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The origin and assignment of the complex main and satellite X-ray photoelectron spectroscopy (XPS) features of the cations in ionic compounds have been the subject of extensive theoretical studies using different methods. There is agreement that within a molecular orbital model, one needs to take into account different types of configurations. Specifically, those where a core electron is removed, but no other configuration changes are made and those where in addition to ionization, there are also shake or charge-transfer changes to the ionic configuration. However, there are strong disagreements about the assignment of XPS features to these configurations. The present work is directed toward resolving the origin of main and satellite features for the Ni 2p XPS of NiO based on ab initio molecular orbital wave functions (WFs) for a cluster model of NiO. A major problem in earlier ab initio XPS studies of ionic compounds has been the use of a common set of orbitals that was not able to properly describe all the ionic configurations that contribute to the full XPS spectra. This is resolved in the present work by using orbitals that are optimized for averages of the occupations of the different configurations that contribute to the XPS. The approach of using state-averaged (SA) orbitals is validated through comparisons between different averages and through use of higher order excitations in the WFs for the ionic states. It represents a major extension of our earlier work on the main and satellite features of the Fe 2p XPS of Fe2O3 and proves the reliability and the generality of the assignments of the character and origin of the different features of the XPS obtained with orbitals optimized for SAs. These molecular orbital methods permit the characterization of the ionic states in terms of the importance of shake excitations and of the coupling of ionization of 2p1/2 and 2p3/2 spin-orbit split sub shells. The work lays the foundation for definitive assignments of the character of main and satellite XPS features and points to their origin in the electronic structure of the material.
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Characterizing the chemical state and physical disposition of uranium that has persisted over geologic time scales is key for modeling the long-term geologic sequestration of nuclear waste, accurate uranium-lead dating, and the use of uranium isotopes as paleo redox proxies. X-ray absorption spectroscopy coupled with molecular dynamics modeling demonstrated that pentavalent uranium is incorporated in the structure of 1.6 billion year old hematite (α-Fe2O3), attesting to the robustness of Fe oxides as waste forms and revealing the reason for the great success in using hematite for petrogenic dating. The extreme antiquity of this specimen suggests that the pentavalent state of uranium, considered a transient, is stable when incorporated into hematite, a ubiquitous phase that spans the crustal continuum. Thus, it would appear overly simplistic to assume that only the tetravalent and hexavalent states are relevant when interpreting the uranium isotopic record from ancient crust and contained ore systems.
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Uranio , Compuestos Férricos/química , Oxidación-Reducción , Uranio/química , Espectroscopía de Absorción de Rayos XRESUMEN
We have developed a specialized microfluidic electrochemical cell that enables in situ investigation of the electrochemical corrosion of microgram quantities of redox active solids. The advantage of downscaling is the reduction of hazards, waste, expense, and greatly expanding data collection for hazardous materials, including radioactive samples. Cyclic voltammetry was used to monitor the oxidation-reduction cycle of minute quantities of micron-size uraninite (UO2) particles, from the formation of hexavalent uranium (U(vi)), U3O7 and reduction to UO2+x . Reaction progress was also studied in situ with scanning electron microscopy. The electrochemical measurements matched those obtained at the bulk-scale and were consistent with ex situ characterization of the run products by X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and atomic force microscopy; thus, demonstrating the utility of the microfluidic approach for studying radioactive materials.
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We used IR and XRD, with supporting theoretical calculations, to investigate the swelling behavior of Na+-, NH4+-, and Cs+-montmorillonites (SWy-2) in supercritical fluid mixtures of H2O, CO2, and CH4. Building on our prior work with Na-clay that demonstrated that H2O facilitated CO2 intercalation at relatively low RH, here we show that increasing CO2/CH4 ratios promote H2O intercalation and swelling of the Na-clay at progressively lower RH. In contrast to the Na-clay, CO2 intercalated and expanded the Cs-clay even in the absence of H2O, while increasing fluid CO2/CH4 ratios inhibited H2O intercalation. The NH4-clay displayed intermediate behavior. By comparing changes in the HOH bending vibration of H2O intercalated in the Cs-, NH4-, and Na-clays, we posit that CO2 facilitated expansion of the Na-clay by participating in outer-sphere solvation of Na+ and by disrupting the H-bond network of intercalated H2O. In no case did the pure CH4 fluid induce expansion. Our experimental data can benchmark modeling studies aimed at predicting clay expansion in humidified fluids with varying ratios of CO2 and CH4 in real reservoir systems with implications for enhanced hydrocarbon recovery and CO2 storage in subsurface environments.
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Hematite (α-Fe2O3) exerts a strong control over the transport of minor but critical metals in the environment and is used in multiple industrial applications; the photocatalysis community has explored the properties of hematite nanoparticles over a wide range of transition metal dopants. Nonetheless, simplistic assumptions are used to rationalize the local coordination environment of impurities in hematite. Here, we use ab initio molecular dynamics (AIMD)-guided structural analysis to model the extended X-ray absorption fine structure (EXAFS) of Cu2+- and Zn2+-doped hematite nanoparticles. Specific defect-impurity associations were identified, and the local coordination environments of Cu and Zn both displayed considerable configurational disorder that, in aggregate, approached Jahn-Teller-like distortion for Cu but, in contrast, maintained hematite-like symmetry for Zn. This study highlights the role of defects in accommodating impurities in a nominally low-entropy phase and the limits to traditional shell-by-shell fitting of EXAFS for dopants/impurities in unprecedented bonding environments.
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Birnessite is a layered MnO2 mineral capable of intercalating nanometric water films in its bulk. With its variable distributions of Mn oxidation states (MnIV, MnIII, and MnII), cationic vacancies, and interlayer cationic populations, birnessite plays key roles in catalysis, energy storage solutions, and environmental (geo)chemistry. We here report the molecular controls driving the nanoscale intercalation of water in potassium-exchanged birnessite nanoparticles. From microgravimetry, vibrational spectroscopy, and X-ray diffraction, we find that birnessite intercalates no more than one monolayer of water per interlayer when exposed to water vapor at 25 °C, even near the dew point. Molecular dynamics showed that a single monolayer is an energetically favorable hydration state that consists of 1.33 water molecules per unit cell. This monolayer is stabilized by concerted potassium-water and direct water-birnessite interactions, and involves negligible water-water interactions. Using our composite adsorption-condensation-intercalation model, we predicted humidity-dependent water loadings in terms of water intercalated in the internal and adsorbed at external basal faces, the proportions of which vary with particle size. The model also accounts for additional populations condensed on and between particles. By describing the nanoscale hydration of birnessite, our work secures a path for understanding the water-driven catalytic chemistry that this important layered manganese oxide mineral can host in natural and technological settings.
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The bulk behavior of materials is often controlled by minor impurities that create nonperiodic localized defect structures due to ionic size, symmetry, and charge balance mismatches. Here, we used transmission electron microscopy (TEM) of atom-resolved dynamics to directly map the topology of Fe vacancy clusters surrounding structurally incorporated U6+ in nanohematite (α-Fe2O3). Ab initio molecular dynamic simulations provided additional independent constraints on coupled U, Fe, and vacancy mobility in the solid. A clearer understanding of how such an apparently incompatible element can be accommodated by hematite emerged. The results were readily interpretable without the need for sophisticated data reconstruction methods, model structures, or ultrathin samples, and with the proliferation of aberration-corrected TEM facilities, the approach is accessible. Given sufficient z-contrast, the ability to observe impurity-vacancy structures by means of atom hopping can be used to directly probe the association of impurities and such defects in other materials, with promising applications across a broad range of disciplines.
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Forsterite carbonated in thin H2O films to magnesite via amorphous magnesium carbonate during reaction with H2O-bearing liquid CO2 at 25 °C. This novel reaction pathway contrasts with previous studies that were carried out at higher H2O activity and temperature, where more highly hydrated nesquehonite was the metastable intermediate.
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In geologic carbon sequestration, CO2 is injected into geologic reservoirs as a supercritical fluid (scCO2). The carbonation of divalent silicates exposed to humidified scCO2 occurs in angstroms to nanometers thick adsorbed H2O films. A threshold H2O film thickness is required for carbonate precipitation, but a mechanistic understanding is lacking. In this study, we investigated carbonation of forsterite (Mg2SiO4) in humidified scCO2 (50 °C and 90 bar), which serves as a model system for understanding subsurface divalent silicate carbonation reactivity. Attenuated total reflection infrared spectroscopy pinpointed that magnesium carbonate precipitation begins at 1.5 monolayers of adsorbed H2O. At about this same H2O coverage, transmission infrared spectroscopy showed that forsterite dissolution begins and electrical impedance spectroscopy demonstrated that diffusive transport accelerates. Molecular dynamics simulations indicated that the onset of diffusion is due to an abrupt decrease in the free-energy barriers for lateral mobility of outer-spherically adsorbed Mg2+. The dissolution and mass transport controls on divalent silicate reactivity in wet scCO2 could be advantageous for maximizing permeability near the wellbore and minimize leakage through the caprock.
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Dióxido de Carbono , Agua , Carbonatos , Compuestos de Silicona , SolubilidadRESUMEN
The origins of the complex Fe 2p X-Ray Photoelectron Spectra (XPS) of hematite (α-Fe2O3) are analyzed and related to the character of the bonding in this compound. This analysis provides a new and novel view of the reasons for XPS binding energies (BEs) and BE shifts, which deepens the current understanding and interpretation of the physical and chemical significance of the XPS. In particular, many-body effects are considered for the initial and the final, 2p-hole configuration wavefunctions. It is shown that a one-body or one-configuration analysis is not sufficient and that the many-body, many-determinantal, and many-configurational character of the wavefunctions must be taken into account to describe and understand why the XPS intensity is spread over an extremely large number of final 2p-hole multiplets. The focus is on the consequences of angular momentum coupling of the core and valence open shell electrons, the ligand field splittings of the valence shell orbitals, and the degree of covalent mixing of the Fe(3d) electrons with the O(2p) electrons. Novel theoretical methods are used to estimate the importance of these various terms. An important consequence of covalency is a reduction in the energy separation of the multiplets. Although shake satellites are not considered explicitly, the total losses of intensity from the angular momentum multiplets to shake satellites is determined and related to the covalent character of the Fe-O interaction. The losses are found to be the same for Fe 2p1/2 and 2p3/2 ionization.
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Zn is an essential micronutrient that is often limited in tropical, lateritic soils in part because it is sequestered in nominally refractory iron oxide phases. Stable phases such as goethite and hematite, however, can undergo reductive recrystallization without a phase change under circumneutral pH conditions and release metal impurities such as Zn into aqueous solutions. Further, the process appears to be driven by Fe vacancies. In this contribution, we used ab initio molecular dynamics informed extended X-ray absorption fine structure spectra to show that Zn incorporated in the structure of hematite is associated with coupled O-Fe and protonated Fe vacancies, providing a potential link between crystal chemistry and the bioavailability of Zn.
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Oligoelementos , Zinc , Compuestos Férricos , Minerales , AguaRESUMEN
Oxygen defects govern the behavior of a range of materials spanning catalysis, quantum computing, and nuclear energy. Understanding and controlling these defects is particularly important for the safe use, storage, and disposal of actinide oxides in the nuclear fuel cycle, since their oxidation state influences fuel lifetimes, stability, and the contamination of groundwater. However, poorly understood nanoscale fluctuations in these systems can lead to significant deviations from bulk oxidation behavior. Here we describe the use of aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy to resolve changes in the local oxygen defect environment in [Formula: see text] surfaces. We observe large image contrast and spectral changes that reflect the presence of sizable gradients in interstitial oxygen content at the nanoscale, which we quantify through first-principles calculations and image simulations. These findings reveal an unprecedented level of excess oxygen incorporated in a complex near-surface spatial distribution, offering additional insight into defect formation pathways and kinetics during [Formula: see text] surface oxidation.
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Reaction pathways and kinetics in highly structured H2O adsorbed as Ångstrom to nanometer thick layers on mineral surfaces are distinct from those facilitated by bulk liquid water. We investigate the role of the interfacial H2O structure in the reaction of H2O and CO2 to form carbonic acid (H2CO3) in thin H2O films condensed onto silica nanoparticles from humidified supercritical CO2. Rates of carbonic acid formation are correlated with spectroscopic signatures of H2O structure using oxygen isotopic tracers and infrared spectroscopy. While carbonic acid virtually does not form in the supercritical phase, the silica surface catalyzes this reaction by concentrating H2O through adsorption at hydrophilic silanol groups. Within measurement uncertainty, we found no evidence that carbonic acid forms when exclusively ice-like structured H2O is detected at the silica surface. Instead, formation of H2C18O16O2 from H218O and C16O2 was found to be linearly correlated with liquid-like structured H2O that formed on the ice-like layer.
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Aluminum-bearing minerals show different hydrogen evolution and dissolution properties when subjected to radiation, but the complicated sequence of events following interaction with high-energy radiation is not understood. To gain insight into the possible mechanisms of hydrogen production in nanoparticulate minerals, we study the electronic response and determine the bandgap energies of three common aluminum-bearing minerals with varying hydrogen content: gibbsite (Al(OH)3), boehmite (AlOOH), and alumina (Al2O3) using electron energy loss spectroscopy, X-ray photoelectron spectroscopy, and first-principles electronic structure calculations employing hybrid density functionals. We find that the amount of hydrogen has only a small effect on the number and spectrum of photoexcitations in this class of materials. Electronic structure calculations demonstrate that low energy electrons are isotropically mobile, while holes in the valence band are likely constrained to move in layers. Furthermore, holes in the valence band of boehmite are found to be significantly more mobile than those in gibbsite, suggesting that the differences in radiolytic and dissolution behavior are related to hole transport.
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Radiotoxic uranium contamination in natural systems and nuclear waste containment can be sequestered by incorporation into naturally abundant iron (oxyhydr)oxides such as hematite (α-Fe2O3) during mineral growth. The stability and properties of the resulting uranium-doped material are impacted by the local coordination environment of incorporated uranium. While measurements of uranium coordination in hematite have been attempted using extended X-ray absorption fine structure (EXAFS) analysis, traditional shell-by-shell EXAFS fitting yields ambiguous results. We used hybrid functional ab initio molecular dynamics (AIMD) simulations for various defect configurations to generate synthetic EXAFS spectra which were combined with adsorbed uranyl spectra to fit experimental U L3-edge EXAFS for U6+-doped hematite. We discovered that the hematite crystal structure accommodates a trans-dioxo uranyl-like configuration for U6+ that substitutes for structural Fe3+, which requires two partially protonated Fe vacancies situated at opposing corner-sharing sites. Surprisingly, the best match to experiment included significant proportions of vacancy configurations other than the minimum-energy configuration, pointing to the importance of incorporation mechanisms and kinetics in determining the state of an impurity incorporated into a host phase under low temperature hydrothermal conditions.
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Hierro , Uranio , Compuestos Férricos , MineralesRESUMEN
Olivines are divalent orthosilicates with important geologic, biological, and industrial significance and are typically comprised of mixtures of Mg2+ and Fe2+ ranging from forsterite (Mg2SiO4) to fayalite (Fe2SiO4). Investigating the role of Fe(II) in olivine reactivity requires the ability to synthesize olivines that are nanometer-sized, have different percentages of Mg2+ and Fe2+, and have good bulk and surface purity. This article demonstrates a new method for synthesizing nanosized fayalite and Mg-Fe mixture olivines.First, carbonaceous precursors are generated from sucrose, PVA, colloidal silica, Mg2+, and Fe3+. Second, these precursors are calcined in air to burn carbon and create mixtures of Fe(III)-oxides, forsterite, and SiO2. Finally, calcination in reducing CO-CO2 gas buffer leads to Fe(II)-rich olivines. XRD, Mössbauer, and IR analyses verify good bulk purity and composition. XPS indicates that surface iron is in its reduced Fe(II) form, and surface Si is consistent with olivine. SEM shows particle sizes predominately between 50 and 450â¯nm, and BET surface areas are 2.8-4.2â¯m2/g. STEM HAADF analysis demonstrates even distributions of Mg and Fe among the available M1 and M2 sites of the olivine crystals. These nanosized Fe(II)-rich olivines are suitable for laboratory studies with in situ probes that require mineral samples with high reactivity at short timescales.
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Cluster models of condensed systems are often used to simulate the core-level spectra obtained with X-ray Photoelectron Spectroscopy, XPS, or with X-ray Absorption Spectroscopy, XAS, especially for near edge features. The main objective of this paper is to examine the dependence of the predicted L2,3 edge XAS of α-Fe2O3, an example of a high spin ionic crystal, on increasingly realistic models of the condensed system. It is shown that an FeO6 cluster model possessing the appropriate local site symmetry describes most features of the XAS and is a major improvement over the isolated Fe3+ cation. In contrast, replacing next nearest neighbor positive point charges with Sc3+, a closed shell cation of similar spatial extent to Fe3+, only marginally improves the match to experiment. This work suggests that second nearest neighbor effects are negligible. Rather, major improvements to the predicted L2,3 edge XAS likely requires additional many body effects that go beyond the present study in which the multiplets are restricted to arise from angular momentum coupling within a single open shell configuration.
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This Critical Review reviews the origin and chemical and rheological complexity of radioactive waste at the U.S. Department of Energy Hanford Site. The waste, stored in underground tanks, was generated via three distinct processes over decades of plutonium extraction operations. Although close records were kept of original waste disposition, tank-to-tank transfers and conditions that impede equilibrium complicate our understanding of the chemistry, phase composition, and rheology of the waste. Tank waste slurries comprise particles and aggregates from nano to micro scales, with varying densities, morphologies, heterogeneous compositions, and complicated responses to flow regimes and process conditions. Further, remnant or changing radiation fields may affect the stability and rheology of the waste. These conditions pose challenges for transport through conduits or pipes to treatment plants for vitrification. Additionally, recalcitrant boehmite degrades glass quality and the high aluminum content must be reduced prior to vitrification for the manufacture of waste glass of acceptable durability. However, caustic leaching indicates that boehmite dissolves much more slowly than predicted given surface normalized rates. Existing empirical models based on ex situ experiments and observations generally only describe material balances and have not effectively predicted process performance. Recent advances in the areas of in situ microscopy, aberration-corrected transmission electron microscopy, theoretical modeling across scales, and experimental methods for probing the physics and chemistry at mineral-fluid and mineral-mineral interfaces are being implemented to build robustly predictive physics-based models.
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Plutonio , Residuos Radiactivos , MineralesRESUMEN
The silver-functionalized silica aerogel (Ag0-aerogel) is being developed for the removal and sequestration of iodine compounds from the off-gas of a nuclear fuel reprocessing plant. This material shows high selectivity and sorption capacity for iodine. However, its sorption performance decreases when exposed to air containing H2O and NO x at 150 °C for extended periods of time. This phenomenon is referred to as "aging" and simulates exposure of the sorbent during plant idling. This extensive study of unaged and aged samples of Ag0-aerogel with and without iodine revealed that decreased efficiency of I capture after NO-aging can be attributed to an increase in size of silver nanoparticles and by the formation of free sulfate on their surfaces from oxidized thiol groups. The smaller reactive surface areas of bigger particles and thin sulfate layer on particle surfaces prevented a complete utilization of the silver. By contrast, formation of silver sulfate appears to be the main factor in decreasing the sorption capacity for samples aged in dry or humid air. It is hypothesized that a short period exposure of the Ag0-aerogel to a reducing gas stream would reduce oxidized silver back to metal and sulfate to sulfide. This may recover the sorption performance of Ag0-aerogel close to original levels.
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We describe a detailed analysis of the features of the X-ray adsorption spectra at the Fe L2,3 edge of FeCl4-. The objective of this analysis is to explain the origin of the complex features in relation to properties of the wavefunctions, especially for the excited states. These properties include spin-orbit and ligand field splittings where a novel aspect of the dipole selection rules is applied to understand the influence of these splittings on the spectra. We also explicitly take account of the intermediate coupling of the open core and valence shell electrons. Our analysis also includes comparison of theory and experiment for the Fe L2,3 edge and comparison of theoretical predictions for the Fe3+ cation and FeCl4-. The electronic structure is obtained from theoretical wavefunctions for the ground and excited states.