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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 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere

Methacryloyl peroxynitrate (MPAN), the acyl peroxynitrate of methacrolein, has been suggested to be an important secondary organic aerosol (SOA) precursor from isoprene oxidation. Yet, the mechanism by which MPAN produces SOA through reaction with the hydroxyl radical (OH) is unclear. We systematically evaluate three proposed mechanisms in controlled chamber experiments and provide the first experimental support for the theoretically-predicted lactone formation pathway from the MPAN + OH reaction, producing hydroxymethyl-methyl-α-lactone (HMML). The decomposition of the MPAN–OH adduct yields HMML + NO 3 (~75%) and hydroxyacetone + CO + NO 3 (~25%), out-competing its reaction with atmospheric oxygen. The production of other proposed SOA precursors, e.g., methacrylic acid epoxide (MAE), from MPAN and methacrolein are negligible (<2%). Furthermore, we show that the beta-alkenyl moiety of MPAN is critical for lactone formation. Alkyl radicals formed cold via H-abstraction by OH do not decompose to HMML, even if they are structurally identical to the MPAN–OH adduct. The SOA formation from HMML, from polyaddition of the lactone to organic compounds at the particle interface or in the condensed phase, is close to unity under dry conditions. However, the SOA yield is sensitive to particle liquid water and solvated ions. In hydrated inorganic particles, HMML reacts primarily with H 2 O to produce the monomeric 2-methylglyceric acid (2MGA) or with aqueous sulfate and nitrate to produce the associated organosulfate and organonitrate, respectively. 2MGA, a tracer for isoprene SOA, is semivolatile and its accommodation in aerosol water decreases with decreasing pH. Conditions that enhance the production of neutral 2MGA suppress SOA mass from the HMML channel. In conclusion, considering the liquid water content and pH ranges of ambient particles, 2MGA will exist largely as a gaseous compound in some parts of the atmosphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Decoration of the layered manganese oxide birnessite with Mn( II / III ) gives a new water oxidation catalyst with fifty-fold turnover number enhancement

The role of the manganese average oxidation state (AOS) in water oxidation catalysis by birnessite was investigated. In this work, low AOS samples were most active, generating O 2 immediately. Samples with a relatively high AOS showed an initial induction period and decreased turnover. Mn( II - and III ) -enriched samples gave a 10–50 fold enhancement in turnover number.

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

Hydrogen adsorption on two catalysts for the ortho- to parahydrogen conversion: Cr-doped silica and ferric oxide gel

Molecular hydrogen exists in two spin-rotation coupled states: parahydrogen and orthohydrogen. Due to the variation of energy with rotational level, the occupation of ortho- and parahydrogen states is temperature dependent, with parahydrogen being the dominant species at low temperatures. Here, the equilibrium at 20 K (99.8% parahydrogen) can be reached by natural conversion only after a lengthy process. With the use of a suitable catalyst, this process can be shortened significantly. Two types of commercial catalysts currently being used for ortho- to parahydrogen conversion are: iron(III) oxide (Fe 2 O 3 , IONEX®), and chromium(II) oxide doped silica catalyst (CrO·SiO 2 , OXISORB®). We investigate the interaction of ortho- and parahydrogen with the surfaces of these ortho–para conversion catalysts using neutron vibrational spectroscopy. The catalytic surfaces have been characterized using X-ray absorption fine structure (XAFS) and X-ray/neutron pair distribution function measurements.

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

Cross dehydrogenative coupling of N -aryltetrahydroisoquinolines (sp 3 C–H) with indoles (sp 2 C–H) using a heterogeneous mesoporous manganese oxide catalyst [Mesoporous manganese oxide catalyzed cross dehydrogenative coupling of N -aryltetrahydroisoquinolines (sp 3 C–H) with indoles (sp 2 C–H)]

Here, we disclose a novel, heterogeneous catalytic approach for selective coupling of C1 of N -aryltetrahydroisoquinolines with C3 of indoles in the presence of mesoporous manganese oxides. Our work involves a detailed mechanistic investigation of the reaction on the catalyst surface, backed by DFT computational studies, to understand the superior catalytic activity of manganese oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Cobalt-substituted SrTi 0.3 Fe 0.7 O 3–δ : a stable high-performance oxygen electrode material for intermediate-temperature solid oxide electrochemical cells

A key need in the development of solid oxide cells (SOCs) is for electrodes that promote fast oxygen reduction and oxygen evolution reactions at reduced operating temperature (≤700 °C), with sufficient durability to allow operation over desired 40 000 h lifetimes. A wide range of electrode materials have been investigated, with some providing resistance low enough for cell operation below 700 °C, but it is generally found that the electrode performance degrades over time. Here we demonstrate an oxygen electrode material, Sr(Ti 0.3 Fe 0.7–x Co x )O 3–δ (STFC), that provides a unique combination of excellent oxygen electrode performance and long-term stability. The addition of a relatively small amount of Co to Sr(Ti 0.3 Fe 0.7 )O 3–δ , e.g., x = 0.07, reduces the electrode polarization resistance by >2 times. The STFC electrode yields stable performance in both fuel cell and electrolysis modes at 1 A cm –2 . The fundamental oxygen diffusion and surface exchange coefficients of STFC are determined, and shown to be substantially better than those of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3–δ , the most widely used SOC oxygen electrode material. Here, while other electrode materials have been shown to exhibit better oxygen transport coefficients than STFC, they do not match its stability.

25 ENERGY STORAGE↗
DOE OSTI2019

Intracellular Dynamics of Superparamagnetic Iron Oxide Nanoparticles for Magnetic Partical Imaging

Superparamagnetic iron oxide nanoparticles (SPIONs) are a foundational platform for a variety of biomedical applications. Of particular interest is Magnetic Particle Imaging (MPI), which is a growing area of research and development due to its advantages including high resolution and sensitivity with positive contrast. There has been signicant work in the area of in vivo optimization of SPIONs for MPI as well as their biodistribution in and clearance from the body. However, little is known about the dynamics of SPIONs following cellular internalization which may limit their usefulness in a variety of potential imaging and treatment applications. This work shows a clear 20% decrease in magnetic performance of SPIONs, as observed by Magnetic Particle Spectroscopy (MPS), after internalization and systematic consideration of applicable factors that aect SPION signal generation, including microstructure, environment, and interparticle interactions. There is no observed change to SPION microstructure after internalization, and the surrounding environment plays little to no role in magnetic response for the SPIONs studied here. Interparticle interactions described by dipole-dipole coupling of SPIONs held close to one another after internalization are shown to be the dominant cause of decreased magnetic performance in cells. These conclusions were drawn from transmission electron microscopy (TEM) image analysis at relevant length scales, experimentally prepared and characterized SPIONs in varied environmental conditions, and theoretical modeling with Monte Carlo simulations.

Teeman, Eric M.↗
DOE OSTI2021

Identification of the acetaldehyde oxide Criegee intermediate reaction network in the ozone-assisted low-temperature oxidation of trans -2-butene

Uni- and bi-molecular reactions involving Criegee intermediates (CIs) have been the focus of many studies due to the role these molecules play in atmospheric chemistry. The reactivity of CIs is known to strongly depend on their structure. The reaction network of the second simplest CI, acetaldehyde oxide (CH 3 CHOO), is investigated in this work in an atmospheric pressure jet-stirred reactor (JSR) during the ozonolysis of trans-2-butene to explore the kinetic pathways relevant to atmospheric chemistry and low-temperature combustion. The mole fraction profiles of reactants, intermediates, and final products are determined by means of molecular-beam mass spectrometry in conjunction with single-photon ionization employing tunable synchrotron-generated vacuum ultraviolet radiation. A network of CI reactions is identified in the temperature region below 600 K, characterized by CI addition to trans-2-butene, water, formaldehyde, formic acid, and methanol. No sequential additions of the CH 3 CHOO CI are observed, in contrast with the reactivity of the simplest CI (H 2 COO) and the earlier observation of an extensive reaction network with up to four H 2 COO sequential additions (Phys. Chem. Chem. Phys., 2019, 21, 7341–7357). Experimental photoionization efficiency scans recorded at 300 K and 425 K and ab initio threshold energy calculations lead to the identification and quantification of previously elusive intermediates, such as ketohydroperoxide and hydroperoxide species. Specifically, the C 4 H 8 + O 3 adduct is identified as a ketohydroperoxide (KHP, 3-hydroperoxybutan-2-one, CH 3 C([double bond, length as m-dash]O)CH(CH 3 )OOH), while hydroxyacetaldehyde (glycolaldehyde, HCOCH 2 OH) formation is attributed to unimolecular isomerization of the CIs. Other hydroperoxide species such as methyl hydroperoxide (CH 3 OOH), ethyl hydroperoxide (C 2 H 5 OOH), butyl hydroperoxide (OOH), hydroperoxyl acetaldehyde (HOOCH 2 CHO), hydroxyethyl hydroperoxide (CH 3 CH(OH)OOH), but-1-enyl-3-hydroperoxide, and 4-hydroxy-3-methylpentan-2-one (HOCH(CH 3 )CH(CH 3 )C([double bond, length as m-dash]O)CH 3 ) are also identified. Detection of additional oxygenated species such as methanol, ethanol, ketene, and aldehydes suggests multiple active oxidation routes. Finally, these results provide additional evidence that CIs are key intermediates of the ozone-unsaturated hydrocarbon reactions providing critical inputs for improved kinetics models.

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DOE OSTI2023

Structural and reactive evolution of oxidatively grafted Pd catalysts on MnO 2 for the low-temperature oxidation of CO

We report Isolated Pd atoms supported on high surface area MnO 2 , prepared by the oxidative grafting of (bis(tricyclohexylphosphine-palladium(0)), catalyze (>50 turnovers, 17 h) the low temperature (≤325 K) oxidation of CO (7.7 kPa O 2 , 2.6 kPa CO) with results of in situ/operando and ex situ spectroscopic characterization signifying a synergistic role of Pd and MnO 2 in facilitating redox turnovers.

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