Unlocking the Potential: Atomically Thin 2D Fluoritene from Exfoliated Fluorite Ore and Its Electrochemical Activity.

Fluorite mineral holds significant importance because of its optoelectronic properties and wide range of applications. Here, we report the successful exfoliation of bulk fluorite ore (calcium fluoride, CaF2) crystals into atomically thin two-dimensional fluoritene (2D CaF2) using a highly scalable liquid-phase exfoliation method. The microscopic and spectroscopy characterizations show the formation of (111) plane-oriented 2D CaF2 sheets with exfoliation-induced material strain due to bond breaking, leading to the changes in lattice parameter. Its potential role in electrocatalysis is further explored for deeper insight, and a probable mechanism is also discussed. The 2D CaF2 with long-term stability shows overpotential values of 670 and 770 mV vs RHE for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, at 10 mA cm-2. Computational simulations demonstrate the unique "direct-indirect" band gap switching with odd and even numbers of layers. Current work offers new avenues for exploring the structural and electrochemical properties of 2D CaF2 and its potential applicability.

Synthesis and Characterization of Biotene: A New 2D Natural Oxide From Biotite.

In this work, the synthesis and characterization of ultrathin metal oxide, called biotene, using liquid-phase exfoliation from naturally abundant biotite are demonstrated. The atomically thin biotene is used for energy harvesting using its flexoelectric response under multiple bending. The effective flexoelectric response increases due to the presence of surface charges, and the voltage increases up to ≈8 V, with a high mechano-sensitivity of 0.79 V N-1 for normal force. This flexoelectric response is further validated by density functional theory (DFT) simulations. The atomically thin biotene shows an increased response in the magnetic field and thermal heating. The synthesis of two-dimensional (2D) metal-oxide biotene suggests a wealth of future 2D-oxide material for energy generation and energy harvesting applications.

Scale-Enhanced Magnetism in Exfoliated Atomically Thin Magnetite Sheets.

The discovery of ferromagnetism in atomically thin layers at room temperature widens the prospects of 2D materials for device applications. Recently, two independent experiments demonstrated magnetic ordering in two dissimilar 2D systems, CrI3 and Cr2 Ge2 Te6 , at low temperatures and in VSe2 at room temperature, but observation of intrinsic room-temperature magnetism in 2D materials is still a challenge. Here a transition at room temperature that increases the magnetization in magnetite while thinning down the bulk material to a few atom-thick sheets is reported. DC magnetization measurements prove ferrimagnetic ordering with increased magnetization and density functional theory calculations ascribe their origin to the low dimensionality of the magnetite layers. In addition, surface energy calculations for different cleavage planes in passivated magnetite crystal agree with the experimental observations of obtaining 2D sheets from non-van der Waals crystals.

Thermoelectricity Enhanced Electrocatalysis.

We show that thermoelectric materials can function as electrocatalysts and use thermoelectric voltage generated to initiate and boost electrocatalytic reactions. The electrocatalytic activity is promoted by the use of nanostructured thermoelectric materials in a hydrogen evolution reaction (HER) by the thermoelectricity generated from induced temperature gradients. This phenomenon is demonstrated using two-dimensional layered thermoelectric materials Sb2Te3 and Bi0.5Sb1.5Te3 where a current density approaching ∼50 mA/cm2 is produced at zero potential for Bi0.5Sb1.5Te3 in the presence of a temperature gradient of 90 °C. In addition, the turnover frequency reaches to 2.7 s-1 at 100 mV under this condition which was zero in the absence of temperature gradient. This result adds a new dimension to the properties of thermoelectric materials which has not been explored before and can be applied in the field of electrocatalysis and energy generation.

Biotene: Earth-Abundant 2D Material as Sustainable Anode for Li/Na-Ion Battery.

Natural ores are abundant, cost-effective, and environmentally friendly. Ultrathin (2D) layers of a naturally abundant van der Waals mineral, Biotite, have been prepared in bulk via exfoliation. We report here that this 2D Biotene material has shown extraordinary Li-Na-ion battery anode properties with ultralong cycling stability. Biotene shows 302 and 141 mAh g-1 first cycle-specific charge capacity for Li- and Na-ion battery applications with ∼90% initial Coulombic efficiency. The electrode exhibits significantly extended cycling stability with ∼75% capacity retention after 4000 cycles even at higher current densities (500-2000 mA g-1). Further, density functional theory studies show the possible Li intercalation mechanism between the 2D Biotene layers. Our work brings new directions toward designing the next generation of metal-ion battery anodes.

A 5-km-thick reservoir with > 380,000 km3 of magma within the ancient Earth's crust.

Several recent studies have argued that large, long-lived and molten magma chambers may not occur in the shallow Earth's crust. Here we present, however, field-based observations from the Bushveld Complex that provide evidence to the contrary. In the eastern part of the complex, the magmatic layering continuously drapes across a ~ 4-km-high sloping step in the chamber floor. Such deposition of magmatic layering implies that the resident melt column was thicker than the stepped relief of the chamber floor. Prolonged internal differentiation within this thick magma column is further supported by evolutionary trends in crystallization sequence and mineral compositions through the sequence. The resident melt column in the Bushveld chamber during this period is estimated at > 5-km in thickness and > 380,000 km3 in volume. This volume of magma is three orders of magnitude larger than any known super-eruption in the Earth's history and is only comparable to the extrusive volumes of some of Earth's large igneous provinces. This suggests that super-large, entirely molten, and long-lived magma chambers occur, at least occasionally, in the geological history of our planet. Therefore, the classical view of magma chambers as 'big magma tanks' remains a viable research concept for some of Earth's magmatic provinces.

Geochemistry and mineral chemistry of pelitic gneiss of Ikare area, southwestern Nigeria.

This study conducts Electron Probe Microanalysis (EPMA), X-ray Fluorescence (XRF) and Laser Ablation Inductively Coupled Plasma Spectrometry (LA-ICP-MS) analysis on the pelitic gneiss of the Basement complex of Nigeria. Phase equilibrium modeling was undertaken in the MnO-Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O-TiO2-O2 (MnNCKFMASHTO) chemical system using THERMOCALC. The rock comprises of sillimanite + biotite + garnet + K-feldspar + quartz + ilmenite + plagioclase ± cordierite. Garnet has inclusions of sillimanite, biotite, and quartz. There is a very close association between biotite and sillimanite. Fibrolitic and prismatic sillimanite are both present. Fibrolitic sillimanite surrounding biotite could have possibly formed through melt-residue back reactions involving crystallization of melt. Garnet has almandine higher than 60 % and pyrope less than 33 %. Plagioclase feldspar has anorthite content between 29 and 39 %, comprising of both oligoclase and andesine. Microtextures such as cordierite corona round garnet, symplectite and kinked biotite were observed. The textural association indicates that cordierite was formed at the expense of garnet and sillimanite; garnet + sillimanite + plagioclase => cordierite + melt/fluid. Metamorphic peak conditions of 770-840 °C and 5.5-7 kbar were obtained for the mineral assemblage garnet-biotite-sillimanite-K-feldspar-quartz indicating medium-pressure granulite facies metamorphism.

Friction of magnetene, a non-van der Waals 2D material.

Two-dimensional (2D) materials are known to have low-friction interfaces by reducing the energy dissipated by sliding contacts. While this is often attributed to van der Waals (vdW) bonding of 2D materials, nanoscale and quantum confinement effects can also act to modify the atomic interactions of a 2D material, producing unique interfacial properties. Here, we demonstrate the low-friction behavior of magnetene, a non-vdW 2D material obtained via the exfoliation of magnetite, showing statistically similar friction to benchmark vdW 2D materials. We find that this low friction is due to 2D confinement effects of minimized potential energy surface corrugation, lowered valence states reducing surface adsorbates, and forbidden low-damping phonon modes, all of which contribute to producing a low-friction 2D material.

Monomineralic anorthosites in layered intrusions are indicators of the magma chamber replenishment by plagioclase-only-saturated melts.

The formation of some Earth's monomineralic igneous rocks appears to be prohibited by constraints imposed by liquidus phase-equilibria on evolution of mantle-derived magmas. Yet, these rocks exist as stratiform layers in many mafic-ultramafic intrusions. One conspicuous example is monomineralic anorthosites in the Bushveld Complex that occur as stratiform layers up to hundreds of kilometres in length. Such monomineralic anorthosites appear to require parental melts saturated in plagioclase only but where and how to produce these melts remains a contentious issue. Here we argue that they are likely sourced from deep-seated magma reservoirs. In response to pressure reduction, these ascending melts become first superheated and then saturated in plagioclase after stalling and cooling in shallow-level chambers. Adcumulus growth of plagioclase from such melts at the chamber floor results in the formation of monomineralic anorthosites. We propose that stratiform layers of monomineralic anorthosites in layered intrusions are products of the chamber replenishment by melts whose saturation in plagioclase as a single liquidus phase is triggered by their transcrustal ascent towards the Earth's surface.

Crustal thickening and endogenic oxidation of magmatic sulfur.

Porphyry ore deposits, Earth's most important resources of copper, molybdenum, and rhenium, are strongly associated with felsic magmas showing signs of high-pressure differentiation and are usually found in places with thickened crust (>45 kilometers). This pattern is well-known, but unexplained, and remains an outstanding problem in our understanding of porphyry ore deposit formation. We approach this problem by investigating the oxidation state of magmatic sulfur, which controls the behavior of ore-forming metals during magma differentiation and magmatic-hydrothermal transition. We use sulfur in apatite to reconstruct the sulfur oxidation state in the Gangdese batholith, southern Tibet. We find that magma sulfate content increased abruptly after India-Eurasia collision. Apatite sulfur content and the calculated magma S6+/ΣS ratio correlate with whole-rock dysprosium/ytterbium ratio, suggesting that residual garnet, favored in thickened crust, exerts a first-order control on sulfur oxidation in magmatic orogens. Our findings link sulfur oxidation to internal petrogenic processes and imply an intrinsic relationship of magma oxidation with synmagmatic crustal thickening.

The fate of nitrogen during core-mantle separation on Earth.

Nitrogen, the most dominant constituent of Earth's atmosphere, is critical for the habitability and existence of life on our planet. However, its distribution between Earth's major reservoirs, which must be largely influenced by the accretion and differentiation processes during its formative years, is poorly known. Sequestration into the metallic core, along with volatility related loss pre- and post-accretion, could be a critical process that can explain the depletion of nitrogen in the Bulk Silicate Earth (BSE) relative to the primitive chondrites. However, the relative effect of different thermodynamic parameters on the alloy-silicate partitioning behavior of nitrogen is still poorly known. Here we present equilibrium partitioning data of N between alloy and silicate melt ( D N alloy / silicate ) from 67 new high pressure (P = 1-6 GPa)-temperature (T = 1500-2200 °C) experiments under graphite saturated conditions at a wide range of oxygen fugacity (logfO2 ~ΔIW - 4.2 to - 0.8), mafic to ultramafic silicate melt compositions (NBO/T = 0.4 to 2.2), and varying chemical composition of the alloy melts (S and Si contents of 0-32.1 wt.% and 0-3.1 wt.%, respectively). Under relatively oxidizing conditions (~ΔIW - 2.2 to - 0.8) nitrogen acts as a siderophile element ( D N alloy / silicate between 1.1 and 52), where D N alloy / silicate decreases with decrease in fO2 and increase in T, and increases with increase in P and NBO/T. Under these conditions D N alloy / silicate remains largely unaffected between S-free conditions and up to ~17 wt.% S content in the alloy melt, and then drops off at > ~20 wt.% S content in the alloy melt. Under increasingly reduced conditions (< ~ ΔIW - 2.2), N becomes increasingly lithophile ( D N alloy / silicate between 0.003 and 0.5) with D N alloy / silicate decreasing with decrease in fO2 and increase in T. At these conditions fO2, along with Si content of the alloy under the most reduced conditions (< ~ΔIW - 3.0), is the controlling parameter with T playing a secondary role, while, P, NBO/T, and S content of the alloy have minimal effects. A multiple linear least-squares regression parametrization for D N alloy / silicate based on the results of this study and previous studies suggests, in agreement with the experimental data, that fO2 (represented by Si content of the alloy melt and FeO content of the silicate melt), followed by T, has the strongest control on D N alloy / silicate . Based on our modeling, to match the present-day BSE N content, impactors that brought N must have been moderately to highly oxidized. If N bearing impactors were reduced, and/or there was significant disequilibrium core formation, then the BSE would be too N-rich and another mechanism for N loss, such as atmospheric loss, would be required.

Delivery of carbon, nitrogen, and sulfur to the silicate Earth by a giant impact.

Earth's status as the only life-sustaining planet is a result of the timing and delivery mechanism of carbon (C), nitrogen (N), sulfur (S), and hydrogen (H). On the basis of their isotopic signatures, terrestrial volatiles are thought to have derived from carbonaceous chondrites, while the isotopic compositions of nonvolatile major and trace elements suggest that enstatite chondrite-like materials are the primary building blocks of Earth. However, the C/N ratio of the bulk silicate Earth (BSE) is superchondritic, which rules out volatile delivery by a chondritic late veneer. In addition, if delivered during the main phase of Earth's accretion, then, owing to the greater siderophile (metal loving) nature of C relative to N, core formation should have left behind a subchondritic C/N ratio in the BSE. Here, we present high pressure-temperature experiments to constrain the fate of mixed C-N-S volatiles during core-mantle segregation in the planetary embryo magma oceans and show that C becomes much less siderophile in N-bearing and S-rich alloys, while the siderophile character of N remains largely unaffected in the presence of S. Using the new data and inverse Monte Carlo simulations, we show that the impact of a Mars-sized planet, having minimal contributions from carbonaceous chondrite-like material and coinciding with the Moon-forming event, can be the source of major volatiles in the BSE.

Nb/Ta systematics in arc magma differentiation and the role of arclogites in continent formation.

The surfaces of rocky planets are mostly covered by basaltic crust, but Earth is unique in that it also has extensive regions of felsic crust, manifested in the form of continents. Exactly how felsic crust forms when basaltic magmas are the dominant products of melting the mantles of rocky planets is unclear. A fundamental part of the debate is centered on the low Nb/Ta of Earth's continental crust (11-13) compared to basalts (15-16). Here, we show that during arc magma differentiation, the extent of Nb/Ta fractionation varies with crustal thickness with the lowest Nb/Ta seen in continental arc magmas. Deep arc cumulates (arclogites) are found to have high Nb/Ta (average ~19) due to the presence of high Nb/Ta magmatic rutiles. We show that the crustal thickness control of Nb/Ta can be explained by rutile saturation being favored at higher pressures. Deep-seated magmatic differentiation, such as in continental arcs and other magmatic orogens, is thus necessary for making continents.

Tuning the Electrocatalytic Activity of Co3O4 through Discrete Elemental Doping.

To gain constructive insight into the possible effect of doping on the electrocatalytic activity of materials, a catalytic framework with a discrete distribution of dopants is an appropriate model system. Such a system assures well-defined active centers, maximum atom utilization efficiency, and hence enhanced selectivity, catalytic activity, and stability. Herein, a comprehensive investigation of the electrocatalytic activity of iron-doped cobalt oxide (Fe-Co3O4) nanosheets is presented. In order to understand the contribution of dopants, a series of materials with controlled doping levels are investigated. By controlled iron inclusion into the structure of Co3O4, an apparent improvement in the oxygen evolution reaction activity which is reflected in the decrease of 160 mV in the overpotential to reach the current density of 10 mA/cm2 is manifested. Additionally, it is shown that there exists an optimum doping content above which the catalytic activity fades. Further investigation of the system with density functional calculations reveals that, along with the optimization of adsorption energy toward the reaction intermediates, substantial downshift of the Fermi level and delocalization of electron density occurs on introducing iron ions into the structure.

Platinum-bearing chromite layers are caused by pressure reduction during magma ascent.

Platinum-bearing chromitites in mafic-ultramafic intrusions such as the Bushveld Complex are key repositories of strategically important metals for human society. Basaltic melts saturated in chromite alone are crucial to their generation, but the origin of such melts is controversial. One concept holds that they are produced by processes operating within the magma chamber, whereas another argues that melts entering the chamber were already saturated in chromite. Here we address the problem by examining the pressure-related changes in the topology of a Mg2SiO4-CaAl2Si2O8-SiO2-MgCr2O4 quaternary system and by thermodynamic modelling of crystallisation sequences of basaltic melts at 1-10 kbar pressures. We show that basaltic melts located adjacent to a so-called chromite topological trough in deep-seated reservoirs become saturated in chromite alone upon their ascent towards the Earth's surface and subsequent cooling in shallow-level chambers. Large volumes of these chromite-only-saturated melts replenishing these chambers are responsible for monomineralic layers of massive chromitites with associated platinum-group elements.

Exfoliation of a non-van der Waals material from iron ore hematite.

With the advent of graphene, the most studied of all two-dimensional materials, many inorganic analogues have been synthesized and are being exploited for novel applications. Several approaches have been used to obtain large-grain, high-quality materials. Naturally occurring ores, for example, are the best precursors for obtaining highly ordered and large-grain atomic layers by exfoliation. Here, we demonstrate a new two-dimensional material 'hematene' obtained from natural iron ore hematite (α-Fe2O3), which is isolated by means of liquid exfoliation. The two-dimensional morphology of hematene is confirmed by transmission electron microscopy. Magnetic measurements together with density functional theory calculations confirm the ferromagnetic order in hematene while its parent form exhibits antiferromagnetic order. When loaded on titania nanotube arrays, hematene exhibits enhanced visible light photocatalytic activity. Our study indicates that photogenerated electrons can be transferred from hematene to titania despite a band alignment unfavourable for charge transfer.

Iranite, CuPb10(CrO4)6(SiO4)2(OH)2, isomorphous with hemihedrite.

This study presents the first structural report of iranite, ideally CuPb10(CrO4)6(SiO4)2(OH)2 [copper decalead hexachromate bis(orthosilicate) dihydroxide], based on single-crystal X-ray diffraction data. Iranite is isomorphous with hemihedrite, with substitution of Cu for Zn and OH for F. The Cu atom is situated at the special position with site symmetry 1. The CrO4 and SiO4 tetrahedra and CuO4(OH)2 octahedra form layers that are parallel to (120) and are linked together by five symmetrically independent Pb2+ cations displaying a rather wide range of bond distances. The CuO4(OH)2 octahedra are corner-linked to two CrO4 and two SiO4 groups, while two additional CrO4 groups are isolated. The mean Cr-O distances for the three nonequivalent CrO4 tetrahedra are all slightly shorter than the corresponding distances in hemihedrite, whereas the CuO4(OH)2 octahedron is more distorted than the ZnO4F2 octahedron in hemihedrite in terms of octahedral quadratic elongation.

Isokite, CaMg(PO(4))F(0.8)(OH)(0.2), isomorphous with titanite.

This study presents the first structural report of natural isokite (calcium magnesium phosphate fluoride), with the formula CaMg(PO(4))F(0.8)(OH)(0.2) (i.e. some substitution of OH for F), based on single-crystal X-ray diffraction data. Isokite belongs to the C2/c titanite mineral group, in which Mg is on an inversion centre and the Ca, P and F/OH atoms are on twofold axes. The structure is composed of kinked chains of corner-sharing MgO(4)F(2) octahedra that are crosslinked by isolated PO(4) tetrahedra, forming a three-dimensional polyhedral network. The Ca(2+) cations occupy the interstitial sites coordinated by six O atoms and one F anion.

Tyrrellite, Cu(Co0.68Ni0.32)2Se4, isostructural with spinel.

Tyrrellite, a naturally occurring Co-Ni-Cu selenide, has been studied by single-crystal X-ray diffraction. It possesses the normal spinel-type structure, with Cu occupying the tetrahedral site and (Co+Ni) the octahedral site. The average Cu-Se distance of 2.3688 (2) A is close to that of 2.3703 (8) A in CuCr(2)Se(4), whereas the average (Co+Ni)-Se distance of 2.3840 (1) A appears to be slightly shorter than most octahedral Co-Se or Ni-Se distances ( approximately 2.40-2.50 A) in other selenides. The refined structure provides a basis for a redefinition of the ideal chemical formula of tyrrellite, which should be Cu(Co,Ni)(2)Se(4), rather than the previously suggested (Cu,Co,Ni)(3)Se(4).

Kolbeckite, ScPO(4).2H(2)O, isomorphous with metavariscite.

This study presents the first structural report of kolbeckite, with the ideal formula ScPO(4).2H(2)O (scandium phosphate dihydrate), based on single-crystal X-ray diffraction data. Kolbeckite belongs to the metavariscite mineral group, in which each PO(4) tetrahedron shares four vertices with four ScO(4)(H(2)O)(2) octahedra and vice versa, forming a three-dimensional network of polyhedra.