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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 OSTI2012

Catalysts and methods for reforming oxygenated compounds

Disclosed are catalysts and methods that can reform aqueous solutions of oxygenated compounds such as ethylene glycol, glycerol, sugar alcohols, and sugars to generate products such as hydrogen and alkanes. In some embodiments, aqueous solutions containing at least 20 wt % of the oxygenated compounds can be reformed over a catalyst comprising a Group VIII transition metal and a Group VIIB transition metal, preferably supported on an activated carbon-supported catalyst. In other embodiments, catalysts are provided for the production of hydrogen or alkanes at reaction temperatures less than 300° C.

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

Simple Autoignition Model for the Derived Cetane Number of Oxygenated Compounds and Fuel Blends

A four-step autoignition model was used to derive an expression for the ignition delay and derived cetane number (DCN) measured by ignition quality testers (IQT) for oxygenated compounds and blends as a function of each compound’s global initiation and net chain branching rate constants. Expressions for these values were determined assuming they could be related to the functional groups present in a compound. Measurements for 124 compounds and 94 binary and ternary blends, gathered from the literature and performed at UW-Madison, were used to obtain the dependence of the measured ignition delay on each functional group. The new model was able to describe the ignition behavior of both the compounds and blends, with an average DCN error of 5.0 (22%) and 3.5 (15%), respectively. Additionally, the blend model was transformed into a mixing rule by incorporating existing IQT ignition delay data for each compound. Use of the mixing rule was found to offer improvements over the full prediction, with an average DCN error of 3.2 (14%).

Witkowski, Dustin↗
DOE OSTI2022

Simple Autoignition Model for the Derived Cetane Number of Oxygenated Compounds and Fuel Blends

A simple four-step autoignition model was used to derive an expression for the ignition delay and derived cetane number (DCN) measured by ignition quality testers (IQT) for oxygenated compounds and blends as a function of each compound’s global initiation and net chain branching rate constants. Expressions for these values were determined assuming they could be related to the functional groups present in a given compound. Measurements for 124 compounds and 94 binary and ternary blends, gathered from the literature and performed at UW-Madison, were used to obtain the explicit dependence of the measured ignition delay on each functional group. The new model was able to successfully describe the ignition behavior of both the compounds and blends, with an average DCN error of 5.0 (22%) and 3.5 (15%), respectively. Additionally, the blend model could naturally be modified into a mixing rule by incorporating existing IQT ignition delay data for each compound. Use of the mixing rule was found to offer improvements over the full prediction, with an average DCN error of 3.2 (14%).

09 BIOMASS FUELS↗
DOE OSTI2018

Electrocatalytic Hydrogenation of Oxygenated Compounds in Aqueous Phase

Electrocatalytic hydrogenation is a fascinating strategy to hydrogenate biogenic compounds at ambient conditions by replacing the thermal and H2 inputs by cathodic potential. This work compares the performance of this approach (in aqueous phase at room temperature) for a variety of model oxygenated compounds reacted over a series of metals. The target functionalities were carbonyl groups, aromatic rings, and ether bonds. All metals explored (Pt, Rh, Pd, Cu) are active for the reduction of carbonyl compounds to alcohols. For instance, conversion rates of benzaldehyde increased as a function of metal as: Pt < Rh < Pd (Cu was tested at different conditions). In contrast, only Rh and Pt were found active for hydrogenation of aromatic rings (Rh was more active than Pt). Comparing among the target functionalities, carbonyl groups are more reactive than aromatic rings and ether bonds in phenolic compounds and di-aryl ethers on all explore metals. This carbonyl reactivity, however, is enabled by the aromaticity of the molecule. Hence, the reactivity trend of the examined molecules is: butyraldehyde < furfural < acetophenone < benzaldehyde. For phenolic compounds, phenol is more reactive than cresol and methoxy phenol. Thus, the presence of substituting groups at the functionality being converted (either carbonyl or aromatic ring) decreases conversion rates. Ether bonds are cleaved under electrocatalytic conditions, which opens two main pathways for the conversion of aryl ethers: hydrogenation of the aromatic ring and hydrogenolysis of the ether bonds, whereas hydrolysis occurs as a minor pathway. Electrocatalytic hydrogenation competes with the H2 evolution reaction at the conditions of the tests, therefore Faradaic efficiency (fraction of current utilized in hydrogenation) and hydrogenation rates are correlated. That is, within the potential range explored, increasing hydrogenation rates lead to higher Faradaic efficiencies. The slope of this correlation, however, depends on the potential and on the functionality being hydrogenated. Keywords: Hydrogenation, electrocatalysis, metal catalysis, aqueous phase hydrogenation, biomass conversion. Acknowledgements The authors would like to thank Yang Song, Prof. Johannes Lercher, and the group of Prof. Hubert A. Gasteiger at the Technische Universität München for advice and support. The authors are grateful to Donald M. Camaioni, Nirala Singh, and Juan Herranz for fruitful discussions. The research described in this paper is part of the Chemical Transformation Initiative at Pacific Northwest National Laboratory (PNNL), conducted under the Laboratory Directed Research and Development Program at PNNL, a multi-program national laboratory operated by Battelle for the U.S. Department of Energy.

Hydrogenation, electrocatalysis, metal catalysis, ↗
NASA NTRS2011

Influence of Oxygenated Compounds on Reaction Products in a Microwave Plasma Methane Pyrolysis Assembly for Post-Processing of Sabatier Methane

The state-of-the-art Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS) in April 2010. The system is designed to accept carbon dioxide from the Carbon Dioxide Removal Assembly and hydrogen from the Oxygen Generation Assembly. The two gases are reacted in the CRA in a Sabatier reactor to produce water and methane. Venting of methane results in an oxygen resupply requirement of about 378 lbs per crew member per year. If the oxygen is supplied as water, the total weight for resupply is about 476 lb per crew member per year. For long-term missions beyond low Earth orbit, during which resupply capabilities will be further limited, recovery of hydrogen from methane is highly desirable. For this purpose, NASA is pursuing development of a Plasma Pyrolysis Assembly (PPA) capable of recovering hydrogen from methane. Under certain conditions, water vapor and carbon dioxide (nominally intended to be separated from the CRA outlet stream) may be present in the PPA feed stream. Thus, testing was conducted in 2010 to determine the effect of these "oxygenated" compounds on PPA performance, particularly the effect of inlet carbon dioxide and water variations on the PPA product stream. This paper discusses the test set-up, analysis, and results of this testing

Mansell, J. Matthew↗
NASA NTRS2012

Influence of Oxygenated Compounds on Reaction Products in a Microwave Plasma Methane Pyrolysis Assembly for Post-Processing of Sabatier Methane

The state-of-the-art Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS) in April 2010. The system is designed to accept carbon dioxide from the Carbon Dioxide Removal Assembly and hydrogen from the Oxygen Generation Assembly. The two gases are reacted in the CRA in a Sabatier reactor to produce water and methane. Venting of methane results in an oxygen resupply requirement of about 378 lbs per crew member per year. If the oxygen is supplied as water, the total weight for resupply is about 476 lb per crew member per year. For long-term missions beyond low Earth orbit, during which resupply capabilities will be further limited, recovery of hydrogen from methane is highly desirable. For this purpose, NASA is pursuing development of a Plasma Pyrolysis Assembly (PPA) capable of recovering hydrogen from methane. Under certain conditions, water vapor and carbon dioxide (nominally intended to be separated from the CRA outlet stream) may be present in the PPA feed stream. Thus, testing was conducted in 2010 to determine the effect of these oxygenated compounds on PPA performance, particularly the effect of inlet carbon dioxide and water variations on the PPA product stream. This paper discusses the test set-up, analysis, and results of this testing.

Mansell, J. Matthew↗
DOE OSTI2022

Chloride Salt Purification by Reaction With Thionyl Chloride Vapors to Remove Oxygen, Oxygenated Compounds, and Hydroxides

Molten chloride salts (including MgCl 2 , KCl, NaCl, and ZnCl 2 ) are being considered for heat transfer media for renewable (solar) and nuclear power generators, as fuel carrier for nuclear reactors, and as thermal energy storage media. Impurities such as oxygen, hydroxides, moisture, and sulfur are known to negatively influence the corrosion of materials in contact with the salt (e.g., structural metals). Commercially available chloride salts come with a range of impurities. Before using the chloride salts at high temperature, it is desirable to remove the impurities to increase the performance of the salt and reduce corrosion. In this study, we tested the use of thionyl chloride vaporized into a stream of argon to react with oxygenated impurities in a mixture of MgCl 2 -KCl-NaCl, removing them as HCl and SO 2 . The reagent was bubbled through the salt when both above and below the melting point. The reaction was followed using thermocouple data from the salt and by Fourier transform infrared (FTIR) spectroscopy on the exhaust of the reactor. The reaction kinetics were followed by comparing the peaks from SO 2 product to SOCl 2 reagent in the FTIR spectra. The purity of the salt was assessed at the end of the purification process by x-ray diffraction and inductively coupled plasma analysis. Although the process was effective in removing the oxygen content of the mixture, ternary compounds were formed in the process, including KNiCl 3 and KMgCl 3 . The nickel in KNiCl 3 came from the reaction between the salt and the nickel vessel. Thus, these experiments suggest that improvements to the process must be made before using SOCl 2 vapors for the purification of chloride salts.

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

Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron microcopy (STEM) to measure size and structure, energy dispersive X-ray spectroscopy (EDS) to measure atomic composition, X-ray absorption spectroscopy (XAS) to measure oxidation state and metal coordination, Fourier transform infrared spectroscopy (FTIR) to study adsorbed species, laser Raman spectroscopy to probe metal oxide promoters, and temperature programmed reaction/desorption to study the energetics of adsorption and desorption processes. We have studied our bimetallic catalysts for the selective cleavage of carbon-oxygen bonds, and we have studied the effects of adding metal oxide promoters to supported platinum and gold catalysts for water-gas shift (i.e., the production of hydrogen by reaction of carbon monoxide with water). We anticipate that the knowledge obtained from our studies will allow us to identify promising directions for new catalysts that show high activity, selectivity, and stability for important reactions, such as the conversion of biomass-derived oxygenated hydrocarbons to fuels and chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate

The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

Non-NASA Center↗
DOE OSTI2020

Performance of Base and Noble Metals for Electrocatalytic Hydrogenation of Bio-Oil-Derived Oxygenated Compounds

Electrocatalytic hydrogenation is a particularly attractive approach for converting the most unstable compounds in biogenic feedstocks at ambient conditions without external hydrogen. Here, we synthesized a variety of carbon-supported transition metal catalysts and characterized their activity for the electrocatalytic hydrogenation of a series of model compounds and pyrolysis oil. Carbonyl compounds, especially aromatic aldehydes, such as furfural and benzaldehyde, are particularly inclined to hydrogenation driven by an applied current. This was verified with pure solutions of the model compounds and with pyrolysis oil, where we achieved stable and steady continuous operation on Pd. By choosing the optimal catalyst composition, the conversion of benzaldehyde shifted from alcohol production (e.g., on Pd and Cu) to dimerization (e.g., on Co, Ni, and Zn). Pd and Cu were shown to offer the best compromise between reaction rates and efficiency although, in general, base metals offer similar conversions but better efficiencies that noble metals. Thus, the present work offers foundational results and guidelines for choosing the optimal metal catalyst and the applied potential for processing organic feedstocks as a function of its composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Photochemistry of Oxygen Compounds in Neptune's Stratosphere

ISO SWS observations of H2O and CO2 on Neptune (Feuchtgruber et al. 1997, Nature 389, 159) coupled with ground based millimeter observations of CO (Marten et al., 1993, Ap. J. 406 285) provide strong constraints on the photochemistry of these compounds in Neptune's stratosphere. Additional constraints on the photochemistry and vertical mixing come from the rich suite of hydrocarbons observed by ISO: CH4, C2H2, C2H6 (Bezard, 1998, Ann. Geophysicae 16, Sup. III C1037), CH3 (Bezard, et al. Ap. J. 515, 868), and C2H4 (Encrenaz et al. this DPS). We will use a one-dimensional global average photochemical model to analyze these compounds. In particular, we will better constrain the estimated external flux of H2O to Neptune's stratosphere given in Feuchtgruber et al., which is important in understanding the source of the observed stratospheric CO2. Kingdoms will come and go, the relentless march of time will continue, all will be explained.

Romani, P. N.↗
DOE OSTI2019

Understanding the Role of Metal and Molecular Structure on the Electrocatalytic Hydrogenation of Oxygenated Organic Compounds

Electrocatalytic hydrogenation is increasingly studied as an alternative to integrate the utilization of recycled carbon feedstocks with renewable energy sources. However, the abundant empiric observations available have not been correlated with fundamental properties of substrates and catalysts. In this paper, we investigated the electrocatalytic hydrogenation of homologues series of carboxylic acids, ketones, phenolics, and aldehydes on a variety of metals (Pd, Rh, Ru, Cu, Ni, Zn, and Co). We found that the rates of carbonyl reduction in aldehydes correlate with the corresponding binding energies between the aldehydes and the metals according to the Sabatier principle. That is, the highest rates are obtained at intermediate binding energies. The rates of H 2 evolution, occurring in parallel to hydrogenation, also correlate with the H-metal binding energies, following the same Volcano-type behavior. Within the boundaries of this model (e.g., compounds reactive at room temperature and without important steric effects over the carbonyl group), the reported correlations help to explain the complex trends derived from the experimental observations, allowing for the correlation of rates with binding energies and the differentiation of mechanistic routes.

Sabatier principle↗
DOE OSTI2017

Stereochemistry of silicon in oxygen-containing compounds

Specific stereochemical features of silicon in oxygen-containing compounds, including hybrid silicates with all oxygen atoms of SiO{sub n} groups ({sub n} = 4, 5, or 6) entering into the composition of organic anions or molecules, are described by characteristics of Voronoi—Dirichlet polyhedra. It is found that in rutile-like stishovite and post-stishovite phases with the structures similar to those of СаСl{sub 2}, α-PbO{sub 2}, or pyrite FeS{sub 2}, the volume of Voronoi—Dirichlet polyhedra of silicon and oxygen atoms decreases linearly with pressure increasing to 268 GPa. Based on these results, the possibility of formation of new post-stishovite phases is shown, namely, the fluorite-like structure (transition predicted at ~400 GPa) and a body-centered cubic lattice with statistical arrangement of silicon and oxygen atoms (~900 GPa).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1975

Bibliography on contaminants and solubility of organic compounds in oxygen

A compilation of a number of document citations is presented which contains information on contaminants in oxygen. Topics covered include contaminants and solubility of organic compounds in oxygen, reaction characteristics of organic compounds with oxygen, and sampling and detection limits of impurities. Each citation in the data bank contains many items of information about the document. Some of the items are title, author, abstract, corporate source, description of figures pertinent to hazards or safety, key references, and descriptors (keywords) by which the document can be retrieved. Each citation includes an evaluation of the technical contents as to being good/excellent, acceptable, or poor. The descriptors used to define the contents of the documents and subsequently used in the computerized search operations were developed for the cryogenic fluid safety by experts in the cryogenics field.

Ordin, P. M.↗
DOE OSTI2020

Near-canopy horizontal concentration heterogeneity of semivolatile oxygenated organic compounds and implications for 2-methyltetrols primary emissions

Semivolatile oxygenated organic compounds (SV-OVOCs) are important atmospheric species, in particular for the production and chemistry of atmospheric particulate matter and related impacts on air quality and climate. In this study, SV-OVOCs were collected in the horizontal plane of the roughness layer over the tropical forest in the central Amazon during the wet season of 2018. A sampler mounted to a copter-type, hovering unmanned aerial vehicle was used. Underlying the collection region, a plateau forest transitioned into a slope forest across several hundred meters. The concentrations of pinonic and pinic acids, which are monoterpene oxidation products, had no statistical difference over the two forests. By comparison, across the study period, differences in the concentration of 2-methyltetrols, which are products of isoprene oxidation, ranged from -70% to +480% over the two forests. The chemical lifetime of 2-methyltetrols in the atmosphere is sufficiently long that heterogeneity in the isoprene emission rate from the two forests followed by atmospheric oxidation does not explain the concentration heterogeneity of 2-methyltetrols. Standing waves and local meteorology also cannot account for the heterogeneity. Of the possibilities considered, the most plausible explanation is the direct emission from the forest of 2-methyltetrols produced through biological processes within the plants. Under this explanation, the rate of direct SV-OVOC emissions should be modulated by forest type and related environmental stressors. Direct emissions of SV-OVOCs should be more broadly considered for constraining and improving models of atmospheric composition, transport, and chemistry over tropical forests.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗