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Improved synthesis of ceramic superconductors with alkaline earth peroxides - Synthesis and processing of Ba2YCu3O(7-x)

Synthesis processes for the preparation of ceramic conductors Ba2YCu3O(7-x) from BaO2 or BaCO3 in flowing O2 or N2 are described, and the characteristics of the materials produced in these processes are compared. Results of EDAX, XRD, SEM, and dc resistivity analyses demonstrated that superconducting materials made from BaO2 were more homogeneous, denser, and more metallic than materials produced from BaCO3, because of the higher reactivity of BaO2. Potential applications of this processes are discussed.

Hepp, A. F.↗

Elucidating the role of earth alkaline doping in perovskite-based methane dry reforming catalysts

To elucidate the role of earth alkaline doping in perovskite-based dry reforming of methane (DRM) catalysts, we embarked on a comparative and exemplary study of a Ni-based Sm perovskite with and without Sr doping. While the Sr-doped material appears as a structure-pure Sm 1.5 Sr 0.5 NiO 4 Ruddlesden Popper structure, the undoped material is a NiO/monoclinic Sm 2 O 3 composite. Hydrogen pre-reduction or direct activation in the DRM mixture in all cases yields either active Ni/Sm 2 O 3 or Ni/Sm 2 O 3 /SrCO 3 materials, with albeit different short-term stability and deactivation behavior. The much smaller Ni particle size after hydrogen reduction of Sm 1.5 Sr 0.5 NiO 4 , and of generally all undoped materials stabilizes the short and long-term DRM activity. Carbon dioxide reactivity manifests itself in the direct formation of SrCO 3 in the case of Sm 1.5 Sr 0.5 NiO 4 , which is dominant at high temperatures. For Sm 1.5 Sr 0.5 NiO 4 , the CO : H 2 ratio exceeds 1 at these temperatures, which is attributed to faster direct carbon dioxide conversion to SrCO 3 without catalytic DRM reactivity. As no Sm 2 O 2 CO 3 surface or bulk phase as a result of carbon dioxide activation was observed for any material – in contrast to La 2 O 2 CO 3 – we suggest that oxy-carbonate formation plays only a minor role for DRM reactivity. Rather, we identify surface graphitic carbon as the potentially reactive intermediate. Graphitic carbon has already been shown as a crucial reaction intermediate in metal-oxide DRM catalysts and appears both for Sm 1.5 Sr 0.5 NiO 4 and NiO/monoclinic Sm 2 O 3 after reaction as crystalline structure. It is significantly more pronounced for the latter due to the higher amount of oxygen-deficient monoclinic Sm 2 O 3 facilitating carbon dioxide activation. Despite the often reported beneficial role of earth alkaline dopants in DRM catalysis, we show that the situation is more complex. In our studies, the detrimental role of earth alkaline doping manifests itself in the exclusive formation of the sole stable carbonated species and a general destabilization of the Ni/monoclinic Sm 2 O 3 interface by favoring Ni particle sintering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Workshop on Oxygen in the Terrestrial Planets

This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in Lunar Metal Grains: Solar, Lunar or Terrestrial Origin? 22) Isotopic Zoning in the Inner Solar System; 23) Redox Conditions on Small Bodies; 24) Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update; 25) Mantle Redox Evolution and the Rise of Atmospheric O2; 26) Variation of Kd for Fe-Mg Exchange Between Olivine and Melt for Compositions Ranging from Alkaline Basalt to Rhyolite; 27) Determining the Partial Pressure of Oxygen (PO,) in Solutions on Mars; 28) The Influence of Oxygen Environment on Kinetic Properties of Silicate Rocks and Minerals; 29) Redox Evolution of Magmatic Systems; 30) The Constancy of Upper Mantlefo, Through Time Inferred from V/Sc Ratios in Basalts: Implications for the Rise in Atmospheric 0 2; 31) Nitrogen Solubility in Basaltic Melt. Effects of Oxygen Fugacity, Melt Composition and Gas Speciation; 32) Oxygen Isotope Anomalies in the Atmospheres of Earth and Mars; 33) The Effect of Oxygen Fugacity on Interdiffusion of Iron and Magnesium in Magnesiowiistite 34) The Calibration of the Pyroxene Eu-Oxybarometer for the Martian Meteorites; 35) The Europium Oxybarometer: Power and Pitfalls; 36) Oxygen Fugacity of the Martian Mantle from PigeoniteMelt Partitioning of Samarium, Europium and Gadolinium; 37) Oxidation-Reduction Processes on the Moon: Experimental Verification of Graphite Oxidation in the Apollo 17 Orange Glasses; 38) Oxygen and Core Formation in the Earth; 39) Geologic Record of the Atmospheric Sulfur Chemistry Before the Oxygenation of the Early Earth s Atmosphere; 40) Comparative Planetary Mineralogy: V/(CrCAl) Systematics in Chromite as an Indicator of Relative Oxygen Fugacity; 41) How Well do Sulfur Isotopes Constrain Oxygen Abundance in the Ancient Atmospheres? 42) Experimental Constraints on the Oxygen Isotope (O-18/ O-16) Fractionation in the Ice vapor and Adsorbant vapor Systems of CO2 at Conditions Relevant to the Surface of Mars; 43) Micro-XANES Measurements on Experimental Spinels andhe Oxidation State of Vanadium in Spinel-Melt Pairs; 44) Testing the Magma Ocean Hypothesis Using Metal-Silicate Partitioning of Te, Se and S; 45) Solubility of Oxygen in Liquid Iron at High Pressure and Consequences for the Early Differentiation of Earth and Mars Metallic Liquid Segregation in Planetesimals; 46) Oxygen Fugacity of Lunar Basalts and the Lunar Mantle. Range of fo2 and the Effectiveness of Oxybarometers; 47) Thermodynamic Study of Dissociation Processes of Molecular Oxygen in Vapor over Oxide Compounds; 48) Oxygen Profile of a Thermo-Haliophilic Community in the Badwater Salt Flat; 49) Oxygen Barometry Using Synchrotron MicroXANES of Vanadium; 50) Mass-Independent Isotopic Fractionation of Sulfur from Sulfides in the Huronian Supergroup, Canada; 51) Mass Independent Isotopes and Applications to Planetary Atmospheres; 52) Electrical Conductivity, Oxygen Fugacity, and Mantle Materials; 53) Crustal Evolution and Maturation on Earth: Oxygen Isotope Evidence; 54) The Oxygen Isotope Composition of the Moon: Implications for Planet Formation; 55) Oxygen Isotope Composition of Eucrites and Implications for the Formation of Crust on the HED Parent Body; and 56) The Role of Water in Determining the Oxygen Isotopic Composition of Planets.

Source record↗

A Strategy for Mars Exopaleontology

There is compelling geological evidence that the climate of early Mars was much more Earth-like, with a denser atmosphere and abundant surface water. Given that life developed on the Earth very quickly (between 4.2 and 3.5 Ga), it is quite plausible that life may have also developed on Mars during this early clement period. If Martian life developed, it is likely to have left behind a fossil record. Thus, an important focus for upcoming Mars missions is to explore for an ancient biosphere. This presents a set of goals and problems that are quite distinct from Exobiology. I call this new activity "Exopaleontology", whose core principles derive from studies of the Precambrian fossil record on Earth, biosedimentology and microbial fossilization. Such studies reveal that the most important factor favoring the long-term preservation of microbial fossils is rapid entombment of microorganisms by fine-grained, stable mineral phases such as silica, phosphate, carbonate and metal sulfides. Terrestrial environments where such aqueous mineral phases frequently entomb and preserve microorganisms include subaerial and subaqueous springs and shallow hydrothermal systems, evaporitic alkaline lakes, "hardpan" soils (e.g. calcretes, silcretes, ferracretes), and frozen soils or ground ice. With the exception of ice, which has a short crustal residence time, such deposits am known to retain a record of terrestrial life for billions of years. Current activities seek to refine and apply this strategy to the Mars Global Surveyor missions and beyond. Ongoing studies of microbial fossilization in each of the target environments identified above are aimed at improving our understanding of how biological information is incorporated into aqueous mineral deposits and preserved. Viking data is being used to target sites for high resolution orbital imaging and spectroscopy during upcoming Mars missions. Such data will provide a basis for selecting sites for future landed missions and eventually, sample return.

Farmer, Jack D.↗

Crystalline compounds for remediation of rare-earth fission products: A review

Rare-earth (RE) containing crystals have been investigated as media for the immobilization of RE fission products. During reprocessing of spent nuclear fuels, various fission products including REs, alkalis, and alkaline earths are found after the extraction of actinides. One viable option to immobilize the RE fission products is to incorporate them into chemically durable crystalline phases in specific waste forms. This study summarizes the crystal structures and synthesis methods of six RE-containing compounds that have applications in remediation of RE fission products. These compounds include oxyapatite [Ca2RE8(SiO4)6O2], oxychloride [REOCl], borosilicate [RE3BSi2O10], pyrochlore [RE2A2O7], monazite [REPO4], and perovskite [REAO3] where A denotes transitional metals. This review provides an overview of literature on the usage of these six compounds for immobilizing RE fission products and summarizes different synthesis methods for producing these compounds. Comparisons of structural parameters with different REs in each compound are also discussed.

rare-earth oxychloride, rare-earth oxyapatite, rar↗

Light Weight Design Nickel-Alkaline Cells Using Fiber Electrodes

Using fiber electrode technology, currently produced by Bekaert Corporation (Bekaert), Electro Energy, Inc., (EEI) Mobile Energy Products Group (formerly, Eagle-Picher Technologies, LLC., Power Systems Department) in Colorado Springs, CO has demonstrated that it is feasible to manufacture flight weight nickel-hydrogen cells having about twice the specific energy (80 vs. 40 watt-hr/kg) as state-of-the-art nickel-hydrogen cells that are flown on geosynchronous communications satellites. Although lithium-ion battery technology has made large in-roads to replace the nickel-alkaline technology (nickel-cadmium, nickel-metal hydride), the technology offered here competes with lithium-ion weight and offers alternatives not present in the lithium-ion chemistry such as ability to undergo continuous overcharge, reversal on discharge and sustain rate capability sufficient to start automotive and aircraft engines at subzero temperatures. In development to date seven 50 ampere-hour nickel-hydrogen have been constructed, acceptance tested and briefly tested in a low earth orbit (LEO) cycle regime. The effort was jointly funded by Electro Energy, Inc. and NASA Glenn Research Center, Cleveland, OH. Five of the seven cells have been shipped to NASA GRC for further cycle testing. Two of the cells experienced failure due to internal short circuits during initial cycle testing at EEL Destructive Physical Analysis (DPA) of one of the cells has shown the failure mode to be due to inadequate hydrogen catalyst electrodes that were not capacity balanced with the higher energy density nickel oxide electrodes. In the investigators opinion, rebuild of the cells using proper electrode balance would result in cells that could sustain over 30,000 cycles at moderate depths-of-discharge in a LEO regime or endure over 20 years of geosynchronous orbit (GEO) cycling while realizing a two-fold increase in specific energy for the battery or a 1.1 kg weight savings per 50 ampere-hour cell. Additional information is included in the original extended abstract.

Pickett, David F.↗

Theoretical dissociation energies for ionic molecules

Ab initio calculations at the self-consistent-field and singles plus doubles configuration-interaction level are used to determine accurate spectroscopic parameters for most of the alkali and alkaline-earth fluorides, chlorides, oxides, sulfides, hydroxides, and isocyanides. Numerical Hartree-Fock (NHF) calculations are performed on selected systems to ensure that the extended Slater basis sets employed for the diatomic systems are near the Hartree-Fock limit. Extended Gaussian basis sets of at least triple-zeta plus double polarization equality are employed for the triatomic system. With this model, correlation effects are relatively small, but invariably increase the theoretical dissociation energies. The importance of correlating the electrons on both the anion and the metal is discussed. The theoretical dissociation energies are critically compared with the literature to rule out disparate experimental values. Theoretical (sup 2)Pi - (sup 2)Sigma (sup +) energy separations are presented for the alkali oxides and sulfides.

Langhoff, S. R.↗

Evolution of ore deposits on terrestrial planets

Ore deposits on terrestrial planets materialized after core formation, mantle evolution, crustal development, interactions of surface rocks with the hydrosphere and atmosphere, and, where life exists on a planet, the involvement of biological activity. Core formation removed most of the siderophilic and chalcophilic elements, leaving mantles depleted in many of the strategic and noble metals relative to their chondritic abundances. Basaltic magma derived from partial melting of the mantle transported to the surface several metals contained in immiscible silicate and sulfide melts. Magmatic ore deposits were formed during cooling, fractional crystallization and density stratification from the basaltic melts. Such ore deposits found in earth's Archean rocks were probably generated during early histories of all terrestrial planets and may be the only types of igneous ores on Mars. Where plate tectonic activity was prevalent on a terrestrial planet, temporal evolution of ore deposits took place. Repetitive episodes of subduction modified the chemical compositions of the crust and upper mantles, leading to porphyry copper and molybdenum ores in calc-alkaline igneous rocks and granite-hosted tin and tungsten deposits. Such plate tectonic-induced mineralization in relatively young igneous rocks on earth may also have produced hydrothermal ore deposits on Venus in addition to the massive sulfide and cumulate chromite ores associated with Venusian mafic igneous rock. Sedimentary ore deposits resulting from mechanical and chemical weathering in reducing atmospheres in Archean earth included placer deposits (e.g., uraninite, gold, pyrite ores). Chromite, ilmenite, and other dense unreactive minerals could also be present on channel floors and in valley networks on Mars, while banded iron formations might underlie the Martian northern plains regions. As oxygen evolved in earth's atmosphere, so too did oxide ores. By analogy, gossans above sulfide ores probably occur on Mars, but not submarine ferromanganese nodules and crusts which have precipitated in oxygenated seawater on earth.

Burns, R. G.↗

Structure–property relations of binary ferrite melts

Molten ferrite systems are used in the smelting and refining processes in steelmaking, to reduce the loss of metals in slags and to accelerate reaction rates. Here, high-energy x-ray diffraction experiments have been performed on aerodynamically levitated molten spheres of 43BaO–57FeO X and 43SrO–57FeO X at 1873 K using laser beam heating. The composition was varied within the range of x = 1–1.5 by changing the oxygen partial pressure of the levitation gas. The corresponding x-ray pair distribution functions have been interpreted using empirical potential structure refinement (EPSR) modeling. In oxygen-rich melts (x = 1.5), our EPSR models indicate very similar structures for the different alkaline-earth liquids, with both the Ba–O and Sr–O coordination numbers to be ∼8.4 and the total Fe–O coordination numbers ∼5.7. However, our models show that in reducing environments, the Fe 3+ and Fe 2+ ions exhibit very different behaviors in the Ba- and Sr-ferrite liquids. In the Ba-ferrite melt, the Fe 3+ –O coordination number decreases from 5.7 (at x = 1.5) to 5.2 (at x = 1.07), whereas Fe 2+ –O remains constant at ∼5.0 across the same compositional range. In the Sr melts, both the Fe 2+ –O and Fe 3+ –O coordination numbers rise from ∼5.7 (at x = 1.5) to 6.3 (at x = 1.07). All models show the structures to be heterogeneous with intertwined nanometer sized clusters or channels of Ba/Sr–O and Fe–O polyhedra that grow as oxygen content is reduced. Changes in the viscosity and electrical properties are interpreted in terms of the number of bridging and non-bridging oxygens associated with FeO 4 tetrahedra and concentration of charge carriers, respectively.

Benmore, Chris J. [Argonne National Laboratory (AN↗

Ir–Ru Particles Enable Low-Loading Acidic Oxygen Evolution for Integrated Solar Devices

Integrated photoelectrochemical (PEC) devices for water splitting represent a compelling pathway for sustainable hydrogen production, directly converting solar energy into chemical fuels. While alkaline systems have achieved state-of-the-art solar-to-hydrogen (STH) efficiencies above 20% using earth-abundant catalysts, acidic PEC architectures provide unique advantages for compact device integration, fast proton transport, and stable operation under highly dynamic solar conditions. Proton-exchange membrane (PEM)-based configurations enable high current densities, low gas crossover, and rapid ionic response, making them especially well-suited for intermittent, bias-free PEC operation, despite alkaline electrolysis being more technologically mature. A critical limitation of acidic PEC systems remains, the oxygen evolution reaction (OER), which currently relies on scarce and costly iridium catalysts, restricting scalability. Here, in this study, we report a series of low-iridium mixed-metal oxide catalysts synthesized via a surfactant-assisted borohydride reduction method. An optimized Ir 0.5 Ru 0.5 O x catalyst exhibits exceptional intrinsic activity (>400 A g –1 Ir at 1.55 V vs RHE) in 0.1 M HClO 4 and maintains stable operation for over 10 days in an integrated PEC flow-cell. Sustained hydrogen production is achieved at 1.65 V with a total iridium loading of only 0.1 mg cm –2 , substantially below commercial PEM benchmarks. These results demonstrate a viable pathway toward scalable, high-performance acidic PEC hydrogen technologies.

Acidic electrolysis↗

Nuclear waste reduction: Exploring new pathways one step at a time

In my home country of Venezuela, nuclear energy is not a topic that attracts much attention. The government briefly oversaw some nuclear energy programs during the 1950s, but currently there are no active nuclear power facilities in the country. In fact, the Venezuelan government signed and ratified the treaty of the prohibition of nuclear weapons in 2021, which states that Venezuela has never owned, possessed or controlled nuclear weapons or programs of any kind. When I moved to the United States, however, nuclear energy became an extremely relevant topic. In the 1940s, the U.S. government established and oversaw the Manhattan Project to build atomic bombs for use in World War II. After the war, the government encouraged scientists to use this information on nuclear reactions to develop nuclear energy for peaceful civilian purposes instead.1 During these early days of nuclear research, there were no formal regulatory standards for nuclear waste management. Policies usually were self-regulated and often created based on existing policies of disposal for non-nuclear waste.2 As a result, there were instances of nuclear waste leaching into the environment and affecting local communities. So, much research has been conducted since then to characterize and store nuclear waste safely and securely.3 I first became interested in nuclear energy during my undergraduate studies when I worked on a project involving ligand synthesis to help extract actinides from nuclear waste. I then studied electrochemistry in molten salt systems for nuclear energy applications during my Ph.D. As I approached graduation, I started looking into national laboratories that have programs involving nuclear energy and waste management. At Idaho National Laboratory (INL), the focus is more on applied processes and how nuclear energy can be innovated to realize next-generation reactor design and technologies. This focus led me to apply for a Seaborg distinguished postdoctoral position at INL, for which I was chosen based on my proposal of a way to improve nuclear waste recycling. To understand my proposal, we must familiarize ourselves with the makeup of nuclear waste. After uranium dioxide is used as nuclear fuel in a reactor, the fuel matrix is then characterized by various fission products, including rare earth elements, alkali and alkaline earths, and actinides. Some of these fission products can potentially be recovered through pyroprocessing, 4 which involves the electrochemical dissolution of the used nuclear fuel in a molten chloride salt mixture at high temperatures. Though some of the fission products can be easily recovered—for example, uranium is reduced onto an inert cathode by applied potentials—numerous other fission products such as rare earth elements are difficult to recover due to their multivalent oxidation states and side reactions.5 To improve the recovery efficiency of rare earth elements specifically, I proposed investigating the fundamental interactions between rare earth elements in the molten chloride salt and their metallic form (Figure 1). The kinetic pathways and the chemical reactions of these elements, which will be elucidated through spectro-electrochemistry at high temperatures, will give insights on how the recovery efficiency can be improved. Although my research focuses on fundamental science, it will benefit the applied process by generating new scientific knowledge and closing the gap for efficient recycling of the waste: one step at a time.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Thermion: Verification of a thermionic heat pipe in microgravity

The design and development is examined of a small excore heat pipe thermionic space nuclear reactor power system (SEHPTR). The need was identified for an in-space flight demonstration of a solar powered, thermionic heat pipe element. A demonstration would examine its performance and verify its operation in microgravity. The design of a microsatellite based technology demonstration experiment is proposed to measure the effects of microgravity on the performance of an integrated thermionic heat pipe device in low earth orbit. The specific objectives are to verify the operation of the liquid metal heat pipe and the cesium reservior in the space environment. Two design configurations are described; THERMION-I and THERMION-II. THERMION-I is designed for a long lifetime study of the operations of the thermionic heat pipe element in low earth orbit. Heat input to the element is furnished by a large mirror which collects solar energy and focuses it into a cavity containing the heat pipe device. THERMION-II is a much simpler device which is used for short term operation. This experiment remains attached to the Delta II second stage and uses energy from 500 lb of alkaline batteries to supply heat energy to the heat pipe device.

Source record↗

Metal-insulator transition and magnetism of SU(3) fermions in the square lattice

We study the SU(3) symmetric Fermi-Hubbard model (FHM) in the square lattice at 1/3-filling using numerically exact determinant quantum Monte Carlo and numerical linked-cluster expansion techniques. We present the different regimes of the model in the T–U plane, which are characterized by local and short-range correlations, and capture signatures of the metal-insulator transition and magnetic crossovers. These signatures are detected as the temperature scales characterizing the rise of the compressibility, and an interaction-dependent change in the sign of the diagonal spin-spin correlation function. The analysis of the compressibility estimates the location of the metal-insulator quantum critical point at U c /t ~ 6, and provides a temperature scale for observing Mott physics at finite T. Furthermore, from the analysis of the spin-spin correlation function we observe that for U/t ≳ 6 and T ~ J = 4⁢t 2 /U there is a development of a short-range two-sublattice (2SL) antiferromagnetic structure, as well as an emerging three-sublattice (3SL) antiferromagnetic structure as the temperature is lowered below T/J ≲ 0.57. This crossover from 2SL to 3SL magnetic ordering agrees with Heisenberg limit predictions, and has observable effects on the density of on-site pairs. Finally, we describe how the features of the regimes in the T–U plane can be explored with alkaline-earth-like atoms in optical lattices with currently achieved experimental techniques and temperatures. Furthermore, the results discussed in this paper provide a starting point for the exploration of the SU(3) FHM upon doping.

74 ATOMIC AND MOLECULAR PHYSICS↗

Direct Laser Writing of Multimetal Bifunctional Catalysts for Overall Water Splitting

Water electrolysis is of interest as a sustainable way to produce clean hydrogen and oxygen fuel and help mitigate the rising problems of climate change while meeting global energy demands. High-efficiency, stable, and earth-abundant bifunctional catalysts are needed to enable more effective electrochemical cells for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Here, we investigate the synthesis, composition, performance, and mechanism of multimetal catalysts serving dual functionality in both OER and HER of water electrolysis. Through a laser synthesis method, we synthesized heterogeneous catalysts of nanocrystalline multimetallic alloy pockets embedded within an amorphous oxide matrix. We evaluated the performance and composition of a range of mixed transition-metal oxide materials for both OER and HER, ultimately synthesizing a Cr 0.01 Fe 0.27 Co 0.34 Ni 0.38 O x /C y catalyst that has a stable, high-rate, and competitive overall water splitting performance of 1.76 V at 100 mA cm –2 in an alkaline medium. Using density functional theory to gain insight as the active site and mechanism, we propose that the inclusion of a minor amount of Cr increases the degeneracy of energetic states that lowers the cost of forming the O 2 p–d bond and H 1 s–d bond due to the hybridization of s, p, and d orbitals from Cr. Using a two-electrode water electrolysis cell with a constant potential of 1.636 V to mimic the setup for fuel production, we found the catalyst to be stable at 14–15 mA cm –2 for 40 h. Furthermore, this laser synthesis method allowing for facile and rapid synthesis of complex multimetal systems demonstrates how doping a Fe, Co, and Ni heterogeneous amorphous/nanocrystalline structure with small amounts of Cr is important for bifunctional catalytic behavior, particularly for increasing HER functionality in advancing our understanding for future electrocatalytic design.

08 HYDROGEN↗

Theoretical study of the diatomic alkali and alkaline-earth oxides

Theoretical dissociation energies for the ground states of the alkali and alkaline earth oxides are presented that are believed to be accurate to 0.1 eV. The 2 Pi - 2 Sigma + separations for the alkali oxides are found to be more sensitive to basis set than to electron correlation. Predicted 2 Pi ground states for LiO and NaO and 2 Sigma + ground states for RbO and CsO are found to be in agreement with previous theoretical and experimental work. For KO, a 2 Sigma + state is found at both the numerical Hartree-Fock (NHF) level and at the singles plus doubles configuration interaction level using a Slater basis set that is within 0.02 eV of the NHF limit. It is found that an accurate balanced treatment of the two states requires correlating the electrons on both the metal and oxide ion.

Langhoff, S. R.↗

Site Selection for Mars Exopaleontology in 2001

The microbial fossil record encompasses a wide range of information, including cellular remains, stromatolites, biofabrics, trace fossils, biominerals and chemofossils. The preservation of fossils is strongly influenced by the physical, chemical and biological factors of the environment which, acting together, ultimately determine the types of information that will be captured and retained in the rock record. The critical factor in assessing the suitability of a site for a microbial fossil record is the paleoenvironment. The reconstruction of ancient sedimentary environments usually requires the integration of a wide variety of geological information, including the shape, geometry and internal structure of sedimentary deposits, their mineralogy, and geochemistry. For Mars, much of our knowledge about past environments is based on orbital imaging of geomorphic features. This evidence provides an important context and starting point for site selection. However, our knowledge of the martian surface is quite limited, and a major goal of the upcoming exploration effort is to reconstruct the history of Martian volatiles, climate, and hydrology as a context for the exploration for past or present life. Mineralogical mapping from orbit will be an important key in this effort. In exploring for evidence of past life, terrestrial experience suggests that the long-term preservation of biological information as fossils occurs under a fairly narrow range of geological conditions that are well known to paleontologists (1). In detrital sedimentary systems, microbial fossilization is favored by rapid burial in fine-grained, clay-rich sediments. In chemical sedimentary systems, preservation is enhanced by rapid entombment in fine-grained chemical precipitates. For long term preservation, host rocks must be composed of stable minerals that resist chemical weathering, and which form an impermeable matrix and closed chemical system that can protect biosignatures from alteration during subsequent diagenetic change or metamorphism. In this context, host rocks composed of highly ordered, chemically-stable mineral phases, like silica (forming cherts) or phosphate (forming phosphorites), are especially favored. Such lithologies tend to have very long crustal residence times and (along with carbonates and shales), are the most common host rocks for the Precambrian microfossil record on Earth. If we assume that a subsurface hydrosphere has been present throughout martian history, then life could have originated there at any time, perhaps emerging at the surface periodically when climate changes, induced by external forcing or endogenous processes (e.g. volcanism), allowed liquid water to exist at the surface. The recent discovery of subsurface chemolithoautotrophic organisms which are capable of synthesizing organic substrates from C02 and H2 liberated from the aqueous weathering of basalt, is especially. relevant as a model for martian life. While a subsurface habitable zone may yet exist on Mars, access to such environments will likely require drilling to depths of several kilometers. Given the technological challenge of deep drilling, this is unlikely to occur prior to human missions. So, even if there is extant life on Mars today in subsurface habitats, it may be much easier to find its fossil counterparts in ancient deposits exposed at the surface. In exploring for a fossil record in subsurface environments on Mars there are several geological situations that may provide access to the appropriate materials. These include 1) ejecta from impact craters, 2) talus slopes, debris flows or alluvial fans developed below the walls of deep canyons, and 3) the deposits of outflood channels. Examples of aqueous mineral deposits of formed in subsurface environments that could harbor a microbial fossil record include such things as cements in detrital sedimentary rocks, low temperature diagenetic minerals deposited in veins, or filling vesicles in volcanic rocks, and hydrothermal deposits formed below the upper temperature limit for life (about 160 degrees C). There are many sites within the present latitudinal constraints for the 2001 mission (15 deg S to 30 deg N) that meet these requirements. But the practical problem with these kinds of deposits is that they tend to be disseminated, making up only a small percentage of a host rock. Even with mineralogical information provided by the Thermal Emission Spectrometer (TES) presently in orbit around Mars, predicting their occurrence ahead of time may be quite difficult. The deposits of surficial aqueous sedimentary systems are likely to provide the largest targets for site selection in 2001. Of these, the deposits of hydrothermal systems (subaerial and subaqueous thermal springs) have been discussed previously. It is likely that hydrothermal systems were widespread on Mars early in its history and a number of common geo-tectonic settings on Mars are likely to have hosted hydrothermal activity. Most of these are represented within the latitudinal constraints presently identified for 2001. However, the deposits of surface spring systems are likely to be difficult to find as well. On Earth, exposure areas for hydrothermal spring mounds are typically a few square kms, less than a single TES pixel. But such deposits may be quite abundant within some volcanic terrains, It is estimated, for example, that between 15-20% of the floor of Yellowstone caldera is covered by thermal spring deposits. In such abundances, subaerial sinters could well be detected by TES. Where exposed, the shallow subsurface portions of these systems may be quite a lot larger (perhaps tens of square kms), although (as noted above) mineralization may be finely disseminated in the basement rock, making remote detection more difficult. Paleolake Basins. There are a large number of potential paleolake basins on Mars (inclusive of impact craters and volcanic calderas) that have been previously identified using Viking images. Most of these lie in the southern highlands beyond the l5 deg S constraint for 2001. However, deposits of paleolakes may offer the largest and most easily identified exopaleontological targets from orbit. Based on a variety of arguments, some workers have suggested that there was once an ancient ocean on the northern plains, and some sites of interest (potential shoreline terraces) fall within the 30 deg N constraint. From a paleontological standpoint the most interesting places of this type are terminal paleolake basins which are likely to have been both saline and alkaline. Models by Schaefer suggest such environments could be widespread on Mars. The conditions in terminal lake basin settings favor widespread chemical sedimentation, an important condition for microbial fossilization. Important lithological targets for a microbial fossil record in terminal lake basins include spring-deposited carbonates, shoreline cements, a wide variety of evaporite minerals and fine-grained detrital sediments including shales, marls, and water-lain volcanic ash deposits. In developing a strategy to explore for ancient hydrothermal deposits on Mars, we can learn from the methods that have been developed by explorationists to explore for economic mineral deposits on Earth. Due to their simple mineralogy, hydrothermal deposits can often be detected using remote sensing methods. Common thermal spring mineral assemblages include silica, carbonate, and various metallic oxides and sulfides. But there are also a number of diagnostic silicate minerals, including clays, formed by the hydrothermal alteration of country rocks. These hydrothermal minerals have characteristic spectral signatures that could be detected from Mars orbit using high resolution infrared remote sensing methods. In playa lake settings, evaporite deposits often form a predictable "bull's eye" pattern with carbonates being deposited in marginal basin areas, and sulfates and halides occurring progressively more basinward. The floors of some impact craters on Mars, such as "White Rock" and Bequeral Crater (see Oxia Palus NE, Site 148), have floor deposits that could be evaporites, inclusive of carbonates. Evaporite minerals possess characteristic spectral signatures in the infrared and could similarly be identified from Mars orbit using high resolution remote sensing methods. Clearly, utilization of TES data will be important for optimizing site selection for Exopaleontology, and every effort should be made to benefit from that data before a final decision is made.

Farmer, Jack↗

Single-component-at-a-time variation study for glass-ceramic waste forms

Here, a 51-sample composition variation study was performed on glass-ceramic waste forms for a raffinate waste stream from aqueous reprocessing of used nuclear fuel containing high fractions of Mo, alkalis, alkaline earths (AEs), and rare earths (REs). The study was designed with a single-component-at-a-time variation approach off a centroid composition. The components that were varied included Al, B, Ca, Li, Mo, Na, REs, Si, Zr, and Others (containing minor components). Data analysis included crystallization curves, microstructure, and phase compositions. A number of components (i.e., Li 2 O, B 2 O 3 , REO x , MoO 3 , Na 2 O, and ZrO 2 ) significantly impacted the concentration and chemistry of phases, especially the primary phases of oxyapatite [i.e., Ca 2 RE 8 (SiO 4 ) 6 O 2 ] and powellite (i.e., AEMoO 4 ), precipitated in the slow-cool heat-treated waste forms; minor phases included cerianite [i.e., Ce x Zr (1-x) O 2 ], Ba-molybdate [i.e., Ba(Gd 0.67 Mo 0.33 O 3 ], noble metals, pollucite (i.e., CsAlSiO 4 ), and RE-borosilicate (i.e., RE 3 BSi 2 O 10 ).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗