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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Anion–Anion Bonding and Topology in Ternary Iridium Seleno–Stannides

The synthesis and physical properties of two new and one known Ir–Sn–Se compound are reported. Their crystal structures are elucidated with transmission electron microscopy and powder X-ray diffraction. IrSn0.45Se1.55 is a pyrite phase which consists of tilted corner-sharing IrX6 octahedra with randomly distributed (Sn–Se)4– and (Se–Se)2– dimers. Ir2Sn3Se3 is a known trigonally distorted skutterudite that consists of cooperatively tilted corner-sharing IrSn3Se3 octahedra with ordered (Sn–Se)24– tetramers. Ir2SnSe5 is a layered, distorted β-MnO2 (pyrolusite) structure consisting of a double IrSe6 octrahedral row, corner sharing in the a direction and edge sharing in the b direction. This distorted pyrolusite contains (Se–Se)2– dimers and Se2– anions, and each double row is “capped” with a (Sn–Se)n polymeric chain. Resistivity, specific heat, and magnetization measurements show that all three have insulating and diamagnetic behavior, indicative of low-spin 5d6 Ir3+. Electronic structure calculations on Ir2Sn3Se3 show a single, spherical, nonspin–orbit split valence band and suggest that Ir2Sn3Se3 is topologically nontrivial under tensile strain due to inversion of Ir-d and Se-p states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Structure-Controlled Oxygen Concentration in Fe 2 O 3 and FeO 2

Solid-solid reaction, particularly in the Fe-O binary system, has been extensively studied in the past decades because of its various applications in chemistry and materials and earth sciences. The recently synthesized pyrite-FeO 2 at high pressure suggested a novel oxygen-rich stoichiometry that extends the achievable O-Fe ratio in iron oxides by 33%. Although FeO 2 was synthesized from Fe 2 O 3 and O 2 , the underlying solid reaction mechanism remains unclear. Herein, combining in situ X-ray diffraction experiments and first-principles calculations, we identified that two competing phase transitions starting from Fe 2 O 3 : (1) without O 2 , perovskite-Fe2O3 transits to the post-perovskite structure above 50 GPa; (2) if free oxygen is present, O diffuses into the perovskite-type lattice of Fe 2 O 3 leading to the pyritetype FeO 2 phase. We found the O-O bonds in FeO 2 are formed by the insertion of oxygen into the Pv lattice via the external stress and such O-O bonding is only kinetically stable under high pressure. This may provide a general mechanism of adding extra oxygen to previous known O saturated oxides to produce unconventional stoichiometries. Our results also shed light on how O is enriched in mantle minerals under pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Partial Surface Selenization of Cobalt Sulfide Microspheres for Enhancing the Hydrogen Evolution Reaction

Electrocatalysis of water is a scalable and easily available source of the production of hydrogen (H 2 ), the future energy carrier. This drive for clean energy inspired us to develop an inexpensive, readily producible, highly active, and stable catalyst to replace current state of the art platinum catalysts. Building on the promising hydrogen evolution reaction (HER) activity of many pyrites, their structural tuning by different metals and nonmetals has been found to be effective in several instances. We present here one such effort by partial surface selenization of mesoporous cobalt sulfide material, which displayed long-term operational stability (for at least 25 h) besides attaining a current density of 100 mA cm –2 at an overpotential of 160 mV versus the reversible hydrogen electrode (RHE) (in acidic media). A low Tafel slope (of 52 mV dec –1 ) and high exchange current density ( j 0 ) (of 70 μA cm –2 ) make our catalyst better to most existing systems. More importantly, using a variety of analytical techniques, electrochemical measurements, and theoretical calculations, we have analyzed the morphology of the material and rationalized the key to the enhanced intrinsic activity (as compared to the meso-CoS 2 ) per active site. This study is expected to explain similar systems and modify approaches to enhancing the electrochemical activity of metal chalcogenides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Molybdenum Burial Mechanism in Sulfidic Sediments: Iron-Sulfide Pathway

Relative to continental crust, sediments underlying sulfidic marine waters are molybdenum-rich, a property preserved in the rock record and useful for characterizing paleoenvironments. The enrichment mechanism is not agreed upon but is attributed at least partly to deposition of Fe–Mo–S compounds, which are as yet uncharacterized. Here, we determine the composition and stability of colloidal Fe–Mo–S precipitates formed at mildly basic pH and H 2 S(aq) > 10 –5 M. The first product consists simply of FeMoS 4 , with K sp = 10 –14.95 . Within hours, FeMoS 4 irreversibly transforms by internal self-reduction to a Mo(IV) product of similar composition. The reduced product is insoluble in 1 M HCl but soluble in concentrated HNO3, implying that it would be recovered with pyrite in a common assay of sediments. X-ray absorption fine structure data show that Mo(IV) in the colloids is coordinated by a split first shell of about five sulfur atoms at average distances of 2.31 and 2.46 Å and in its second shell by an iron atom at about 2.80 Å. These properties resemble those determined for Mo in modern anoxic lake sediments and in Phanerozoic black shales. The atomic environment around Mo suggests that the colloidal products may be inorganic polymers containing cuboid, Fe 2 Mo 2 S 4 4+ cores. Such materials are so far unreported by mineralogists, although a rare mineral, jordisite, may be a related, but more Mo-rich material. The low solubility of FeMoS 4 makes it a feasible precipitate in euxinic waters like those in the modern Black Sea. We propose that colloids similar to those studied here could account for Mo-enrichment in euxinic basin sediments and black shales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Ultrafine Mineral Associations in Superhigh-Organic-Sulfur Kentucky Coals

Two high-organic-sulfur Kentucky coals, the eastern Kentucky River Gem coal and the western Kentucky Davis coal, are examined by scanning electron microscopy, (SEM) and transmission electron microscopy (TEM), both including elemental analysis by energy-dispersive spectroscopy (EDS). From the SEM-EDS analysis, it is observed that the western Kentucky coal had areas with Pb and Cd in addition to the expected Fe and S and the eastern Kentucky coal had individual Fe-S-rich areas with La and Ni and with Si, Al, Cr, Ni, and Ti. TEM and selected area electron diffraction (SAED) analyses demonstrate that anglesite with a rim of Pb-bearing amorphous Fe-oxide occurs in the western Kentucky coal. Melanterite, an Fe-sulfate, with minor Al, Si, and K EDS peaks, suggests that clay minerals may be in close association with the sulfate, is also detected in the coal. A polycrystalline metal in the eastern Kentucky sample with a composition similar to stainless steel is adjacent to an Al-rich shard. Euhedral pyrite grains surrounded by kaolinite and gibbsite are detected. Overall, it is noted that element associations should not be assumed to be organic just because minerals cannot be seen with optical microscopy or with standard bulk analytical techniques, such as X-ray diffraction (XRD).

organic sulfur, kentucky coals, geoscience, SEM↗
DOE OSTI2015

Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal–Organic Framework-177

Metal–organic framework-177 (MOF-177) is one of the most porous materials whose structure is composed of octahedral Zn 4 O(-COO) 6 and triangular 1,3,5-benzenetribenzoate (BTB) units to make a three-dimensional extended network based on the qom topology. This topology violates a long-standing thesis where highly symmetric building units are expected to yield highly symmetric networks. In the case of octahedron and triangle combinations, MOFs based on pyrite (pyr) and rutile (rtl) nets were expected instead of qom. In this study, we have made 24 MOF-177 structures with different functional groups on the triangular BTB linker, having one or more functionalities. We find that the position of the functional groups on the BTB unit allows the selection for a specific net (qom, pyr, and rtl), and that mixing of functionalities (-H, -NH 2 , and -C 4 H 4 ) is an important strategy for the incorporation of a specific functionality (-NO 2 ) into MOF-177 where otherwise incorporation of such functionality would be difficult. Such mixing of functionalities to make multivariate MOF-177 structures leads to enhancement of hydrogen uptake by 25%.

membrane, carbon capture, materials and chemistry ↗
DOE OSTI2017

Hydrogen-Bond Symmetrization Breakdown and Dehydrogenation Mechanism of FeO 2 H at High Pressure

The cycling of hydrogen plays an important role in the geochemical evolution of our planet. Under high-pressure conditions, asymmetric hydroxyl bonds tend to form a symmetric O–H–O configuration in which H is positioned at the center of two O atoms. The symmetrization of O–H bonds improves their thermal stability and as such, water-bearing minerals can be present deeper in the Earth’s lower mantle. However, how exactly H is recycled from the deep mantle remains unclear. Here, we employ first-principles free-energy landscape sampling methods together with high pressure-high temperature experiments to reveal the dehydrogenation mechanism of a water-bearing mineral, FeO 2 H, at deep mantle conditions. Experimentally, we show that ~50% H is released from symmetrically hydrogen-bonded ε-FeO 2 H upon transforming to a pyrite-type phase (Py-phase). By resolving the lowest-energy transition pathway from ε-FeO 2 H to the Py-phase, we demonstrate that half of the O–H bonds in the mineral rupture during the structural transition, leading toward the breakdown of symmetrized hydrogen bonds and eventual dehydrogenation. In conclusion, our study sheds new light on the stability of symmetric hydrogen bonds during structural transitions and provides a dehydrogenation mechanism for hydrous minerals existing in the deep mantle

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Spectral induced polarization of shaly sands: Influence of the electrical double layer

I developed a new model named POLARIS describing the complex conductivity of (pyrite‐free) shaly poorly sorted sands. This model is based on the solution given by the effective medium theory for grains coated by an electrical double layer and immersed in a background electrolyte. The electrical double layer comprises the Stern layer and the diffuse layer. Both layers play very distinct roles in the in‐phase and quadrature conductivities. The polarization of the shaly sands is mainly controlled by the polarization of the Stern layer (except at very high salinities) with a very small mobility of the counterions contained in this layer. The in‐phase component of the conductivity is controlled by the conductivity of the pore water with a contribution associated with the diffuse layer (the contribution of the Stern layer seems negligible). The fraction of counterions in the Stern layer is computed from a simple sorption isotherm and is used to infer the quadrature conductivity. The quadrature conductivity is assumed to be frequency independent, which is a reasonable approximation in clayey sands and sandstones, in agreement with observations. The polarization model is also based on the assumption that the Stern layer is discontinuous between grains, an assumption that is consistent with recent models of ionic transport in clayey sands. POLARIS explains the dependence of the quadrature conductivity on the salinity, cation exchange capacity, specific surface area (or specific surface per unit pore volume), and temperature. It can be used to predict the saturation and the permeability (inside 1 order of magnitude).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

The Relationship Between Topography, Bedrock Weathering, and Water Storage Across a Sequence of Ridges and Valleys

Abstract Bedrock weathering regulates nutrient mobilization, water storage, and soil production. Relative to the mobile soil layer, little is known about the relationship between topography and bedrock weathering. Here, we identify a common pattern of weathering and water storage across a sequence of three ridges and valleys in the sedimentary Great Valley Sequence in Northern California that share a tectonic and climate history. Deep drilling, downhole logging, and characterization of chemistry and porosity reveal two weathering fronts. The shallower front is ∼7 m deep at the ridge of all three hillslopes, and marks the extent of pervasive fracturing and oxidation of pyrite and organic carbon. A deeper weathering front marks the extent of open fractures and discoloration. This front is 11 m deep under two ridges of similar ridge‐valley spacing, but 17.5 m deep under a ridge with nearly twice the ridge‐valley spacing. Hence, at ridge tops, the fraction of the hillslope relief that is weathered scales with hillslope length. In all three hillslopes, below this second weathering front, closed fractures and unweathered bedrock extend about one‐half the hilltop elevation above the adjacent channels. Neutron probe surveys reveal that seasonally dynamic moisture is stored to approximately the same depth as the shallow weathering front. Under the channels that bound our study hillslopes, the two weathering fronts coincide and occur within centimeters of the ground surface. Our findings provide evidence for feedbacks between erosion and weathering in mountainous landscapes that result in systematic subsurface structuring and water routing.

58 GEOSCIENCES↗
DOE OSTI2024

Oxidized Sulfur Species in Slab Fluids as a Source of Enriched Sulfur Isotope Signatures in Arcs

Recycling of oxidized sulfur from subducting slabs to the mantle wedge provides simultaneous explanations for the elevated oxygen fugacity (fO 2 ) in subduction zones, their high hydrothermal and magmatic sulfur outputs, and the enriched sulfur isotopic signatures (i.e., δ 34 S > 0‰) of these outputs. However, a quantitative understanding of the abundance and speciation of sulfur in slab fluids consistent with high pressure experiments is lacking. Here we analyze published experimental data for anhydrite solubility in H 2 O-NaCl solutions to calibrate a high-pressure aqueous speciation model of sulfur within the framework of the deep earth water model. We characterize aqueous complexes, required to account for the high experimental anhydrite solubilities. We then use this framework to predict the speciation and solubility of sulfur in chemically complex fluids in equilibrium with model subducting mafic and ultramafic lithologies, from 2 to 3 GPa and 400 to 800°C at log fO 2 from FMQ-2 to FMQ+4. We show that sulfate complexes of calcium and sodium markedly enhance the stability of sulfate in moderately oxidized fluids in equilibrium with pyrite at fO 2 conditions of FMQ+1 to +2, causing large sulfur isotope fractionations up to 10‰ in the fluid relative to the slab. Such fluids could impart oxidized, sulfur-rich and high δ 34 S signatures to the mantle wedge that are ultimately transferred to arc magmas, without the need to invoke 34 S-rich subducted lithologies.

58 GEOSCIENCES↗
DOE OSTI2021

Superionic iron oxide–hydroxide in Earth’s deep mantle

Water ice becomes a superionic phase under the high pressure and temperature conditions of deep planetary interiors of ice planets such as Neptune and Uranus, which affects interior structures and generates magnetic fields. The solid Earth, however, contains only hydrous minerals with a negligible amount of ice. Here we combine high pressure and temperature electrical conductivity experiments, Raman spectroscopy and first-principles simulations to investigate the state of hydrogen in the pyrite-type FeO 2 H x (x ≤ 1), which is a potential H-bearing phase near the core–mantle boundary. We find that when the pressure increases beyond 73 GPa at room temperature, symmetric hydroxyl bonds are softened and the H + (or proton) becomes diffusive within the vicinity of its crystallographic site. Increasing temperature under pressure, the diffusivity of hydrogen is extended beyond the individual unit cell to cover the entire solid, and the electrical conductivity soars, indicating a transition to the superionic state, which is characterized by freely moving protons and a solid FeO 2 lattice. Furthermore, the highly diffusive hydrogen provides fresh transport mechanisms for charge and mass, which dictate the geophysical behaviours of electrical conductivity and magnetism, as well as geochemical processes of redox, hydrogen circulation and hydrogen isotopic mixing in Earth’s deep mantle.

58 GEOSCIENCES↗
DOE OSTI2020

Evidence of shock-compressed stishovite above 300 GPa

SiO 2 is one of the most fundamental constituents in planetary bodies, being an essential building block of major mineral phases in the crust and mantle of terrestrial planets (1–10 M E ). Silica at depths greater than 300 km may be present in the form of the rutile-type, high pressure polymorph stishovite (P4 2 /mnm) and its thermodynamic stability is of great interest for understanding the seismic and dynamic structure of planetary interiors. Previous studies on stishovite via static and dynamic (shock) compression techniques are contradictory and the observed differences in the lattice-level response is still not clearly understood. Here, laser-induced shock compression experiments at the LCLS- and SACLA XFEL light-sources elucidate the high-pressure behavior of stishovite on the lattice-level under in situ conditions on the Hugoniot to pressures above 300 GPa. We find stishovite is still (meta-)stable at these conditions, and does not undergo any phase transitions. This contradicts static experiments showing structural transformations to the CaCl 2 , α-PbO 2 and pyrite-type structures. However, rate-limited kinetic hindrance may explain our observations. These results are important to our understanding into the validity of EOS data from nanosecond experiments for geophysical applications.

58 GEOSCIENCES↗
DOE OSTI2024

The application of synthetic antibacterial minerals to combat topical infections: exploring a mouse model of MRSA infection

Abstract The development of new antibiotics has stalled, and novel strategies are needed as we enter the age of antibiotic resistance. Certain naturally occurring clays have been shown to be effective in killing antibiotic resistant bacteria. However, these natural clays are too variable to be used in clinical settings. Our study shows that synthetic antibacterial minerals exhibit potent antibacterial activity against topical MRSA infections and increase the rate of wound closure relative to controls. The antibacterial minerals maintain a redox cycle between Fe 2+ /Fe 3+ and the surfaces of pyrite minerals, which act as a semiconductor and produce reactive oxygen species (ROS), while smectite minerals act as a cation exchange reservoir. Acidic conditions are maintained throughout the application of the hydrated minerals and can mitigate the alkaline pH conditions observed in chronic non-healing wounds. These results provide evidence for the strategy of ‘iron overload’ to combat antibiotic resistant infections through the maintained release of Fe 2+ and generation of ROS via distinct geochemical reactions that can break the chronic wound damage cycle.

58 GEOSCIENCES↗
DOE OSTI2015

From lithotroph- to organotroph-dominant: directional shift of microbial community in sulphidic tailings during phytostabilization

Engineering microbial diversity to enhance soil functions may improve the success of direct revegetation in sulphidic mine tailings. Therefore, it is essential to explore how remediation and initial plant establishment can alter microbial communities, and, which edaphic factors control these changes under field conditions. A long-term revegetation trial was established at a Pb-Zn-Cu tailings impoundment in northwest Queensland. The control and amended and/or revegetated treatments were sampled from the 3-year-old trial. In total, 24 samples were examined using pyrosequencing of 16S rRNA genes and various chemical properties. The results showed that the microbial diversity was positively controlled by soil soluble Si and negatively controlled by soluble S, total Fe and total As, implying that pyrite weathering posed a substantial stress on microbial development in the tailings. All treatments were dominated by typical extremophiles and lithotrophs, typically Truepera , Thiobacillus , Rubrobacter ; significant increases in microbial diversity, biomass and frequency of organotrophic genera (typically Nocardioides and Altererythrobacter ) were detected in the revegetated and amended treatment. We concluded that appropriate phytostabilization options have the potential to drive the microbial diversity and community structure in the tailings toward those of natural soils, however, inherent environmental stressors may limit such changes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2013

Structures and stabilities of alkaline earth metal peroxides XO2 (X=Ca, Be, Mg) studied by a genetic algorithm

The structures and stabilities of alkaline earth metal peroxides XO2 (X = Ca, Be, Mg) were studied using an adaptive genetic algorithm (GA) for global structure optimization in combination with first-principles calculations. From the adaptive GA search, we obtained an orthorhombic structure for CaO2 with 12 atoms in the unit cell, which is energetically more favorable than the previously proposed structures. Reaction energy of the decomposition CaO2 → CaO + 1/2O2 determined by density functional theory (DFT) calculation shows that this orthorhombic calcium peroxide structure is thermodynamically stable. The simulated X-ray diffraction (XRD) pattern using our predicted structure is in excellent agreement with experimental data. We also show that crystal phase BeO2 is unlikely to exist under normal conditions. MgO2 has a cubic pyrite structure, but it is not stable against decomposition: MgO2 → MgO + 1/2O2.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Persistent arsenate–iron( iii ) oxyhydroxide–organic matter nanoaggregates observed in coal

Understanding how natural nanoaggregates of iron (Fe) and organic matter (OM), currently identified in organic rich soil or peat, interact with metals and metalloids is environmentally significant. Here, coal is also organic-rich and exemplifies anoxic sedimentary environments with Fe usually as pyrite and not oxides. Here, we analyze the local structure of Fe (6880–21 700 mg kg –1 ) and As (45–5680 mg kg –1 ) in representative Guizhou coal samples using X-ray absorption near-edge structure and extended X-ray absorption fine structure (XANES and EXAFS) to illustrate how Fe(III) and As(V) are preserved in coal formed from reduced, organic-rich precursors. Arsenic XANES indicates that >80% of As exists as As(V) with <14% of As associated with sulfides in 5 Guizhou coal samples, confirming published but unexplained results. An As–Fe shell at 3.25–3.29 Å in the As EXAFS suggests that this As(V) is adsorbed on Fe(III) oxyhydroxides as evidenced by Fe EXAFS in these coal samples. Significantly, lower Fe–Fe coordination numbers (CN) of 0.6–1.1 relative to those in 2-line ferrihydrite (CN = 1.6) and goethite (CN = 2.1) suggest that these Fe(III) oxyhydroxides are likely Fe–OM nanoaggregates protected by OM encapsulation and adsorption of arsenate. Such structurally stabilized composites of As(V)–Fe(III)–OM may be more widely distributed and allow oxidized As and Fe to persist in other organic-rich, reducing environments.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Electronic structure and crystal phase stability of palladium hydrides

The results of electronic structure calculations for a variety of palladium hydrides are presented. The calculations are based on density functional theory and used different local and semilocal approximations. The thermodynamic stability of all structures as well as the electronic and chemical bonding properties are addressed. For the monohydride, taking into account the zero-point energy is important to identify the octahedral Pd-H arrangement with its larger voids and, hence, softer hydrogen vibrational modes as favorable over the tetrahedral arrangement as found in the zincblende and wurtzite structures. Stabilization of the rocksalt structure is due to strong bonding of the 4d and 1s orbitals, which form a characteristic split-off band separated from the main d-band group. Increased filling of the formerly pure d states of the metal causes strong reduction of the density of states at the Fermi energy, which undermines possible long-range ferromagnetic order otherwise favored by strong magnetovolume effects. For the dihydride, octahedral Pd-H arrangement as realized, e.g., in the pyrite structure turns out to be unstable against tetrahedral arrangement as found in the fluorite structure. Yet, from both heat of formation and chemical bonding considerations, the dihydride turns out to be less favorable than the monohydride. Finally, the vacancy ordered defect phase Pd{sub 3}H{sub 4} follows the general trend of favoring the octahedral arrangement of the rocksalt structure for Pd:H ratios less or equal to one.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗