Carbon Wall Research Articles

Geochemistry of garnet and scheelite as indicators for skarn-type Mo-W mineralization: A case study from the Shibaogou deposit, Qinling Orogen, China

To understand the mechanism of skarn-type Mo-W mineralization, it is crucial to study fluid evolution. In-situ elemental analysis was conducted on garnet and scheelite from the Shibaogou deposit, a representative large-scale skarn Mo-W deposit in Luanchuan orefield, Qinling orogen, aiming to constrain the origin and evolution of ore-forming fluid and to analyze the skarn mineralization process. Multiple generations of garnet and scheelite were observed along with the multistage of skarnization. I. Anhydrous skarn stage, three generations of garnet (Grt-c, Grt-m, Grt-r) with molybdenite (Mo-I) occurring around Grt-r and scheelite occurring in coarse-grained (primary Sch-I, altered rim Sch-Ia). II. Hydrous skarn stage, minor scheelite (Sch-II) coexisted with actinolite. III. Oxide stage, scheelite (Sch-III) occurred in feldspar-fluorite veins, with minor molybdenite (Mo-II). IV. Quartz sulfide stage, early quartz-molybdenite (Mo-III) veins and later quartz Fe-Zn-Pb-sulfide veins occurred with a few scheelites (Sch-IV). V. Carbonite stage.The Y/Ho ratios of garnet and scheelite indicate that the ore-forming fluid was originally magmatic-hydrothermal. The variations in U and Sn contents of garnet indicate a gradual increase in oxidation state during the anhydrous skarn stage. The high andradite proportion in Grt-m resulted from an increased pH of the fluid, related to the presence of Ca(HCO3)2. This increased pH and Ca2+ activity of fluid led to the main tungsten mineralization (Sch-I). The subordinate Mo mineralization formed at the end of stage I, as the expansion of the molybdenite logfO2-pH stability field, controlled by the decrease in temperature. The redox state evolutions indicated by the consistent Mo contents and (EuN vs. EuN*) of scheelite, with the highest oxidation state occurring in the hydrous skarn stage. The oxidation state reached the lowest level in the sulfide stage with sufficient reduced sulfur, leading to main Mo mineralization. The REE patterns, Nb, and ∑REE contents of scheelite suggest a change in fluid composition to F enrichment after anhydrous skarn, which enhanced the fluid’s ability to dissolve W. In the oxide stage, scheelite formed a second significant mineralization with fluorite: H3WO4F2– + 2Ca2+ = CaWO4 + CaF2 + 3H+. The carbonate wall rocks played a controlling role in the evolution of ore-forming fluid and mineralization mechanism through the fluid-rock interactions.

Nanosized CeO2C2 with rich oxygen vacancies embedded in hollow mesoporous carbon as a multifunctional sulfur-loaded matrix for lithium-sulfur batteries

The innovative structural and compositional design of sulfur-loaded matrices is an effective strategy to improve the performance of lithium-sulfur batteries (LSBs). Herein, nanosized CeO2C2 with rich oxygen vacancies embedded in hollow mesoporous carbon composites (HMC/CeO2C2) were synthesized by hydrothermal and annealing reduction processes. This structure has several advantages: the large specific surface area and mesoporous carbon walls facilitate sulfur penetration and electron/ion transport; the abundant mesopores and hollow inner cavities provide the structural basis for sulfur storage and buffer its volume expansion; the oxygen vacancy-rich CeO2C2 nanoparticles grown in situ in HMC and in close contact with carbon form an electrically favorable CeO2C2/C heterointerface as an efficient catalyst, which is conducive to catalyzing the redox reaction of sulfur. Consequently, the retention capacity of the HMC/CeO2C2/S electrode is 728 mAh g−1 after 500 cycles at 0.5 C with a decay rate of 0.056 % per cycle, and it maintains a high reversible area capacity of 3.18 mAh cm−2 and excellent cycling performance even under a high sulfur loading of 4.7 mg cm−2. It provides an idea for the development of multifunctional sulfur-loaded materials with high sulfur loading, high conductivity, and high catalytic activity.

On the molecular mechanisms of H2/N2 uptake in confined ionic liquids: A computational study

Classical molecular dynamics and hybrid grand canonical Monte Carlo/molecular dynamics simulations were combined to analyze the gas uptake mechanism of hydrogen and nitrogen molecules inside carbon nanotubes filled with an ionic liquid. Several nanotube diameters (from 6 Å to 12.24 Å) and two different ionic liquids (ethylammonium nitrate and 1-ethyl-3-methylimidazolium tetrafluoroborate) were considered to study their effect on the gas capture capacity and on the location of gas molecules within the nanotubes. The simulations showed that nitrogen absorption ability is, in general, greater than that of hydrogen, with the aprotic ionic liquid being more efficient for gas confinement. In addition, gas capture was observed to increase from a scarce 0.4% in bulk ionic liquids up to 8%-25% inside small nanotubes, and the maximum gas uptake was observed for those nanotubes that allow for a greater degree of conformational freedom of the ionic liquid. However, our calculations show that, whereas hydrogen storage is mainly governed by the amount of accessible free volume, for understanding that of nitrogen solvation energetics must be also considered. In all cases, gas molecules are absorbed in the ionic liquid-rich-region, but the interactions with the other components of the system favour their accommodation closer to the carbon wall than to the nanotube centre. Finally, single-particle dynamics of gas molecules was analyzed by means of the velocity autocorrelation functions and the vibrational density of states, which show a blue-shifting when increasing the radius of the nanotube.

The Impact of Chemical Modifications on The Ionic Conductivity of Ionic Liquid Encapsulated in Carbon Nanotubes, Potential Application in Aluminum Ion Battery

The transport and thermodynamic properties of 1-ethyl-3methyl imidazolium hexafluorophosphate ([EMIM][PF6]) ionic liquid encapsulated in carbon nanotubes or graphite represent a significant challenge in the development of Aluminum-ion batteries. To achieve high energy density in Aluminum-ion batteries, it is explored the use of ionic liquid solvents as electrolytes to enhance the ionic conductivity of the ionic liquid when encapsulated in carbon nanotubes as electrodes. The doping effects of sulfur and boron atoms in single-walled carbon nanotubes (SWCNTs) have been investigated to determine their impact on the ionic transfer number of the ionic liquid encapsulated in SWCNTs. The Green-Kubo formalism has been employed to calculate the ionic transfer number and electrical conductivity of the ionic liquid when encapsulated in SWCNTs doped with sulfur and boron atoms. The results obtained using the Green-Kubo formalism indicate that sulfur doping in SWCNTs, particularly in those with a larger radius, serves as a selective porous electrode material, significantly enhancing the electrical conductivity of the confined ionic liquid. Furthermore, the radial distribution function between the carbon alkyl groups in the ionic liquid and the carbon wall of the carbon nanotube, which is doped with sulfur and boron atoms, demonstrates that the doping effect does not alter the radial distribution function. The Green-Kubo result obtained for the electrical conductivity of the ([EMIM][PF6]) ionic liquid demonstrates excellent agreement with the experimental data.

Fabrication of a stacked Archimedean spiral reactor with porous carbon walls using 3D-printed PLA as internal sacrificial template and carbonized whey powder as porous carbon matrix

This study introduces a method to create porous carbon structures with intricate internal voids. 3D-printed PLA acts as an internal sacrificial template, combined with carbonized whey powder as the porous carbon matrix. Sintering whey powder at 150°C yields solid pieces that, upon carbonization, result in highly porous carbon objects while maintaining the original mold shape. Temperature control ensures successful whey powder sintering before PLA melting. The use of PLA sacrificial templates, along with whey carbonization, allows for developing devices with finely tailored internal voids, as demonstrated through a double Archimedean spiral reactor with porous carbon walls.Graphical abstract

Effects of organic carbon and subsurface dams on saltwater intrusion and nitrate pollution in sandy coastal aquifers.

This study explores the impact of a novel approach on the levels of SWI (saltwater intrusion) and NO3- (nitrate) contamination. Some numerical simulations were conducted utilizing a coupled model that incorporates variably saturation and density, as well as convection diffusion reaction within a sandy coastal aquifer. We verified the reliability of the model for SWI based on comparison lab experiments and for chemical reactions based on a comparison of previous in situ observations. Cutoff walls and subsurface dams cannot simultaneously control SWI and reduce NO3- contamination. A novel approach that combines subsurface dams and permeable CH2O (organic carbon) walls (PC-Wall) is proposed. Subsurface dams are utilized to prevent SWI, while PC-Walls are employed to mitigate NO3- pollution. Results demonstrate that the construction of a PC-Wall with a concentration of 1.0mM facilitated a transition from nitrification (Ni)-dominated to denitrification (Dn)-dominated. An increase in CH2O concentration to 1.0mM caused a significant 1942.5 % rise in mDn (the mass of NO3- removed through Dn). Increment of the distance between the PC-Wall and the ocean from 35 to 45m could result in a 103.7 % mDn increase and reduce mN (the compound mass of NO3- remaining in the aquifer) by 11.7 %. The study offers a detailed comprehension of the intricate hydrodynamics of SWI and NO3- pollution. In addition, it provides design guidance for engineering to mitigate contamination by NO3- and controlling SWI, thus fostering the management of groundwater quality.

Overview of tritium retention in divertor tiles and dust particles from the JET tokamak with the ITER-like wall

Divertor tiles after Joint European Torus-ITER like wall (JET-ILW) campaigns and dust collected after JET-C and JET-ILW operation were examined by a set of complementary techniques (full combustion and radiography) to determine the total, specific and areal tritium activities, poloidal tritium distribution in the divertor and the presence of that isotope in individual dust particles. In the divertor tiles, the majority of tritium is detected in the surface region and, the areal activities in the ILW divertor are in the 0.5–12 kBq cm−2 range. The activity in the ILW dust is associated mainly with the presence of carbon particles being a legacy from the JET-C operation. The total tritium activities show significant differences between the JET operation with ILW and the earlier phase with the carbon wall (JET-C) indicating that tritium retention has been significantly decreased in the operation with ILW.

Hollow Nitrogen-Doped Carbon Spheres with Presiding Graphitic Nitrogen for Oxygen Reduction Reaction

Hollow nitrogen-doped carbons, a class of metal free electrocatalysts, offer a wide range of modifications due to their tunable diameter and carbon wall thickness. Herein, hollow nitrogen-doped carbon spheres (HNCS-1000) with numerous structural defects, thin carbon wall of about 8 nm, high (sp2-sp3)/sp3 bond ratio of 3.11 and graphitic-N proportion of 71.4% are prepared using a double pyrolysis strategy. When employed as ORR catalyst in O2-saturated 0.1 M KOH solution, HNCS-1000 retains high onset and halfwave potentials of 1.03 V and 0.88 V, respectively. In addition, it also demonstrates excellent stability/durability with 90.25% current density retention after 84000 s continuous chronoamperometric operation and only 33 mV loss in halfwave potential after 7000 CV cycles. Overall, the ORR performance of HNCS-1000 surpasses most of the previously reported nitrogen-doped carbon catalysts, and it is among the best catalysts for ORR in alkaline environment.

CONAN─Novel Tool to Create and Analyze Liquids in Confined Space.

Modeling of complex liquids at solid surfaces and in confinement is gaining attention due to an increase in computer power and advancement of simulation techniques. Therefore, tools to set up structures and for analysis are needed. In this paper, we present CONAN─a Python code designed to facilitate the study of liquids interacting with solid structures, such as walls or pores. Among other things, the program provides the option to generate a variety of different structures, including carbon walls and nanotubes and their boron nitride analogs, as well as the ability to analyze various structural properties of confined and interfacial liquids. In the case of the ionic liquid 1-butyl-3-methylimidazolium acetate in carbon nanotubes of different sizes, we demonstrate the abilities of our tool. The average density within the confinement highly depends on the carbon nanotube size, and it is generally lower than the density of the bulk liquid. The arrangement of the individual species within the tube also depends on size, with radial layers forming within the tubular confinement. The density is largely increased in the respective layers, while it is drastically reduced between the layers.

The JET hybrid scenario in Deuterium, Tritium and Deuterium-Tritium

The JET hybrid scenario has been developed from low plasma current carbon wall discharges to the record-breaking Deuterium-Tritium plasmas obtained in 2021 with the ITER-like Be/W wall. The development started in pure Deuterium with refinement of the plasma current, and toroidal magnetic field choices and succeeded in solving the heat load challenges arising from 37 MW of injected power in the ITER like wall environment, keeping the radiation in the edge and core controlled, avoiding MHD instabilities and reaching high neutron rates. The Deuterium hybrid plasmas have been re-run in Tritium and methods have been found to keep the radiation controlled but not at high fusion performance probably due to time constraints. For the first time this scenario has been run in Deuterium-Tritium (50:50). These plasmas were re-optimised to have a radiation-stable H-mode entry phase, good impurity control through edge Ti gradient screening and optimised performance with fusion power exceeding 10 MW for longer than three alpha particle slow down times, 8.3 MW averaged over 5 s and fusion energy of 45.8 MJ.

The role of plasma–atom and molecule interactions on power & particle balance during detachment on the MAST Upgrade Super-X divertor

This paper shows first quantitative analysis of the detachment processes in the MAST Upgrade Super-X divertor (SXD). We identify an unprecedented impact of plasma-molecular interactions involving molecular ions (likely D2+ ), resulting in strong ion sinks (Molecular Activated Recombination—MAR), leading to a reduction of ion target flux. The MAR ion sinks exceed the divertor ion sources before electron-ion recombination (EIR) starts to occur, suggesting that significant ionisation occurs outside of the divertor chamber. In the EIR region, Te≪0.2 eV is observed and MAR remains significant in these deep detached phases. The total ion sink strength demonstrates the capability for particle (ion) exhaust in the Super-X Configuration. Molecular Activated Dissociation is the dominant volumetric neutral atom creation process can lead to an electron cooling of 20% of PSOL . The measured total radiative power losses in the divertor chamber are consistent with inferred hydrogenic radiative power losses. This suggests that intrinsic divertor impurity radiation, despite the carbon walls, is minor in the divertor chamber. This contrasts previous TCV results, which may be associated with enhanced plasma-neutral interactions and reduced chemical erosion in the detached, tightly baffled SXD. The above observations have also been observed in higher heat flux (narrower SOL width) type I ELMy H-mode discharges. This provides evidence that the characterisation in this paper may be general.

Biomass activated carbon supported Keggin-type polyoxometalate as an electrode material for high-performance acidic aqueous supercapacitors

Activated carbon (SSAC-OP) with micropore and mesopore was prepared by using soybean straw as a carbon source. Redox-active H3PMo12O40 (PMo12) was introduced into SSAC-OP by solution impregnation to obtain composite PMo12/SSAC-OP. The effect of loading amount of PMo12 on the supercapacitive performance of the composite was investigated. BET and EDS results confirmed that PMo12 is adsorbed in the micropores of 1–2 nm and mesopores of SSAC-OP, as well as on the carbon wall of SSAC-OP. Meanwhile, SSAC-OP with positive charge is more firmly connected with PMo12 anions via the effect of electrostatic attraction. CV and GCD test results proved that the composite materials have both electric double layer capacitance and pseudocapacitance characteristics. The CV curve of 10-PMo12/SSAC-OP obtained from SSAC-OP impregnating the initial concentration of PMo12 solution of 10 mM shows four pairs of obvious reversible redox peaks, which indicates that the protonation of PMo12 anion in the reduction process is sufficient. The composite 10-PMo12/SSAC-OP has a specific capacitance as high as 397.02F g−1 at scan rate of 5 mV s−1. The assembled symmetric supercapacitor delivers an energy density of 23.90 Wh kg−1 under the power density of 1016.05 W kg−1, with 97.96 % capacitance retention after 10,000 cycles at 3 A g−1.

Waste plastics derived nickel-palladium alloy filled carbon nanotubes for hydrogen evolution reaction

Carbon nanotubes (CNTs) composed of bimetallic nickel-palladium (NiPd) nanoparticles encapsulated in graphitic carbon shells (NdPd@CNT) are prepared by the chemical vapour deposition method using waste polyethylene terephthalate (PET) plastic carbon sources and NiPd-decorated carbon sheets (NiPd@C) catalyst. The characterization results reveal that the face-centered cubic crystalline (fcc)-structured NiPd bimetallic alloy nanoparticles are encased by thin carbon nanotubes. The bimetallic synergism of NiPd nanoparticles actuates the outer CNT layers and accelerates the electrical conductivity, stimulating the electrochemical activity toward an effective hydrogen evolution reaction (HER). By virtue of the collective individualities of highly conductive aligned carbon walls and bimetallic active sites, the NiPd@CNT-equipped HER delivers a minimum overpotential of 87 mV and a Tafel slope value of 95 mV dec−1. The existing intact contact between NiPd and CNT facilitates continuous electron and ion transportation and firm stability toward long-term hydrogen production in HER. Notably, the NiPd@CNT reported here produces excellent electrochemical activity with minimal charge transference resistance, substantiating the efficacy of NiPd@CNT for futuristic green hydrogen production.

Activated three-dimensionally ordered micromesoporous carbons for CO2 capture

Three-dimensionally ordered micromesoporous carbon (3DOmm) has been studied recently as a potential sorbent for CO2 capture at higher pressures. However, the as-synthesized material usually has a low microporous fraction, which could significantly limit CO2 uptake. Herein, we showed that microporosity in 3DOmm carbon can be increased by physical activation, substantially improving its CO2 capture performance in the wide pressure range. The highly porous activated 3DOmm carbons, having amorphous structure, were prepared with ordered spherical mesopores of diameter 22.7–24.7 nm and ultramicropores in the walls of diameter 0.41–0.55 nm. Physical activation was performed by exposing the post-synthesized 3DOmm carbon to high temperatures of 973–1173 K under a CO2 flow for 30 min. The activation procedure did not show any visible destruction of the ordered mesoporous structure in the 3DOmm carbon. However, it had a significant impact on micropore and mesopore volumes and the specific surface area, which in turn affected the CO2 adsorption capacity of the carbons. Accordingly, after activation at 973 K, the micropore volume of 0.23 cm3/g, the mesopore volume of 3.70 cm3/g and the specific surface area of 1058 m2/g in the 3DOmm carbon increased to 0.27 cm3/g, 3.94 cm3/g and 1462 m2/g, respectively. Further increase in activation temperature led to decreasing pore values due to widening and shrinking of the thin carbon walls in the 3DOmm carbon. The 3DOmm carbon activated at 973 K had the highest micropore and mesopore volumes and the highest CO2 adsorption performance over the whole pressure range (3.19 mmol/g at 273 K and 100 kPa; 11.18 mmol/g at 298 K and 2 MPa and 0.38 mmol/g under flue 15% CO2/85% N2 gas conditions at 298 K). All 3DOmm carbons showed fast kinetics, high selectivity for CO2 over N2 (33.2–51.5), the excellent regenerative ability and isosteric heats (18.9–29.2 kJ/mol), indicating physical adsorption.

Two-stage confinement derived small-sized highly ordered L10-PtCoZn for effective oxygen reduction catalysis in PEM fuel cells

Intermetallic ordered PtCo is effective for high oxygen reduction reaction (ORR) activity and stability. However, preparing small-sized, highly ordered PtM alloys is still challenging. Herein, we report a controlled two-stage confinement strategy, in which highly ordered PtCoZn/NC nanoparticles of 5.3 nm size were prepared in a scalable process. The contradiction between the high ordering degree with the small particle size as well as the atomic migration with the space confinement was well resolved. An outstanding PEMFC performance was achieved for L10-PtCoZn/NC with a high mass activity (MA) of 1.21 A/mgPt at 0.9 ViR-free, 80.1 % MA retention after 30 k cycles in H2-O2 operation, and a high mass-specific power density of 8.24 W mg-1Pt in H2-Air operation with a slight loss of cell voltage@0.8 A cm−2 of 28 mV after 30 k cycles. The high performance can be ascribed to the high Pt area exposure, the enhanced Pt-Co coupling, and the prevented agglomeration in the mesoporous carbon wall. Overall, this strategy may contribute to the commercialization of fuel cells.

Spectroscopic measurement of increases in hydrogen molecular rotational temperature with plasma-facing surface temperature and due to collisional-radiative processes in tokamaks

Spatially resolved rotational temperature of ground state hydrogen molecules desorbed from plasma-facing surface was measured in QUEST, LTX-β, and DIII-D tokamaks, and the increases of the rotational temperature with the surface temperature and due to collisional-radiative processes in the plasmas were evaluated. The increase due to collisional-radiative processes was calculated by solving rate equations considering electron and proton collisional excitation and deexcitation and spontaneous emission. The calculation results suggest a high sensitivity for the rotational temperature to electron and proton densities, but a negligible sensitivity to the electron, proton, and surface temperatures. In the three tokamaks with different plasma parameters and plasma-facing surface materials, the spatial profile of the rotational temperature was estimated using Fulcher-α emission lines (600–608 nm). In QUEST, the spatial profile of the rotational temperature was estimated from spatially resolved spectra. In the other tokamaks, the rotational temperature was evaluated assuming a single point emission with a location determined from the Fulcher-α emission profile as measured with a filtered camera. In metal-walled devices QUEST and LTX-β, the rotational temperature increased with the surface temperature, and the calculated collisional-radiative increase is consistent with measured increase assuming that the rotational temperature at the surface is approximately 500–600 K higher than the surface temperature. In DIII-D with carbon walls, a larger collisional-radiative increase than the other tokamaks was observed because of the higher density leading to a large difference from the calculated increase compared to the other smaller tokamaks. Measurement of the Fulcher-α emission profile with higher spatial resolution in DIII-D may reduce the difference and reveal the effect of the surface temperature on the rotational temperature. These results show the increases in the rotational temperature with the surface temperature and due to the collisional-radiative processes.

Microporous carbon foams: The effect of nitrogen-doping on CO2 capture and separation via pressure swing adsorption

This work investigates the effect of nitrogen doping on the porous structure and CO2 adsorption properties of hierarchically porous carbon foams, at different temperatures and pressures. A series of carbon foams with nitrogen contents of ∼7 to 13 at % is prepared by reaction of sodium ethoxide with different amino alcohols (namely monoethanolamine, diethanolamine, and triethanolamine), followed by thermal decomposition of the reaction product. The structure, morphology, porosity and chemical composition are studied using appropriate methods. The resulting material comprises micron-scale macropores combined with unrestricted micropores and mesopores embedded in the carbon walls. It is found that both nitrogen species and ultra-micropores contribute positively to CO2 uptake. The carbon foam with a nitrogen content of ∼7 at % (as well as an ultra-micropore volume of 0.44 cm3 g−1 and a specific surface area of 1549 m2 g-1) displays the highest CO2 uptake, adsorbing 5.14 mmol g−1 at 273 K, 3.22 mmol g−1 at 298 K, or 1.93 mmol g−1 at 323 K. This nitrogen-doped carbon foam adsorbs more CO2 than the undoped carbon foam reference, despite having significantly lower ultra-micropore volume and higher specific surface area. This highlights the importance of nitrogen species in CO2 capture. However, increasing the nitrogen content leads to suppression of the micropore volume, resulting in poor CO2 uptake. High CO2/N2 selectivity with good separation of CO2 from the CO2-N2 gas mixture, fast adsorption via physisorption, and excellent cycling durability are also observed, pointing towards the high regenerative ability of these materials.

Scheelite composition fingerprints pulsed flow of magmatic fluid in the Fujiashan W skarn deposit, eastern China

Abstract Scheelite (CaWO4) is an economically important W mineral in skarns that form when magmatic fluids exsolved from a granitic intrusion react with carbonate wall rocks. In the Fujiashan W skarn deposit, scheelite formed during four stages of the hydrothermal skarn development. We present cathodoluminescence (CL) images and in situ trace element and Sr-O isotope data of scheelite from these four stages, i.e., scheelite in prograde and retrograde skarn, quartz-sulfide veins, and late calcite replacements. Scheelite from prograde skarn and quartz sulfide veins are homogeneous and show oscillatory zoning textures in CL images, whereas scheelite from retrograde skarn and late carbonate stages display dissolution-reprecipitation and patchy textures. The brightness of CL textures decreases with a higher substitution of Mo. Molybdenum-rich scheelite (up to 2.1 wt%) is characterized by relatively high contents of Nb and Ta (up to 156 and 0.9 ppm, respectively), positive Eu anomalies, high-δ18O values (5.2 to 5.9‰), and relatively low-87Sr/86Sr values (0.70661 to 0.70727), and has grown in a system with a continuous supply of magmatic fluid. Molybdenum-poor scheelite (0.2 wt%) has low contents of Nb and Ta, negative Eu anomalies, low-δ18O values (4.2 to 4.3‰), and relatively high-87Sr/86Sr ratios (0.70748 to 0.70804). This type of scheelite formed in a system with a restricted flow of magmatic fluid during scheelite precipitation became increasingly depleted in elements that substitute into scheelite. The continued reaction of the magmatic fluid with the wall rocks and the precipitation of minerals from the fluid resulted in a systematic change of the δ18O and 87Sr/86Sr ratios. Chemical and isotopic variations in scheelite may reflect the pulsed flow of a magmatic fluid and do not require the involvement of different fluids or contrasting redox conditions.

Mineralogy and Geochemistry of Nepheline Syenite From the Bang Phuc Massif of the Alkaline Cho Don Complex in North-Eastern Vietnam—Implications for Magma Evolution and Fluid–Rock Interactions

Abstract The alkaline Cho Don complex in NE Vietnam comprises several mafic-felsic suites related to the widespread magmatism developed during the early Permian–late Triassic. The contribution explores the petrogenesis of nepheline syenite from the Bang Phuc massif and its petrogenetic relationship with cogenetic scapolite-rich gabbro. The nepheline syenite formed through fractional crystallization of pristine mantle-derived basaltic melt modified by subduction-related components (chiefly sediment-derived melts), as shown by, e.g. low Ba/Th and high Th/Nb ratios of the rocks. The transition from gabbro to syenite follows a within-plate enrichment trend (e.g. increasing Ta/Yb, Nb/Yb, and Th/Yb ratios) that might reflect switch from post-orogenic to intra-plate regimes, accompanied by subduction–collision–extension events related to the Indosinian Orogeny. Furthermore, magma evolution involved the progressive contribution of asthenospheric-derived melts that resulted in the appearance of OIB-like signatures (e.g. high Nb/La ratios) in the nepheline syenite. Fractional crystallization of fluorapatite and mafic phases, as well as assimilation of carbonate wall rocks ultimately led to the decrease of LREE contents and/or modification of Zr/Hf ratios. Magmatic phases of the nepheline syenite include nepheline, sodalite, oligoclase, orthoclase, and annite, as well as accessory fluorapatite, fluorite, and minor amounts of zircon and metamict allanite-Ce. The nepheline equilibrated at temperatures ranging between 850°C and 700°C, which reflects protracted residence at a higher temperature. Later, it has been locally altered to cancrinite, dawsonite, and natrolite via CO2- and alkali-rich fluid influx. The fluid–rock interactions were also manifested by the presence of chessboard-twinned albite and coarsening of braid-perthite into patch-perthite, as well as recrystallization of primary orthoclase into microcline. The orthoclase→microcline conversion, albeit fairly indiscrete under a polarizing microscope and confirmed by Raman micro-spectroscopy, is followed by the change of cathodoluminescence colours, i.e. from light-blue (activated by Ti4+ and/or Al-O—Al centres) in orthoclase towards brownish and/or greenish (activated by Mn2+ and structural defects) in microcline.

Direct Evidence of Reversible SnO2-Li Reactions in Carbon Nanospaces.

We present herein that carbon nanospaces are the key reaction space to improve the reversibility of the reaction of SnO2 with Li-ions for lithium-ion batteries, demonstrated by both ex situ and in situ observations using high-resolution scanning transmission electron microscopy with electron energy loss spectroscopy. Conversion-type electrode materials, such as SnO2, undergo large volume changes and phase separation during the charge-discharge process, which lead to degradation in the battery performance. By confining the SnO2-Li reaction within carbon nanopores, the battery performance is improved. However, the exact phase changes of SnO2 in the nanospaces are unclear. By directly observing the electrodes during the charge-discharge process, the carbon walls are capable of preventing the expansion of SnO2 particles and minimizing the conversion-induced phase separation of Sn and Li2O on the sub-nanometer scale. Thus, nanoconfinement structures can effectively improve the reversibility performance of conversion-type electrode materials.