Metal Oxide Phases Research Articles

Probing atomic-scale processes at the ferrihydrite-water interface with reactive molecular dynamics

Interfacial processes involving metal (oxyhydr)oxide phases are important for the mobility and bioavailability of nutrients and contaminants in soils, sediments, and water. Consequently, these processes influence ecosystem health and functioning, and have shaped the biological and environmental co-evolution of Earth over geologic time. Here we employ reactive molecular dynamics simulations, supported by synchrotron X-ray spectroscopy to study the molecular-scale interfacial processes that influence surface complexation in ferrihydrite-water systems containing aqueous MoO42-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext {MoO}_4}^{2-}$$\\end{document}. We validate the utility of this approach by calculating surface complexation models directly from simulations. The reactive force-field captures the realistic dynamics of surface restructuring, surface charge equilibration, and the evolution of the interfacial water hydrogen bond network in response to adsorption and proton transfer. We find that upon hydration and adsorption, ferrihydrite restructures into a more disordered phase through surface charge equilibration, as revealed by simulations and high-resolution X-ray diffraction. We observed how this restructuring leads to a different interfacial hydrogen bond network compared to bulk water by monitoring water dynamics. Using umbrella sampling, we constructed the free energy landscape of aqueous MoO42-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext {MoO}_4}^{2-}$$\\end{document} adsorption at various concentrations and the deprotonation of the ferrihydrite surface. The results demonstrate excellent agreement with the values reported by experimental surface complexation models. These findings are important as reactive molecular dynamics opens new avenues to study mineral-water interfaces, enriching and refining surface complexation models beyond their foundational assumptions.Graphic

Tailoring phases of ferrihydrite/α-Fe2O3@C nanocomposites using syringyl and guaiacyl-rich biomass-derived carbon nanodots for electrochemical application

Biomass-derived carbon nanodots (CNDs) hold promise as effective reducing agents for metal oxide nanoparticles yet understanding the intricate interplay with CND structure remains challenging. This study explores the impact of lignin types, specifically syringyl (S), and guaiacyl (G) units in CNDs on metal oxide phases and their electrochemical activity toward dopamine oxidation. We design phases of ferrihydrite/α-Fe2O3@C nanocomposites, using hazelnut carbon nanodots (HS-CNDs (S-rich)) and beetroot carbon nanodots (BS-CNDs (G-rich)) via a one-pot hydrothermal technique. Our findings show S units in HS-CNDs promote α-FeOOH/α-Fe2O3@CHS, while G units in BS-CNDs favor α (β)-FeOOH/α-Fe2O3@CBS. In contrast to α(β)-FeOOH/α-Fe2O3@CBS, α-FeOOH/α-Fe2O3@CHS exhibits superior electrochemical performance in dopamine oxidation due to its larger electrochemical active surface area, higher absorbance capacity, and shortened electron transfer length. Moreover, α-FeOOH/α-Fe2O3@CHS nanocomposites demonstrate remarkable dopamine selectivity, achieving rapid detection response in 10 s with a low LOD of 4 nM within a broad linear range (0.05–0.3 μM), demonstrating impressive reproducibility (97.5 %), stability (96.4 %), and works in real-time human urine detection with a recovery rate of ranging from 94.57 % and 102.2 %. Therefore, the utilization of biomass-derived CNDs, particularly S and G units-rich CNDs, in tailoring the phases of ferrihydrite/α-Fe2O3@C nanocomposites for electrochemical dopamine detection is promising.

Investigation of the microstructural, surface, and optical properties of WO3-doped ZnO thin films

The paper investigates the microstructural characteristics, surface features, and optical properties of WO3-doped ZnO thin film. The deposited samples exhibit polycrystalline characteristics, with reflections corresponding to bimetal oxides and metals. Specifically, ZnO shows (101) and (200) reflections, while (400) reflections are observed in the WO3 phase of the deposited sample. The crystallite sizes of the ZnO metal oxide phase in the film are 85 nm and 55 nm, while the crystallite size of the Zn nanoparticles is found to be 47 nm. The atomic concentrations of W and Zn are 53.4 % and 46.6 % for films deposited on uncoated glass, and 41.2 % and 58.8 %, for films deposited onto ITO-coated glass, respectively. An optical band gap value of 3.40 eV was obtained for both films. It was found that certain properties remain relatively unchanged despite variations in the substrate.

Elusive supported surface M2Ox dimer active site (M = Re, W, Mo, Cr, V, Nb, and Ta)

Supported transition metal oxide catalysts are extensively used as heterogeneous catalysts for various energy, chemical, and environmental applications. The molecular structures of dehydrated surface metal oxide phases are crucial for understanding structure-activity/selectivity relationships that guide the design of enhanced catalysts. Some early studies suggested that dimeric (aka binuclear) surface metal oxide sites were more active/selective than monomeric (aka mononuclear) sites, prompting interest in synthesizing catalysts with supported dimeric metal oxide structures. This review examines the literature on dehydrated silica-based supported group 7-5 MOx catalysts (ReOx, WOx, MoOx, CrOx, VOx, NbOx, and TaOx on SiO2, MCM-41, AlOx/SiO2, and H-ZSM-5) for their surface metal oxide structures. In situ Raman, extended x-ray absorption fine structure, and ultraviolet-visible spectroscopy indicate that monomeric surface MOx structures predominate in all such catalysts. Therefore, the cursory use of dimeric surface M2Ox sites in catalytic mechanisms and reaction models in heterogeneous catalysis by supported metal oxides is questionable, and moving forward, the invoking of supporting dimeric surface M2Ox sites should be critically examined and backed up with direct spectroscopic methods.

Mixed phase iron oxides thin layers by atmospheric-pressure chemical vapor deposition method

This paper provides a simple method for producing a metal oxide thin layer methodology by atmospheric pressure chemical vapor deposition (APCVD) synthesis over stainless steel substrates. This methodology enables the formation of thin iron oxide layers at its performance at various temperatures of 330 °C, 430 °C, and 530 °C. The deposition arises from thermal decomposition of the iron organometallic precursor Fe3(CO)12, forming a thin layer of iron oxide is, by the ozone present in the reaction chamber promoting the deposition of the iron oxide particles over the substrate. The Raman characterization suggest that at 330 °C, a mixture of hematite and magnetite is predominant on the as deposited substrates, also hematite modes show to be more pronounced as the band at 300 cm-1 narrows. Conversely, magnetite is prominent at higher synthesis temperatures, exhibiting a more intense Eg5 mode at 680 cm-1. The particles exhibit a uniform morphology, with both metal oxide phases coexisting. The average diameter of the particles is 50 nanometers as scanning electronic microscopy shows in a transversal sample section.•The formation of particles is attributed to the combination of iron ions +2 and +3 in the deposition process and their interaction with oxygen in the given synthesis parameters at atmospheric pressure chemical vapor deposition (APCVD).

Redox Mechanisms upon the Lithiation of Wadsley-Roth Phases.

The Wadsley-Roth family of transition metal oxide phases are a promising class of anode materials for Li-ion batteries due to their open crystal structures and their ability to intercalate Li at high rates. Unfortunately, most early transition metal oxides that adopt a Wadsley-Roth crystal structure intercalate Li at voltages that are too high for most battery applications. First-principles electronic structure calculations are performed to elucidate redox mechanisms in Wadsley-Roth phases with the aim of determining how they depend on crystal structure. A comparative study of two very distinct polymorphs of Nb2O5 reveal two redox mechanisms: (i) an atom-centered redox mechanism at early stages of Li intercalation and (ii) a redox mechanism at intermediate to high Li concentrations involving the bonding orbitals of metal-metal dimers formed by edge-sharing Nb cations. Our study motivates several design principles to guide the development of new Wadsley-Roth phases with superior electrochemical properties.

Morphostructural studies of pure and mixed metal oxide nanoparticles of Cu with Ni and Zn

Nano-scale interactions between pure metal or metal-oxide components within an oxide matrix can improve functional performance over basic metal oxides. This study reports on the synthesis of monometallic (CuO), bimetallic (CuO–NiO) and trimetallic (CuO–NiO–ZnO) oxide nanoparticles (NPs) via the co-precipitation method and investigation of morphostructural properties. All of the synthesized metal oxide NPs were calcined at 550 °C temperature and annealed under vacuum. In this work, we applied Scherrer formula, modified Scherrer equation, Williamson-Hall plots, and Halder-Wagner plots to calculate the average crystallite size. The XRD data analysis showed that average crystallite sizes of the as-synthesized metal oxide phases were between 4 nm and 76 nm and average diameters calculated from SEM image were between 15 nm and 83 nm. The XRD studies also disclosed that average crystallite size and lattice microstrain of the CuO phases remain almost same (43 nm–46 nm and 2.074×10−3 to 2.665×10−3) for pure CuO and mixed CuO–NiO; but in case of mixed CuO–NiO–ZnO it is found to decrease in size to 11 nm where lattice microstrain increases to 9.653×10−3. Line broadening of diffraction peaks from microstrain contribution was between 0.02 and 0.01. Degree of crystallinity (%) of CuO phases found to decrease from 81 to 71. Dislocation density of CuO phases found to increase from 6.63×10−4nm−2 to 12.68×10−3nm−2. X-ray density of CuO phases increased from 6.48 to 6.53 g/cm3. Where this calculated small dislocation density well agreed with the high crystallinity. Crystal structure and specific surface area were determined from lattice constants and X-ray density. These synthesized nanopowders showed the existence of monoclinic, cubic, and hexagonal phases. The obtained NPs of multi-metal oxide explained more than one phases with different size, shape, and morphology at nano scale.

Dual-Photosensitizer Synergy Empowers Ambient Light Photoactivation of Indium Oxide for High-Performance NO2 Sensing.

Light-activated chemiresistors offer a powerful approach to achieving lower-temperature gas sensing with unprecedented sensitivities. However, an incomplete understanding of how photoexcited charge carriers enhance sensitivity obstructs the rational design of high-performance sensors, impeding the practical utilization under commonly accessible light sources instead of ultravioletor higher-energy sources. Here, a rational approach is presented to modulate the electronic properties of the parent metal oxide phase, exemplified by this model system of Bi-doped In2O3 nanofibers decorated with Au nanoparticles (NPs) that exhibit superior NO2 sensing performance. Bi doping introduces mid-gap energy levels into In2O3, promoting photoactivation even under visible blue light. Additionally, green-absorbing plasmonic Au NPs facilitate electron transfer across the heterojunction, extending the photoactive region toward the green light. It is revealed that the direct involvement of photogenerated charge carriers in gas adsorption and desorption processes is pivotal for enhancing gas sensing performance. Owing to the synergistic interplay between the Bi dopants and the Au NPs, the Au-BixIn2-xO3 (x=0.04) sensing layers attain impressive response values (Rg/Ra=104 at 0.6ppm NO2) under green light illumination and demonstrate practical viability through evaluation under simulated mixed-light conditions, all of which significantly outperforms previously reported visible light-activated NO2 sensors.

Comparison of Structure and Reactivity of Hydrothermally Prepared Bi−Mo−Co−Fe−O Catalysts in Selective Propylene and Isobutene Oxidation

AbstractThe elucidation of structure‐activity correlations in selective oxidation of propylene and isobutene over mixed metal oxides (MMO) is attractive for knowledge‐based catalyst design and process optimisation. Particularly, 4‐component Bi−Mo−Co−Fe−O catalysts need to be studied since their complex metal oxide phase mixture leads to higher activity and selectivity than 2‐component Bi−Mo−O. Hence, three Bi−Mo−Co−Fe‐oxides with different metal ratios were prepared by hydrothermal synthesis and compared during selective oxidation tests with propylene and isobutene. The active phases after several days on stream were investigated by synchrotron X‐ray diffraction (XRD) and Raman spectroscopy, while the structural evolution under reaction conditions was followed by operando Raman spectroscopy, synchrotron XRD, and multi‐edge X‐ray absorption spectroscopy. Similar structural transformations were observed during selective oxidation of propylene and isobutene, with similar influence on catalytic performance. A phase mixture of β‐CoMoO4/β‐Co0.7Fe0.3MoO4, γ‐Bi2MoO6, Fe3O4 and Bi3FeMo2O12 was observed, whereby high amounts of β‐CoMoO4/β‐Co0.7Fe0.3MoO4 increased selectivity to acrolein/methacrolein. In contrast, high amounts of γ‐Bi2MoO6 and Fe3O4 favoured total oxidation to CO and CO2. The simultaneous presence of β‐CoMoO4/β‐Co0.7Fe0.3MoO4, Bi3FeMo2O12 and Fe2O3 increased selectivity to methacrolein in isobutene oxidation, whereas no comparative increase in acrolein selectivity was observed in propylene oxidation. This suggests different key active phases in both reactions.

Atomic-scale understanding of the impact of CoO phase in cobalt-catalyzed Fischer-Tropsch synthesis: A combined computational and experimental study

In cobalt-catalyzed Fischer-Tropsch synthesis (FTS), the active metallic cobalt phase always suffers from oxidation under FTS reaction conditions, leading to the coexistence of metallic cobalt and cobalt oxide (CoO) phases. However, there still exist contradictory views on the impact of CoO phase in FTS. Some researchers proposed that the oxidation of metallic Co to CoO causes the deactivation of cobalt-based FTS catalysts, while some held the view that CoO phase could act as the potential active phase in FTS. In this study, by combining theoretical calculations and experiments, we systematically investigated the fundamental FTS reactions including CO adsorption and activation, C-C coupling, and CxHy hydrogenation on CoO phase, and compared them with those on metallic cobalt phase, aiming at identifying the exact role of CoO, understanding how CoO influences the activity and selectivity, and unraveling the intrinsic mechanism that determines the catalytic behaviors of CoO phase in FTS. The results reveal that the CoO(200) crystal facet is the dominantly exposed surface structure for CoO phase under FTS reaction conditions. The d-band center of CoO(200) surface shifts downward in comparison with that of active metallic Co surface, which causes difficulties in adsorbing and activating CO and gives rise to high energy barriers for the dissociation of C-O bond. This determines the inactive nature of CoO phase in FTS reaction. As for the product selectivity, the CoO(200) surface restricts the C-C chain growth due to its higher barriers for C-C coupling, facile desorption ability for light olefins, and lower energy barrier for CH4 formation compared with metallic cobalt, and consequently leads to the loss of selectivity to C5+ hydrocarbons and enhancement of selectivity to light olefins and undesired methane. Moreover, a strong linear relationship between the experimental observed selectivity change and the DFT-calculated energy difference of CoO and metallic cobalt phases was found, validating the DFT-calculated results. This study provides a comprehensive understanding of the nature and intrinsic catalytic behaviors of CoO phase in cobalt-catalyzed FTS.

Unconventional thickness dependence of electrical resistivity of silver film electrodes in substoichiometric oxidation states

The scaling down of metallic electrodes into ultrathin film geometries presents significant challenges in precisely controlling electrical resistivity. This difficulty stems from the rapid variation in resistivity with thickness, particularly near the percolation threshold. Currently, our understanding of the prediction of thickness-dependent resistivity in metallic film electrodes in volatile substoichiometric oxide (suboxide) states is limited. This study offers experimental and numerical evidence demonstrating a marked resistivity fluctuation spanning four to five orders of magnitude during the initial growth stages of suboxidized Ag film electrodes. These stages range from cluster coalescence to reaching the percolation threshold. The unusual resistivity change is attributed to the variation in suboxidation states with thickness, as well as the outward migration of interstitial O ions. These findings offer a crucial framework for controlling the electrical properties of thin metallic oxide films in extreme suboxidation states, extending beyond the conventional understanding applicable to thermodynamically stable metallic oxide phases.

Surface design and engineering of ZnMn2O4/RGO composites for highly stable supercapacitor devices

The manipulation of phase and morphology of metal oxides by controlled engineering is considered to be a significant approach for enhancing electrochemical characteristics. The development of composite materials that are both highly efficient and cost-effective is crucial in the context of supercapacitors. A hydrothermal route is opted to fabricate ZnMn2O4/RGO microsphere electrodes. The control of process parameters during the synthesis and subsequent annealing allows for the development of microspheres exhibiting unique topographies of the surface. The incorporation of RGO into the composites has the potential to enhance conductivity, hence improving the overall utilization of the material. The ZnMn2O4/RGO composites exhibited the specific capacitances of 628, 545, 488, 446, 380 and 364 F g−1 at current densities of 1, 2,3,5,10 and 20 A g−1, respectively. Furthermore, the results demonstrated exceptional rate capability as the material retained 58 % of its initial capacitance even under a high current density. In addition, it retained a capacitance of 95.2 % even after 10,000 cycles at 1 A g−1. Furthermore, ZnMn2O4/RGO@ASC device displayed a reasonable specific capacitance of 128.7 F g−1 at 1.5 A g−1 and retained a capacitance of 83.9 % for 5000 cycles at 5 A g−1. The ZnMn2O4/RGO@ASC device had the energy density of 40.2 W h kg−1 at a power density of 1125 W/ kg. As a result, developed supercapacitor devices are preferred for use in portable electronics and industrial applications.

Improved Durability of Ti3C2Tz at Potentials above the Reversible Hydrogen Electrode by Tantalum Substitution

AbstractMXenes have gained significant attention, particularly Ti3C2Tz, as materials with favorable properties for energy storage and conversion applications. The overwhelming majority of electrochemical durability studies are based on durability in the hydrogen evolution window, well below the reversible hydrogen electrode where degradation via electrochemical oxidation is less relevant. Consequently, few strategies have been put forward to protect Ti3C2Tz at higher potentials and widen their applicability to electrochemical systems. Here, the electrochemical degradation of pristine Ti3C2Tz and tantalum (Ta)‐substituted (Ti0.95Ta0.05)3C2Tz is reported. X‐ray photoelectron spectroscopy and electron microscopy revealed that pristine and Ta‐doped MXene went through entirely different degradation mechanisms, and that these mechanisms are driven by electrochemical, rather than chemical effects. Density functional theory is used to explain the role of Ta doping with respect to the binding of oxygen and the formation of metal oxide phases. The influence of the degradation mechanism is observed by accelerated stress tests and anode reversal tests on a polymer electrolyte membrane fuel cell. Therefore, the substitution of titanium (Ti) with other oxyphilic metals in Ti3C2Tz may be an effective route to improve the durability of the otherwise fragile MXene phase.

Highly Porous Polymer Beads Coated with Nanometer-Thick Metal Oxide Films for Photocatalytic Oxidation of Bisphenol A.

Highly porous metal oxide-polymer nanocomposites are attracting considerable interest due to their unique structural and functional features. A porous polymer matrix brings properties such as high porosity and permeability, while the metal oxide phase adds functionality. For the metal oxide phase to perform its function, it must be fully accessible, and this is possible only at the pore surface, but functioning surfaces require controlled engineering, which remains a challenge. Here, highly porous nanocomposite beads based on thin metal oxide nanocoatings and polymerized high internal phase emulsions (polyHIPEs) are demonstrated. By leveraging the unique properties of polyHIPEs, i.e., a three-dimensional (3D) interconnected network of macropores, and high-precision of the atomic-layer-deposition technique (ALD), we were able to homogeneously coat the entire surface of the pores in polyHIPE beads with TiO2-, ZnO-, and Al2O3-based nanocoatings. Parameters such as nanocoating thickness, growth per cycle (GPC), and metal oxide (MO) composition were systematically controlled by varying the number of deposition cycles and dosing time under specific process conditions. The combination of polyHIPE structure and ALD technique proved advantageous, as MO-nanocoatings with thicknesses between 11 ± 3 and 40 ± 9 nm for TiO2 or 31 ± 6 and 74 ± 28 nm for ZnO and Al2O3, respectively, were successfully fabricated. It has been shown that the number of ALD cycles affects both the thickness and crystallinity of the MO nanocoatings. Finally, the potential of ALD-derived TiO2-polyHIPE beads in photocatalytic oxidation of an aqueous bisphenol A (BPA) solution was demonstrated. The beads exhibited about five times higher activity than nanocomposite beads prepared by the conventional (Pickering) method. Such ALD-derived polyHIPE nanocomposites could find wide application in nanotechnology, sensor development, or catalysis.

Controllable synthesis of hexagonal h-WO3 microflowers for water oxidation reaction

Tailoring the morphology and crystalline phase of metal oxides induces the variation in structure and surficial microenvironment, in turn influencing their catalytic activity. To date, metastable hexagonal phase WO3 is nearly inactive in electrochemical water oxidation reaction owing to the poor conductivity. Here, we report a facile route to precisely fabricate hexagonal WO3 microflowers with the nanosheet building blocks. In comparison to WO3·0.33H2O microflowers, h-WO3 microflowers could significantly catalyze the transformation of H2O to O2 via water oxidation reaction with high activity of 276 mV at 10 mA/cm2. The synthesized h-WO3 microflowers exhibit superior oxygen evolution efficiency than WO3·0.33H2O microflowers and commercial IrO2. Coordinative unsaturated W sites and hexagonal channels enable them to greatly activate and dissociate the O–H bond into O2 in alkaline electrolyte.

Coupling FeMgAl-LDH and sludge biofilm for simultaneous and effective removal of nitrate and ammonium in water

The existence of redundant nitrate (NO3−) and ammonium (NH4+) in water caused negative impacts on the ecosystem's stability while the simultaneous removal of these nitrogenous substances has become a challenging task. The intimately coupled photocatalysis and biodegradation (ICPB) system has shown great potential in the efficient removal of aquatic pollutants. In this study, the FeMgAl layered double hydroxide (FeMgAl-LDH) capable of removing NO3− and NH4+ concurrently through adsorption and photocatalysis was successfully synthesized based on the hydrothermal method. The characterization of the material has verified its lamellar structure and the inclusion of metal oxide phases. Then, the ICPB system was constructed by coupling FeMgAl-LDH and biofilm from activated sludge onto a polyurethane carrier. After 12-hour water treatment, the ICPB system could realize 54.45 % and 42.57 % of the NO3− and NH4+ removal rates at a pH of 7 and dissolved oxygen (DO) of 2 mg/L, which was superior to the single photocatalysis and biological treatment. The removal performances of the ICPB system under different pH and DO levels were assayed. Meanwhile, microbial activities, community variation, and relational genes were studied to analyze the microbial mechanisms. The microorganisms in the ICPB system possessed high activity to form extracellular polymeric substances (EPSs), nitrogen transformation, and electron transfer. In all, this study constructed a new ICPB system and revealed its mechanism to simultaneously remove the NO3− and NH4+ from the water.

Influence of carbon target power on the tribological and electrochemical properties of NbMoSiC composite films in seawater

Because the wear and corrosion of marine engineering equipment will cause huge economic losses to enterprises every year, thus it is necessary to develop advanced protective films to ensure the normal operation of marine equipment. Here NbMoSiC composite films are deposited using DC magnetron sputtering in an argon atmosphere through varying the carbon target sputtering power, and their microstructure and mechanical properties are investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS)，Raman spectroscopy and dynamic ultra-micro hardness tester, respectively. The tribological properties of the films in air and artificial seawater are determined by a reciprocating ball-on-disc tester, while the electrochemical properties of the films in seawater were evaluated by an electrochemical workstation. The results demonstrate that the presence of Nb2C, MoSi2, free silicon, and amorphous carbon (a-C) in the NbMoSiC composite films. Particularly, Sample C250, featuring a carbon content of 35.02 at.%, exhibits higher hardness, elastic modulus, excellent wear resistance, and superior corrosion resistance. However, a further increase in carbon target sputtering power leads to escalated surface roughness and microchannels, ultimately resulting in reduced wear and corrosion performance. Electrochemical analysis reveal that the strong synergistic effect of amorphous carbon as well as the metal oxide phase formed on the surface significantly enhanced the corrosion resistance of the film in artificial seawater with a corrosion current density as low as 1.8 × 10−8 A/cm2.

Solvent-free direct salt precursor mechanochemical synthesis of La0.5Sr0.5Ti0.5Mn0.5O3-δ oxide perovskite and its electrocatalytic behavior as oxygen electrode for solid oxide cells

In this work, a solvent-free mechanochemical route is proposed as a direct salt precursor solid state synthesis for the mixed ionic-electronic conducting (MIEC) Lanthanum Strontium Titanium Manganese oxide perovskite (La0.5Sr0.5Ti0.5Mn0.5O3-δ, LSTM). The resulting mechanochemically synthesized powder is structurally and morphologically characterized and is comprised of fine spherical nanostructures in the sub-micron scale (≤100 nm), with low polydispersity and homogeneous morphology, while the obtained perovskite structure is pure single-phase without any precursor residuals or metal oxide phases. For comparison, conventional synthetic routes (sol-gel and precursor calcination) are presented which result in inferior samples of mixed metal oxides and micron-sized particles. Symmetrical solid oxide cells with single-phase LSTM and LSTM-YSZ composite electrodes reveal a mixed conduction behavior in the temperature range of 700–850 °C under flowing synthetic air atmosphere. With a developed current density of 172 mA cm−2 at 850 °C and +2 V overpotential, and an electrode polarization resistance of 7.5 Ω cm2, perovskite LSTM synthesized by the presented solvent-free direct salt precursor mechanochemical synthesis is therefore proposed as a potential candidate for MIEC electrodes in symmetrical reversible solid oxide cells (r-SOCs).

Effects of transition metal carbide dispersoids on helium bubble formation in dispersion-strengthened tungsten

The formation of helium bubbles and subsequent property degradation poses a significant challenge to tungsten as a plasma-facing material in future long-pulse plasma-burning fusion reactors. In this study, we investigated helium bubble formation in dispersion-strengthened tungsten doped with transition metal carbides, including TaC, ZrC, and TiC. Of the three dispersoids, TaC exhibited the highest resistance to helium bubble formation, possibly due to the low vacancy mobility in the Group VB metal carbide and oxide phases. Under identical irradiation conditions, large helium bubbles formed at grain boundaries in tungsten, while no bubbles were observed at the interfaces between the carbide dispersoid and tungsten matrix. Moreover, our results showed the interfaces could suppress helium bubble formation in the nearby tungsten matrix, suggesting that the interfaces are more effective in trapping helium as tiny clusters. Our research provided new insights into optimizing the microstructure of dispersion-strengthened tungsten alloys to enhance their performance.

Separating Si phases from diagenetically-modified sediments through sequential leaching

Silicon (Si) phases such as biogenic silica, lithogenic silicate and authigenic silica/silicate in marine sediments provide valuable information about past Si cycling. Wet-chemical sequential leaching methods are often applied to extract different Si phases from marine sediments to study Si diagenetic processes in shallow subsurface. The potential of this method to separate Si phases from deeply-buried and diagenetically-modified sediments has not been systematically examined. We applied a sequential leaching protocol to drill core sediments retrieved from the Ulleung Basin, East/Japan Sea. We performed geochemical (elemental abundance and stable Si isotopes, δ30Si) and microscopic (X-ray diffraction and scanning electron microscope) analyses to monitor leaching efficiency in separating different Si phases. We show that, prior to alkaline leaching, applying weak acid is able to remove metal oxide and/or clay-like phases. The following Na2CO3 leaching, based on a commonly-adopted protocol, is able to dissolve some but not all diatoms. The results of elemental contents and δ30Si values of leachates suggest that, in diagenetically-modified sediments, either a longer digesting time or a harsher alkaline leaching is needed to dissolve all diatoms. This is attributed to increased resistance of diatoms to Na2CO3 leaching as a result of reduced surface area and/or improved SiO2 tetrahedron ordering during diagenetic processes over time and burial depths. Lithogenic silicate minerals can be dissolved by NaOH and potentially separated from diatoms if the latter is completely removed in the preceding leaching steps. Even if a trace amount of diatom is left undissolved in the NaOH leaching, it is still possible to separate the two through a mass balance calculation given the knowledge of composition for the two end-members. We conclude that a successful separation of Si phases in diagenetically modified sediments relies on the knowledge of elemental abundance and even δ30Si values of the leachates, as well as information such as species of Si-skeleton organisms, contents and maturation degree of biogenic silica.