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At least 109 records · Page 6

Conversion of Uranium Metal to Uranyl Sulfate Solution

Experiments involving conversion of uranium (U) metal to U 3 O 8 , followed by dissolution to form uranyl sulfate solution, were performed with batches of up to 300 g of U metal. The focus was to identify major U species formed during the oxidation process, determine the particle size distribution of the uranium oxide product, and identify the size of the dissolution vessel needed to accommodate the exothermic reaction during the conversion of U 3 O 8 to uranyl sulfate using 30% hydrogen peroxide and H 2 SO 4 . The information obtained in this study will be used for designing full-scale processes to convert kilogram quantities of U metal to uranyl sulfate solution with a concentration of 300 g U/L.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Emission control system

Methods and apparatus utilizing hydrogen peroxide are useful to reduce SOx and mercury (or other heavy metal) emissions from combustion flue gas streams. The methods and apparatus may further be modified to reduce NOx emissions. Continuous concentration of hydrogen peroxide to levels approaching or exceeding propellant-grade hydrogen peroxide facilitates increased system efficiency. In this manner, combustion flue gas streams can be treated for the removal of SOx and heavy metals, while isolating useful by-products streams of sulfuric acid as well as solids for the recovery of the heavy metals. Where removal of NOx emissions is included, nitric acid may also be isolated for use in fertilizer or other industrial applications.

Parrish, Clyde F.↗

Corrosion of 347 stainless steel in the presence of uranyl sulfate solution and radiation

The U.S. molybdenum 99 (Mo-99) industry is pursuing production of fission-made Mo-99 using a uranium solution such as uranyl sulfate. In this process, uranyl sulfate solution containing low-enriched uranium will be bombarded by neutrons creating Mo-99 and other fission products. During the production, the uranyl sulfate solution will be irradiated until an acceptable activity level of Mo-99 is produced. The uranyl sulfate solution containing Mo-99 and other fission products will then undergo a series of separation steps. First, uranyl sulfate can be separated from Mo-99 using a primary titania column to recover Mo-99, with the uranyl sulfate solution to be used for another irradiation cycle. Then, raffinate from a primary titania column containing Mo-99 can be concentrated and purified using a LEU modified Cintichem process developed by Argonne National Laboratory. During irradiation, the temperature of the uranyl sulfate solution can reach near boiling (up to ~80° C assumed), causing radiolysis of water and the resultant formation of hydrogen peroxide. Because high-radiation fields will be present during each irradiation cycle, it is important to determine the corrosion rates of SS-347 under such conditions to estimate the life cycle of the target solution vessel. The buildup of corrosion products from the SS components in the uranyl sulfate solution also needs to be well understood because potential accumulation of iron, nickel, and other corrosion products may affect the Mo-99 recovery and purification process. To study the corrosion rates of SS-347 material under conditions relevant to future Mo-99 production facility, SS-347 coupons in uranyl sulfate solution at ~80° C were irradiated using Argonne’s Van de Graaff generator, which can generate high-radiation fields without fissioning of uranium or production of activation products.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Emission control system

Methods and apparatus utilizing hydrogen peroxide are useful to reduce NOx, SOx and mercury (or other heavy metal) emissions from combustion flue gas streams. Continuous concentration of hydrogen peroxide to levels approaching or exceeding propellant-grade hydrogen peroxide facilitates increased system efficiency. In this manner, combustion flue gas streams can be treated for the removal of NOx, SOx and heavy metals, while isolating useful by-products streams of sulfuric acid and nitric acid as well as solids for the recovery of the heavy metals.

Parrish, Clyde F.↗

Carbon nanospikes have improved sensitivity and antifouling properties for adenosine, hydrogen peroxide, and histamine

Carbon nanospikes (CNSs) are a new nanomaterial that has enhanced surface roughness and surface oxide concentration, increasing the sensitivity for dopamine detection. However, CNS-modified electrodes (CNSMEs) have not been characterized for other neurochemicals, particularly those with higher oxidation potentials. The purpose of this study was to evaluate CNSMEs for the detection of adenosine, hydrogen peroxide (H 2 O 2 ), and histamine. The sensitivity increased with CNSs, and signals at CNSMEs were about 3.3 times higher than CFMEs. Normalizing for surface area differences using background currents, CNSMEs show an increased signal of 4.8 times for adenosine, 1.5 times for H 2 O 2 , and 2 times for histamine. CNSMEs promoted the formation of secondary products for adenosine and histamine, which enables differentiation from other analytes with similar oxidation potentials. Furthermore, CNSs also selectively enhance the sensitivity for adenosine and histamine compared to H 2 O 2 . A scan rate test reveals that adenosine is more adsorption-controlled at CNS electrodes than CFMEs. CNSMEs are antifouling for histamine, with less fouling because the polymers formed after histamine electrooxidation do not adsorb due to an elevated number of edge planes. CNSMEs were useful for detecting each analyte applied in brain slices. Because of the hydrophilic surface compared to CFMEs, CNSMEs also have reduced biofouling when used in tissue. Therefore, CNSMEs are useful for tissue measurements of adenosine, hydrogen peroxide, and histamine with high selectivity and low fouling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cumene-to-Phenol Process Mediated by Bromine Radicals through Photoinduced Ligand-to-Metal Charge Transfer

Selective C–H activation via hydrogen atom transfer (HAT) has gained significant interest recently. One industrial application for HAT can be found in the tertiary benzylic C–H bond of cumene for producing phenol, a versatile chemical feedstock for various industries. However, the overall phenol yield remains low using the existing Hock process due to the poor selectivity towards the key reaction intermediate, cumene hydroperoxide (CHP). Here, in this work, we demonstrate an efficient strategy for phenol production through photooxidation of cumene to CHP using iron bromide under blue light irradiation, where bromine radicals (generated in situ via ligand-to-metal charge transfer) are used as hydrogen atom abstractors. Mechanistic studies revealed the cumene-to-CHP conversion occurred via a tertiary C–H bond abstraction by a radical mechanism, and the acetic acid and water additives increased CHP selectivity through stabilizing peroxides. The cumene-phenol process achieved up to 88% yield of CHP in 1 hour and could be used with a wide range of substrates. We thus developed a selective, mild, and efficient phenol production method using iron bromide under photooxidative conditions.

HAT↗

Catalase protects against nonenzymatic decarboxylations during photorespiration in Arabidopsis thaliana

Abstract Photorespiration recovers carbon that would be otherwise lost following the oxygenation reaction of rubisco and production of glycolate. Photorespiration is essential in plants and recycles glycolate into usable metabolic products through reactions spanning the chloroplast, mitochondrion, and peroxisome. Catalase in peroxisomes plays an important role in this process by disproportionating H 2 O 2 resulting from glycolate oxidation into O 2 and water. We hypothesize that catalase in the peroxisome also protects against nonenzymatic decarboxylations between hydrogen peroxide and photorespiratory intermediates (glyoxylate and/or hydroxypyruvate). We test this hypothesis by detailed gas exchange and biochemical analysis of Arabidopsis thaliana mutants lacking peroxisomal catalase. Our results strongly support this hypothesis, with catalase mutants showing gas exchange evidence for an increased stoichiometry of CO 2 release from photorespiration, specifically an increase in the CO 2 compensation point, a photorespiratory‐dependent decrease in the quantum efficiency of CO 2 assimilation, increase in the 12 CO 2 released in a 13 CO 2 background, and an increase in the postillumination CO 2 burst. Further metabolic evidence suggests this excess CO 2 release occurred via the nonenzymatic decarboxylation of hydroxypyruvate. Specifically, the catalase mutant showed an accumulation of photorespiratory intermediates during a transient increase in rubisco oxygenation consistent with this hypothesis. Additionally, end products of alternative hypotheses explaining this excess release were similar between wild type and catalase mutants. Furthermore, the calculated rate of hydroxypyruvate decarboxylation in catalase mutant is much higher than that of glyoxylate decarboxylation. This work provides evidence that these nonenzymatic decarboxylation reactions, predominately hydroxypyruvate decarboxylation, can occur in vivo when photorespiratory metabolism is genetically disrupted.

59 BASIC BIOLOGICAL SCIENCES↗

More About N2O-Based Propulsion and Breathable-Gas Systems

A concept was evaluated of using nitrous oxide as (1) a monopropellant in thrusters for space suits and spacecraft and (2) a source of breathable gas inside space suits and spacecraft, both by exploiting the controlled decomposition of N2O into N2 and O2. Relative to one prior monopropellant hydrazine, N2O is much less toxic, yet offers comparable performance. N2O can be stored safely as a liquid at room temperature and unlike another prior monopropellant hydrogen peroxide does not decompose spontaneously. A prototype N2O-based thruster has been demonstrated. It has also been proposed to harness N2O-based thrusters for generating electric power and to use the N2 + O2 decomposition product as a breathable gas. Because of the high performance, safety, and ease of handling of N2O, it can be expected to be economically attractive to equip future spacecraft and space suits with N2O-based thrusters and breathable-gas systems.

Zubrin, Robert↗

Removal of Tc-99, Zr-95, and Nb-95, From Solutions Obtained After Dissolution of Irradiated Mo Targets

Decontamination of 99 Tc, Nb, and Zr impurities in dissolved irradiated Mo disks can be accomplished using Fe(II) precipitation. Here, we report bench-scale experiments and large-scale demonstrations on removal of 99 Tc (0.1 mM), 95 Nb, and 95 Zr from dissolved Mo disk simulant solutions. Tc removal is accomplished through the reduction and simultaneous immobilization of Tc(VII) by Fe(II), producing an insoluble, Tcincorporated Fe(II)-Fe(III) solid that is removed by filtration. Large-scale testing showed that Tc (97.6% ± 1.7%) is removed without affecting 99 Mo yields. Other important side reaction product impurities in irradiated Mo targets, namely various isotopes of Nb and Zr, are also removed (>99%) in this process. The effects of metal (Fe, Tc, Mo) concentrations, Fe(II)/Fe(III) ratio, pH, temperature, Fe addition method, and hydrogen peroxide addition were tested. The minimum amount of Fe(II) needed to remove up to 99% Tc is 10 mM and the optimal pH value for simultaneous removal of Tc, Nb, and Zr impurities is pH 13.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Studying Interfacial Dark Reactions of Glyoxal and Hydrogen Peroxide Using Vacuum Ultraviolet Single Photon Ionization Mass Spectrometry

Aqueous secondary organic aerosol (aqSOA) formation from volatile and semivolatile organic compounds at the air–liquid interface is considered as an important source of fine particles in the atmosphere. However, due to the lack of in situ detecting techniques, the detailed interfacial reaction mechanism and dynamics still remain uncertain. In this study, synchrotron-based vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) was coupled with the System for Analysis at the Liquid Vacuum Interface (SALVI) to investigate glyoxal dark oxidation products at the aqueous surface. Mass spectral analysis and determination of appearance energies (AEs) suggest that the main products of glyoxal dark interfacial aging are carboxylic acid related oligomers. Furthermore, the VUV SPI-MS results were compared and validated against those of in situ liquid time-of-flight secondary ion mass spectrometry (ToF-SIMS). The reaction mechanisms of the dark glyoxal interfacial oxidation, obtained using two different approaches, indicate that differences in ionization and instrument operation principles could contribute to their abilities to detect different oligomers. Therefore, the mechanistic differences revealed between the VUV SPI-MS and ToF-SIMS indicate that more in situ and real-time techniques are needed to investigate the contribution of the air–liquid interfacial reactions leading to aqSOA formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pendent Relay Enhances H 2 O 2 Selectivity during Dioxygen Reduction Mediated by Bipyridine-Based Co–N 2 O 2 Complexes

Generally, cobalt–N 2 O 2 complexes show selectivity for hydrogen peroxide during electrochemical dioxygen (O 2 ) reduction. We recently reported a Co(III)–N 2 O 2 complex with a 2,2'-bipyridine-based ligand backbone which showed alternative selectivity: H 2 O was observed as the primary reduction product from O 2 (71 ± 5%) with decamethylferrocene as a chemical reductant and acetic acid as a proton donor in methanol solution. We hypothesized that the key selectivity difference in this case arises in part from increased favorability of protonation at the distal O position of the key intermediate Co(III)–hydroperoxide species. To interrogate this hypothesis, in this study we have prepared a new Co(III) compound that contains pendent –OMe groups poised to direct protonation toward the proximal O atom of this hydroperoxo intermediate. Mechanistic studies in acetonitrile (MeCN) solution reveal two regimes are possible in the catalytic response, dependent on added acid strength and the presence of the pendent proton donor relay. In the presence of stronger acids, the activity of the complex containing pendent relays becomes O 2 dependent, implying a shift to Co(III)–superoxide protonation as the rate-determining step. Interestingly, the inclusion of the relay results in primarily H 2 O 2 production in MeCN, despite minimal difference between the standard reduction potentials of the three complexes tested. EPR spectroscopic studies indicate the formation of Co(III)–superoxide species in the presence of exogenous base, with greater O 2 reactivity observed in the presence of the pendent –OMe groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Ti‐incorporated Zeolite Topology and Pore Condensation on Vapor Phase Propylene Epoxidation Kinetics with Gaseous H 2 O 2

Abstract Vapor‐phase propylene (C 3 H 6 ) epoxidation kinetics with hydrogen peroxide (H 2 O 2 ) strongly reflects the physical properties of Ti‐incorporated zeolite catalysts and the presence of spectating molecules (“solvent”) near active sites even without a bulk liquid phase. Steady‐state turnover rates of C 3 H 6 epoxidation and product selectivities vary by orders of magnitudes, depending on the zeolite silanol ((SiOH) x ) density, pore topology (MFI, *BEA, FAU), and the quantity of condensed acetonitrile (CH 3 CN) molecules nearby active sites, under identical reaction mechanisms sharing activated H 2 O 2 intermediates on Ti surfaces. Individual kinetic analyses for propylene oxide (PO) ring‐opening, homogeneous diol oxidative cleavage, and homogeneous aldehyde oxidation reveal that secondary reaction kinetics following C 3 H 6 epoxidation responds more sensitively to the changes in zeolite physical properties and pore condensation with CH 3 CN. Thus, higher PO selectivities achieved in hydrophilic Ti‐MFI at steady‐state reflect the preferential stabilization of transition states for C 3 H 6 epoxidation (a primary reaction) relative to PO ring‐opening and oxidative cleavage (secondary reactions) that solvation effects that reflect interactions among condensed CH 3 CN within pores and the extended pore structure.

Kwon, Ohsung↗

Collaborative Research Proposal: Time Resolved Optical Emissions Spectroscopy and Laser Induced Fluorescence Spectroscopy of Nanosecond Pulsed Discharges in a Gas-Liquid Water Film Reactor

Electrical discharge plasma formed in contact with liquid water is of interest for a wide range of applications in chemical, biomedical, agricultural, electrical, and materials science and engineering. Such plasma reactors are of very timely importance since they also have significant disinfection capability by inactivating bacteria, viruses and other pathogens. Many types of plasma sources including those driven by AC, DC, RF, microwave, and pulsed electrical power supplies coupled to a wide range of different electrode configurations and reactor designs have been developed and explored which contact the plasma with liquid water. Recent roadmaps have recommended that further work is needed to develop our understanding of the fundamental chemical and physical process which occur at the interface of non-thermal plasma with liquid water solutions in order to advance this large diversity of applications which ultimately depend upon efficient production of key reactive chemical species. There is a wide range of interacting factors that affect the chemical reactions that occur in the plasma, in the liquid phase, and at the interface. These factors ultimately govern the key reactive chemical species formed and used in the various applications and they include a) the reactor design and input parameters, b) the discharge and transport processes, c) the plasma properties, and d) the resulting chemical reactions. For pulsed discharges, the power supply design and output parameters control the applied voltage, frequency, rise time, and width (duration) of the applied pulses. The reactor design involves specification of the gas-liquid contacting methods, electrode gap distance, reactor volume and shape, and gas and liquid flow rates achievable. The gas and liquid compositions as well as the liquid properties such as pH and conductivity are also of key importance in determination of the resulting chemical reactions. In addition, the important plasma properties include plasma gas temperature, electron density, electron energy (distribution), and size of the plasma channels which are all affected by the discharge and transport properties. Many studies have focused on specific aspects of these various processes. Of particular important and relevance to the proposed work is the utilization of nanosecond pulses to generate plasma in gas-liquid systems, liquid bubbles, underwater, and in gases. Recent advances in nanosecond pulses provide significant advantages in utilization with liquid water. For example, fast rise time and short pulses are less sensitive to water conductivity, such short pulses may provide advantages in fast temporal quenching of the plasma, and fundamental analysis of pulse properties, including pulse shape and width, may be facilitated by investigation of single filamentary fast pulses. Many studies have also dealt with the role of the gas composition on formation of reactive oxygen species (ROS) (i.e., hydroxyl radicals – ·OH, hydrogen peroxide – H 2 O 2 , various atomic oxygen species, ozone-O 3 , hydroperoxyl radicals HO 2 ·) and reactive nitrogen species (RNS) (i.e., nitrogen oxides – NO, NO 2 , N 2 O - collectively termed NO X , nitrite-NO 2 - , nitrate-NO 3 - , peroxynitrite-ONOO - ). The hydroxyl radical is the critical species in many chemical oxidation reactions for chemical degradation of toxic compounds in water and gases and for synthesis of some compounds. The mixture of various nitrogen oxide species is important for many biochemical and biological processes involved in biomedical and agricultural applications including disinfection and fertilizer production. The present proposal focuses on determination of the effects of time resolved electron density and hydroxyl radicals on plasma chemical reactions through collaboration with the Princeton Collaborative Low Temperature Plasma Research Facility (PCRF) at the Princeton Plasma Physics Laboratory (PPPL). In order to further investigate the role of the plasma generated electrons and hydroxyl radicals on the overall formation of the key species including hydrogen peroxide, hydroxyl radicals, and nitrogen oxides, the proposed work, thus seeks to determine high resolution time resolved electron density by optical emissions spectroscopy and time resolved hydroxyl radicals using laser induced fluorescence in the nanosecond discharge reactor. The combination of data on electron density and hydroxyl radical concentration will be utilized in the present work to more fully characterize the chemical reaction processes in this system and to advance the design, development, and operation of such chemical reactors for a wide range of applications.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Influence of Ti‐incorporated Zeolite Topology and Pore Condensation on Vapor Phase Propylene Epoxidation Kinetics with Gaseous H 2 O 2

Vapor-phase propylene (C 3 H 6 ) epoxidation kinetics with hydrogen peroxide (H 2 O 2 ) strongly reflects the physical properties of Ti-incorporated zeolite catalysts and the presence of spectating molecules (“solvent”) near active sites even without a bulk liquid phase. Steady-state turnover rates of C 3 H 6 epoxidation and product selectivities vary by orders of magnitudes, depending on the zeolite silanol ((SiOH) x ) density, pore topology (MFI, *BEA, FAU), and the quantity of condensed acetonitrile (CH 3 CN) molecules nearby active sites, under identical reaction mechanisms sharing activated H 2 O 2 intermediates on Ti surfaces. Individual kinetic analyses for propylene oxide (PO) ring-opening, homogeneous diol oxidative cleavage, and homogeneous aldehyde oxidation reveal that secondary reaction kinetics following C 3 H 6 epoxidation responds more sensitively to the changes in zeolite physical properties and pore condensation with CH 3 CN. Thus, higher PO selectivities achieved in hydrophilic Ti-MFI at steady-state reflect the preferential stabilization of transition states for C 3 H 6 epoxidation (a primary reaction) relative to PO ring-opening and oxidative cleavage (secondary reactions) that solvation effects that reflect interactions among condensed CH 3 CN within pores and the extended pore structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Innovative techniques for the production of energetic radicals for lunar materials processing including photogeneration via concentrated solar energy

The Department of Materials Science and Engineering (MSE) is investigating the use of monatomic chlorine produced in a cold plasma to recover oxygen and metallurgically significant metals from lunar materials. Development of techniques for the production of the chlorine radical (and other energetic radicals for these processes) using local planetary resources is a key step for a successful approach. It was demonstrated terrestrially that the use of UV light to energize the photogeneration of OH radicals from ozone or hydrogen peroxide in aqueous solutions can lead to rapid reaction rates for the breakdown of toxic organic compounds in water. A key question is how to use the expanded solar resource at the lunar surface to generate process-useful radicals. This project is aimed at investigating that question.

Osborn, D. E.↗

Economical methods for performing oxidative catalytic pretreatment of plant biomass using a single-stage two oxidant process

An improved alkaline pretreatment of biomass is provided that is a single-stage, two oxidant alkaline oxidative pretreatment process. The process uses a homogenous catalyst with at least two oxidants (Hydrogen peroxide and enhanced levels of oxygen) in an alkaline environment to catalytically pretreat lignocellulosic biomass in a single-stage oxidation reaction. The provided single-stage alkaline-oxidative pretreatment improves biomass pretreatment and increase enzymatic digestibility to improve the economic feasibility of production of lignocellulose derived sugars.

Hegg, Eric L.↗

Chelator-mediated Fenton post-treatment enhances methane yield from lignocellulosic residues via microbial community modulation

Advancing biomethane production from anaerobic digestion (AD) is essential for building a more reliable and resilient bioenergy system. However, incomplete conversion of lignocellulose-rich agricultural waste remains a key limitation, often leaving energy-dense residues in the digestate by-product. In this study, we introduce a novel application of chelator-mediated Fenton (CMF) post-treatment to recover untapped biomethane potential from these recalcitrant residues, representing a significant departure from conventional pre-treatment strategies. By systematically varying pH, iron-chelator concentration, and hydrogen peroxide dosage, we identified reaction conditions (pH 6–8, 5 mM Fe 2+ -dihydroxybenzene, 3–4 wt.% H 2 O 2 ) that enhanced lignocellulose deconstruction and increased dissolved organic carbon (DOC) availability for methanogenesis. CMF post-treatment led to up to a tenfold increase in biomethane potential compared to untreated controls. Microbial community analysis revealed enrichment of cellulolytic species, suggesting enhanced hydrolytic activity as a driver of improved conversion. Application of the CMF post-treatment method to isolated poplar lignin further demonstrated its versatility for diverse lignocellulosic substrates. These findings position CMF post-treatment as a promising strategy to enhance AD efficiency and valorize digestate.

Martinez, Daniella Victoria [Sandia National Labor↗