Search Results (37)

Mid-Neoproterozoic magmatism provides important constraints for revealing the break-up history of the Rodinia supercontinent. Large-sized mid-Neoproterozoic magmatic rocks are distributed within the Dabie Orogen located on the northern Yangtze Block. This study performed zircon LA-ICP-MS geochronology, whole-rock major and trace elements, and zircon Lu-Hf isotope analyses on orthogneisses with a mid-Neoproterozoic protolith age of the northern Dabie Orogen. The analysis results show that the intrusion times of mid-Neoproterozoic granitoids and mafic rocks are all ~750 Ma, with ε_Hf(t) values ranging from −6.60 to −2.57 and a two-stage Hf model age of ~1.8 Ga. They are characterized by light rare earth element (LREE) enrichment and heavy rare earth element (HREE) depletion. In the primitive mantle-normalized trace element diagram, these rocks are enriched in La, Ce, Th, K, Zr, Nd, and Sm and depleted in Nb, Ta, P, Ti, and Sr, with negative Eu anomaly or no significant Eu anomaly. Based on the discrimination diagrams, most of the samples are plotted into the A-type granite field, and which was formed in a post-orogenic extension setting. Comprehensive analysis shows that these mid-Neoproterozoic magmatic rocks were produced by melting of juvenile crust of the Paleoproterozoic and late Mesoproterozoic, having a heterogeneous distribution of δ¹⁸O, indicating that these rocks were developed mainly through high-temperature meteoric-hydrothermal alteration during syn-rift magmatic activity. Full article

The Hugushan banded iron formation (BIF) is one of the most representative iron ore deposits in the central part of the North China Craton, and its ore formation mechanism remains highly controversial. This study presents whole-rock and Fe–Si–O isotope geochemical evidence, offering a new perspective on the ore formation mechanism of the Hugushan BIFs. The samples from the upper and lower parts of the Hugushan BIFs are characterized by slight enrichment of heavy and light Fe isotopes, respectively. Additionally, the samples from the upper part of the Hugushan BIFs show characteristics of slightly positive Ce anomalies and negative La anomalies, suggesting that the shallow ancient seawater was in a partially oxidized state, whereas the deep seawater remained in a reductive environment during the depositional period. The low Al₂O₃ and TiO₂ concentrations, as well as the depletion of Zr and Hf in the Hugushan BIFs, suggest that the contribution of terrestrial detrital materials to deposition is extremely limited. The BIFs all exhibit positive Eu anomalies, and the quartz in the BIFs is depleted in ³⁰Si, a characteristic similar to that observed in siliceous rocks formed in hydrothermal vent environments and during hydrothermal plume activity. Additionally, the δ¹⁸O values of quartz in Hugushan BIFs are similar to the O isotope compositions of hydrothermal sedimentary siliceous rocks, further suggesting that the silicon in BIFs originates primarily from seafloor hydrothermal activity. The combination of Eu/Sm, Sm/Yb, and Y/Ho ratios indicates that the major components (iron and silica) of the Hugushan Iron Ore Deposit originated from the mixing of high-temperature hydrothermal fluids with seawater, with the hydrothermal fluid contributing slightly less than 0.1%. The magnetite and quartz bands in the BIFs exhibit inhomogeneous and covariant δ⁵⁶Fe and δ³⁰Si isotope characteristics, suggesting that the alternating siliceous and ferruginous layers are products of original chemical deposition in the ocean. Periodic hydrothermal activity and ocean transgression caused the recurring deposition of siliceous and ferruginous layers, resulting in the characteristic banded structure of the Hugushan Iron Ore Deposit. Full article

The Kongco area of Nima in the northern part of the Lhasa terrane has a suite of alkaline granitic porphyry dykes associated with Early Cretaceous granites and accompanied by Cu/Mo mineralization. LA-ICP-MS ²⁰⁶Pb/²³⁸U zircon geochronology performed on the dykes produced an age of 104.15 ± 0.94 Ma (MSWD = 0.98), indicating the Early Cretaceous emplacement of the dykes. The dykes exhibit high silica (SiO₂ = 76.22~77.90 wt.%), high potassium (K₂O = 4.97~6.21 wt.%), high alkalinity (K₂O + Na₂O = 8.07~8.98 wt.%), low calcium (CaO = 0.24~0.83 wt.%), low magnesium (MgO = 0.06~0.20 wt.%), and moderate aluminum content (Al₂O₃ = 11.93~12.45 wt.%). The Rieterman index (σ) ranges from 1.93 to 2.34. A/NK (molar ratio Al₂O₃/(Na₂O + K₂O)) and A/CNK (molar ratio Al₂O₃/(CaO + Na₂O + K₂O)) values of the dykes range from 1.06 to 1.18 and 0.98 to 1.09, respectively. The dykes are relatively enriched in Rb, Th, U, K, Ta, Ce, Nd, Zr, Hf, Sm, Y, Yb, and Lu, and they show a noticeable relative depletion in Ba, Nb, Sr, P, Eu, and Ti, as well as an average differentiation index (DI) of 96.42. The dykes also exhibit high FeO_T/MgO ratios (3.60~10.41), Ga/Al ratios (2.22 × 10⁻⁴~3.01 × 10⁻⁴), Y/Nb ratios (1.75~2.40), and Rb/Nb ratios (8.36~20.76). Additionally, they have high whole-rock Zr saturation temperatures (884~914 °C), a pronounced Eu negative anomaly (δEu = 0.04~0.23), and a rightward-sloping “V-shaped” rare earth element pattern. These characteristics suggest that the granitic porphyry dykes can be classified as A2-type granites formed in a post-collisional tectonic environment and that they are weakly peraluminous, high-potassium, and Calc-alkaline basaltic rocks. Positive ε_Hf(t) values = 0.43~3.63 and a relatively young Hf crustal model age (T_DM2 = 826~1005 Ma, ⁸⁷Sr/⁸⁶Sr ratios = 0.7043~0.7064, and ε_Nd(t) = −8.60~−2.95 all indicate lower crust and mantle mixing. The lower crust and mantle mixing model is also supported by (²⁰⁶Pb/²⁰⁴Pb)t = 18.627~18.788, (²⁰⁷Pb/²⁰⁴Pb)t = 15.707~15.719, (²⁰⁸Pb/²⁰⁴Pb)t = 39.038~39.110). Together, the Hf, Sr and Pb isotopic ratios indicate that the Kongco granitic porphyry dykes where derived from juvenile crust formed by the addition of mantle material to the lower crust. From this, we infer that the Kongco granitic porphyry dykes are related to a partial melting of the lower crust induced by subduction slab break-off and asthenospheric upwelling during the collision between the Qiangtang and Lhasa terranes and that they experienced significant fractional crystallization dominated by potassium feldspar and amphibole. These dykes are also accompanied by significant copper mineralization (five samples, copper content 0.2%), suggesting a close relationship between the magmatism associated with these dykes and regional metallogenesis, indicating a high potential for mineral exploration. Full article

Tailoring the bandgap of a material is necessary for improving its optical properties. Here, the optical bandgap of high-entropy oxide Ce_0.2Gd_0.2Sm_0.2Y_0.2Zr_0.2O_2-δ (HEO) nanoparticles was modified using Pr³⁺. Various concentrations of Pr³⁺ (x = 0, 0.01, 0.02, 0.05, 0.075, 0.1, 0.15) were incorporated into the host high-entropy oxide using a gel combustion synthesis. After the gel combustion step, the powders were heat-treated at various temperatures (650 °C, 800 °C, 950 °C) for 2 h. The obtained Pr³⁺-incorporated HEO powders were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and UV–visible spectroscopy. The results indicate that, when the samples are calcined at 950 °C, a single-phase cubic fluorite structure is obtained without any phase separation or impurity. The optical absorbance red-shifts to higher wavelengths when the concentration of Pr³⁺ is increased. This reduces the bandgap of the material from 3.15 eV to 1.87 eV for Pr³⁺ concentrations of x = 0 (HEO-0) and x = 0.15 (HEO-6), respectively. The obtained HEOs can be suitable candidates for photocatalytic applications due to their absorbance in the visible region. Full article

The development and characterization of synthesis techniques for oxide materials based on ceria is a subject of extensive study with the objective of their wide-ranging applications in pursuit of sustainable development. The present study demonstrates the feasibility of controlled synthesis of Ce_1−xM_xO_2−δ (M = Fe, Ni, Co, Mn, Cu, Ag, Sm, Cs, x = 0.0–0.3) in combustion reactions from precursors comprising glycine, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, and cellulose as organic components. Controlled synthesis is achieved by varying the composition of the precursor, the type of organic component, and the amount of organic component, which allows for the influence of the generation of high-density electrical charges and outgassing during synthesis. The intensity of charge generation is quantified by measuring the value of the precursor–ground potential difference. It has been demonstrated that an increase in the intensity of charge generation results in a more developed morphology, which is essential for the practical implementation of ceria as a catalyst to enhance contact with gases and solid particles. The maximum value of the potential difference, equal to 68 V, is obtained during the synthesis of Ce_0.7Ni_0.3O_2−δ with polyvinyl alcohol in stoichiometric relations, which corresponds to a specific surface area of 21.7 m² g⁻¹. A correlation is established between the intensity of gas release for systems with different organic components, the intensity of charge generation, morphology, and the value of the specific surface area of the samples. Full article

A series of Mo-polymetallic deposits have been developed in the Jiaodong Peninsula. Notably, these Mo-dominant deposits formed essentially during the same period as the well-known world-class Au deposits in this area, hinting at a potentially unique geological correlation between them. Therefore, conducting thorough research on Mo deposits in Jiaodong holds significant importance in exploring the area’s controlling factors of Mesozoic metal endowments. To reveal the petrogenesis and metallogenic potentials of Mo-fertile and ore-barren granitoid, apatite grains from the Late Aptian Nansu granodiorite and Aishan monzogranite are investigated in this study. Detailed petrographical observations, combined with in situ analysis of electron probe micro-analyzer (EPMA) and Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), have been conducted on apatite grains from the Nansu and Aishan plutons. This comprehensive analysis, encompassing both major and trace elements as well as isotopic characteristics of apatite, aims to elucidate the metallogenic differences within the late Early Cretaceous granitoids of Jiaodong. The results reveal that the apatite grains across all samples belong to fluorapatites, suggesting their magmatic origin. Additionally, chondrite-normalized rare earth element (REE) patterns of apatites in ore-fertile and ore-barren granitoids exhibit a “right-leaning” trend, characterized by relative enrichments in light REEs and depletions in heavy REEs. Both the Nansu and Aishan plutons exhibit moderately negative Eu anomalies (with averages δEu values of 0.44 and 0.51, respectively), along with slightly positive Ce anomalies (averaging δCe values of 1.08 and 1.11, respectively). A negative correlation is observed between their δEu and δCe values, indicating that the parental magmas of ore-fertile and ore-barren granitoids were formed in a relatively oxidizing environment. The calculated apatite OH contents for the Nansu pluton range from 0.26 to 1.38, while those for the Aishan pluton vary between 0.24 and 1.51, indicating comparable melt H₂O abundances. Consequently, the results suggest that neither the oxygen fugacities nor the water contents of the parental magma can account for the metallogenic differences between Nansu and Aishan plutons. The apatite in the Nansu pluton exhibits a higher Ce/Pb ratio and a relatively lower Th/U ratio, indicating the involvement of a greater volume of fluids in the magmatic evolution process of this ore-bearing granitoid. Apatite grains sourced from the Nansu and Aishan plutons exhibit ε_Nd(t) values ranging from −16.63 to −17.61 (t = 115.7 Ma) and −17.86 to −20.86 (t = 116.8 Ma), respectively. These results suggest that their parental magmas primarily originated from the partial melting of Precambrian metamorphic basement rocks within the North China Craton, with a minor contribution from mantle-derived materials. Additionally, the presence of mafic microgranular enclaves in both the Nansu and Aishan plutons indicates that both have undergone magma mixing processes. The binary diagrams plotting the ratios of Ba/Th, Sr/Th, and U/Th against La/Sm demonstrate that apatite grains of ore-fertile granitoid exhibit a distinct trend towards sediment melting. This suggests the potential incorporation of sedimentary materials, particularly those rich in molybdenum, into the magmatic source of the Nansu pluton, ultimately leading to the occurrence of molybdenum mineralization. Full article

The oxygen vacancy formation behavior and electrochemical and thermal properties of Ba_0.5Sr_0.5Fe_1−xMn_xO_3−δ (BSFMnx, x = 0–0.15) cathode materials were investigated. For thermogravimetric analysis, the weight decreased from 1.98% (x = 0) to 1.81% (x = 0.15) in the 400–950 °C range, which was due to oxygen loss from the lattice. The average oxidation state of the B-site increased, the O_ads/O_lat ratio decreased, and the binding energy of the O_lat peak increased with Mn doping. These results indicate that Mn doping increases the strength of the metal–oxygen bond and decreases the amount of oxygen vacancies in the lattice. The electrical conductivity of BSFMnx increased with the temperature due to the thermally activated small-polaron hopping mechanism showing a maximum value of 10.4 S cm⁻¹ (x = 0.15) at 450 °C. The area-specific resistance of BSFMn0.15 was 0.14 Ω cm² at 700 °C and the thermal expansion coefficient (TEC) gradually decreased to 12.7 × 10⁻⁶ K⁻¹, which is similar to that of Ce_0.8Sm_0.2O₂ (SDC) (12.2 × 10⁻⁶ K⁻¹). Mn doping increased the metal–oxygen bonding energy, which reduced the oxygen reduction reaction activity but improved the electrical conductivity and thermal stability with SDC. Full article

Strontium and cobalt-free LaNi_0.6Fe_0.4O_3–δ is considered one of the most promising electrodes for solid-state electrochemical devices. LaNi_0.6Fe_0.4O_3–δ has high electrical conductivity, a suitable thermal expansion coefficient, satisfactory tolerance to chromium poisoning, and chemical compatibility with zirconia-based electrolytes. The disadvantage of LaNi_0.6Fe_0.4O_3–δ is its low oxygen-ion conductivity. In order to increase the oxygen-ion conductivity, a complex oxide based on a doped ceria is added to the LaNi_0.6Fe_0.4O_3–δ. However, this leads to a decrease in the conductivity of the electrode. In this case, a two-layer electrode with a functional composite layer and a collector layer with the addition of sintering additives should be used. In this study, the effect of sintering additives (Bi_0.75Y_0.25O_2–δ and CuO) in the collector layer on the performance of LaNi_0.6Fe_0.4O_3–δ-based highly active electrodes in contact with the most common solid-state membranes (Zr_0.84Sc_0.16O_2–δ, Ce_0.8Sm_0.2O_2–δ, La_0.85Sr_0.15Ga_0.85Mg_0.15O_3–δ, La₁₀(SiO₄)₆O_3–δ, and BaCe_0.89Gd_0.1Cu_0.01O_3–δ) was investigated. It was shown that LaNi_0.6Fe_0.4O_3–δ has good chemical compatibility with the abovementioned membranes. The best electrochemical activity (polarization resistance about 0.02 Ohm cm² at 800 °C) was obtained for the electrode with 5 wt.% Bi_0.75Y_0.25O_1.5 and 2 wt.% CuO in the collector layer. Full article

The isotopic content (δ¹³C, δ²H, δ¹⁸O) and concentrations of 30 elements (Li, Na, Mg, P, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Rb, Sr, Ag, Cd, Ba, Pb, La, Ce, Pr, Nd, Sm, Eu, Gd, and Tb) were determined in different wild and cultivated berries (raspberry, seaberry, blackberry, cranberry, and blueberry). Partial least squares discriminant analysis (PLS-DA) was applied in order to develop models for differentiating berries according to their botanical origin and growing system. δ¹³C, δ²H, δ¹⁸O, Li, Na, Mg, P, Ca, V, Mn, Co, Ni, Zn, As, Rb, Sr, Ba, and Eu were identified as significant elements for the differentiation of berry species, based on which an 85% PLS-DA model accuracy was obtained. Similarly, the PLS-DA model developed for the growing system differentiation correctly classified 94.4% of the cultivated berries and 77.2% of the wild ones, based on the main predictors: δ¹³C, δ¹⁸O, Li, Na, Ca, Cr, Mn, Ni, Rb, and Ba. The developed PLS-DA model for the discrimination of wild blueberries from cultivated ones showed excellent levels of sensitivity (100%), specificity (100%), and accuracy (100%). Full article

This paper examines the electrochemical and microstructural features of SrCo_0.8Fe_0.1Ga_0.1O_3−δ (SCFG) with a fibrous structure infiltrated by an SDC electrolyte for use as a cathode in solid oxide fuel cells (SOFCs). An electrospinning process is used to produce SCFG fibers. In a symmetrical cell, Sm_0.2Ce_0.8O_1.9 (SDC) nanoparticles are infiltrated into the porous fibrous SCFG cathode layer after it was applied to the SDC dense electrolyte. Electrochemical impedance spectroscopy (EIS) analysis reveals that the polarization resistance of the SCFG cathode with fiber morphology is significantly lower than that of the same combination with powder morphology. In addition, it is shown that infiltration of SDC oxygen ion conductor nanoparticles enhanced electrochemical performance. The lowest value of polarization resistance, 0.03 Ω cm² at 800 °C, is attained by the SCFG with a fibrous structure containing 14 wt% SDC nanoparticles. Full article

The surface exchange and bulk transport of oxygen are highly relevant to ceria-based redox materials, which are envisaged for the solar thermochemical splitting of carbon dioxide in the future. Experimental investigations of oxygen isotope exchange on CeO_2-δ, Ce_0.9M³⁺_0.1O_1.95-δ (with M³⁺ = Y, Sm) and Ce_0.9M⁴⁺_0.1O_2-δ (with M⁴⁺ = Zr) samples were carried out for the first time utilizing oxygen-isotope-enriched C¹⁸O₂ gas atmospheres as the tracer source, followed by Secondary Ion Mass Spectrometry (SIMS), at the temperature range 300 ≤ T ≤ 800 °C. The experimental ${\tilde{K}}_{\mathrm{O}}$ and ${\tilde{D}}_{\mathrm{O}}$ data reveal promising results in terms of CO₂ splitting when trivalent (especially Sm)-doped ceria is employed. The reaction temperatures are lower than previously proposed/reported due to the weak temperature dependency of the parameters ${\tilde{K}}_{\mathrm{O}}$ and ${\tilde{D}}_{\mathrm{O}}$. The majority of isotope exchange experiments show higher values of ${\tilde{K}}_{\mathrm{O}}$ and ${\tilde{D}}_{\mathrm{O}}$ for Sm-doped cerium dioxide in comparison to Y-doped and Zr-doped ceria, as well as nominally undoped ceria. The apparent activation energies for both ${\tilde{K}}_{\mathrm{O}}$ and ${\tilde{D}}_{\mathrm{O}}$ are lowest for Sm-doped ceria. Using Zr-doped cerium oxide exhibits various negative aspects. The Zr-doping of ceria enhances the reducibility, but the possible Zr-based surface alteration effects and dopant-induced migration barrier enhancement in Zr-doped ceria are detrimental to surface exchange and oxygen diffusion at lower temperatures of T ≤ 800 °C. Full article

In recent years, tuning perovskite and fluorite-based materials and modifying them to ionic conductors has been an interesting but challenging topic for advanced low-temperature ceramic fuel cells (LT-CFCs). In this regard, we prepared a new composite heterostructure, BaCe_0.4Zr_0.4Y_0.1Yb_0.1O3-Sm_0.2Ce_0.8O₂ (BCZYYb-SDC), and evaluated it as an electrolyte to realize the fuel cell reaction. The developed electrolyte could be a hybrid ionic conductor, possess a very small ohmic area-specific resistance, and exhibit excellent fuel cell performance of over 1.0 W/cm² along with higher OCV of more than 1.1 V at a low operating temperature of 550 °C. The attained performance and ionic conductivity are specially accredited to constructing the heterostructure of BCZYYb-SDC. Moreover, various spectroscopy and microscopic analysis methods have been used to investigate the ions’ transportation, while on the other hand suppressing the electronic conduction. The developed composite heterostructure proposes and suggests new insight to design new electrolytes for LT-CFCs. Full article

In this paper, NiO, La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) and (CeO₂)_0.8(Sm₂O₃)_0.2 (SDC) nanopowders with different microstructures were obtained using hydrothermal and glycol–citrate methods. The microstructural features of the powders were examined using scanning electron microscopy (SEM). The obtained oxide powders were used to form functional inks for the sequential microextrusion printing of NiO-SDC, SDC and LSCF-SDC coatings with resulting three-layer structures of (NiO-SDC)/SDC/(LSCF-SDC) composition. The crystal structures of these layers were studied using an X-ray diffraction analysis, and the microstructures were studied using atomic force microscopy. Scanning capacitance microscopy was employed to build maps of capacitance gradient distribution over the surface of the oxide layers, and Kelvin probe force microscopy was utilized to map surface potential distribution and to estimate the work function values of the studied oxide layers. Using SEM and an energy-dispersive X-ray microanalysis, the cross-sectional area of the formed three-layer structure was analyzed—the interfacial boundary and the chemical element distribution over the surface of the cross-section were investigated. Using impedance spectroscopy, the temperature dependence of the electrical conductivity was also determined for the printed three-layer nanostructure. Full article

The La_1.7Ca_0.3Ni_1−yCu_yO_4+δ (y = 0.0–0.4) nickelates, synthesized via a solid-state reaction method, are investigated as prospective materials for oxygen permeation membranes and IT-SOFC cathodes. The obtained oxides are single-phase and possess a tetragonal structure (I4/mmm sp. gr.). The unit cell parameter c and the cell volume increase with Cu-substitution. The interstitial oxygen content and total conductivity decrease with Cu-substitution. The low concentration of mobile interstitial oxygen ions results in a limited oxygen permeability of Cu-substituted La_1.7Ca_0.3NiO_4+δ ceramic membranes. However, increasing the Cu content over y = 0.2 induces two beneficial effects: enhancement of the electrochemical activity of the La_1.7Ca_0.3Ni_1−yCu_yO_4+δ (y = 0.0; 0.2; 0.4) electrodes and decreasing the sintering temperature from 1200 °C to 900 °C. Enhanced electrode activity is due to better sintering properties of the developed materials ensuring excellent adhesion and facilitating the charge transfer at the electrode/electrolyte interface and, probably, faster oxygen exchange in Cu-rich materials. The polarization resistance of the La_1.7Ca_0.3Ni_1.6Cu_0.4O_4+δ electrode on the Ce_0.8Sm_0.2O_1.9 electrolyte is as low as 0.15 Ω cm² and 1.95 Ω cm² at 850 °C and 700 °C in air, respectively. The results of the present work demonstrate that the developed La_1.7Ca_0.3Ni_0.6Cu_0.4O_4+δ-based electrode can be considered as a potential cathode for intermediate-temperature solid oxide fuel cells. Full article

The samples of ceramics (Y,Ce,Mg,Sr)O_2-δ; 10YCe3Mg5Sr; 10SmCe3Mg5Sr were obtained by the method of standard solid-state reaction. According to X-ray analysis, all systems have the fluorite cubic structure, but in the (Y,Ce,Mg,Sr)O_2-δ system, the presence of the second orthorhombic phase was observed. The microstructure of powders and synthesized tablets were characterized by electron-microscopy. The average particle size of the powder was shown to be 23.88 nm; 22.32 nm; and 13.4 nm for the compositions (Y,Ce,Mg,Sr)O_2-δ; 10YCe3Mg5Sr; and 10SmCe3Mg5Sr, respectively. After the sintering at temperature 1450 °C; the grain size increased to 5.1 μm; 3.95 μm; 5.07 μm for (Y,Ce,Mg,Sr)O_2-δ; 10YCe5Mg5Sr; and 10SmCe5Mg5Sr, respectively. The ionic conduction of the obtained samples was defined by ac impedance spectroscopy. The activation energy was then calculated. The 10SmCe5Mg5Sr system was found to have the highest electrical conductivity, reaching 20.5 mS/cm at a temperature of 700 °C. The activation energy was 0.62 eV in the temperature range of 600–800 °C. The results of the density, microhardness, and crack resistance measurements of the solid solutions under investigation were obtained. Full article