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At least 73 records · Page 4

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NASA NTRS2015

Martian Superoxide and Peroxide O2 Release (OR) Assay: A New Technology for Terrestrial and Planetary Applications

This study presents an assay for the detection and quantification of soil metal superoxides and peroxides in regolith and soil. The O2 release (OR) assay is based on the enzymatic conversion of the hydrolysis products of metal oxides to O2, and their quantification by an O2 electrode based on the stoichiometry of the involved reactions: The intermediate product O2 from the hydrolysis of metal superoxides is converted by cytochrome c to O2, and also by superoxide dismutase (SOD) to 1/2 mol O2 and 1/2 mol H2O2, which is then converted by catalase (CAT) to 1/2 mol O2. The product H2O2 from the hydrolysis of metal peroxides and hydroperoxides is converted to 1/2 mol O2 by CAT. The assay-method was validated in a sealed sample chamber using a liquid-phase Clark-type O2 electrode with known concentrations of O2 and H2O2, and with commercial metal superoxide and peroxide mixed with Mars analogue Mojave and Atacama Desert soils. Carbonates and perchlorates, both present on Mars, do not interfere with the assay. The assay lower limit of detection, using luminescence quenching/optical sensing O2-electrodes, is 1 nmol O2 cm(exp. -3) or better. The activity of the assay enzymes SOD and cytochrome c was unaffected up to 6 Gy exposure by gamma-radiation, while CAT retained 100% and 40% of its activity at 3 and 6 Gy, respectively, demonstrating the suitability of these enzymes for planetary missions, e.g., in Mars or Europa.

soil metal superoxides and peroxides↗

DOE OSTI2020

The Unexpected Role of Se VI Species in Epoxidations with Benzeneseleninic Acid and Hydrogen Peroxide

Abstract Benzeneperoxyseleninic acid has been proposed as the key intermediate in the widely used epoxidation of alkenes with benzeneseleninic acid and hydrogen peroxide. However, it reacts sluggishly with cyclooctene and instead rapidly decomposes in solution to a mixed selenonium–selenonate salt that was identified by X‐ray absorption and 77 Se NMR spectroscopy, as well as by single crystal X‐ray diffraction. This process includes a selenoxide elimination of the peroxyseleninic acid with liberation of oxygen and additional redox steps. The salt is relatively stable in the solid state, but generates the corresponding selenonic acid in the presence of hydrogen peroxide. The selenonic acid is inert towards cyclooctene on its own; however, rapid epoxidation occurs when hydrogen peroxide is added. This shows that the selenonic acid must first be activated through further oxidation, presumably to the heretofore unknown benzeneperoxyselenonic acid. The latter is the principal oxidant in this epoxidation.

Sands, Kai N.↗

DOE OSTI2020

The Unexpected Role of Se VI Species in Epoxidations with Benzeneseleninic Acid and Hydrogen Peroxide

Sands, Kai N.↗

DOE OSTI2025

High Pressure Synthesis of Pr 2 O 5 – A Unique Lanthanoid(IV) Oxide Peroxide

Abstract Reacting praseodymium(IV) oxide with oxygen at 27 GPa in a diamond anvil cell yielded the oxide peroxide Pr 2 IV (O 2 )O 3 , which was characterized by single crystal X‐ray diffraction on multi‐grain samples, Raman spectroscopy and quantum theoretical calculations at various pressure points. The presence of tetravalent praseodymium ions is supported by electronic structure calculations, showing a band gap of ca. 1.2 eV, which is consistent with the anticipated chemical model of an ionic solid. Pr 2 (O 2 )O 3 thus far represents the most oxygen rich phase of any binary compound of a lanthanoid and oxygen and is the first example of a peroxide anion next to Pr 4+ . Additionally, these results demonstrate that instead of oxidizing the praseodymium ions past their +IV oxidation state, oxygen undergoes a comproportionation to form peroxide anions. Direct oxidation of the oxide anions by Pr 4+ ‐ions was ruled out by a control experiment in argon instead of oxygen, where no oxidation of oxide ions was observed.

Chemistry↗

DOE OSTI2026

A Bis(arenesulfonyl) Peroxide, an Ambient-Stable Oxidant, Is a Strong p-Dopant for Organic Semiconductors

Strong p-dopants are required to dope high-ionization energy organic semiconductors for a variety of potential applications, but strong, simple one-electron oxidants are typically sensitive to reduction by atmospheric moisture and thus challenging to store or handle. Here we show that bis(3,5-bis(trifluoromethyl)benzenesulfonyl) peroxide─a dimer formed by two highly oxidizing radicals─can function as a water-stable yet powerful oxidant, cleanly reacting with some organic semiconductors to form two radical cations and two 3,5-bis-(trifluoromethyl)benzenesulfonate anions, although in other cases sulfonylation reactions can also occur. Notably, this peroxide is capable of p-doping the high-ionization energy polymer poly[(9,9-dioctylfluorene-2,7-diyl)- alt -(benzo[2,1,3]thiadiazol-4,7-diyl)] (F8BT) to afford electrical conductivities of up to 0.03 S cm –1 , while its use with electron-rich poly(3,4-dialkoxythiophene-2,5-diyl) derivatives can afford values up to 100 S cm –1 . Quantum-chemical calculations reveal the peroxide oxidant behaves in a fashion mirroring that of relatively oxygen-stable, but highly reducing, n-dopants that have been developed based on dimers of organic radicals or organometallic sandwich compounds.

doping↗

DOE OSTI2022

Assembly of Uranyl Peroxides from Ball Milled Solids

Mechanochemistry enables transformations of highly insoluble materials such as uranium dioxide or the mineral studtite [(UO 2 )(O 2 )(H 2 O) 2 ]·(H 2 O) 2 into uranyl triperoxide compounds that can subsequently assemble into hydroxide-bridged uranyl peroxide dimers in the presence of lithium hydroxide. Dissolution of these solids in water yields uranyl peroxide nanoclusters including U 24 , Li 24 [(UO 2 )(O 2 )(OH)] 24 . Insoluble uranium solids can transform into highly soluble uranyl peroxide phases in the solid state with miniscule quantities of water. Furthermore, such reactions are potentially applicable to uranium processing in the front and back end of the nuclear fuel cycle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Detailed Characterization of an Annealed Reduced Graphene Oxide Catalyst for Selective Peroxide Formation Activity

Recently, electrochemical hydrogen peroxide (H 2 O 2 ) generation from oxygen molecules has been extensively studied. Thus far, the best peroxide activity under alkaline conditions has been reported at the surface of a mild reduced graphene oxide annealed at 600 °C (mrGO-600). However, the detailed material information, such as chemical functionality and structural morphology, is unknown, which results in ambiguous debates on its catalytic active sites. Therefore, to solve this problem, we intensively characterize the structure of mrGO-600 to clarify the origin of its catalytic activity. Various characterizations, including X-ray photoelectron spectroscopy, Raman spectroscopy, infrared spectroscopy, near-edge X-ray absorption fine spectroscopy, and high-resolution transmittance electron microscopy coupled with in situ infrared spectroelecrochemistry, reveal that the annealing process generates not only various hole edge defects that are related to the ring ether group but also numerous point defects that result in a small-sized disconnected graphitic carbon region. These defects are believed to form a unique atomic level configuration in mrGO-600, which enables it to facilitate high peroxide-generated activity from oxygen molecules in an alkaline electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1980

Absolute rate constant of the reaction between chlorine /2P/ atoms and hydrogen peroxide from 298 to 424 K

The absolute rate constant of the reaction between chlorine (2P) atoms and hydrogen peroxide was determined from 298 to 424 K, using the discharge flow resonance fluorescence technique. Pseudo-first-order conditions were used with hydrogen peroxide in large excess. A fast flow-sampling procedure limited hydrogen peroxide decomposition to less than 5% over the temperature range studied. At 298 K, the rate constant is (4.1 plus or minus 0.2) x 10 to the minus 13th cu cm/molecule-sec.

Keyser, L. F.↗

NASA NTRS1979

Frost-weathering on Mars - Experimental evidence for peroxide formation

The weathering of silicates by frost is investigated in relation to the formation of surface peroxides to which Viking biology experiment results have been attributed. Samples of the minerals olivine and pyroxene were exposed to water vapor at -11 to -22 C and resultant gas evolution and pH were monitored. Experiments reveal the formation of an acidic oxidant upon interaction of the mineral and H2O frost at subfreezing temperatures, which chemical indicators have suggested to be chemisorbed hydrogen peroxide. A model for the formation of chemisorbed peroxide based on the chemical reduction of the mineral by surface frost is proposed, and it is predicted that the perioxide would decay at high temperatures to H2O and adsorbed O, consistent with the long-term storage and sterilization behavior of the soil oxidants observed in the Viking Gas Exchange and Labeled Release experiments.

Huguenin, R. L.↗

NASA NTRS1981

Chemistry of peroxide compounds

The history of Soviet research from 1866 to 1967 on peroxide compounds is reviewed. This research dealt mainly with peroxide kinetics, reactivity and characteristics, peroxide production processes, and more recently with superoxides and ozonides and emphasis on the higher oxides of group 1 and 2 elements. Solid state fluidized bed synthesis and production of high purity products based on the relative solubilities of the initial, intermediate, and final compounds and elements in liquid ammonia are discussed.

Volnov, I. I.↗

NASA NTRS1956

Simulated afterburner performance with hydrogen peroxide injection for thrust augmentation

Combustion performance of three afterburner configurations was evaluated at simulated altitude flight conditions with liquid augmentation to the primary combustor. Afterburner combustion efficiency and stability were better with injection of high-strength hydrogen peroxide than with no injection or with water injection. Improvements were observed in afterburner configurations with and without flameholders and in a short-length afterburner. At a peroxide-air ratio of 0.3, combustion was stable and 85 to 90 percent efficient in all configurations tested. Calculated augmented net-thrust ratios for peroxide injection with afterburning were approximately 60 percent greater than those for water injection.

Metzler, Allen J↗

NASA NTRS1999

The Peroxide Pathway

NASA's current focus on technology roadmaps as a tool for guiding investment decisions leads naturally to a discussion of NASA's roadmap for peroxide propulsion system development. NASA's new Second Generation Space Transportation System roadmap calls for an integrated Reusable Upper-Stage (RUS) engine technology demonstration in the FY03/FY04 time period. Preceding this integrated demonstration are several years of component developments and subsystem technology demonstrations. NASA and the Air Force took the first steps at developing focused upper stage technologies with the initiation of the Upper Stage Flight Experiment with Orbital Sciences in December 1997. A review of this program's peroxide propulsion development is a useful first step in establishing the peroxide propulsion pathway that could lead to a RUS demonstration in 2004.

McNeal, Curtis I., Jr.↗

NASA NTRS1998

Surface Passivation of CdZnTe Detector by Hydrogen Peroxide Solution Etching

The spectral resolution of room temperature nuclear radiation detectors such as CdZnTe is usually limited by the presence of conducting surface species that increase the surface leakage current. Studies have shown that the leakage current can be reduced by proper surface preparation. In this study, we try to optimize the performance of CdZnTe detector by etching the detector with hydrogen peroxide solution as function of concentration and etching time. The passivation effect that hydrogen peroxide introduces have been investigated by current-voltage (I-V) measurement on both parallel strips and metal-semiconductor-metal configurations. The improvements on the spectral response of Fe-55 and 241Am due to hydrogen peroxide treatment are presented and discussed.

Hayes, M.↗

NASA NTRS2003

Isothermal Microcalorimetric Evaluation of Compatibility of Proposed Injector Materials with High-Test Hydrogen Peroxide Propellant

High-test hydrogen peroxide (HTP) is receiving renewed interest as a monopropellant and as the oxidizer for bipropellant systems. HTP is hydrogen peroxide in concentrations ranging from 70 to 98%. All surfaces wetted by HTP must be evaluated for compatibility with the fluid. In the case of tanks, lines and valves compatibility is required to preserve the HTP oxygen and energy content and to avoid overpressurization due to decomposition. With injectors and regenerative cooling passages shorter exposure time reduces these concerns. However, phase changes from fluid to gas impact heat transfer and become the dominant compatibility concern. Isothermal microcalorimetry (IMC) provides a convenient and reproducible means to observe the decomposition of HTP when exposed to structural materials and therefore the compatibility of those materials'. The instrument provides heat flow values in terms of watts that may be converted to a reaction rate given the heat of reaction for the decomposition of hydrogen peroxide. These values are then converted to percent active oxygen loss per week (%AOL/wk) to preserve an earlier convention for quantifying HTP compatibility. Additionally, qualitative designations of compatibility have been assigned to these values. This scheme consists of four classes with Class 1 being the most compatible. While historical compatibility data is available its current applicability is in question due to subtle changes in the compositions of both HTP and structural materials. Trace levels of molecules can have significant influence on compatibility. Therefore representative samples of materials must be evaluated with current HTP formulations. In this work seven materials were selected for their strength characteristics at high temperature as expected in a HTP injector. The materials were then evaluated by IMC for HTP compatibility.

Gostowski, Rudy↗

NASA NTRS2002

Propulsion Ground Testing with High Test Peroxide: Lessons Learned

Propulsion Ground Testing with High Test Peroxide (85 to 98% concentration) began at the NASA John C. Stennis Space Center in calendar year 1998, when the E3 Test Facility was modified to accomodate hydrogen peroxide (H2O2) in order to suport the research and development testing of the USAF Upper Stage Flight Experiment rocket engine. Since that time, efforts have continued to provide actual and planned test services to various customers, both U.S. Government and Commercial, in the ground test of many test articles, ranging from gas generators, to catalyst beds, to turbomachinery, to main injectors, to combustion chambers, to integrated rocket engines, to integrated stages. Along this path, and over the past 4 years, there has been both the rediscovery of previously learned lessons, through literature search, archive review, and personal interviews, as well as the learning of many new lessons as new areas are explored and new endeavors are tried. This paper will summarize those lessons learned in an effort to broaden the knowledge base as High Test Peroxide is considered more widely for use in rocket propulsion applications.

Bruce, Robert↗

NASA NTRS2000

Ozonation and alkaline-peroxide pretreatment of wheat straw for Cryptococcus curvatus fermentation

Crop residues in an Advanced Life Support System (ALS) contain many valuable components that could be recovered and used. Wheat is 60% inedible, with approximately 90% of the total sugars in the residue cellulose and hemicellulose. To release these sugars requires pretreatment followed by enzymatic hydrolysis. Cryptococcus curvatus, an oleaginous yeast, uses the sugars in cellulose and hemicellulose for growth and production of storage triglycerides. In this investigation, alkaline-peroxide and ozonation pretreatment methods were compared for their efficiency to release glucose and xylose to be used in the cultivation of C. curvatus. Leaching the biomass with water at 65 degrees C for 4 h prior to pretreatment facilitated saccharification. Alkaline-peroxide and ozone pretreatment were almost 100% and 80% saccharification efficient, respectively. The sugars derived from the hydrolysis of alkaline-peroxide-treated wheat straw supported the growth of C. curvatus and the production of edible single-cell oil.

Non-NASA Center↗

NASA NTRS1999

Hydrogen peroxide on the surface of Europa

Spatially resolved infrared and ultraviolet wavelength spectra of Europa's leading, anti-jovian quadrant observed from the Galileo spacecraft show absorption features resulting from hydrogen peroxide. Comparisons with laboratory measurements indicate surface hydrogen peroxide concentrations of about 0.13 percent, by number, relative to water ice. The inferred abundance is consistent with radiolytic production of hydrogen peroxide by intense energetic particle bombardment and demonstrates that Europa's surface chemistry is dominated by radiolysis.

Non-programmatic↗

NASA NTRS2004

High Temperature Decomposition of Hydrogen Peroxide

Nitric oxide (NO) is oxidized into nitrogen dioxide (NO2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydropemxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

Clyde F. Parrish↗