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Storage device is applicable in memory systems and in high-resolution arrays for light-responsive image sensing. The device offers high yield in multiple arrays and allows charge release with light striking only the edge of a metal electrode.
Certain metals and related alloys can combine with hydrogen in a reversible fashion, so that on being heated, they release a portion of the gas. Such materials may find application in the large scale storage of hydrogen. Metal and alloys which show high dissociation pressure at low temperatures, and low endothermic heat of dissociation, and are therefore desirable for hydrogen storage, give values of the Hildebrand-Scott solubility parameter that lie between 100-118 Hildebrands, (Ref. 1), close to that of dissociated hydrogen. All of the less practical storage systems give much lower values of the solubility parameter. By using the Hildebrand solubility parameter as a criterion, and applying the mixing rule to combinations of known alloys and solid solutions, correlations are made to optimize alloy compositions and maximize hydrogen storage capacity.
The abundance and isotopic composition of Hg was determined in bulk samples of both the Murchison (CM) and Allende (CV) carbonaceous chondrites using single- and multi-collector inductively coupled plasma mass spectrometry (ICP-MS). The bulk abundances of Hg are 294 6 15 ng/g in Murchison and 30.0 6 1.5 ng/g in Allende. These values are within the range of previous measurements of bulk Hg abundances by neutron activation analysis (NAA). Prior studies suggested that both meteorites contain isotopically anomalous Hg, with d l 96/202Hg values for the anomalous, thermal-release components from bulk samples ranging from 2260 %o to 1440 9/00 in Murchison and from 2620 9/00 to 1540 9/00 in Allende (Jovanovic and Reed, 1976a; 1976b; Kumar and Goel, 1992). Our multi-collector ICP-MS measurements suggest that the relative abundances of all seven stable Hg isotopes in both meteorites are identical to terrestrial values within 0.2 to 0.5 9/00m. On-line thermal-release experiments were performed by coupling a programmable oven with the singlecollector ICP-MS. Powdered aliquots of each meteorite were linearly heated from room temperature to 900 C over twenty-five minutes under an Ar atmosphere to measure the isotopic composition of Hg released fiom the meteorites as a h c t i o n of temperature. In separate experiments, the release profiles of S and Se were determined simultaneously with Hg to constrain the Hg distribution within the meteorites and to evaluate the possibility of Se interferences in previous NAA studies. The Hg-release patterns differ between Allende and Murchison. The Hg-release profile for Allende contains two distinct peaks, at 225" and 343"C, whereas the profile for Murchison has only one peak, at 344 C. No isotopically anomalous Hg was detected in the thermal-release experiments at a precision level of 5 to 30 9/00, depending on the isotope ratio. In both meteorites the Hg peak at ;340"C correlates with a peak in the S-release profile. This correlation suggests that Hg is associated with S-bearing phases and, thus, that HgS is a major Hg-bearing phase in both meteorites. The Hg peak at 225 C for Allende is similar to release patterns of physically adsorbed Hg on silicate and metal grains.
We demonstrate that atomic-scale surface disorder can control the first-cycle redox sequence of Li-rich layered oxides, eliminating the detrimental process of oxygen release and lattice collapse that degrades performance. In Li1.14Ni0.32Mn0.54O2 (LNMO), a simple chemical treatment introduces oxygen and transition metal (TM) vacancies confined to the particle surface while preserving the bulk layered framework. Multi-modal synchrotron analyses reveal that these vacancies trigger an early oxygen oxidation below 4.4 V, delay nickel oxidation to higher potential, and suppress the formation of covalent Ni4+─O states. This modified pathway prevents irreversible oxygen release, suppresses manganese dissolution, and maintains metal-oxygen coordination at high voltages. Consequently, the treated cathode delivers higher first-cycle Coulombic efficiency (CE), mitigated voltage fade, and superior capacity retention. By directly linking engineered surface disorder to redox reactions and associated structural transformations, this work establishes a general design principle for durable, high-energy-density cathodes.
Global Nuclear Fuel – Americas LLC (GNF) has partnered with Argonne National Laboratory to demonstrate electroreduction of uranium oxides produced by deconversion of UF 6 to uranium metal through the Gateway for Accelerated Innovation in Nuclear (GAIN) program under the U.S. Department of Energy to accelerate the domestic production of metallic advanced reactor fuels. Electroreduction of uranium oxide was first demonstrated and patented by Argonne in the early 2000s as a technology to convert used oxide nuclear fuel from light water reactors to metal for further fuel reprocessing. More recently, electroreduction has been proposed as a front-end technology for metallization of uranium oxides produced by deconversion of UF 6 and for scrap recovery of oxide materials. During the electroreduction process, UO 2 powder is contained in a stainless-steel mesh basket with a cathode lead located in the center of the UO 2 bed. The basket is immersed in lithium chloride molten salt electrolyte containing 1 wt% lithium oxide along with a platinum anode and a nickel/nickel oxide (Ni/NiO) reference electrode. Current is applied to the cell between the cathode and anode to reduce the UO 2 to metallic uranium via a solid-state reduction reaction. Oxide ions released from the UO 2 during reduction are transported through the salt to the anode where oxygen gas is evolved. Once reduction is complete, the basket containing the metallicized uranium is removed from the salt and can be processed to remove the salt and consolidate the uranium into an ingot for use in metallic fuel fabrication. This project was performed to provide evidence of the electroreduction technology readiness level for metallization of UO 2 powder, identify and retire technical risks for industrialization of electroreduction, and accelerate the path to commercialization for metallic fast reactor fuel production. To that end, five electroreduction tests were performed with UO 2 provided by GNF and the resulting product was analyzed for the extent of conversion to metal and for impurity contents of the metal product to verify that electroreduction does not introduce impurities that would prevent use of the product in metallic fuel fabrication.
Polyvinyl chloride (PVC) is ubiquitous yet challenging to recycle due to its tendency to thermally decompose above 250 °C, releasing toxic, corrosive chlorinated compounds, and its inability to melt. Here, we report a catalytic strategy for PVC upcycling at 160 °C using gallium liquid metal particles (Ga-LMP) featuring a dynamic Ga-GaOOH core–shell architecture. These catalysts enable concurrent dechlorination and hydrogen evolution, yielding up to 7% H2 (based on initial hydrogen atoms in PVC) along with a highly dechlorinated (>95%) carbonaceous solid and aqueous HCl. Mechanistic investigations combining X-ray photoelectron spectroscopy, infrared spectroscopy, solid-state NMR, inelastic neutron scattering, and ab initio molecular dynamics reveal a synergistic interplay between Gaδ+ sites in the GaOOH shell and metallic Ga0 in the core. Cationic Ga initiates C–Cl bond activation and HCl formation, while progressive reduction of the shell exposes Ga0 sites that promote C–H activation and H2 evolution. Control experiments with a Ga salt and bulk Ga liquid metal confirmed that neither oxidation state alone can achieve both transformations efficiently. This work establishes a dynamic dual-site paradigm for liquid metal catalysis, in which the in situ evolution and coexistence of oxidized and metallic species enable sequential and cooperative bond activation pathways. These findings provide a general design principle for novel liquid metal catalysts that target challenging polymer transformations under mild conditions.
The effects of surface preparation and gas flow on the recombination of nitrogen atoms at copper and platinum surfaces were determined. Atoms were generated by an electrodeless 2450-megacycle-per-second discharge, and their concentration was measured by gas-phase titration with nitric oxide. Test surfaces were either vacuum-evaporated films or spheres machined from bulk metal and cemented around small glass-bead thermistors. Heat released by recombination was measured as the difference in electrical energy required to maintain a given thermistor temperature with and without a catalytic surface exposed. Recombination coefficients measured at flow velocities of 1120, 1790, 2250, and 3460 centimeters per second and at pressures of 0.42 and 0.59 millimeter of mercury showed that flow conditions had no effect. The results were also independent of atom concentration. A rough indication of the temperature dependence was obtained; it was greater for copper than for platinum. Platinum films deposited on platinum or on glass had the same activity - about 3 percent of the atoms impinging recombined. With copper, however, the glass substrate greatly reduced the percent of atoms recombining over that of a bulk copper substrate where 4 percent of the impinging atoms recombined. This effect could be overcome by depositing a second film on top of the first. Bulk metal samples were subjected to various surface treatments including polishing, degreasing with a chlorinated hydrocarbon, washing with nitric acid, and rinsing with water. Polished, degreased platinum had low activity compared to an evaporated film, but nitric acid treatment made it equivalent. Polished, degreased copper was only slightly less active than a copper film; nitric acid etching decreased the activity still further, probably by preferentially exposing facets of low catalytic efficiency.
Natural aquatic systems undergo fluctuating redox conditions due to microbial activity, varying water saturation levels, and nutrients dynamics. With fluctuating redox conditions, trace metals can mobilize or sequester in response to changes in iron and sulfur speciation and the concentrations and lability of organic carbon. This study examined the effect of redox fluctuations on trace metal mobility in samples collected from two different natural aquatic systems: riparian wetlands and a stream. The wetland soils contained low sulfur and total Fe contents as compared to stream sediments. The mineral composition at both sites was dominated by quartz. We incubated water-saturated soils under three cycles of anoxic-oxic conditions (τanoxic:τoxic = 3) spanning 24 days and monitored the change in dissolved and bioavailable metal concentrations. For both natural systems, reduction of iron oxides under anoxic conditions caused Co and Zn release. In contrast, oxidation of sulfides mobilized Cu under oxic conditions in both sites. In wetland soils, dissolution of Fe (hydr)oxides increased Ni solubility; however, in stream sediments, Ni release occurred when sulfides or organic matter were oxidized. For stream sediments, each subsequent redox cycle increased the bioavailability of trace metals. Redox fluctuations in wetland soils increased bioavailable Zn and Cu and decreased bioavailable Ni and Co. This study illustrates that different trace metals display distinct bioavailability patterns during redox fluctuations in natural environments. The biogeochemical cycling of nutrients in systems with redox fluctuations may be influenced by these trace metal availability patterns in addition to the availability of electron donors and acceptors.
Lithiated transition metal oxide cathode materials that combine oxygen-anion redox [O 2 – /(O 2 ) n– ] with cation redox offer substantial capacities and higher voltage than cathodes without oxygen redox, but oxygen-anion redox is usually accompanied by the formation of peroxo or superoxo species that may cause oxygen release. To clarify the relationship between the oxygen release and peroxide and superoxide dimers without the complication of transition-metal redox, we performed density functional theory calculations to study the layered Li 8 SnO 6 cathode because it has only oxygen-anion redox during delithiation. Features with O–O distances of ~1.5 Å (corresponding to the formation of a peroxide) were observed at 75% lithium concentration, and further delithiation to 62.5% lithium concentration shortened the O–O bond distance to ~1.3 Å (corresponding to the formation of superoxide). The solely anionic oxygen redox stabilizes the delithiated structure of Li 8–x SnO 6 , and it does not cause structural disorder or release oxygen gas. Ab initio molecular dynamics calculations in the supercell at 300 K indicate that oxygen dimerization may occur at 75% lithium concentration. On the (0001) surface with a high lithium concentration (98%), oxygen dimerization is unfavorable. The calculations by HSE06 show that oxygen redox in Li 8 SnO 6 offers an initial voltage (vs Li/Li + ) greater than 4.2 V. The GGA+U calculations indicate that the Li + -polaron in Li 95 Sn 12 O 72 migrates with a migration barrier of only 0.43 eV. Here, this work also quantifies a solely anionic oxygen redox mechanism in Li 8 SnO 6 , and it provides a deeper understanding of anionic oxygen redox in Li-excess oxide cathode materials.
ThorCon is developing a thermal thorium / uranium molten salt fueled reactor that uses a fuel salt consisting of NaF - BeF 2 - ThF 4 - UF 4 - UF 3 , which uses 19.75% enriched uranium. It is not a breeder reactor but requires regular additions of fissile material. On-site fuel processing is limited to adding make-up fuel, and adding beryllium to maintain redox balance in the fuel salt. The fluoride salt is an excellent flux that will strip the protective oxygen away from all metal surfaces it contacts. In order to protect the metal surfaces in the primary loop, no free fluorine is allowed. Maintaining a ratio of UF 4 to UF 3 provides a chemical buffer that can absorb any free fluorine released during the fission process before it can harm the structure. Periodic additions of metallic beryllium to the fuel salt will react with UF 4 to form BeF 2 and UF 3 , which will maintain the desired UF 4 /UF 3 ratio. A means to measure the UF 4 /UF 3 ratio is important to maintain the fuel salt in a non-corrosive state and could also provide additional insight into the corrosion behavior and chemical constitution of the system. A promising measurement technique is based on electrochemistry.
This presentation contains a review of fast reactor metal fuel phenomena, fuel failure mechanisms, and associated design parameters followed by discussion of which design parameters were a consideration for VTR fuel. The technology is all found in previously released and published sources, though the perspective on what it means for design of metal fuel for advanced reactor designs is new. The content related to VTR fuel does not include design details that were previously determined to be export controlled, and any previous pre-decisional aspects that might be implied are not relevant today, given that the VTR project was not funded.
We are in the process of archiving the approximately 1.2Tbytes of imaging data acquired in support of UIT observations. The UIT is one of three telescopes comprising the ASTRO spacecraft and is a 38-cm f/9 Ritchey-Chretien telescope with wavelength coverage 1200 A to 3000 A and a 40 arcminute diameter field-of-view at 4 min FWHM resolution. During the ASTRO shuttle mission, there were 65 different pointings (some with multiple targets) of the UIT and hence 65 fields. Our support data of these fields were obtained with the KPNO and CTIO 0.9m telescopes and several of the 2048x2048 CCD's. Our images are typically about 20 acrminutes on a side and contain the entire UV target except for nearby galaxies, for which mosaiced images were created. All good quality images in the broadband and narrow band filters for every target are being archived. Though all of the UIT targets were well studied astronomical objects, these frames are many of the first large field format images of them and, when combined with the soon to be released UV frames, provide a unique dataset. These data were already used to address a wide variety of astronomical questions. Vacuum ultraviolet (VUV) observations were used to study star formation in a sample of nearby galaxies, since integrated VUV - optical colors provide the most sensitive available measure of the formation rate of massive stars. The blue stages later in stellar evolution are also being studied. These data allow more accurate determination of the helium and metallicities of hothorzontal branch stars. These data are being prepared to release to the public in CD-ROM format through the National Space Science Data Center.
Metal–organic frameworks are promising materials for many biomedical technologies due to their ability to store and release large quantities of guest molecules in a predictable and tunable fashion. In biological fluids, proteins readily adsorb to the external surfaces of metal–organic framework particles through a combination of hydrophobic and electrostatic interactions. However, much remains to be understood about the nature of these protein coatings and how they influence the bulk properties of aqueous dispersions of metal–organic frameworks. Here, in this work, we show that a variety of proteins can be used to manipulate the properties of aqueous dispersions of zeolitic-imidazolate framework (ZIF) particles. Specifically, noncovalently associated protein coatings promote the formation of dispersions of hydrophobic ZIFs in water with high colloidal and hydrolytic stability, as long as the density of adsorbed proteins exceeds a critical, protein-dependent threshold. Further, these dispersions feature low viscosity and complete retention of gas carrying capacity. The wide range of properties accessible with protein coatings provides a highly modular approach to design hydrophobic metal–organic frameworks with properties tailored for specific biological applications.
Described here is the effect of anionic metalates─chlorocobaltate and nitratocobaltate─on the heat-driven separation of the critical element cobalt from potentially competing transition metal salts. Resins bearing the hexadentate glycolamide receptor L (PS-L) exhibit sorption capacities, Q = 1.33 mmol/g for CoCl 2 and Q = 0.66 mmol/g for Co(NO 3 ) 2 , as inferred from sorption isotherm studies. This trend runs counter to the typical Hofmeister series for anion selectivity. Ion chromatographic analysis of a mixed CoCl 2 /Co(NO 3 ) 2 solution revealed an increase in chloride content from 55 mol % to 90 mol % after a single thermally driven catch-and-release cycle. This chloride-selective behavior was recapitulated in a mixed-metal cation, mixed-anion system containing the chloride and nitrate salts of Mn(II), Co(II), and Ni(II) at near-equimolar concentrations. PS-L also displayed enhanced selectivity for Co using this mixed stock solution as observed by ICP-OES. In contrast, for a nitrate-only solution containing Mn(II), Co(II), and Ni(II), PS-L showed increased affinity for Mn, with its proportion rising from 36.6 mol % to 58.1% after a single catch-and-release cycle. Density functional theory calculations support the suggestion that the enhanced uptake of Co(II) in chloride-rich media arises from the high thermodynamic stability of [CoCl 4 ] 2– , which facilitates its outer-sphere coordination to cationic resin-bound cobalt species. Single crystal X-ray crystallographic analyzes of L•MCl 2 (M = Mn, Co, Ni) and L•M(NO 3 ) 2 (M = Mn, Co) confirmed metal complexation by L in the solid state and the concomitant formation of metalate counteranions. Here, the present study highlights a relatively simple approach for separating cobalt from its transition metal congeners.
Olsalazine (H 4 olz), a prodrug of the anti-inflammatory 5-aminosalicylic acid, is used as a ligand to synthesize a suite of M(H 2 olz) and M 2 (olz) materials, where M is a dication (e.g. Mg, Ca, Sr, Fe, Co, Ni, Cu, Zn). A family of metal olsalazine coordination polymers, coordination solids, and metal organic frameworks are described, which include 1-, 2-, and 3-dimensional structures. The materials resist degradation at acidic pH and release olsalazine preferentially at neutral pH. The mesoporous M 2 (olz) frameworks exhibit high surface areas with hexagonal pore apertures that are approximately 27 Å in diameter and contain coordinatively unsaturated metal sites. Biologically active molecules containing a Lewis-basic functional group can be grafted directly to the open metal sites of the frameworks. Dissolution of the frameworks under physiological conditions releases olsalazine (H 4 olz) and the grafted molecules so that multiple therapeutic components can be delivered together at different rates.
Nitrogen fixation by nitrogenase begins with accumulation of four reducing equivalents at the active-site FeMo-cofactor (FeMo-co), generating a state (denoted E4(4H)) with two [Fe-H-Fe] bridging hydrides. Recently, photolytic reductive elimination (re) of the E4(4H) hydrides showed that enzymatic re of E4(4H) hydride yields an H2-bound complex (E4(H2,2H)), in a process corresponding to a formal 2-electron reduction of the metal-ion core of FeMo-co. The resulting electron-density redistribution from Fe-H bonds to the metal ions themselves enables N2 to bind with concomitant H2 release, a process illuminated here by QM/MM molecular dynamics simulations. What is the nature of this redistribution? Although E4(H2,2H) hasn’t been trapped, cryogenic photolysis of E4(4H) provides a means to address this question. Photolysis of E4(4H) causes hydride-re with release of H2, generating doubly-reduced FeMo-co (denoted E4(2H)*), the extreme limit of the electron-density redistribution upon formation of E4(H2,2H). Here we examine the doubly-reduced FeMo-co core of the E4(2H)* limiting-state by 1H, 57Fe, and 95Mo ENDOR to illuminate the partial electron-density redistribution upon E4(H2,2H) formation during catalysis, complementing these results with corresponding DFT computations. Inferences from the E4(2H)* ENDOR results as extended by DFT computations include: (i) the Mo-site participates negligibly, and overall it is unlikely that Mo changes valency throughout the catalytic cycle; (ii) two distinctive E4(4H) 57Fe signals are suggested as associated with ‘anchors’ of one bridging hydride, two others with anchors of the second, with NBO-analysis identifying one anchor of each hydride as a major recipient of electrons released upon breaking Fe-H bonds.
Tritium (T 2 ) is a radioactive isotope of hydrogen that is produced in nuclear fission reactions and is often used in nuclear fusion reactions and accelerator-based applications for medical isotope production. As a hydrogen isotope, tritium can readily bind to hydroxyl radicals (OH), forming tritiated water (HTO or T 2 0), and to carbon atoms. Tritium decays to helium-3 ( 3 He) via beta-decay with max decay energy of 18.6 keV. While it is not an external radiation hazard, it can be an internal radiation hazard if tritium is inhaled, ingested, or absorbed through the skin. In applications where tritium is handled, tritium confinement is performed using different barriers to minimize releases to the environment. For gaseous (elemental), liquid (oxide), and metal (hydride) tritium, process piping and components provide the primary confinement function. Secondary tritium confinement is typically provided by inert (i.e. non-flammable gases such as nitrogen, argon, or helium) gloveboxes which are connected to a tritium stripper system. Primary tritium confinement barriers typically produce low volumes of high tritium concentrations of tritiated methane from carbon in steels or organic materials along with tritiated water/tritium oxide (e.g. HTO) and tritiated ammonia from reactions with oxygen and nitrogen. Tritium escaping primary confinement into secondary confinement atmospheres (e.g. gloveboxes) produce higher volumes of lower activity contamination than found in process piping. Tritium contamination also occurs by leaks or tritium permeation/diffusion through confinement materials. Tritium from inside primary confinement barriers will diffuse or leak out of the primary confinement barrier and usually into the air, if the system is inside an air hood or ventilated hot cell, or into the secondary confinement (e.g. glovebox) atmosphere which is either exhausted or stripped based on the function of the secondary confinement (glovebox) system. Accelerator based processes for medical isotope production represent an atypical tritium contamination challenge. In medical isotope production, deuterium supply gas is ionized and accelerated to a tritium gas target to produce neutrons that are then used to produce the medical isotopes through additional nuclear fission reactions. To create large voltage differentials for accelerator operations, an electrical insulation medium is needed to prevent or rapidly quench electric discharges. A common electrical insulation medium utilized in accelerator applications is sulfur hexafluoride (SF 6 ) gas. SF 6 has a high dielectric strength and allows for the construction of smaller accelerator systems compared to other electrical insulation mediums such as air or dry nitrogen. Due to tritium permeation/diffusion through accelerator process and confinement materials, there is the possibility that tritium can contaminate the electrical insulation medium of the accelerator. Tritium contaminated SF 6 creates a material without any obvious processes for managing the contamination, reuse, or disposal of the used SF 6 . This document will discuss possible management strategies for tritium contaminated SF 6 for accelerator-based processes for Molybdenum-99 (Mo-99) production.
The current FIPD library contains two main sets of fission gas chemistry data. The first set is data collected during the Integral Fast Reactor (IFR) program from 1984 to 1994, using a gas mass spectrometry system located in the Analytical Laboratory (AL) at Argonne National Laboratory-West (Argonne-West). Throughout this period, numerous fission gas release and chemistry datasets were gathered from a variety of metallic fuel pins. The fission gas was sampled by the Gas Assay, Sample and Recharge (GASR) System in the Hot Fuel Examination Facility (HFEF) and transferred to the AL to perform gas composition and isotopic abundance analysis. The second set is data collected after the IFR program. The fission gas samples were also collected by the GASR system at the HFEF, but analyzed using a similar gas mass spectrometer located in Pacific Northwest National Laboratory (PNNL). Many fuel pins irradiated in Experimental Breeder Reactor II (EBR-II) and the Fast Flux Test Facility (FFTF) were measured, including the fuel pins for the MFF series of experiments, designed to qualify metal fuel for use as driver fuel in the FFTF and X496 experiment. For either set of data, fission gas was sampled with the gas sampling line in GASR using sample bottles after the capsule/element volume has been determined and the system is still full of radioactive gas. The sample bottles were then transferred to the sample packaging cylinder or an approved storage location pending transfer to the AL or prepared for shipment to another laboratory (such as PNNL) for analysis of the collected gas as directed on the GASR data form, other approved form. The receiving laboratories (AL or PNNL) required their Analytical Service Request form to be completed prior to sample transfer. Typical sample transfer processes were initiated at HFEF by the principal or process engineer. The laboratories performing the analyses (AL or PNNL) use the sample bottle numbers as well as a sample number produced by the respective laboratory. HFEF and the responsible experimenter tracked the sample using the analysis number, the gas bottle number, and the fuel pin number.