CO 2 treatment. Bacterial/archaeal α-diversity increased significantly with increasing temperature, and fungal α-diversity was lower under elevated CO 2 treatments. Trans domain microbial networks showed higher complexity of microbial communities in decomposition ladder depths from the warmed enclosures, and the number of highly connected hub taxa within the networks was positively correlated with temperature. Methanogenic hubs were identified in the networks constructed from the warmest enclosures, indicating increased importance of methanogenesis in response to warming. Microbial community responses were not however reflected in measures of peat soil decomposition, as warming and elevated CO 2 had no significant short-term effects on soil mass loss or composition. Regardless of treatment, on average only 4.5% of the original soil mass was lost after 3 years and variation between replicates was high, potentially masking treatment effects. Previous results at the SPRUCE experiment have shown warming is accelerating organic-matter decomposition and CO 2 and CH 4 production, and our results suggest these changes may be driven by warming-induced shifts in microbial communities. IMPORTANCE Microbial community changes in response to climate change drivers have the potential to alter the trajectory of important ecosystem functions. In this paper, we show that while microbial communities in peatland systems responded to manipulations of temperature and CO 2 concentrations, these changes were not associated with similar responses in peat decomposition rates over 3 years. It is unclear however from our current studies whether this functional resiliency over 3 years will continue over the longer time scales relevant to peatland ecosystem functions.

54 ENVIRONMENTAL SCIENCES↗