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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Copper(II) complexes with 4-(1H-1, 2, 4-trizol-1-ylmethyl) benzoic acid: Syntheses, crystal structures and antifungal activities

Reaction of Cu(II) with an asymmetric semi-rigid organic ligand 4-(1H-1, 2, 4-trizol-1-ylmethyl) benzoic acid (HL), yielded five compounds, [Cu{sub 0.5}L]{sub n} (1), [Cu(HL){sub 2}Cl{sub 2}]{sub n} (2), [Cu(HL){sub 2}Cl{sub 2}(H{sub 2}O)] (3), [Cu(L){sub 2}(H{sub 2}O)]{sub n} (4) and [Cu(L)(phen)(HCO{sub 2})]{sub n} (5), which have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. As for compounds 1, 2 and 5, Cu(II) is bridged through HL, Cl{sup -}, and formic acid, respectively, featuring 1D chain-structure. In compound 3, Cu(II) with hexahedral coordination sphere is assembled through hydrogen-bonding into 3D supramolecular framework. In compound 4, 1D chain units –Cu–O–Cu–O– are ligand-bridged into a 3D network. All compounds were tested on fungi (Fusarium graminearum, Altemaria solani, Macrophoma kawatsukai, Alternaria alternata and Colletotrichum gloeosporioides). Compound 1 exhibits a better antifungal effect compared to other compounds. An effect of structure on the antifungal activity has also been correlated. - Graphical abstract: Copper(II) compounds with 4-(1H-1, 2, 4-trizol-1-ylmethyl) benzoic acid, were prepared, structurally characterized and investigated for antifungal activity. - Highlights: • The title compounds formed by thermodynamics and thermokinetics. • The five compounds show higher inhibition percentage than reactants. • The structure effect on the antifungal activity.

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

Interim glycol flowsheet reduction/oxidation (redox) model for the Defense Waste Processing Facility (DWPF)

Control of the REDuction/OXidation (REDOX) state of glasses containing high concentrations of transition metals, such as High Level Waste (HLW) glasses, is critical in order to eliminate processing difficulties caused by overly reduced or overly oxidized melts. Operation of a HLW melter at Fe +2 /ΣFe ratios of between 0.09 and 0.33, a range which is not overly oxidizing or overly reducing, helps retain radionuclides in the melt, i.e. long-lived radioactive 99 Tc species in the less volatile reduced Tc 4+ state, 104 Ru in the melt as reduced Ru +4 state as insoluble RuO 2 , and hazardous volatile Cr 6+ in the less soluble and less volatile Cr +3 state in the glass. The melter REDOX control balances the oxidants and reductants from the feed and from processing additives such as antifoam. Currently, the Defense Waste Processing Facility (DWPF) is running a formic acid-nitric acid (FN) flowsheet where formic acid is the main reductant and nitric acid is the main oxidant. During decomposition formate and formic acid releases H 2 gas which requires close control of the melter vapor space flammability. A switch to a nitric acid-glycolic acid (GN) flowsheet is desired as the glycolic acid flowsheet releases considerably less H 2 gas upon decomposition. This would greatly simplify DWPF processing. Development of an EE term for glycolic acid in the GN flowsheet is documented in this study.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Lipids from High-Protein Algae Biomass

Biofuels from renewable and sustainable sources will be a critical component of reducing greenhouse gasses. To this end, in achieving maximum biomass productivity in outdoor ponds at a reasonable cost, algae must be grown at a maximal rate. This current algae cultivation strategy results in high-protein biomass because there is insufficient time for deplete-hold steps that increase lipids but also cost. Thus methods to convert high-protein (>50%) need to be developed for biofuels. The Consolidated Algae Processing (CAP) strategy has previously shown utility on high-carbohydrate algae biomass and has now been expanded to include methods aimed at converting the protein fraction to lipids. After acid-pretreatment, hydrolysate liquor is oxidatively treated to deaminate and convert soluble proteins and amino acids into four main carboxylate acids; formic, acetic, succinic, and propionic. These acids are readily and completely fermented into intracellular lipids using oleaginous yeast. Using a fed-batch fermentation strategy and no added nutrients, we achieved nearly 30% intracellular lipids and 1.3 g/L lipids demonstrating the potential of our expanded CAP process to generate additional lipids for conversion to biofuels as part of an algae-focused biorefinery.

AAD↗
NASA NTRS1989

An intercomparison of measurement systems for vapor and particulate phase concentrations of formic and acetic acids

During June 1986, eight systems for measuring vapor phase and four for measuring particulate phase concentrations of formic acid (HCOOH) and acetic acid (CH3COOH) were intercompared in central Virginia. HCOOH and CH3COOH vapors were sampled by condensate, mist, Chromosorb 103 GC resin, NaOH-coated annular denuders, NaOH-impregnated quartz filters, K2CO3 and NaCO3-impregnated cellulose filters, and Nylasorb membranes. Atmospheric aerosol was collected on Teflon and Nuclepore filters using both hi-vol and lo-vol systems to measure particulate phase concentrations. Performances of the mist chamber and K2CO3-impregnated filter techniques were evaluated using zero air and ambient air spiked with HCOOH(g) and CH3COOH(g), and formaldehyde from permeation sources. The advantages and drawbacks of these methods are reported and discussed.

Keene, William C.↗
DOE OSTI2012

Literature review on impact of glycolate on the 2H evaporator and the effluent treatment facility

Glycolic acid (GA) is being studied as an alternate reductant in the Defense Waste Processing Facility (DWPF) feed preparation process. It will either be a total or partial replacement for the formic acid that is currently used. A literature review has been conducted on the impact of glycolate on two post-DWPF downstream systems - the 2H Evaporator system and the Effluent Treatment Facility (ETF). The DWPF recycle stream serves as a portion of the feed to the 2H Evaporator. Glycolate enters the evaporator system from the glycolate in the recycle stream. The overhead (i.e., condensed phase) from the 2H Evaporator serves as a portion of the feed to the ETF. The literature search revealed that virtually no impact is anticipated for the 2H Evaporator. Glycolate may help reduce scale formation in the evaporator due to its high complexing ability. The drawback of the solubilizing ability is the potential impact on the criticality analysis of the 2H Evaporator system. It is recommended that at least a theoretical evaluation to confirm the finding that no self-propagating violent reactions with nitrate/nitrites will occur should be performed. Similarly, identification of sources of ignition relevant to glycolate and/or update of the composite flammability analysis to reflect the effects from the glycolate additions for the 2H Evaporator system are in order. An evaluation of the 2H Evaporator criticality analysis is also needed. A determination of the amount or fraction of the glycolate in the evaporator overhead is critical to more accurately assess its impact on the ETF. Hence, use of predictive models like OLI Environmental Simulation Package Software (OLI/ESP) and/or testing are recommended for the determination of the glycolate concentration in the overhead. The impact on the ETF depends on the concentration of glycolate in the ETF feed. The impact is classified as minor for feed glycolate concentrations {le} 33 mg/L or 0.44 mM. The ETF unit operations that will have minor/major impacts are chlorination, pH adjustment, 1st mercury removal, organics removal, 2nd mercury removal, and ion exchange. For minor impacts, the general approach is to use historical process operations data/modeling software like OLI/ESP and/or monitoring/compiled process operations data to resolve any uncertainties with testing as a last resort. For major impacts (i.e., glycolate concentrations > 33 mg/L or 0.44 mM), testing is recommended. No impact is envisaged for the following ETF unit operations regardless of the glycolate concentration - filtration, reverse osmosis, ion exchange resin regeneration, and evaporation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Polyvinylpyrrolidone adsorption effects on the morphologies of synthesized platinum particles and its catalytic activity

Flower-like Platinum micro-structures were synthesized from different concentration of the PVP using solvothermal method. At 5.0×10{sup −3} mmol of PVP, well-defined flower-like pattern consists of triangular petals radiating from the centre were produced whereas larger flower network developed at higher PVP concentration. High degree of crystallinity was obtained upon each increment of PVP. The well defined flower like pattern synthesized using 5.0×10{sup −3} mmol PVP exhibit the highest catalytic activity and stability towards electro-oxidation of formic acid.

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

Observation of hydroxymethyl hydroperoxide in a reaction system containing CH{sub 2}OO and water vapor through pure rotational spectroscopy

Pure rotational transitions of hydroxymethyl hydroperoxide (HMHP) were observed in the discharged plasma of a CH{sub 2}I{sub 2}/O{sub 2}/water gas mixture, where the water complex with the simplest Criegee intermediate CH{sub 2}OO has been identified [M. Nakajima and Y. Endo, J. Chem. Phys. 140, 134302 (2014)]. Isotope experiments using heavy water support that the currently observed HMHP molecule was produced by the reaction of CH{sub 2}OO with water vapor. The observed species was identified as the most stable conformer with the help of quantum chemical calculations. We also clarified that productions of formic acid and dioxirane are promoted by the existence of water vapor in the discharged reaction system.

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

Understanding the Reactivity and Decomposition of a Highly Active Iron Pincer Catalyst for Hydrogenation and Dehydrogenation Reactions

The iron pincer complex ( iPr PNP)Fe(H)(CO) (1, iPr PNP – = N(CH 2 CH 2 PiPr 2 ) 2 - ) is an active (pre)catalyst for many hydrogenation and dehydrogenation reactions. This is in part because 1 can reversibly add H 2 across the iron-amide bond to form ( iPr PN H P)Fe(H) 2 (CO) (2, iPr PN H P = HN(CH 2 CH 2 P i Pr 2 ) 2 ). However, rapid decomposition limits the catalytic performance of 1 and related complexes. We explored the pathways through which catalytic intermediates related to 1 and 2 undergo decomposition. This involved characterizing the unstable and previously unobserved complexes [( iPr PN H P)Fe(H)(CO)(L)] + (5-L; L = THF or N 2 ) and [( iPr PN H P)Fe(H)(H 2 )(CO)] + (8), which are proposed as intermediates when 1 and 2 are used as catalysts. Compound 8 was synthesized through the reaction of ( iPr PN H P)Fe(H)(CO)(PF 6 ) (6) with H 2 , and the solid-state structure was established using both X-ray and neutron diffraction. As part of our studies on understanding the reactivity of 5-L, we determined the thermodynamic hydricity of 2, which is valuable for predicting its reactivity as a hydride donor. Further, it is shown that species such as 5-L decompose to the same inactive species observed in catalysis using 1 and 2, and theoretical calculations suggest that this likely occurs via a bimolecular pathway. To provide support for this hypothesis, we isolated the dimeric species [{( iPr PN H P)Fe(H)(CO)} 2 {μ-CN}] + (11) and [{( iPr PN H P)Fe(H)(CO)} 2 {μ-OC(H)O}] + (12), which show that catalytic intermediates ligated by iPr PN H P can form dimeric species. Our results provide general strategies for improving catalysis using 1 and 2, and we used this information to rationally increase the performance of 1 in formic acid dehydrogenation.

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

Electroreduction of CO{sub 2} using copper-deposited on boron-doped diamond (BDD)

Electroreduction of CO{sub 2} was studied at copper-modified boron-doped diamond (Cu-BDD) electrodes as the working electrode. The Cu-BDD electrodes were prepared by electrochemical reduction with various concentrations of CuSO{sub 4} solutions. FE-SEM was utilized to characterize the electrodes. At Cu-BDD electrodes, a reduction peak at around -1.2 V (vs Ag/AgCl) attributtable to CO{sub 2} reductions could be observed by cyclic voltammetry technique of CO{sub 2} bubbled in water containing 0.1M NaCl. Accordingly, electroreduction of CO{sub 2} was conducted at -1.2 V (vs Ag/AgCl) using amperometry technique. The chemical products of the electroreduction analyzed by using HPLC showed the formation of formaldehyde, formic acid, and acetic acid at Cu-BDD electrodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Effect of Strength of Soluble and Solid Acid Catalysts on Selectivity in Aldol Reactions

Aldol reactions can follow the classical condensation path and produce an α,β-unsaturated carbonyl compound and water, however in some cases, aldol chemistry may be steered towards a fission that gives an olefin and a carboxylic acid. This investigation examines how the strength of Brønsted acid sites—both in homogeneous and heterogeneous catalysis—controls these two pathways and their kinetics. The cross-aldol reaction between benzaldehyde and 3-pentanone served as test case. Batch reactions, conducted in toluene as solvent at a temperature of 140 °C under autogenous pressure, were analyzed by GC and in situ ATR-FTIR spectroscopy to determine product distributions and rate constants for condensation and fission pathways. A series of soluble acids including a family of sulfonic acids mostly favored the condensation pathway, with formic acid as the weakest in the series by its pKa being inactive for aldol chemistry. Significant amounts of fission products were rare except for the known selectivity of phosphoric acid, and the circumstances were difficult to delineate. For the sulfonic acid family, the logarithm of the first-order condensation rate constants scaled only roughly with pKa (water) values, whereas a good correlation was obtained with calculated deprotonation Gibbs energies in toluene. A series of H-forms of isomorphously substituted beta zeolites, HESiBEA with E = Al, Ga, Fe, or B, favored the fission pathway. Site density and site strength were characterized by calorimetric measurements of the heats of adsorption of isopropylamine, which decreased in the order Al > Ga, Fe > B. The logarithm of the site-normalized first-order fission rate constants scaled roughly with the heats of adsorption and correlated excellently with reported deprotonation energies. In conclusion, acid strength mainly affects activity and can be seen as a pre-requisite for either aldol condensation or fission chemistry, whereas additional, yet to be full clarified catalyst properties and reaction conditions are required to steer aldol chemistry towards fission selectivity.

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

Positional effects of hydroxy groups on catalytic activity of proton-responsive half-sandwich Cp*Iridium(III) complexes

Proton-responsive half-sandwich Cp*Ir(III) complexes possessing a bipyridine ligand with two hydroxy groups at the 3,3'-, 4,4'-, 5,5'- or 6,6'-positions (3DHBP, 4DHBP, 5DHBP, or 6DHBP) were systematically investigated. UV-vis titration data provided average pK a values of the hydroxy groups on the ligands. Both hydroxy groups were found to deprotonate in the pH 4.6–5.6 range for the 4–6DHBP complexes. One of the hydroxy groups of the 3DHBP complex exhibited the low pK a value of < 0.4 because the deprotonation is facilitated by the strong intramolecular hydrogen bond formed between the generated oxyanion and the remaining hydroxy group, which in turn leads to an elevated pK a value of ~13.6 for the second deprotonation step. The crystal structures of the 4– and 6DHBP complexes obtained from basic aqueous solutions revealed their deprotonated forms. The intramolecular hydrogen bond in the 3DHBP complex was also observed in the crystal structures. The catalytic activities of these complexes in aqueous phase reactions, at appropriate pH, for hydrogenation of carbon dioxide (pH 8.5), dehydrogenation of formic acid (pH 1.8), transfer hydrogenation reactions using formic acid/formate as a hydrogen source (pH 7.2 and 2.6) were investigated to compare the positional effects of the hydroxy groups. The 4– and 6DHBP complexes exhibited remarkably enhanced catalytic activities under basic conditions because of the resonance effect of the strong electrondonating oxyanions, whereas the 5DHBP complex exhibited negligible activity despite the presence of electron-donating groups. The 3DHBP complex exhibited relatively high catalytic activity at low pH owing to the one strong electron-donating oxyanion group stabilized by the intramolecular hydrogen bond. DFT calculations were employed to study the mechanism of CO₂ hydrogenation by the 4DHBP and 6DHBP complexes, and comparison of the activation free energies of the H₂ heterolysis and CO₂ insertion steps indicated that H₂ heterolysis is the rate-determining step for both complexes. The presence of a pendent base in the 6DHBP complex was found to facilitate the rate-determining step, and renders 6DHBP a more effective catalyst for formate production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Controlling product selectivity in hybrid gas/liquid reactors using gas conditions, voltage, and temperature

For the conversion of CO 2 into fuels and chemical feedstocks, hybrid gas/liquid-fed electrochemical flow reactors provide advantages in selectivity and production rates over traditional liquid phase reactors. However, fundamental questions remain about how to optimize conditions to produce desired products. Here, using an alkaline electrolyte to suppress hydrogen formation and a gas diffusion electrode catalyst composed of copper nanoparticles on carbon nanospikes, we investigate how hydrocarbon product selectivity in the CO 2 reduction reaction in hybrid reactors depends on three experimentally controllable parameters: (1) supply of dry or humidified CO 2 gas, (2) applied potential, and (3) electrolyte temperature. Changing from dry to humidified CO 2 dramatically alters product selectivity from C 2 products ethanol and acetic acid to ethylene and C 1 products formic acid and methane. Water vapor evidently influences product selectivity of reactions that occur on the gas-facing side of the catalyst by adding a source of protons that alters reaction pathways and intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

A Survey of Large Molecules toward the Protoplanetary Nebula CRL 61 8

We present the results of our survey toward the protoplanetary nebula CRL 618 for several large, highly saturated, oxygen bearing organic molecules of biological importance including acetaldehyde (CH3CHO), acetic acid (CH3OOH), dimethyl ether (CH3OCH3), ethanol (CH3CH2OH), formic acid (HCOOH) and methyl formate (HCOOCH3); large carbon chain molecules including methyl cyanide (CH3CN) , methylcyanoacetylene (CH3C3N), cyanoacetylene (HC3N), cyanodiacetylene (HC5N), and C6H; and finally smaller molecules including SO-34, SO2, O(C-34)S and MgNC. No biologically important organic molecules were detected. However, we report the first interferometric detections of CH3CN and vibrationally excited HC3N and HC5N toward this source. The temperature and distribution of CH3CN toward CRL 618 indicates it is formed in the outer envelope surrounding the UC HII region. Furthermore, the P-Cygni line profile and corresponding channel maps of vibrationally excited HC5N supports its distribution in the extended envelope expanding radially from the central star. The detection of vibrationally excited HC3N confirmed the temperature structure and column density of HC3N in the inner envelope found by Wyrowski and colleagues (2003). Finally, our observations clearly indicate that CRL 618 is a good source of large carbon chain species but is a very poor source to detect or produce organic species of biological importance.

Remijan, Anthony J.↗
DOE OSTI2021

N-Heterocyclic Carbene Complexes of Nickel, Palladium, and Iridium Derived from Nitron: Synthesis, Structures, and Catalytic Properties

Nitron, has been employed as a “crypto-N-heterocyclic carbene” to afford 1,2,4-triazolylidene compounds of nickel, palladium and iridium. Significantly, the ligand derived from Nitron, namely Nitron NHC , affords catalytic systems, as illustrated by the ability of the iridium compound (Nitron NHC )Ir(CO) 2 Cl to effect (i) dehydrogenation of formic acid, (ii) aldehyde hydrosilyation, (iii) dehydrocoupling of hydrosilanes and alcohols, and (iv) ketone reduction via transfer hydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Challenges and opportunities for using formate to store, transport, and use hydrogen

In this perspective article, the synthesis and thermodynamic properties of aqueous solutions of formate salts (FS, HCO 2 - ) are described in relationship to the concept of H 2 carriers. The physiochemical properties of solid FS, aqueous formate solutions, and aqueous bicarbonate solutions set the limitations for storage capacity, deliverable capacity, and usable H 2 capacity of these H 2 carriers, respectively. These parameters will help in the design of systems that use H 2 carriers for storage and transport of H 2 for fuel cell power applications. We suggest FS, as well as admixtures with formic acid (FA, H 2 CO 2 ), have potential to address the goals outlined in the U.S. Department of Energy’s H2@scale initiative to store in chemical bonds a significant quantity of energy (hundreds of megawatts) obtained from large scale renewable resources.

08 HYDROGEN↗
DOE OSTI2016

Synthesis of ruthenium metal doped titanium dioxide nanoparticles for CO{sub 2} hydrogenation

Two different types of Ru metal doped TiO{sub 2} nanoparticles were synthesized using a sole gel method with and without ionic liquid. It was clearly observed during characterizing the Ru-TiO{sub 2}-IL catalyst with respect to Ru-TiO{sub 2} catalyst that Ru metal is dispersed while using ionic liquid as reaction medium for catalyst synthesis. TEM image also reveals the presence of agglomeration free, stable and well dispersed Ru metal doped TiO{sub 2} nanoparticles in Ru-TiO{sub 2}-IL over a Ru-TiO{sub 2} catalyst. Such unique feature of the Ru-TiO{sub 2}-IL catalyst reflected in terms of high TON /TOF value of formic acid during the hydrogenation reaction of CO{sub 2} in task specific ionic liquid medium. Low catalysts loading, moisture/air stability, high selectivity, an easy reaction protocol for catalyst synthesis as well as stress-free reaction condition along with 6 times catalysts recycling is the major outcomes of the proposed protocol.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Design for Carbon Conversion Product Pathways with Nuclear Power Plant Integration (PCC)

Coal is a globally abundant resource that historically has been used for power generation via combustion. As the power industry replaces coal with cleaner methods of generation, energy rich coal could be used in other chemical and fuel applications. This study presents a coal utilization option in which coal combustion is replaced with a carbon-free nuclear power plant and the coal is upgraded to valuable products for a variety of markets. Coal is prepared for conversion first by the pyrolysis process, which will optimize solid, liquid, and gaseous products based on the market size and potential product value, maximizing the monetary value of coal. This process is designed using bituminous coal from the Appalachian region as a basis to provide a pathway to preserve or transition coal-related jobs and create new jobs associated with the clean energy transition. Process modeling will be used to determine each component’s sensitivities, costs, inputs, and outputs Advanced and light-water reactors are considerations to supply the heat, steam, and electricity to the process. This paper focuses on the technical and market analysis used to determine the optimal processes and product pathways for the carbon refinery. Product pathways are on activated carbon, formic acid synthesis, and methanol synthesis for further upgrading to marketable chemical and polymer products.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2017

Designing Efficient Catalysts through Bimetallic Architecture: Rh@Pt Nanocubes as a Case Study

Bimetallic nanocatalysts often have increased activities and stabilities over their monometallic counterparts due to surface strain effects and electron transfer between the two metals. We demonstrate that the performance of a nanocatalyst can be precisely manipulated in shape-controlled nanocrystals through a bimetallic core@shell architecture. This ability is achieved in a model core@shell Rh@Pt nanocube system through control of shell thickness. The enhanced performance with thin-shelled nanocrystals is correlated with the weakening of surface–adsorbate interactions. In these thin-shelled Rh@Pt nanocubes, the maximum current density achieved during formic acid oxidation was over 2 times greater than that achieved with similarly sized Pt nanocubes, with a decreased CO poisoning ratio as well. Finally, the strategy employed here should also enhance the performance of many other bimetallic nanomaterials composed of more cost-effective metals too.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗