Search Results (45)

The Dongping manganese (Mn) deposit, located within the Lower Triassic Shipao Formation of the Youjiang Basin, is one of South China’s most significant sedimentary Mn carbonate ore deposits. To resolve longstanding debates over its metallogenic pathway, we conducted integrated sedimentological, mineralogical, and geochemical analyses on three drill cores (ZK5101, ZK0301, and ZK1205) spanning the Mn ore body. X-ray diffraction and backscatter electron imaging reveal that the ores are dominated by kutnohorite, with subordinate quartz, calcite, dolomite, and minor sulfides. The low enrichment of U/Al, V/Al, and Mo/Al, as well as positive Ce anomalies, consistently suggest that Mn, in the form of oxides, was deposited in an oxic water column. Carbon isotope compositions of Mn carbonate ores (δ¹³C_VPDB: −2.3 to −6.1‰) and their negative correlation with MnO suggest that Mn carbonate, predominantly kutnohorite, show a diagenetic reduction in pre-existing Mn oxides via organic-matter oxidation in anoxic sediments pore waters. Elemental discrimination diagramms (Mn-Fe-(Co+Ni+Cu) × 10 and Co/Zn vs. Co+Cu+Ni) uniformly point to a hydrothermal Mn source. We therefore propose that hydrothermal fluids supplied dissolved Mn²⁺ to an oxic slope-basin setting, precipitating initially as Mn oxides, which were subsequently transformed to Mn carbonates during early diagenesis. This model reconciles both the hydrothermal and sedimentary-diagenetic processes of the Dongping Mn deposit. Full article

This study presents a comprehensive analysis of the microstructural characteristics and chemical composition of base and weld materials from reactor pressure vessels in the first (units 1 and 2) and second (unit 8) generations of Russian VVER 440 reactors at the Greifswald nuclear power plant. We measured the specific activities of ⁶⁰Co and ¹⁴C in activated samples from units 1 and 2. ⁶⁰Co, with its shorter half-life (t_1/2 = 5.27 a), is a key dose-contributing radionuclide during decommissioning, while ¹⁴C (t_1/2 = 5700 a) plays an important role in a geological repository for low- and intermediate-level radioactive waste. Our findings reveal differences in the proportions of trace elements between the base and weld materials as well as between the two reactor generations. Microstructural analysis identified Mo-rich precipitates and (Mn, S)-rich inclusions containing secondary micro-inclusions in the unit 1 and 2 samples. Raman spectroscopy confirmed iron oxides (γ-Fe₂O₃, Fe₃O₄), silicates (Mn-SiO₃), and Cr₂O₃/NiCr₂O₄ in the base metal as well as MnFe₂O₃ in the weld metal. X-ray photoelectron spectroscopy identified Mn inclusions as MnS, MnS₂, or mixed Mn, Fe sulfides, and the Mo precipitates as MoSi₂. These findings offer valuable insights into the speciation of elements and the potential release of radionuclides through corrosion processes under repository conditions. Full article

This review analyzes TiO₂-based coatings formed by the plasma electrolytic oxidation (PEO) process of titanium for the photocatalytic degradation of methyl orange (MO) under simulated solar irradiation conditions. PEO is recognized as a useful technique for creating oxide coatings on various metals, particularly titanium, to assist in the degradation of organic pollutants. TiO₂-based photocatalysts in the form of coatings are more practical than TiO₂-based photocatalysts in the form of powder because the photocatalyst does not need to be recycled and reused after wastewater degradation treatment, which is an expensive and time-consuming process. In addition, the main advantage of PEO in the synthesis of TiO₂-based photocatalysts is its short processing time (a few minutes), as it excludes the annealing step needed to convert the amorphous TiO₂ into a crystalline phase, a prerequisite for a possible photocatalytic application. Pure TiO₂ coatings formed by PEO have a low photocatalytic efficiency in the degradation of MO, which is due to the rapid recombination of the photo-generated electron/hole pairs. In this review, recent advances in the sensitization of TiO₂ with narrow band gap semiconductors (WO₃, SnO₂, CdS, Sb₂O₃, Bi₂O₃, and Al₂TiO₅), doping with rare earth ions (example Eu³⁺) and transition metals (Mn, Ni, Co, Fe) are summarized as an effective strategy to reduce the recombination of photo-generated electron/hole pairs and to improve the photocatalytic efficiency of TiO₂ coatings. Full article

Developing more effective gold–support synergy is essential for enhancing the catalytic performance of supported gold nanoparticles (AuNPs) in the gas-phase oxidation of ethanol to acetaldehyde (AC) at lower temperatures. This study demonstrates a significantly improved Au–support synergy achieved by copper doping in LaMO₃ (M = Mn, Fe, Co, Ni) perovskites. Among the various Au/LaMCuO₃ catalysts, Au/LaMnCuO₃ exhibited exceptional catalytic activity, achieving an AC yield of up to 91% and the highest space-time yield of 764 g_AC g_Au⁻¹ h⁻¹ at 225 °C. Notably, this catalyst showed excellent hydrothermal stability, maintaining performance for at least 100 h without significant deactivation when fed with 50% aqueous ethanol. Comprehensive characterization reveals that Cu doping facilitates the formation of surface oxygen vacancies on the Au/LaMCuO₃ catalysts and enhances Au–support interactions. The LaMnCuO₃ perovskite stabilizes the crucial Cu⁺ species, resulting in a stable Au-Mn-Cu synergy within the Au/LaMnCuO₃ catalyst, which facilitates the activation of O₂ and ethanol at lower temperatures. The optimization of the reaction conditions further improves AC productivity. Kinetic studies indicate that the cleavages of both the O-H bond and the α-C-H bond of ethanol are the rate-controlling steps. Full article

Integrated Li- and Mn-rich layered cathodes yLi₂MnO₃∙(1-y)LiMO₂ (M = Mn, Co, and Ni) have shown their ability to deliver specific capacities close to 300 mAh g⁻¹, but their significant drawbacks are capacity fading and voltage decay during cycling. In this study, new stoichiometric high-voltage Li-rich oxides with y = 0.0, 0.3, and 0.5 are synthesized in identical conditions using a sol–gel method. These compositions were analyzed to determine their optimal configuration and to understand their extraordinary behavior. Their nanostructural properties were investigated using XRD and Raman spectroscopy, while the morphology and grain-size distribution of the samples were characterized by BET, SEM and HRTEM analyses. The electrochemical performances of the integrated Li- and Mn-rich compounds were evaluated through galvanostatic cycling and electrochemical impedance spectroscopy. The best cathode material 0.5Li₂MnO₃∙0.5LiNi_1/3Co_1/3Mn_1/3O₂ had a capacity retention of 83.6% after 100 cycles in the potential range 2.0–4.8 V vs. Li⁺/Li. Full article

The persistence of peroxydisulfate anion (S₂O₈²⁻) in soil is a key factor influencing the effectiveness of in situ chemical oxidation (ISCO) treatments, which use S₂O₈²⁻ (S₂O₈²⁻ based ISCO) to remediate contaminated groundwater. However, only a few studies have addressed aspects of S₂O₈²⁻ persistence, such as the effect of temperature and the fate of sulfates (SO₄²⁻) generated by S₂O₈²⁻ decomposition in real soil and/or aquifer materials. Additionally, there are no studies comparing batch and dynamic column tests. To address these knowledge gaps, we conducted batch tests with varying temperatures (30–50 °C) and initial S₂O₈²⁻ concentrations (2.7 g/L and 16.1 g/L) along with dynamic column experiments (40 °C, 16.1 g/L) with comprehensively characterized real soil/aquifer materials. Furthermore, the principal component analysis (PCA) method was employed to investigate correlations between S₂O₈²⁻ decomposition and soil material parameters. We found that S₂O₈²⁻ decomposition followed the pseudo-first-order rate law in all experiments. In all tested soil materials, thermal dependence of S₂O₈²⁻ decomposition followed the Arrhenius law with the activation energies in the interval 65.2–109.1 kJ/mol. Decreasing S₂O₈²⁻ concentration from 16.1 g/L to 2.7 g/L led to a several-fold increase (factor 2–11) in bulk S₂O₈²⁻ decomposition rate coefficients (k′) in individual soil/aquifer materials. Although k′ in the dynamic column tests showed higher values compared to the batch tests (factor 1–3), the normalized S₂O₈²⁻ decomposition rate coefficients to the total BET surface were much lower, indicating the inevitable formation of preferential pathways in the columns. Furthermore, mass balance analysis of S₂O₈²⁻ decomposition and SO₄²⁻ generation suggests the ability of some systems to partially accumulate the produced SO₄²⁻. Principal Component Analysis (PCA) identified total organic carbon (TOC), Ni, Mo, Co, and Mn as key factors influencing the decomposition rate under varying soil conditions. These findings provide valuable insights into how S₂O₈²⁻ behaves in real soil and aquifer materials, which can improve the design and operation of ISCO treatability studies for groundwater remediation. Full article

CoCrFeMnNi-XZrO₂ (X is a mass percentage, X = 1, 3, 5, and 10) high-entropy alloy composite coatings were successfully prepared on 0Cr13Ni5Mo martensitic stainless steel substrates using laser cladding technology. The phase composition, microstructure, mechanical properties, and cavitation erosion behavior of the composite coatings under different contents of ZrO₂ were studied. The mechanism of ZrO₂ particle-reinforced cavitation corrosion resistance was studied using ABAQUS2023 finite element software. The results show that the phase structure of the composite coating organization is composed of FCC phase reinforced by ZrO₂ phase. The addition of ZrO2 causes lattice distortion. The coatings have typical branch crystals and an equiaxed crystal microstructure. With the increase in ZrO₂ content, the microhardness of the composite coatings gradually increases. When X = 10%, the coating’s microhardness reached 348 HV, which was 95.53% higher than the high-entropy alloys without ZrO₂ added. Adding ZrO₂ can prolong the incubation period of high-entropy alloys; the high-entropy alloy composite coating with 5 wt.% ZrO₂ exhibited the best cavitation resistance, with a cumulative volume loss rate of only 15.74% of the substrate after 10 h of ultrasonic cavitation erosion. The simulation results indicate that ZrO₂ can withstand higher stress and deformation in cavitation erosion, reduce the degree of substrate damage, and generate higher compressive stress on the coating surface to cope with cavitation erosion. Full article

This study presents the synthesis of a multicomponent metal oxide electrocatalyst that increases the activity of the oxygen evolution reaction (OER). We synthesized transition metal oxides (MnO_x, FeO_x, CoO_x, and NiO_x) with MoO₃ heterostructures through a solid-state reaction approach at low cost. In comparison to the other compositions, CoO_x garnered higher attention and demonstrated superior performance on account of its large surface area and varied crystal facets. The MnO_x-MoO₃, FeO_x-MoO₃, CoO_x-MoO₃, and NiO_x-MoO₃ compositions attained an overpotential of 390 mV, 350 mV, 310 mV, and 340 mV, respectively, at a current density of 10 mA cm⁻² in alkaline solution. The performance of OER was enhanced in CoO_x-MoO₃ at 10 mA cm⁻², while FeO_x-MoO₃ exhibited a lower current density at 100 mA cm⁻² than other metal oxides. The CoO_x-MoO₃ material exhibited a favorable crystal interface transition due to the presence of MoO₃ oxide. For the first time, we report on the MoO₃-to-(MnO_x, FeO_x, CoO_x, and NiO_x) interface crystal transition and the active surface area for OER catalytic activity in water-splitting processes. This investigation intends to develop an electrocatalyst that is capable of producing hydrogen with the use of heterostructure metal oxides. Full article

The Upper Silesian Coal Basin (USCB), located in southern Poland, is the major coal basin in Poland, and all technological types of hard coal, including coking coal, are exploited. It is also an area of high potential for coal-bed methane (CBM). Despite the increasing availability of alternative energy sources globally, it is a fact that the use of fossil fuels will remain necessary for the next few decades. Therefore, research on coal-bearing formations using modern research methods is still very important. The application of geochemistry and chemostratigraphy in reservoir characterization has become increasingly common in recent years. This paper presents the possibility of applying chemostratigraphic techniques to the study of the Carboniferous coal-bearing succession of the Upper Silesian Coal Basin. The material studied comes from 121 core samples (depth 481–1298 m), representing the Mudstone Series (Westphalian A, B). Major oxide concentrations of Al₂O₃, SiO₂, Fe₂O₃, P₂O₅, K₂O, MgO, CaO, Na₂O, K₂O, MnO, TiO₂, and Cr₂O₃ were obtained using X-ray fluorescence (XRF) spectrometry. Trace elements were analyzed using inductively coupled plasma mass spectrometry (ICP/MS). The geochemical record from the Mudstone Series shows changes in the concentration of major elements and selected trace elements, leading to the identification of four chemostratigraphic units. These units differ primarily in the content of Fe, Ca, Mg, Mn, and P as well as the concentration of Zr, Hf, Nb, Ta, and Ti. The study also discusses quartz origin (based on SiO₂ and TiO₂), sediment provenance and source-area rock compositions (based on Al₂O₃/ TiO₂, TiO₂/Zr, and La/Th), and paleoredox conditions (based on V/Cr, Ni/Co, U/Th, (Cu+Mo)/Zn, and Sr/Ba) for the chemostratigraphic units. Chemostratigraphy was used for the first time in the study of the Carboniferous coal-bearing series of the USCB, concluding that it can be used as an effective stratigraphic tool and provide new information on the possibility of correlating barren sequences of the coal-bearing succession. Full article

This study investigates the impacts of bismuth and tin on the production of CH₄ and volatile fatty acids in a microbial electrosynthesis cell with a continuous CO₂ supply. First, the impact of several transition metal ions (Ni²⁺, Fe²⁺, Cu²⁺, Sn²⁺, Mn²⁺, MoO₄²⁻, and Bi³⁺) on hydrogenotrophic and acetoclastic methanogenic microbial activity was evaluated in a series of batch bottle tests incubated with anaerobic sludge and a pre-defined concentration of dissolved transition metals. While Cu is considered a promising catalyst for the electrocatalytic conversion of CO₂ to short chain fatty acids such as acetate, its presence as a Cu²⁺ ion was demonstrated to significantly inhibit the microbial production of CH₄ and acetate. At the same time, CH₄ production increased in the presence of Bi³⁺ (0.1 g L⁻¹) and remained unchanged at the same concentration of Sn²⁺. Since Sn is of interest due to its catalytic properties in the electrochemical CO₂ conversion, Bi and Sn were added to the cathode compartment of a laboratory-scale microbial electrosynthesis cell (MESC) to achieve an initial concentration of 0.1 g L⁻¹. While an initial increase in CH₄ (and acetate for Sn²⁺) production was observed after the first injection of the metal ions, after the second injection, CH₄ production declined. Acetate accumulation was indicative of the reduced activity of acetoclastic methanogens, likely due to the high partial pressure of H₂. The modification of a carbon-felt electrode by the electrodeposition of Sn metal on its surface prior to cathode inoculation with anaerobic sludge showed a doubling of CH₄ production in the MESC and a lower concentration of acetate, while the electrodeposition of Bi resulted in a decreased CH₄ production. Full article

Marine Co-rich ferromanganese crusts and polymetallic nodules, which are widely distributed in oceanic environments, are salient potential mineral resources that are enriched with many critical metals. Many investigations have achieved essential progress and findings regarding critical metal enrichment in Fe-Mn crusts and nodules. This study systematically reviews the research findings of previous investigations and elaborates in detail on the enrichment characteristics, enrichment processes and mechanisms and the influencing factors of the critical metals enriched in Fe-Mn crusts and nodules. The influencing factors of critical metal enrichments in Fe-Mn crusts and nodules mainly include the growth rate, water depth, post-depositional phosphatization and structural uptake of adsorbents. The major enrichment pathways of critical metals in marine Fe-Mn (oxy)hydroxides are primarily as follows: direct substitution on the surface of δ-MnO₂ for Ni, Cu, Zn and Li; oxidative substitution on the δ-MnO₂ surface for Co, Ce and Tl; partition between Mn and Fe phases through surface complexation according to electro-species attractiveness for REY (except for Ce), Cd, Mo, W and V; combined Mn-Fe phases enrichment for seawater anionic Te, Pt, As and Sb, whose low-valence species are mostly oxidatively enriched on δ-MnO₂, in addition to electro-chemical adsorption onto FeOOH, while high-valence species are likely structurally incorporated by amorphous FeOOH; and dominant sorption and incorporation by amorphous FeOOH for Ti and Se. The coordination preferences of critical metals in the layered and tunneled Mn oxides are primarily as follows: metal incorporations in the layer/tunnel-wall for Co, Ni and Cu; triple-corner-sharing configurations above the structural vacancy for Co, Ni, Cu, Zn and Tl; double-corner-sharing configurations for As, Sb, Mo, W, V and Te; edge-sharing configurations at the layer rims for corner-sharing metals when they are less competitive in taking up the corner-sharing position or under less oxidizing conditions when the metals are less feasible for reactions with layer vacancy; and hydrated interlayer or tunnel-center sorption for Ni, Cu, Zn, Cd, Tl and Li. The major ore-forming elements (e.g., Co, Ni, Cu and Zn), rare earth elements and yttrium, platinum-group elements, dispersed elements (e.g., Te, Tl, Se and Cd) and other enriched critical metals (e.g., Li, Ti and Mo) in polymetallic nodules and Co-rich Fe-Mn crusts of different geneses have unique and varied enrichment characteristics, metal occurrence states, enrichment processes and enrichment mechanisms. This review helps to deepen the understanding of the geochemical behaviors of critical metals in oceanic environments, and it also bears significance for understanding the extreme enrichment and mineralization of deep-sea critical metals. Full article

In the Carajás Mineral Province, gossan formation and lateritization have produced numerous supergene orebodies at the expense of IOCG deposits and host rocks. The Alvo 118 deposit comprises massive and disseminated hypogene copper sulfides associated with gossan and mineralized saprolites. The hypogene reserves are 170 Mt, with 1% Cu and 0.3 ppm Au, while the supergenes are 55 Mt, comprised of 30% gossan and 70% saprolite, with 0.92% Cu and 0.03 ppm Au. The gossan includes goethite, malachite, cuprite, and libethenite zones. The saprolite comprises kaolinite, vermiculite, smectite, and relics of chlorite. In the hypogene mineralization, Ag, Te, Pb, Se, Bi, Au, In, Y, Sn, and U are mainly hosted by chalcopyrite and petzite, altaite, galena, uraninite, stannite, and cassiterite. In the gossan, Ag, Te, Pb, Se, and Bi are hosted by Cu minerals, while Au, In, Y, Sn, and U are associated with iron oxyhydroxides, in addition to Zn, As, Be, Ga, Ga, Mo, Ni, and Sc. As supporting information, δ⁶⁵Cu values indicate that the gossan is immature and, at least partly, not affected by leaching. In the saprolite, Ga, Sc, Sn, V, Mn, Co, and Cr are associated with the iron oxyhydroxides, partially derived from the host rock weathering. The δ⁵⁶Fe values indicate that hypogene low contribution of the hypogene mineralization to the saprolite iron content. The association of Al₂O₃, Hf, Zr, Th, TiO₂, Ce, La, Ba, and Sr represents the geochemical signature of the host rocks, with dominant contributions from chlorites, while In, Y, Te, Pb, Bi, and Se are the main pathfinders of Cu mineralization. Full article

Exogenous melatonin (MT) regulates plant growth and mitigates stress in response to stress. To analyze the machinery of exogenous melatonin, which improves salt and alkaline tolerance in oats, MT’s function was identified in the oat seed germination stage in our previous study. In this study, morphogenesis, photosynthetic physiology, hormone levels, and ion homeostasis were evaluated using the same MT treatment concentration. The results revealed that compared to the S45 treatment, the 100 μmol·L⁻¹ MT treatment efficiently increased the seedling height and main root length of oat seedlings; promoted secondary root development; enhanced the root volume and root surface area; maintained a higher photosynthetic pigment content (carotenoids; chlorophyll a; chlorophyll b); raised the leaf photosynthetic rate (Pn), intercellular CO₂ concentration (Ci), conductance to H₂O (Gs), and transpiration rate (Tr); enhanced the light energy absorption and conversion of leaves; increased the leaf GA3, Tryptamine (TAM), and IAA contents; and decreased ABA levels. Hierarchical cluster analysis revealed that MT treatment also increased the contents of P, K, Ca, Mn, Cu, Mg, Fe, Zn, Mo, Cd, Al, Se, Ni, Co, and Ti; decreased the Na/K ratio; and maintained cellular ionic homeostasis in oat seedlings under saline–alkali stress, as compared with the untreated group. These findings showed that MT treatment enhanced the adaptation of oat to saline–alkali stress through regulating the physiological process of seedling growth. This suggests that MT plays a different role in improving saline–alkali tolerance in the germination and seedling stages of oat. Full article

Li-rich manganese-based cathode materials (LRMs) are considered one of the most promising cathode materials for the next generation of lithium-ion batteries (LIBs) because of their high energy density. However, there are problems such as a capacity decay, poor rate performance, and continuous voltage drop, which seriously limit their large-scale commercial applications. In this work, Li_1.2Mn_0.54Co_0.13Ni_0.13O₂ coated with Li₂MoO₄ with a unique spinel structure was prepared with the wet chemistry method and the subsequent calcination process. The Li₂MoO₄ coating layer with a spinel structure could provide a 3D Li⁺ transport channel, which is beneficial for improving rate performance, while protecting LRMs from electrolyte corrosion, suppressing interface side reactions, and improving cycling stability. The capacity retention rate of LRMs coated with 3 wt% Li₂MoO₄ increased from 69.25% to 81.85% after 100 cycles at 1 C, and the voltage attenuation decreased from 7.06 to 4.98 mV per cycle. The lower R_ct also exhibited an improved rate performance. The results indicate that the Li₂MoO₄ coating effectively improves the cyclic stability and electrochemical performance of LRMs. Full article

Polymer-assisted deposition (PAD) has been widely used in the preparation of high-quality oxides and sulfides for basic research and applications. Specifically, diverse PAD-prepared magnetic material thin films such as ZnO, Ga₂O₃, SrRuO₃, LaCoO₃, LaMnO₃, Y₃Fe₅O₁₂, MoS₂, MoSe₂, and ReS₂ thin films have been grown, in which thickness-dependent, strain-modulated, doping-mediated, and/or morphology-dependent room-temperature ferromagnetism (RTFM) have been explored. Inspired by the discovery of intrinsic low-temperature FM in two-dimensional (2D) systems prepared using mechanical exfoliation, the search for more convenient methods to prepare 2D ferromagnetic materials with high-temperature FM has seen explosive growth, but with little success. Fortunately, the very recent synthesis of 2D NiO by PAD has shed light on this challenge. Based on these abovementioned developments, the difficulties of PAD when preparing a-few-nanometer single-crystalline materials and the opportunities in PAD for novel materials such as chiral magnetic soliton material Cr_1/3NbS₂ are discussed. Full article