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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Sonoluminescence of Suspensions of Insoluble Chromium Carbonyl Nanoparticles in Water and Inorganic Acids

The preparation and sonoluminescence of Cr(CO){sub 6} nanodispersed suspensions in water, 83% H{sub 2}SO{sub 4}, and 74% H{sub 3}PO{sub 4} are described for the first time. In the spectra of single- and multibubble sonoluminescence of these suspensions, chromium atom lines are found that are analogous to the corresponding lines in the sonoluminescence spectra of true Cr(CO){sub 6} solutions in dodecane. Sonoluminescence of nanodispersed suspensions of metal carbonyl, by which the electronic temperature reached in the bubbles under sonolysis (from 6500 to 16 000 K in water and acids) was measured, expands the scope of the sonochemical model of injection of nanodroplets of low volatile compounds into cavitation bubbles due to the inclusion of injection of suspensions of insoluble substances into it.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

SiB3 simulations of gross primary productivity(GPP) and carbonyl sulfide (COS) plant flux

This data set contains Simple Biosphere Model (SiB3) simulations of North American carbon dioxide (CO2) gross primary productivity (GPP) and carbonyl sulfide (OCS) plant flux (Fplant). There are two Fplant simulation methods included: a methodologically simpler LRU-based method, and a more mechanistic leaf enzyme kinetic approach. These methods are described in detail in the references included with the dataset.Time span: 1 July 2008 through 31 Aug 2008 Spatial extent: Coterminus USA and most of Canada SpatialResolution: 60 km by 60 km

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2013

Quantifying Carbon-Climate Processes at the Regional Scale Using Atmospheric Carbonyl Sulfide

Atmospheric carbonyl sulfide (COS) analysis has the potentially transformative capability for partitioning the regional carbon flux into respiration and photosynthesis components. This emerging approach is based on the observation that continental atmospheric CO2 gradients are dominated by net ecosystem fluxes while continental atmospheric COS gradients are dominated by photosynthesis-related plant uptake. Regional flux partitioning represents a critical knowledge gap due to a lack of robust methods for regional-scale flux partitioning and large uncertainties in forecasting carbon-climate feedbacks. Our completed project characterized the relationship between COS and CO2 surface fluxes using a novel measurement and modeling system in a winter wheat field at the U.S. Department of Energy?s Atmospheric and Radiation Measurement program Central Facility (DOE-ARM CF). The scope of this project included canopy flux measurements, soil flux measurements, regional atmospheric modeling, and analysis of COS and CO2 airborne observations at SGP. Three critical discoveries emerged from this investigation: (1) the new measurement system provided the first field evidence of a robust relationship between COS leaf fluxes and GPP; (2) a previously unknown seasonal soil source of COS was observed and characterized; (3) the regional atmospheric analysis of airborne measurements provided the first COS-based constraints on GPP parameterizations used in earth systems models. Dissemination of these results includes three publications [Billesbach et al., In Press; Campbell et al., In Preparation; Seibt et al., In Review], three presentations at the AGU Fall Meeting (2012), and four invited presentations to department seminars. We have leveraged this foundational project to continue our work on understanding carbon cycle processes at large scales through one funded project (DOE Lab Fee, 2012-2015) and one proposal that is under review (DOE/NASA/USDA/NOAA, 2014-2016).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Carbonyl Sulfide for Tracing Carbon Fluxes Field Campaign Report

The April-June 2012 campaign was located at the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility Southern Great Plains (SGP) site Central Facility and had three purposes. One goal was to demonstrate the ability of current instrumentation to correctly measure fluxes of atmospheric carbonyl sulfide (COS). The approach has been describe previously as a critical approach to advancing carbon cycle science1,2, but requires further investigation at the canopy scale to resolve ecosystem processes. Previous canopy-scale efforts were limited to data rates of 1Hz. While 1 Hz measurements may work in a few ecosystems, it is widely accepted that data rates of 10 to 20 Hz are needed to fully capture the exchange of traces gases between the atmosphere and vegetative canopy. A second goal of this campaign was to determine if canopy observations could provide information to help interpret the seasonal double peak in airborne observations at SGP of CO 2 and COS mixing ratios. A third goal was to detect potential sources and sinks of COS that must be resolved before using COS as a tracer of gross primary productivity (GPP).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

ON THE FORMATION OF AMIDE POLYMERS VIA CARBONYL–AMINO GROUP LINKAGES IN ENERGETICALLY PROCESSED ICES OF ASTROPHYSICAL RELEVANCE

We report on the formation of organic amide polymers via carbonyl–amino group linkages in carbon monoxide and ammonia bearing energetically processed ices of astrophysical relevance. The first group comprises molecules with one carboxyl group and an increasing number of amine moieties starting with formamide (45 u), urea (60 u), and hydrazine carboxamide (75 u). The second group consists of species with two carboxyl (58 u) and up to three amine groups (73 u, 88 u, and 103 u). The formation and polymerization of these linkages from simple inorganic molecules via formamide und urea toward amide polymers is discussed in an astrophysical and astrobiological context. Our results show that long chain molecules, which are closely related to polypeptides, easily form by energetically processing simple, inorganic ices at very low temperatures and can be released into the gas phase by sublimation of the ices in star-forming regions. Our experimental results were obtained by employing reflectron time-of-flight mass spectroscopy, coupled with soft, single photon vacuum ultraviolet photoionization; they are complemented by theoretical calculations.

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

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity

Abstract We report mechanistic studies on the insertion reactions of [(NHC)Cu(μ‐H)] 2 complexes with carbonyl substrates by UV‐vis and 1 H NMR spectroscopic kinetic studies, H/D isotopic labelling, and X‐ray crystallography. The results of these comprehensive studies show that the insertion of Cu‐H with an aldehyde, ketone, activated ester/amide, and unactivated amide consist of two different rate limiting steps: the formation of Cu‐H monomer from Cu‐H dimer for more electrophilic substrates, and hydride transfer from a transient Cu‐H monomer for less electrophilic substrates. We also report spectroscopic and crystallographic characterization of rare Cu‐hemiacetalate and Cu‐hemiaminalate moieties from the insertion of an ester or amide into the Cu−H bond.

Tran, Ba L.↗
DOE OSTI2022

Formation of Organic Acids and Carbonyl Compounds in n ‐Butane Oxidation via γ‐Ketohydroperoxide Decomposition

Abstract A crucial chain‐branching step in autoignition is the decomposition of ketohydroperoxides (KHP) to form an oxy radical and OH. Other pathways compete with chain‐branching, such as “Korcek” dissociation of γ‐KHP to a carbonyl and an acid. Here we characterize the formation of a γ‐KHP and its decomposition to formic acid+acetone products from observations of n ‐butane oxidation in two complementary experiments. In jet‐stirred reactor measurements, KHP is observed above 590 K. The KHP concentration decreases with increasing temperature, whereas formic acid and acetone products increase. Observation of characteristic isotopologs acetone‐ d 3 and formic acid‐ d 0 in the oxidation of CH 3 CD 2 CD 2 CH 3 is consistent with a Korcek mechanism. In laser‐initiated oxidation experiments of n ‐butane, formic acid and acetone are produced on the timescale of KHP removal. Modelling the time‐resolved production of formic acid provides an estimated upper limit of 2 s −1 for the rate coefficient of KHP decomposition to formic acid+acetone.

Popolan‐Vaida, Denisia M.↗
DOE OSTI2022

Formation of Organic Acids and Carbonyl Compounds in $\textit{n}$-Butane Oxidation via γ-Ketohydroperoxide Decomposition

A crucial chain-branching step in autoignition is the decomposition of ketohydroperoxides (KHP) to form an oxy radical and OH. Other pathways compete with chain-branching, such as “Korcek” dissociation of γ-KHP to a carbonyl and an acid. Here we characterize the formation of a γ-KHP and its decomposition to formic acid+acetone products from observations of $\textit{n}$-butane oxidation in two complementary experiments. In jet-stirred reactor measurements, KHP is observed above 590 K. The KHP concentration decreases with increasing temperature, whereas formic acid and acetone products increase. Observation of characteristic isotopologs acetone-$d_3$ and formic acid-$d_0$ in the oxidation of CH 3 CD 2 CD 2 CH 3 is consistent with a Korcek mechanism. In laser-initiated oxidation experiments of $\textit{n}$-butane, formic acid and acetone are produced on the timescale of KHP removal. Further, modelling the time-resolved production of formic acid provides an estimated upper limit of 2 s –1 for the rate coefficient of KHP decomposition to formic acid+acetone.

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

Cobalt Carbonyl Clusters Enable Independent Control of Two Proton Transfer Rates in the Mechanism for Hydrogen Evolution

Abstract Metal carbonyl clusters (MCC's) are atomically defined nanomaterials which can be characterized using the precise tools of molecular (electro)chemistry. HER mechanisms involve two proton transfer (PT) steps in the catalytic cycle. For HER catalyzed by [Co 11 C 2 (CO) 23 ] 3− ( 1 3− ), cyclic voltammetry measurements were used to determine the rate for PT1 as k PT1 =3×10 8 M −1 s −1 , whereas the rate for PT2 is k PT2 =3.7×10 3 M −1 s −1 . The fast, diffusion‐limited rate for PT1 is consistent with a previous report describing [Co 13 C 2 (CO) 24 ] 4− ( 2 4− ), with PT=2.9×10 9 M −1 s −1 . In both cases rate enhancement in PT1 is promoted by the many Co−Co bonds on the surface of the MCC that serve as PT sites: a statistical enhancement of rate akin to the effects of proton relays. In contrast, k PT2 varies and is five orders of magnitude slower for 1 2− compared with 2 4− . Thus, MCC's and nanomaterials offer an opportunity to enhance the rate for PT1 while maintaining thermochemical or kinetic control of PT2.

Pattanayak, Santanu↗
DOE OSTI2025

Ionic Liquid Aided [ 11 C]CO Fixation for Synthesis of 11 C‐carbonyls

Tributyl(ethyl)phosphonium oxopentenolate ([P 4442 ][Pen]) is an ionic liquid developed to capture CO and has shown ability to catalyze carbonylation reactions in organic chemistry. Carbon-11 ( 11 C, t 1/2 =20.4 min) labeled CO is a highly versatile building block for the synthesis of positron emission tomography (PET) radiotracers that are applied for medical imaging. The use of [ 11 C]CO is limited by its low solubility in organic solvents. Herein, we report a proof-of-concept study evaluating a new method to prepare 11 C-labeled amides, ureas and carbamates via reaction of [ 11 C]CO in [P 4442 ][Pen] and applied for fully automated radiosyntheses of Bruton's tyrosine kinase inhibitors, [ 11 C]evobrutinib and [ 11 C]ibrutinib.

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

Synthesis and structural characterization of 2,2’-bipyridine zinc formate: Analysis of formate bonding and hydrosilylation of CO 2 and carbonyl compounds

The zinc formate compound (bipy)Zn(O 2 CH) 2 is obtained via the reaction of Zn(O 2 CH) 2 with 2,2’-bipyridine (bipy). In addition, (bipy)Zn(O 2 CH) 2 may be formed from zinc hydride via addition of bipy followed by addition of (i) HCO 2 H and (ii) CO 2 . The molecular structure of (bipy)Zn(O 2 CH) 2 has been determined by X-ray diffraction, thereby demonstrating that it exists as a monomeric species with a distorted tetrahedral zinc center and monodentate formate ligands. Analysis of the bonding within the formate ligand indicates that the zinc–formate moiety is not best represented by a Zn–O–C(=O)H resonance structure, but instead possesses a significant ionic component that reduces the C=O bond order and increases the C–O bond order. The formate compound (bipy)Zn(O 2 CH) 2 participates in hydrosilylation transformations involving CO 2 and carbonyl compounds.

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

Electron microscopy study of the formation mechanism of catalytic nickel-rich particles and the role of carbonyl sulphide in the suppression of carbon deposition on 20Cr-25Ni steel

Highlights: • Carbon deposition has been significantly reduced under the presence of CoS. • The origin of catalytic nickel-rich particles in stainless steel revealed • High resolution EDS study showed that sulphur was observed to be surrounding nickel-rich particles. - Abstract: Austenitic stainless steel is used as fuel cladding in advanced gas-cooled nuclear reactors (AGR). At elevated temperatures, when the steel is exposed to CO{sub 2} based environments filamentary carbon deposits form on the surface of the steel. This filamentary carbon deposition is known to be catalysed by metallic nickel-rich particles. Adding trace amount of carbonyl sulphide (COS) into the gas mixtures suppresses the carbon deposition. In this current work, it has been shown that at 600 °C, the formation of filamentary carbon was suppressed by the addition of 215 ppb COS to a depositing gas mixture (containing approximately 1000 vppm C{sub 2}H{sub 4}/1% CO/bal. CO{sub 2}) which was known to provide the environment suitable for carbon deposition. Samples exposed to the gas mixtures with and without 215 ppb COS were characterised using electron microscopy techniques to understand the formation mechanism of the nickel-rich particles and the inhibition mechanism due to the addition of COS. Electron diffraction study shows that the nickel-rich particles in the oxide layers assume the same crystallography as that of the austenitic metal underneath, regardless of the COS addition. The current observations also show that the metal-oxide interfaces was nickel-rich and a simple model has been proposed to explain the formation of nickel-rich particles within the subsurface oxide. Furthermore, it was found that when COS was added the surface of the nickel-rich particles in the oxide layer was found to be sulphur-rich by energy dispersive spectroscopy (EDS) on a scanning transmission electron microscope (STEM). It is believed that the surface sulphur adsorption onto the nickel-rich particles, rather than bulk sulphide formation, resulted in the inhibition of carbon deformation on the steel.

36 MATERIALS SCIENCE↗
DOE OSTI2016

The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes

In this study, the coordination chemistry of Mn(CO) 5 Br was investigated with a series of PNP-pincer ligands. The ligands iPr PONOP ( iPr PONOP = 2,6-bis(diisopropylphosphinito)pyridine) and iPr PN H P ( iPr PN H P = HN{CH 2 CH 2 (PiPr 2 )} 2 ) gave the desired organometallic manganese complexes ( iPr PONOP)Mn(CO) 2 Br and ( iPr PN H P)Mn(CO) 2 Br, respectively, upon chelation to Mn(CO) 5 Br. The reactivity of iPr PNNNP ( iPr PNNNP = N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine) with Mn(CO) 5 Br yielded a pair of products, [( iPr PNNNP)Mn(CO) 3 ][Br] and ( iPr PNNNCO)Mn(CO) 3 . The formation of the asymmetric chelate arises from a formal loss of iPr 2 PBr and C–N bond formation from a carbonyl ligand and NH, yielding a Mn(I) amide core. The nitration reactions of ( iPr PONOP)Mn(CO) 2 Br and ( iPr PN H P)Mn(CO) 2 Br were carried out using silver nitrite, yielding the nitro compounds ( iPr PONOP)Mn(CO) 2 (NO 2 ) and ( iPr PN H P)Mn(CO) 2 (NO 2 ), respectively. The analogous iron complex ( iPr PONOP)Fe(CO)Cl 2 was nitrated under the same conditions to yield the salt pair [( iPr PONOP)Fe(CO) 2 ][FeCl 3 NO]. This reactivity underlines the difference between iso-valent iron and manganese centers. The manganese complexes ( iPr PONOP)Mn(CO) 2 (NO 2 ) and ( iPr PN H P)Mn(CO) 2 (NO 2 ) were ineffective as oxygen atom transfer reagents for a variety of substrates.

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

Synthesis and structural characterization of 2,2′:6′,2″-terpyridine zinc formate: Hydroboration and hydrosilylation of CO 2 and carbonyl compounds

The zinc formate compound (terpy)Zn(O 2 CH) 2 is obtained via the reaction of Zn(O 2 CH) 2 with 2,2′:6′,2″-terpyridine (terpy) and has been structurally characterized by X-ray diffraction as possessing formate ligands that coordinate via a κ 1 -monodentate coordination mode, which is in accord with IR spectroscopic studies. In terms of reactivity, (terpy)Zn(O 2 CH) 2 participates in catalytic transformations involving CO 2 and carbonyl compounds via hydrosilylation and hydroboration reactions. For example, (terpy)Zn(O 2 CH) 2 achieves hydroboration of Me 2 CO and Ph 2 CO by HBpin to afford R 2 C(H)OBpin, and triple insertion of Ph 2 CO, PhC(O)Me, Me 2 CO and PhCHO into the Si–H bonds of PhSiH 3 to afford PhSi[OCH(R)R’] 3 . In addition, CO 2 also undergoes hydroboration and hydrosilylation by HBpin and (MeO) 3 SiH in the presence of (terpy)Zn(O 2 CH) 2 to afford HCO 2 Bpin and HCO 2 Si(OMe) 3 , respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Alumina Priming-Mediated Enhanced Binding of Diethylzinc with Carbonyl Groups in Poly(Methyl Methacrylate) during Vapor-Phase Infiltration

Vapor-phase infiltration (VPI) of inorganic materials in polymers is increasingly becoming popular for synthesizing various functional hybrid materials. While AlO x infiltration using trimethylaluminum (TMA) has been extensively studied, the mechanism of diethylzinc (DEZ)-based ZnO x infiltration, especially one that is initiated by AlO x priming, has not received much attention because highly reactive hydroxyl groups generated by AlO x -priming are expected to dominate the initial binding of DEZ, thus enabling the overall ZnO x VPI. Here, we interrogate the ZnO x infiltration mechanism in AlO x -primed poly(methyl methacrylate) (PMMA) in comparison to the control AlO x -only infiltration by utilizing a suite of complementary characterizations, including quartz crystal microbalance mass gain measurement, transmission electron microscopy, infrared reflection–absorption spectroscopy (IRRAS), and synchrotron X-ray absorption spectroscopy (XAS). The multivalent TMA precursor and associated hyperbranched AlO x network can quickly saturate the AlO x infiltration by clogging the polymer-free volume near the top. On the contrary, the ZnO x infiltration using divalent DEZ precursor, once activated via AlO x -priming, can lead to accelerated ZnOx infiltration. With the help of IRRAS, XAS, and density functional theory (DFT) simulations, we uncover that the AlO x -priming enhances the reactivity of neighboring carbonyl groups toward DEZ and opens up simultaneous reaction pathways, leading to accelerated high-fidelity infiltration of ZnO x .

36 MATERIALS SCIENCE↗