More Like this

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

   https://doi.org/10.1039/d1dt01684a  

   Sanden, Sebastian A.; Szilagyi, Robert K.; Li, Yamei; Kitadai, Norio; Webb, Samuel M.; Yano, Takaaki; Nakamura, Ryuhei; Hara, Masahiko; McGlynn, Shawn E. (August 2021, Dalton Transactions)

   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+ 1−3 x Fe 3+ 2 x 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− ). 

   more » « less
2. Pyrochlore-type lanthanide titanates and zirconates: Synthesis, structural peculiarities, and properties

   https://doi.org/10.1063/5.0192415  

   Fuentes, Antonio_F; O'Quinn, Eric_C; Montemayor, Sagrario_M; Zhou, Haidong; Lang, Maik; Ewing, Rodney_C (June 2024, Applied Physics Reviews)

   This contribution provides a thorough examination of the structural characteristics of pyrochlore-type lanthanide titanates and zirconates Ln2Ti2O7 and Ln2Zr2O7, across various length scales. This paper also examines their processing, interesting physical properties (electrical, magnetic, and thermal characteristics), and responses to high pressure and ion irradiation. Brief sections on the elemental oxides' crystal chemistry, pertinent phase diagrams, and energetics of defect formation are also provided. Pyrochlore-type Ln2Ti2O7 and Ln2Zr2O7 stand out as truly multifunctional materials. Moreover, they have emerged as fascinating materials due to magnetic geometrical frustration, arising from the ordering of magnetic Ln3+ and non-magnetic Ti4+ (or Zr4+) cations into separate, interpenetrating lattices of corner-sharing tetrahedra. This results in a diverse array of exotic magnetic ground states, such as spin-ice (e.g., Dy2Ti2O7 or Ho2Ti2O7) or quantum spin ice (e.g., Tb2Ti2O7), observed at both low and room temperatures. They also exhibit varied electrical and electrochemical characteristics. Some members such as Gd2Zr2O7, function as fast ion conductors with a conductivity (σ) of ≈10−2 S·cm−1 at 800 °C and activation energy (Ea) ranging from 0.85 to 1.52 eV, depending on the degree of structural disorder. Others, such as Gd2TiMoO7, are mixed ionic-electronic conductors with σ ≈ 25 S·cm−1 at 1000 °C, making them promising candidate materials for applications in energy conversion and storage devices and oxygen separation membranes. Their exceptionally low thermal conductivity (e.g., κ ∼ 1.1–1.7 W·m−1·K−1 between 700 and 1200 °C for Ln2Zr2O7), close to the glass-like lower limit of highly disordered solids, positions them as valuable materials for thermal barrier coatings. They can also effectively accommodate actinides (e.g., Pu, Np, Cm, Am) in solid solutions and sustain prolonged exposure to radiation due to alpha-decay events, while preserving the integrity of the periodic atomic structure. Proposed as major components in actinide-bearing ceramics, they contribute to the long-term immobilization and disposal of long-lived waste radionuclides from nuclear programs. Some of these properties are displayed simultaneously, opening avenues for new applications. Despite the wealth of data available in the literature, this review highlights the need for a better understanding of order/disorder processes in pyrochlore-type materials and the influence of the structural length scale on their physical and chemical properties. Recent experimental evidence has revealed that pyrochlore short-range structure is far more complex than originally thought. Moreover, pyrochlore local structure is now believed to include short-range, lower symmetry, ordered domains, such as the orthorhombic weberite-type of structure. Notably, short- and long-range structures appear decoupled across different length scales and temperature regimes, and these differences persist even in well-ordered samples. We believe that the pyrochlore structure offers a unique opportunity for examining the interplay between chemical composition, defect chemistry, and properties. In Memoriam: Rodney C. Ewing, Fondly Remembered. 

   more » « less
3. Deep crustal source of gneiss dome revealed by eclogite in migmatite (Montagne Noire, French Massif Central)

   https://doi.org/10.1111/jmg.12523  

   Whitney, Donna L.; Hamelin, Clémentine; Teyssier, Christian; Raia, Natalie H.; Korchinski, Megan S.; Seaton, Nicholas C. A.; Bagley, Brian C.; von der Handt, Anette; Roger, Françoise; Rey, Patrice F. (February 2020, Journal of Metamorphic Geology)

   Abstract In orogens worldwide and throughout geologic time, large volumes of deep continental crust have been exhumed in domal structures. Extension‐driven ascent of bodies of deep, hot crust is a very efficient mechanism for rapid heat and mass transfer from deep to shallow crustal levels and is therefore an important mechanism in the evolution of continents. The dominant rock type in exhumed domes is quartzofeldspathic gneiss (typically migmatitic) that does not record its former high‐pressure (HP) conditions in its equilibrium mineral assemblage; rather, it records the conditions of emplacement and cooling in the mid/shallow crust. Mafic rocks included in gneiss may, however, contain a fragmentary record of a HP history, and are evidence that their host rocks were also deeply sourced. An excellent example of exhumed deep crust that retains a partial HP record is in the Montagne Noire dome, French Massif Central, which contains well‐preserved eclogite (garnet+omphacite+rutile+quartz) in migmatite in two locations: one in the dome core and the other at the dome margin. Both eclogites recordP ~ 1.5 ± 0.2 GPa atT ~ 700 ± 20°C, but differ from each other in whole‐rock and mineral composition, deformation features (shape and crystallographic preferred orientation, CPO), extent of record of prograde metamorphism in garnet and zircon, and degree of preservation of inherited zircon. Rim ages of zircon in both eclogites overlap with the oldest crystallization ages of host gneiss atc.310 Ma, interpreted based on zircon rare earth element abundance in eclogite zircon as the age of HP metamorphism. Dome‐margin eclogite zircon retains a widespread record of protolith age (c.470–450 Ma, the same as host gneiss protolith age), whereas dome‐core eclogite zircon has more scarce preservation of inherited zircon. Possible explanations for differences in the two eclogites relate to differences in the protolith mafic magma composition and history and/or the duration of metamorphic heating and extent of interaction with aqueous fluid, affecting zircon crystallization. Differences in HP deformation fabrics may relate to the position of the eclogite facies rocks relative to zones of transpression and transtension at an early stage of dome development. Regardless of differences, both eclogites experienced HP metamorphism and deformation in the deep crust atc.310 Ma and were exhumed by lithospheric extension—with their host migmatite—near the end of the Variscan orogeny. The deep crust in this region was rapidly exhumed from ~50 to <10 km, where it equilibrated under low‐P/high‐Tconditions, leaving a sparse but compelling record of the deep origin of most of the crust now exposed in the dome. 

   more » « less
4. The solubility of monazite (CePO4), SmPO4, and GdPO4 in aqueous solutions from 100 to 250 °C

   https://doi.org/https://doi.org/10.1016/j.gca.2018.08.038  

   Gysi, A.P.; Harlov, D.; Miron, G.D. (January 2018, Geochimica et cosmochimica acta)

   Monazite (CePO4) is a light rare earth element (REE) phosphate occurring as accessory mineral in metamorphic, igneous and sedimentary rocks, and is also a common mineral in REE mineral deposits. Metasomatism of monazite yields important clues about fluid-rock interaction in the crust, in particular, because its compositional variations may enable us to determine conditions of mineralization. The thermodynamic properties of monazite have been determined using several calorimetric methods, but up to the present time only a few solubility studies have been undertaken, which test the reliability of both, the thermodynamic properties of the REE phosphates and associated REE aqueous species. In this study, we have measured the solubility of the monoclinic REE phosphate end-members CePO4, SmPO4, and GdPO4 in aqueous perchloric acid solutions at temperatures from 100 to 250 °C at saturated water vapor pressure (swvp). The solubility products (Ks0) were determined according to the reaction: REEPO4 = REE3+ + PO43−. Combining available calorimetric data for the REE phosphates with the REE aqueous species from the Supcrt92 (slop98.dat) dataset, yields several orders of magnitude differences when compared with our solubility measurements. We have investigated ways to reconcile these discrepancies and propose a consistent set of provisional thermodynamic properties for REE aqueous species and REE phosphates that reproduce our measured solubility values. To reconcile these discrepancies, we have used the GEMS code package and GEMSFITS for parameter optimization by adjusting the standard Gibbs energy of REE3+ and REEOH2+ at 25 °C and 1 bar. An alternative optimization could involve adjustment of the standard Gibbs energy of REEPO4(s) and REEOH2+. Independently of the optimization method used, this study points to a need to revise the thermodynamic properties of REEOH2+ and possibly other REE hydroxyl species in future potentiometric studies. These revisions will have an impact on calculated solubilities of REE phosphates and our understanding of the mobility of REE in natural hydrothermal fluids. 

   more » « less
5. Crystal chemistry and thermoelectric transport of layered AM ₂ X ₂ compounds

   https://doi.org/10.1039/C7QI00813A  

   Peng, Wanyue; Chanakian, Sevan; Zevalkink, Alexandra (January 2018, Inorganic Chemistry Frontiers)

   Compounds that crystallize in the layered CaAl 2 Si 2 structural pattern have rapidly emerged as an exciting class of thermoelectric materials with attractive n- and p-type properties. More than 100 AM 2 X 2 compounds that form this structure type – characterized by anionic M 2 X 2 slabs sandwiched between layers of octahedrally coordinated A cations – provide numerous potential paths to chemically tune every aspect of thermoelectric transport. This review highlights the chemical diversity of this structure type, discusses the rules governing its formation and stability relative to competing AM 2 X 2 structures ( e.g. , ThCr 2 Si 2 and BaCu 2 S 2 ), and attempts to bring some of the most recently discovered compounds into the spotlight. The discussion of thermoelectric transport properties in AM 2 X 2 compounds focuses primarily on the intrinsic parameters that determine the potential for a high figure of merit: the band gap, effective mass, degeneracy, carrier relaxation time, and lattice thermal conductivity. We also discuss routes that have been used to successfully control the carrier concentration, including controlling the cation vacancy concentration, doping, and isoelectronic alloying (approaches that are highly interdependent). Finally, we discuss recent progress made towards n-type doping in this system, highlight opportunities for further improvements, as well as open questions that still remain. 

   more » « less