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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Deciphering the Mechanistic Role of Individual Oxide Phases and Their Combinations in Supported Mn–Na 2 WO 4 Catalysts for Oxidative Coupling of Methane

Oxidative coupling of methane (OCM) is an attractive direct route for upgrading methane to valuable chemicals. In this study, Temporal Analysis of Products (TAP) and steady state experiments are conducted to understand the role of individual oxide phases and their combinations in supported Mn-Na 2 WO 4 /SiO 2 catalysts for OCM. The results from TAP transient kinetic studies indicate that Mn plays an important role in promoting gas phase oxygen activation, while NaO x /SiO 2 and WO x /SiO 2 are relatively inert towards gas phase oxygen and methane activation. However, the supported catalyst combining Na and W in the form Na 2 WO 4 show enhanced gas phase oxygen activation exhibiting a much lower oxygen activation energy (148 kJ/mol) and enhanced activity toward methane activation as compared to the individual supported oxide catalysts. Addition of Mn to Na 2 WO 4 /SiO 2 further decreases the oxygen activation energy by 40 kJ/mol. Moreover, methane activation is also enhanced with CH 3 as the main intermediate but, with increasing Mn content, more CH 2 intermediates are observed. Different forms of oxygen (both dioxygen and atomic) are detected on the catalyst surface using isotopic pump/probe pulsing and their distribution is found to depend on the catalyst composition. An optimal Mn content in the Na 2 WO 4 /SiO 2 catalyst system is needed to enhance the amount of dioxide surface species (e.g., superoxide 16 O 2 - or peroxide 16 O 2 2- ) associated with the Na 2 WO 4 leading to high C 2 selectivity for OCM. When the Mn content is too high, the larger MnOx domains are shown to contribute to the formation of higher concertation of monoxide surface species that lead to nonselective OCM pathways. This insight from transient kinetic characterization using TAP combined with conventional steady state studies, provides a deeper understanding of the role of individual oxide phases and their combination on supported catalysts toward the formation of intermediate surface species and their impact on the OCM reaction mechanism. This knowledge is critical toward designing superior catalyst formulations for OCM.

10 SYNTHETIC FUELS↗
DOE OSTI2024

Chamber studies of OH + dimethyl sulfoxide and dimethyl disulfide: insights into the dimethyl sulfide oxidation mechanism

Abstract. The oxidation of dimethyl sulfide (DMS) in the marine atmosphere represents an important natural source of non-sea-salt sulfate aerosol, but the chemical mechanisms underlying this process remain uncertain. While recent studies have focused on the role of the peroxy radical isomerization channel in DMS oxidation, this work revisits the impact of the other channels (OH addition and OH abstraction followed by bimolecular RO2 reaction) on aerosol formation from DMS. Due to the presence of common intermediate species, the oxidation of dimethyl sulfoxide (DMSO) and dimethyl disulfide (DMDS) can shed light on these two DMS reaction channels; they are also both atmospherically relevant species in their own right. This work examines the OH oxidation of DMSO and DMDS, using chamber experiments monitored by chemical ionization mass spectrometry and aerosol mass spectrometry to study the full range of sulfur-containing products across a range of NO concentrations. The oxidation of both compounds is found to lead to rapid aerosol formation (which does not involve the intermediate formation of SO2), with a substantial fraction (14 %–47 % S yield for DMSO and 5 %–21 % for DMDS) of reacted sulfur ending up in the particle phase and the highest yields observed under elevated NO conditions. Aerosol is observed to consist mainly of sulfate, methanesulfonic acid, and methanesulfinic acid. In the gas phase, the NOx dependence of several products, including SO2 and S2-containing organosulfur species, suggest reaction pathways not included in current mechanisms. Based on the commonalities with the DMS oxidation mechanism, DMSO and DMDS results are used to reconstruct DMS aerosol yields; these reconstructions roughly match DMS aerosol yield measurements from the literature but differ in composition, underscoring remaining uncertainties in sulfur chemistry. This work indicates that both the abstraction and addition channels contribute to rapid aerosol formation from DMS and highlights the need for more study into the fate of small sulfur radical intermediates (e.g., CH3S, CH3SO2, and CH3SO3) that are thought to play central roles in the DMS oxidation mechanism.

Goss, Matthew B. (ORCID:0000000226885463)↗
NASA NTRS1979

Thermal stress analysis of ceramic gas-path seal components for aircraft turbines

Stress and temperature distributions were evaluated numerically for a blade-tip seal system proposed for gas turbine applications. The seal consists of an abradable ceramic layer on metallic backing with intermediate layers between the ceramic layer and metal substrate. The most severe stresses in the seal, as far as failure is concerned, are tensile stresses at the top of the ceramic layer and shear and normal stresses at the layer interfaces. All these stresses reach their maximum values during the deceleration phase of a test engine cycle. A parametric study was carried out to evaluate the influence of various design parameters on these critical stress values. The influences of material properties and geometric parameters of the ceramic, intermediate, and backing layers were investigated. After the parametric study was completed, a seal system was designed which incorporated materials with beneficial elastic and thermal properties in each layer of the seal. An analysis of the proposed seal design shows an appreciable decrease in the magnitude of the maximum critical stresses over those obtained with earlier configurations.

Kennedy, F. E.↗
DOE OSTI2014

Theoretical study of carbon adsorption on Re surfaces: Morphological instability

We report results from new experiments on C/Re(112¯1) to identify threshold conditions for morphological instability of Re(112¯1). We have found that adsorption of carbon from 0.35 to 0.85 ML (0.3–6.0 L exposure of C 2 H 2 ) at T ≥ 800 K leads to faceting of Re(112¯1) with formation of three-sided pyramids. Using density functional theory we have investigated binding sites and binding energies of C on planar and faceted Re surfaces as well as generated a surface phase diagram of C/Re to obtain an atomistic understanding of C-induced pyramidal faceting of Re(112¯1). As a result, the calculations reveal that at low to intermediate coverage, C atoms prefer binding at four-fold sites on the Re surfaces and formation of three-sided pyramids is thermodynamically favored.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Unveiling phase evolution of complex oxides toward precise solid-state synthesis

The precise synthesis of high-purity materials is crucial in accelerating materials discovery. However, the lack of theoretical understanding and practical guidance poses challenges, particularly for materials with compositional and structural complexity. Here, we propose a feasible principle toward synthesizing complex inorganic solids. This principle involves the introduction of an inducer that induces crucial intermediates, which in turn guide the synthesis pathway toward the target materials through structural templating, named inducer-facilitated assembly through structural templating (i-FAST). We validate this principle with three distinct oxides: garnet Li6.5La3Zr1.5Ta0.5O12, perovskite BaCo0.8Sn0.2O3, and pyrochlore Gd1.5La0.5Zr2O7. This structural templating approach enables synthesis along predesigned pathways, forming intermediates that are thermodynamically favored for prior formation and kinetically preferred for the final product, resulting in precisely synthesizing high-purity target materials. This study not only represents a substantial advancement in comprehending the interplay between thermodynamics/kinetics and phase evolution in complex solid synthesis but also provides an effective strategy for guiding exploratory solid-state synthesis.

Yang, Lin↗
DOE OSTI2016

A new structural relaxation pathway of low-density amorphous ice

Low-density amorphous (LDA) ice is involved in critical cosmological processes and has gained prominence as one of the at least two distinct amorphous forms of ice. Despite these accolades, we still have an incomplete understanding of the structural diversity that is encompassed within the LDA state and the dynamic processes that take place upon heating LDA. Heating the high-pressure ice VIII phase at ambient pressure is a remarkable example of temperature-induced amorphisation yielding LDA. We investigate this process in detail using X-ray diffraction and Raman spectroscopy and show that the LDA obtained from ice VIII is structurally different from the more “traditional” states of LDA which are approached upon thermal annealing. This new structural relaxation pathway involves an increase of structural order on the intermediate range length scale. In contrast with other LDA materials the local structure is more ordered initially and becomes slightly more disordered upon annealing. We also show that the cascade of phase transitions upon heating ice VIII at ambient pressure includes the formation of ice IX which may be connected with the structural peculiarities of LDA from ice VIII. Overall, this study shows that LDA is a structurally more diverse material than previously appreciated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Instantons, colloids and convergence of the 1/N expansion for the homogeneous electron gas

We investigate non-perturbative corrections to the large N expansion of the homogeneous electron gas. These are associated with instanton solutions to the effective action of the plasmon field. We show that, although the large field behavior of that action dominates the quadratic bare Coulomb term, there are no solutions at large field, and consequently none at large density. We argue that solutions would exist at low density if the large N theory had a Wigner crystal (WC) phase. However, we argue that this is not the case. Together with the implied convergence of the large N expansion, this implies that the homogeneous electron gas with N component spins and a Coulomb interaction scaling like 1∕N can only have a WC phase below a curve in the plane of N and density, which asymptotes to zero density at infinite N. We argue that for systems with a semi-classical expansion for order parameter dynamics, and a first order quantum transition between fluid and crystal phases, there are instantons associated with the decays of meta-stable fluid and crystal phases in the appropriate regions of the phase diagram. We argue that the crystal will decay into one or more colloidal or bubble phases (Kivelson and Spivak, 2006) rather than directly into the fluid. It is possible that the bubble phases remain stable all the way to the density where the crystal solution disappears. The bubbles of fluid will expand as the density is raised and gradually convert the system into a fluid filled with chunks of crystal. The transition to a translationally invariant phase is likely to be second order. Unfortunately, the HEG does not have a crystal phase at large N, where these semi-classical ideas could be examined in detail. We suggest that the evidence for negative dielectric function at intermediate densities for N=2 is an indicator of this second order transition. While the infinite N limit does not have a negative dielectric function at any density, it is possible that the closed large N equation for the plasmon two point function, derived in Banks (2018) might capture at least the qualitative features of the second order transition.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Investigation of the discontinuous precipitation of U-Nb alloys via thermodynamic analysis and phase-field modeling

U-Nb’s discontinuous precipitation, $\gamma^{bcc}_{matrix}$, $\alpha^{orth}_{cellular}$, $\gamma\prime^{bcc}_{cellular}$, is intriguing in the sense that it allows formation and growth of the metastable $\gamma\prime$ phase during the course of its occurrence. Previous attempts to explain the thermodynamic origin of U-Nb’s discontinuous precipitation hypothesized that the energy of $\alpha$ forms an intermediate common tangent with the first potential of the double-well energy of $\gamma$ at the $\gamma\prime$ composition. In this work, we examine different possible mechanisms by which the discontinuous precipitation product in the U-Nb system can be stabilized. We put forward a mechanism by which the bulk free energy of the $\gamma$ can develop a non-monotonic dependency with composition. Additionally we posit that local contributions due to lattice mismatch between the $\alpha$ and $\gamma$ phases may be responsible for the generation of metastable states that may stabilized by thermodynamics as well as by kinetics. Our work suggests that local misfit strain tends to play a crucial role in the growth of the discontinuous precipitation product. Depending on the magnitude of strain developed at the $\alpha$/$\gamma\prime$ interfaces, either an increasing $\gamma\prime$ composition or a random distribution of $\gamma\prime$ compositions around the equiatomic value with respect to increasing temperature could be expected. Moreover, we show how it is possible to stabilize the discontinuous precipitation front through highly anisotropic and fast interface diffusion.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2011

Impact of the nuclear symmetry energy on the pygmy dipole resonance

The correlation between the pygmy dipole strength and the symmetry energy of nuclear matter is reanalyzed. While previous calculations [A. Klimkiewicz et al., Phys. Rev. C 76, 051603(R) (2007); A. Carbone, G. Colo, A. Bracco, L.-G. Cao, P. F. Bortignon, F. Camera, and O. Wieland, Phys. Rev. C 81, 041301 (2010).] have clearly shown a direct correlation between both quantities, it remains unclear to what extent experimental as well as theoretical uncertainties can allow for an accurate determination of the symmetry energy. For this reason, we have recalculated the low-lying strength distributions of the giant dipole resonances for {sup 130}Sn and {sup 132}Sn that have been recently measured, taking into account the above uncertainties. The calculations are performed within two microscopic models, namely, the discrete quasiparticle random phase approximation (DRPA) and the quasiparticle continuum RPA, which is an extension of the DRPA that takes the coupling to the single-particle continuum into account in an exact way.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1994

The X-ray selected cataclysmic variables H0459 + 246 and H0857 - 242

We report the discovery of two cataclysmic variables located with the assistance of X-ray positions from the HEAO 1 Modulation Collimator and the Large-Area Sky Survey. Each case is distinguished by evidence of two periodic modulations that appear to represent the orbital period and the spin period of the white dwarf, respectively. The first case, H0459 + 246, has been observed optically during faint states (V approximately 16), in which there are spectral features of both an accretion disk and a K star. The light curves in the V and I bands are consistent with ellipsoidal variations in the secondary stars with a binary period of 9.952 hr. X-ray observations with EXOSAT reveal a strong pulsation with a period approximately 62 minutes. This result confirms an 'intermediate polar' classification for H0459 + 246. The pulsation is observed at 63.2 minutes in the optical I band. The long orbital period opens the possibility that H0459 + 246 is a relatively young intermediate polar that might evolve into a polar. The second case, H0857--242, shows radial velocity modulations at 1.78 hr along with photometric variations at a period approximately 49 minutes. The latter are observed only during the decay phase of dwarf nova outbursts (13 less than V less than 17), which apparently recur frequently. Given the lack of X-ray monitoring observations and the absence of proof that the 49 minute periodicity is coherent over long time-scales, we regard H0857--242 as a candidate intermediate polar. Photographic records from th e Harvard Observatory Plate Library further reveal superoutbursts for H0857--242 (V approximately 11). A bright X-ray source that is both an intermediate polar and a continually cycling dwarf nova may provide an effective means of measuring the time delay for the arrival of accreting matter at the white dwarf surface, relative to the onset of optical brightening.

Remillard, R. A.↗
DOE OSTI2016

Interaction of Molecular Oxygen with a Hexagonally Reconstructed Au(001) Surface

Kinetics of molecular oxygen/Au(001) surface interaction has been studied at high temperature and near atmospheric pressures of O 2 gas with in situ X-ray scattering measurements. In this study, we find that the hexagonal reconstruction (hex) of Au(001) surface lifts to (1 × 1) in the presence of O 2 gas, indicating that the (1 × 1) is more favored when some oxygen atoms present on the surface. The measured lifting rate constant vs temperature is found to be highest at intermediate temperature exhibiting a “volcano”-type behavior. At low temperature, the hex-to-(1 × 1) activation barrier (E act = 1.3(3) eV) limits the lifting. At high temperature, oxygen adsorption energy (E ads = 1.6(2) eV) limits the lifting. The (1 × 1)-to-hex activation barrier (E hex = 0.41(14) eV) is also obtained from hex recovery kinetics. The pressure–temperature (PT) surface phase diagram obtained in this study shows three regions: hex at low P and T, (1 × 1) at high P and T, and coexistence of the hex and (1 × 1) at the intermediate P and T.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Development, Testing and Validation of a Waste Assay System for the Measurement and Characterisation of Active Spent Fuel Element Debris From UK Magnox Reactors - 12533

This paper describes the development, testing and validation of a waste measurement instrument for characterising active remote handled radioactive waste arising from the operation of Magnox reactors in the United Kingdom. Following operation in UK Magnox gas cooled reactors and a subsequent period of cooling, parts of the magnesium-aluminium alloy cladding were removed from spent fuel and the uranium fuel rods with the remaining cladding were removed to Sellafield for treatment. The resultant Magnox based spent fuel element debris (FED), which constitutes active intermediate level waste (ILW) has been stored in concrete vaults at the reactor sites. As part of the decommissioning of the FED vaults the FED must be removed, measured and characterised and placed in intermediate storage containers. The present system was developed for use at the Trawsfynydd nuclear power station (NPS), which is in the decommissioning phase, but the approach is potentially applicable to FED characterisation at all of the Magnox reactors. The measurement system consists of a heavily shielded and collimated high purity Germanium (HPGe) detector with electromechanical cooling and a high count-rate preamplifier and digital multichannel pulse height analyser. The HPGe based detector system is controlled by a software code, which stores the measurement result and allows a comprehensive analysis of the measured FED data. Fuel element debris is removed from the vault and placed on a tray to a uniform depth of typically 10 cm for measurement. The tray is positioned approximately 1.2 meters above the detector which views the FED through a tungsten collimator with an inverted pyramid shape. At other Magnox sites the positions may be reversed with the shielded and collimated HPGe detector located above the tray on which the FED is measured. A comprehensive Monte Carlo modelling and analysis of the measurement process has been performed in order to optimise the measurement geometry and eliminate interferences from radioactive sources and FED in the immediate vicinity of the measurement position. The detector system has been calibrated and high activity radioactive sources of Cs-137, Co-60 and Na-22 have been used to validate the measurement process. The data acquisition and analysis software code has been tested and validated in keeping with the software quality assurance requirements of both ISO:9001-2008 - TICK-IT in the UK and NQA-1. The measurement and analysis system has been comprehensively tested with high activity sources, is flexible and may be applicable to a wide range of remote handled radioactive waste measurement applications. It is due to be installed at Trawsfynydd NPS later this year. This paper describes the Waste Tray Assay System (WTAS) that has been developed for the measurement of Magnox FED waste. The WTAS has been tested with a range of radioactive sources and its operation has been simulated with benchmarked MCNP Monte Carlo calculations. The measurement software has been validated as has the operation of the system for a range of strong radioactive sources. A system based on the design is due for installation and operation in 2012. The system has application to the measurement of Magnox Fuel Element Debris (FED) waste at other Magnox reactor sites. The major design objective of the WTAS that has been achieved is the ability of the assay system to determine the content of Cs-137, and in turn to enable the fissile burden to be assessed using a radionuclide fingerprint, in the presence of higher and highly variable quantities of Co-60, typically from nimonic springs. The approach can be used in other Magnox FED waste configurations where the detector is located above the FED waste sorting tray and where the collimation is fixed below the detector and at a distance above the tray. In this case, which has also been investigated, there are different shielding problems and mechanical support issues. The extensive use of MCNP Monte Carlo modelling to simulate the geometry of the sorting cell and the distribution of radioactive sources has helped to ensure that all of the detector shielding requirements are addressed and suitable Cs-137 and Co-60 discrimination can be achieved. The WTAS in its present form or in other configurations has relevance to the measurement of other active ILW and highly active RH waste. Examples include high activity RH LLW and RH TRU (Transuranic) waste as defined in the United States arising from both commercial nuclear and Department of Energy (DOE) operations. The analysis is able to analyse a range of radionuclides beyong those expected in the Magnox FED cases. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Processing of SOFC Anodes for Enhanced Intermediate Temperature Catalytic Activity at High Fuel Utilization (Final Report)

The overall objective was to infiltrate anodes with nanoparticle catalysts so that anode catalytic performance can be improved as anode operation temperature is reduced from 800°C to intermediate temperatures of 700°C and 600°C and as anode fuel utilization is increased. The addition of nickel nanoparticle catalysts into the anode improves performance by providing additional triple phase boundaries (TPBs), increasing the density of electrochemical reaction sites. To achieve this goal, both liquid phase and vapor phase methods for depositing nickel nanoparticles in the anode active layer, the region of the anode near the electrolyte where the electrochemical reaction occurs. It is imperative that nanoparticles are stable against coarsening during long-term operation, so the mechanisms and kinetics of nanoparticle stability during cell operation will be investigated. Finally, priority is given to processes that are scalable and easily transferable to industry, leveraging existing Ni-YSZ cermet anode technology. Utilizing nickel nanoparticles at different temperatures has different considerations that will be addressed. At the upper end of the intermediate temperature range (800°C), it is important that performance improvement is maintained over long periods by mitigating the instability of nanoparticles. At the middle of the temperature range (700°C), it is important that performance improvement is maintained at high fuel utilizations. At the lower end of the temperature range (600°C), where the performance of cells is poor due to increased resistances, it is important to improve anode performance by significantly increasing the electrochemical reaction site density, while nanoparticle durability is less of an issue. Finally, the objective was to explore mixed ionic and electronic (MIEC) nanoparticle catalysts like GDC to see if 2-phase boundaries can be created to increase the electrochemical reactions at the anode.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2018

Enhancing the anticoagulant profile of meizothrombin

Meizothrombin is an active intermediate generated during the proteolytic activation of prothrombin to thrombin in the penultimate step of the coagulation cascade. Structurally, meizothrombin differs from thrombin because it retains the auxiliary Gla domain and two kringles. Functionally, meizothrombin shares with thrombin the ability to cleave procoagulant (fibrinogen), prothrombotic (PAR1) and anticoagulant (protein C) substrates, although its specificity toward fibrinogen and PAR1 is less pronounced. In this study we report information on the structural architecture of meizothrombin resolved by SAXS and single molecule FRET as an elongated arrangement of its individual domains. In addition, we show the properties of a meizothrombin construct analogous to the anticoagulant thrombin mutant W215A/E217A currently in Phase I for the treatment of thrombotic complications and stroke. The findings reveal new structural and functional aspects of meizothrombin that advance our understanding of a key intermediate of the prothrombin activation pathway.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Direct Imaging of Antiferromagnet-Ferromagnet Phase Transition in van der Waals Antiferromagnet CrSBr

The advent of van der Waals (vdW) ferromagnetic (FM) and antiferromagnetic (AFM) materials offers unprecedented opportunities for spintronics and magneto-optic devices. Combining magnetic Kerr microscopy and density functional theory calculations, the AFM-FM transition is investigated and a surprising abnormal magneto-optic anisotropy in vdW CrSBr associated with different magnetic phases (FM, AFM, or paramagnetic state) is discovered. This unique magneto-optic property leads to different anisotropic optical reflectivity from different magnetic states, permitting direct imaging of the AFM Néel vector orientation and the dynamic process of the AFM-FM transition within a magnetic field. Using Kerr microscopy, not only the domain nucleation and propagation process is imaged but also the intermediate spin-flop state in the AFM-FM transition is identified. In conclusion, the unique magneto-optic property and clear identification of the dynamics process of the AFM-FM phase transition in CrSBr demonstrate the promise of vdW magnetic materials for future spintronic technology.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Composite fermions in medium: Extending the Lipkin model

The role of phase space occupation effects for the formation of twoand three-particle bound states in a dense medium is investigated within an algebraic approach suitable for systems with short-range interactions. It is shown that for two-fermion bound states due to the account of the exchange symmetry (phase space occupation) effect (Pauli blocking) in a dense medium the binding energy is reduced and vanishes at a critical density (Mott effect). For three-fermion bound states, within a Faddeev equation approach, the intermediate formation of pair correlations leads to the representation as a suitably symmetrized fermion-boson bound state. It is shown that the Bose enhancement of fermion pairs can partially compensate the Pauli blocking between the fermions. This leads to the general result obtained by algebraic methods: three-fermion bound states in a medium with high phase space occupation appear necessarily as Borromean states beyond the Mott density of the two-fermion bound state.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Electrochemically induced metal- vs. ligand-based redox changes in mackinawite: identification of a Fe 3+ - and polysulfide-containing intermediate

Under anaerobic conditions, ferrous iron reacts with sulfide producing FeS, which can then undergo a temperature, redox potential, and pH dependent maturation process resulting in the formation of oxidized mineral phases, such as greigite or pyrite. A greater understanding of this maturation process holds promise for the development of iron-sulfide catalysts, which are known to promote diverse chemical reactions, such as H + , CO 2 and NO 3 - reduction processes. Hampering the full realization of the catalytic potential of FeS, however, is an incomplete knowledge of the molecular and redox processess ocurring between mineral and nanoparticulate phases. Here, we investigated the chemical properties of iron-sulfide by cyclic voltammetry, Raman and X-ray absorption spectroscopic techniques. Tracing oxidative maturation pathways by varying electrode potential, nanoparticulate n(Fe 2+ S 2- ) (s) was found to oxidize to a Fe 3+ containing FeS phase at -0.5 V vs. Ag/AgCl (pH = 7). In a subsequent oxidation, polysulfides are proposed to give a material that is composed of Fe 2+ , Fe 3+ , S 2- and polysulfide (S n 2- ) species, with its composition described as Fe 2+ 1-3x Fe 3+ 2x S 2- 1-y (S n 2- ) y . Thermodynamic properties of model compounds calculated by density functional theory indicate that ligand oxidation occurs in conjunction with structural rearrangements, whereas metal oxidation may occur prior to structural rearrangement. These findings together point to the existence of a metastable FeS phase located at the junction of a metal-based oxidation path between FeS and greigite (Fe 2+ Fe 3+ 2 S 2- 4 ) and a ligand-based oxidation path between FeS and pyrite (Fe 2+ (S 2 ) 2- ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗