The recent discovery of superconductivity in iron arsenide compounds RFeAsO (R= rare earth) or AFe 2 As 2[1~8] (A= alkaline earth) attracts great attention due to the unexpected high T c in the system containing ferromagnetic elements like Fe. Similar to high T c cuprates, the superconductivity in iron arsenide is related to a layered structure. Searching for new superconductors with [FeAs] layer but of simpler structure will be of scientific significance either to build up new multilayered superconductors that may reach higher T c or to study the mysterious underlined superconducting mechanism in iron arsenide compounds. Here we report that a new superconducting iron arsenide system LiFeAs was found. The compound crystallizes into structure containing [FeAs] conducting layer that is interlaced with Li charge reservoir. Superconductivity was observed with T c up to 18 K in the compounds.
The distribution, accumulation and circulation of oxygen and hydrogen in Earth's interior dictate the geochemical evolution of the hydrosphere, atmosphere and biosphere. The oxygen-rich atmosphere and iron-rich core represent two end-members of the oxygen-iron (O-Fe) system, overlapping with the entire pressure-temperature-composition range of the planet. The extreme pressure and temperature conditions of the deep interior alter the oxidation states, spin states and phase stabilities of iron oxides, creating new stoichiometries, such as Fe4O5 (ref. 5) and Fe5O6 (ref. 6). Such interactions between O and Fe dictate Earth's formation, the separation of the core and mantle, and the evolution of the atmosphere. Iron, in its multiple oxidation states, controls the oxygen fugacity and oxygen budget, with hydrogen having a key role in the reaction of Fe and O (causing iron to rust in humid air). Here we use first-principles calculations and experiments to identify a highly stable, pyrite-structured iron oxide (FeO2) at 76 gigapascals and 1,800 kelvin that holds an excessive amount of oxygen. We show that the mineral goethite, FeOOH, which exists ubiquitously as 'rust' and is concentrated in bog iron ore, decomposes under the deep lower-mantle conditions to form FeO2 and release H2. The reaction could cause accumulation of the heavy FeO2-bearing patches in the deep lower mantle, upward migration of hydrogen, and separation of the oxygen and hydrogen cycles. This process provides an alternative interpretation for the origin of seismic and geochemical anomalies in the deep lower mantle, as well as a sporadic O2 source for the Great Oxidation Event over two billion years ago that created the present oxygen-rich atmosphere.
The orthorhombic SrIrO3 perovskite was synthesized under 5GPa and 1000°C. It is paramagnetic below about 170K and transfers to an unknown magnetism under higher temperature. A band type metal to insulator transition caused by a pseudogap was observed at about 44K. Interestingly a positive magnetoresistance, i.e., resistance increased with applying magnetic field, was observed in the orthorhombic SrIrO3 perovskite below about 170K.
Group V elements in crystal structure isostructural to black phosphorus with unique puckered two-dimensional layers exhibit exciting physical and chemical phenomena. However, as the first element of group V, nitrogen has never been found in the black phosphorus structure. Here, we report the synthesis of the black phosphorus–structured nitrogen at 146 GPa and 2200 K. Metastable black phosphorus–structured nitrogen was retained after quenching it to room temperature under compression and characterized in situ during decompression to 48 GPa, using synchrotron x-ray diffraction and Raman spectroscopy. We show that the original molecular nitrogen is transformed into extended single-bonded structure through gauche and trans conformations. Raman spectroscopy shows that black phosphorus–structured nitrogen is strongly anisotropic and exhibits high Raman intensities in two Ag normal modes. Synthesis of black phosphorus–structured nitrogen provides a firm base for exploring new type of high-energy-density nitrogen and a new direction of two-dimensional nitrogen.
Diamond owes its unique mechanical, thermal, optical, electrical, chemical, and biocompatible materials properties to its complete sp 3-carbon network bonding. Crystallinity is another major controlling factor for materials properties. Although other Group-14 elements silicon and germanium have complementary crystalline and amorphous forms consisting of purely sp 3 bonds, purely sp 3-bonded tetrahedral amorphous carbon has not yet been obtained. In this letter, we combine high pressure and in situ laser heating techniques to convert glassy carbon into “quenchable amorphous diamond”, and recover it to ambient conditions. Our X-ray diffraction, high-resolution transmission electron microscopy and electron energy-loss spectroscopy experiments on the recovered sample and computer simulations confirm its tetrahedral amorphous structure and complete sp 3 bonding. This transparent quenchable amorphous diamond has, to our knowledge, the highest density among amorphous carbon materials, and shows incompressibility comparable to crystalline diamond.
The cycling of hydrogen influences the structure, composition, and stratification of Earth's interior. Our recent discovery of pyrite-structured iron peroxide (designated as the P phase) and the formation of the P phase from dehydrogenation of goethite FeO 2 H implies the separation of the oxygen and hydrogen cycles in the deep lower mantle beneath 1,800 km. Here we further characterize the residual hydrogen, x, in the P-phase FeO 2 Hx. Using a combination of theoretical simulations and high-pressure-temperature experiments, we calibrated the x dependence of molar volume of the P phase. Within the current range of experimental conditions, we observed a compositional range of P phase of 0.39 < x < 0.81, corresponding to 19-61% dehydrogenation. Increasing temperature and heating time will help release hydrogen and lower x, suggesting that dehydrogenation could be approaching completion at the high-temperature conditions of the lower mantle over extended geological time. Our observations indicate a fundamental change in the mode of hydrogen release from dehydration in the upper mantle to dehydrogenation in the deep lower mantle, thus differentiating the deep hydrogen and hydrous cycles.
Hydrous minerals in subducted crust can transport large amounts of water into Earth's deep mantle. Our laboratory experiments revealed the surprising pressure-induced chemistry that, when water meets iron at the core–mantle boundary, they react to form an interlayer with an extremely oxygen-rich form of iron, iron dioxide, together with iron hydride. Hydrogen in the layer will escape upon further heating and rise to the crust, sustaining the water cycle. With water supplied by the subducting slabs meeting the nearly inexhaustible iron source in the core, an oxygen-rich layer would cumulate and thicken, leading to major global consequences in our planet. The seismic signature of the D″ layer may echo the chemical complexity of this layer. Over the course of geological time, the enormous oxygen reservoir accumulating between the mantle and core may have eventually reached a critical eruption point. Very large-scale oxygen eruptions could possibly cause major activities in the mantle convection and leave evidence such as the rifting of supercontinents and the Great Oxidation Event.
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