Earth's lower mantle is a potential water reservoir. The physical and chemical properties of the region are in part controlled by the Fe3+/ΣFe ratio and total iron content in bridgmanite. However, the water effect on the chemistry of bridgmanite remains unclear. We carry out laser-heated diamond anvil cell experiments under hydrous conditions and observe dominant Fe2+ in bridgmanite (Mg, Fe)SiO3 above 105 GPa under the normal geotherm conditions corresponding to depth > 2300 km, whereas Fe3+-rich bridgmanite is obtained at lower pressures. We further observe FeO in coexistence with hydrous NiAs-type SiO2 under similar conditions, indicating that the stability of ferrous iron is a combined result of H2O effect and high pressure. The stability of ferrous iron in bridgmanite under hydrous conditions would provide an explanation for the nature of the low-shear-velocity anomalies in the deep lower mantle. In addition, entrainment from a hydrous dense layer may influence mantle plume dynamics and contribute to variations in the redox conditions of the mantle.
Ferromagnesian silicates are the dominant constituents of the Earth's mantle, which comprise more than 80% of our planet by volume. To interpret the low shear-velocity anomalies in the lower mantle, we need to construct a reliable transformation diagram of ferromagnesian silicates over a wide pressure-temperature (P-T) range. While MgSiO3 in the perovskite structure has been extensively studied due to its dominance on Earth, phase transformations of iron silicates under the lower mantle conditions remain unresolved. In this study, we have obtained an iron silicate phase in the perovskite (Pv) structure using synthetic fayalite (Fe2SiO4) as the starting material under P-T conditions of the lower mantle. Chemical analyses revealed an unexpectedly high Fe/Si ratio of 1.72(3) for the Pv phase in coexistence with metallic iron particles, indicating incorporation of about 25 mol% Fe2O3 in the Pv phase with an approximate chemical formula (Fe2+0.75Fe3+0.25)(Fe3+0.25Si0.75)O3. We further obtained an iron silicate phase in the postperovskite (PPv) structure above 95 GPa. The calculated curves of compressional (VP) and shear velocity (VS) of iron silicate Pv and PPv as a function of pressure are nearly parallel to those of MgSiO3, respectively. To the best of our knowledge, the iron silicate Pv and PPv are the densest phases among all the reported silicates stable at P-T conditions of the lower mantle. The high ferric iron content in the silicate phase and the spin-crossover of ferric iron at the Si-site above ~55 GPa should be taken into account in order to interpret the seismic observations. Our results would provide crucial information for constraining the geophysical and geochemical models of the lower mantle.
Electride possesses electrons localized at interstitial sites without attracting nuclei. It brings outstanding material properties not only originating from its own loosely bounded characteristics but also serving as a quasiatom, which even chemically interacts with other elemental ions. In elemental metals, electride transitions have been reported in alkali metals where valence electrons can easily gain enough kinetic energy to escape nuclei. However, there are few studies on transition metals. Especially iron, the key element of human technology and geophysics, has not been studied in respect of electride formation. In this study, it is demonstrated that electride formation drives the superionic state in iron hydride under high-pressure conditions of the earth's inner core. The electride stabilizes the iron lattice and provides a pathway for hydrogen diffusion by severing the direct interaction between the metal and the volatile element. The coupling between lattice stability and superionicity is triggered near 100 GPa and enhanced at higher pressures. It is shown that the electride-driven superionicity can also be generalized for metal electrides and other rocky planetary cores by providing a fundamental interaction between the electride of the parent metal and doped light elements.
Very recently, a new superconductor with Tc = 80 K has been reported in nickelate (La3Ni2O7) at around 15-40 GPa conditions (Nature, 621, 493, 2023), which is the second type of unconventional superconductor, besides cuprates, with Tc above liquid nitrogen temperature. However, the phase diagram plotted in this report was mostly based on the transport measurement under low-temperature and high-pressure conditions, and the assumed corresponding X-ray diffraction (XRD) results were carried out at room temperature. This encouraged us to carry out in situ high-pressure and low-temperature synchrotron XRD experiments to determine which phase is responsible for the high Tc state. In addition to the phase transition from the orthorhombic Amam structure to the orthorhombic Fmmm structure, a tetragonal phase with the space group of I4/mmm was discovered when the sample was compressed to around 19 GPa at 40 K where the superconductivity takes place in La3Ni2O7. The calculations based on this tetragonal structure reveal that the electronic states that approached the Fermi energy were mainly dominated by the eg orbitals (3dz2 and 3dx2-y2) of Ni atoms, which are located in the oxygen octahedral crystal field. The correlation between Tc and this structural evolution, especially Ni-O octahedra regularity and the in-plane Ni-O-Ni bonding angles, is analyzed. This work sheds new light to identify what is the most likely phase responsible for superconductivity in double-layered nickelate.
Water in Earth's deep interior is predicted to be hydroxyl (OH-) stored in nominally anhydrous minerals, profoundly modulating both structure and dynamics of Earth's mantle. Here, we use a high-dimensional neuro-network potential and machine learning algorithm to investigate the weight percent water incorporation in stishovite, a main constituent of the subducted oceanic crust. We found that stishovite and water prefer forming medium- to long-range ordered superstructures, featuring one-dimensional (1D) water channels. Synthesizing single crystals of hydrous stishovite, we verified the ordering of OH- groups in the water channels through optical and nuclear magnetic resonance spectroscopy and found an average H-H distance of 2.05(3) Å, confirming simulation results. Upon heating, H atoms were predicted to behave fluid-like inside the channels, leading to an exotic 1D superionic state. Water-bearing stishovite could feature high ionic mobility and strong electrical anisotropy, manifesting as electrical heterogeneity in Earth's mantle.
Relaxation dynamics, as a key to understand glass formation and glassy properties, remains an elusive and challenging issue in condensed matter physics. In this work, in situ high-pressure synchrotron high-energy X-ray photon correlation spectroscopy has been developed to probe the atomic-scale relaxation dynamics of a cerium-based metallic glass during compression. Although the sample density continuously increases, the collective atomic motion initially slows down as generally expected and then counterintuitively accelerates with further compression (density increase), showing an unusual nonmonotonic pressure-induced steady relaxation dynamics cross-over at ~3 GPa. Furthermore, by combining in situ high-pressure synchrotron X-ray diffraction, the relaxation dynamics anomaly is evidenced to closely correlate with the dramatic changes in local atomic structures during compression, rather than monotonically scaling with either sample density or overall stress level. These findings could provide insight into relaxation dynamics and their relationship with local atomic structures of glasses.
Iron hydride in Earth's interior can be formed by the reaction between hydrous minerals (water) and iron. Studying iron hydride improves our understanding of hydrogen transportation in Earth's interior. Our high-pressure experiments found that face-centered cubic (fcc) FeHx (x ≤ 1) is stable up to 165 GPa, and our ab initio molecular dynamics simulations predicted that fcc FeHx transforms to a superionic state under lower mantle conditions. In the superionic state, H-ions in fcc FeH become highly diffusive-like fluids with a high diffusion coefficient of â¼3.7 × 10-4 cm2 s-1, which is comparable to that in the liquid Fe-H phase. The densities and melting temperatures of fcc FeHx were systematically calculated. Similar to superionic ice, the extra entropy of diffusive H-ions increases the melting temperature of fcc FeH. The wide stability field of fcc FeH enables hydrogen transport into the outer core to create a potential hydrogen reservoir in Earth's interior, leaving oxygen-rich patches (ORP) above the core mantle boundary (CMB).
It is now well known that solids under ultra-high-pressure shock compression will enter the warm dense matter (WDM) regime which connects condensed matter and hot plasma. How condensed matter turns into the WDM, however, remains largely unexplored due to the lack of data in the transition pressure range. In this letter, by employing the unique high-Z three-stage gas gun launcher technique developed recently, we compress gold into TPa shock pressure to fill the gap inaccessible by the two-stage gas gun and laser shock experiments. With the aid of high-precision Hugoniot data obtained experimentally, we observe a clear softening behavior beyond ~560 GPa. The state-of-the-art ab-initio molecular dynamics calculations reveal that the softening is caused by the ionization of 5d electrons in gold. This work quantifies the partial ionization effect of electrons under extreme conditions, which is critical to model the transition region between condensed matter and WDM.
Earth's inner core (IC) consists of mainly iron with some light elements. Understanding its structure and related physical properties has been elusive as a result of its required extremely high pressure and temperature conditions. The phase of iron, elastic anisotropy, and density-velocity deficit at the IC have long been questions of great interest. Here, we find that the electron correlation effect is enhanced by oxygen and modifies several important features, including the stability of iron oxides. Oxygen atoms energetically stabilize hexagonal-structured iron at IC conditions and induce elastic anisotropy. Electrical resistivity is much enhanced in comparison to pure hexagonal close-packed (hcp) iron as a result of the enhanced electron correlation effect, supporting the conventional thermal convection model. Moreover, our calculated seismic velocity shows a quantitative match with geologically observed preliminary reference Earth model (PREM) data. We suggest that oxygen is the essential light element to understand and model Earth's IC.
Pressure-induced topochemical polymerization of molecular crystals with various stackings is a promising way to synthesize materials with different co-existing sub-structures. Here, by compressing the azobenzene crystal containing two kinds of intermolecular stacking, we synthesized an ordered van der Waals carbon nanoribbon (CNR) heterostructure in one step. Azobenzene polymerizes via a [4 + 2] hetero-Diels-Alder (HDA) reaction of phenylazo-phenyl in layer A and a para-polymerization reaction of phenyl in layer B at 18 GPa, as evidenced by in situ Raman and IR spectroscopies, X-ray diffraction, as well as gas chromatography-mass spectrometry and the solid-state nuclear magnetic resonance of the recovered products. The theoretical calculation shows that the obtained CNR heterostructure has a type II (staggered) band gap alignment. Our work highlights a high-pressure strategy to synthesize bulk CNR heterostructures.
Metal hydrides have wide applications in energy science. A large pressure gradient propels the hydrogen atoms out. A piezovoltaic device, a pressure gradient-driven battery, can therefore be realized when the migrations of protons and electrons are separated by different conductors. Here we investigate the piezovoltaic performance of PdHx with various proton conductors as electrolytes and experimentally detect an output current of â²40 nA and a voltage of â¼0.8 V for a 3 µg sample. We also demonstrate the escape of hydrogen atoms from a palladium lattice under an increasing pressure gradient using X-ray diffraction. The relationship between piezovoltaics (chemical process) and piezoelectricity (physical process) is like that between a chemical battery and a capacitor. Our work demonstrates the piezovoltaic application of metal hydrides and provides a new way to convert mechanical energy into electrical energy.
Seismological observations suggest that Earth's inner core (IC) is heterogeneous and anisotropic. Increasing seismological observations make the understanding of the mineralogy and mechanism for the complex IC texture extremely challenging, and the driving force for the anisotropic texture remains unclear. Under IC conditions, hydrogen becomes highly diffusive like liquid in the hexagonal-close-packed (hcp) solid Fe lattice, which is known as the superionic state. Here, we reveal that H-ion diffusion in superionic Fe-H alloy is anisotropic with the lowest barrier energy along the c-axis. In the presence of an external electric field, the alignment of the Fe-H lattice with the c-axis pointing to the field direction is energetically favorable. Due to this effect, Fe-H alloys are aligned with the c-axis parallel to the equatorial plane by the diffusion of the north-south dipole geomagnetic field into the inner core. The aligned texture driven by the geomagnetic field presents significant seismic anisotropy, which explains the anisotropic seismic velocities in the IC, suggesting a strong coupling between the IC structure and geomagnetic field.
The amount of sulfur in SO2 discharged in volcanic eruptions exceeds that available for degassing from the erupted magma. This geological conundrum, known as the "sulfur excess", has been the subject of considerable interests but remains an open question. Here, in a systematic computational investigation of sulfur-oxygen compounds under pressure, a hitherto unknown S3O4 compound containing a mixture of sulfur oxidation states +II and +IV is predicted to be stable at pressures above 79 GPa. We speculate that S3O4 may be produced via redox reactions involving subducted S-bearing minerals (e.g., sulfates and sulfides) with iron and goethite under high-pressure conditions of the deep lower mantle, decomposing to SO2 and S at shallow depths. S3O4 may thus be a key intermediate in promoting decomposition of sulfates to release SO2, offering an alternative source of excess sulfur released during explosive eruptions. These findings provide a possible resolution of the "excess sulfur degassing" paradox and a viable mechanism for the exchange of S between Earth's surface and the lower mantle in the deep sulfur cycle.
Iron , Sulfur , Sulfur Compounds , Sulfides , Sulfates
2,5-Furandicarboxylic acid (FDCA) is one of the top-12 value-added chemicals from sugar. Besides the wide application in chemical industry, here we found that solid FDCA polymerized to form an atomic-scale ordered sp3-carbon nanothread (CNTh) upon compression. With the help of perfectly aligned π-π stacked molecules and strong intermolecular hydrogen bonds, crystalline poly-FDCA CNTh with uniform syn-configuration was obtained above 11 GPa, with the crystal structure determined by Rietveld refinement of the X-ray diffraction (XRD). The in situ XRD and theoretical simulation results show that the FDCA experienced continuous [4 + 2] Diels-Alder reactions along the stacking direction at the threshold C···C distance of â¼2.8 Å. Benefiting from the abundant carbonyl groups, the poly-FDCA shows a high specific capacity of 375 mAh g-1 as an anode material of a lithium battery with excellent Coulombic efficiency and rate performance. This is the first time a three-dimensional crystalline CNTh is obtained, and we demonstrated it is the hydrogen bonds that lead to the formation of the crystalline material with a unique configuration. It also provides a new method to move biomass compounds toward advanced functional carbon materials.
Diamond
Water transported by subducted oceanic plates changes mineral and rock properties at high pressures and temperatures, affecting the dynamics and evolution of the Earth's interior. Although geochemical observations imply that water should be stored in the lower mantle, the limited amounts of water incorporation in pyrolitic lower-mantle minerals suggest that water in the lower mantle may be stored in the basaltic fragments of subducted slabs. Here, we performed multianvil experiments to investigate the stability and water solubility of aluminous stishovite and CaCl2-structured silica, referred to as poststishovite, in the SiO2-Al2O3-H2O systems at 24 to 28 GPa and 1,000 to 2,000 °C, representing the pressure-temperature conditions of cold subducting slabs to hot upwelling plumes in the top lower mantle. The results indicate that both alumina and water contents in these silica minerals increase with increasing temperature under hydrous conditions due to the strong Al3+-H+ charge coupling substitution, resulting in the storage of water up to 1.1 wt %. The increase of water solubility in these hydrous aluminous silica phases at high temperatures is opposite of that of other nominally anhydrous minerals and of the stability of the hydrous minerals. This feature prevents the releasing of water from the subducting slabs and enhances the transport water into the deep lower mantle, allowing significant amounts of water storage in the high-temperature lower mantle and circulating water between the upper mantle and the lower mantle through subduction and plume upwelling. The shallower depths of midmantle seismic scatterers than expected from the pure SiO2 stishovite-poststishovite transition pressure support this scenario.
Solids can be generally categorized by their structures into crystalline and amorphous states with different interactions among atoms dictating their properties. Crystalline-amorphous hybrid structures, combining the advantages of both ordered and disordered components, present a promising opportunity to design materials with emergent collective properties. Hybridization of crystalline and amorphous structures at the sublattice level with long-range periodicity has been rarely observed. Here, we report a nested order-disorder framework (NOF) constructed by a crystalline matrix with self-filled amorphous-like innards that is obtained by using pressure to regulate the bonding hierarchy of Cu12Sb4S13. Combined in situ experimental and computational methods demonstrate the formation of disordered Cu sublattice which is embedded in the retained crystalline Cu framework. Such a NOF structure gives a low thermal conductivity (~0.24 W·m-1·K-1) and a metallic electrical conductivity (8 × 10-6 Ω·m), realizing the collaborative improvement of two competing physical properties. These findings demonstrate a category of solid-state materials to link the crystalline and amorphous forms in the sublattice-scale, which will exhibit extraordinary properties.
High pressure induces dramatic changes and novel phenomena in condensed volatiles1,2 that are usually not preserved after recovery from pressure vessels. Here we report a process that pressurizes volatiles into nanopores of type 1 glassy carbon precursors, converts glassy carbon into nanocrystalline diamond by heating and synthesizes free-standing nanostructured diamond capsules (NDCs) capable of permanently preserving volatiles at high pressures, even after release back to ambient conditions for various vacuum-based diagnostic probes including electron microscopy. As a demonstration, we perform a comprehensive study of a high-pressure argon sample preserved in NDCs. Synchrotron X-ray diffraction and high-resolution transmission electron microscopy show nanometre-sized argon crystals at around 22.0 gigapascals embedded in nanocrystalline diamond, energy-dispersive Xray spectroscopy provides quantitative compositional analysis and electron energy-loss spectroscopy details the chemical bonding nature of high-pressure argon. The preserved pressure of the argon sample inside NDCs can be tuned by controlling NDC synthesis pressure. To test the general applicability of the NDC process, we show that high-pressure neon can also be trapped in NDCs and that type 2 glassy carbon can be used as the precursor container material. Further experiments on other volatiles and carbon allotropes open the possibility of bringing high-pressure explorations on a par with mainstream condensed-matter investigations and applications.
Valence transition could induce structural, insulator-metal, nonmagnetic-magnetic and superconducting transitions in rare-earth metals and compounds, while the underlying physics remains unclear due to the complex interaction of localized 4f electrons as well as their coupling with itinerant electrons. The valence transition in the elemental metal europium (Eu) still has remained as a matter of debate. Using resonant x-ray emission scattering and x-ray diffraction, we pressurize the states of 4f electrons in Eu and study its valence and structure transitions up to 160 GPa. We provide compelling evidence for a valence transition around 80 GPa, which coincides with a structural transition from a monoclinic (C2/c) to an orthorhombic phase (Pnma). We show that the valence transition occurs when the pressure-dependent energy gap between 4f and 5d electrons approaches the Coulomb interaction. Our discovery is critical for understanding the electrodynamics of Eu, including magnetism and high-pressure superconductivity.
