Search Results (11)

The aim of this work was to verify the possibility of forming Ni-Fe and Co-Fe alloys via topotactic ion exchange exsolution in Fe-infiltrated (La,Sr,Ce)_0.9(Ni,Ti)O_3-δ or (La,Sr,Ce)_0.9(Co,Ti)O_3-δ ceramics. For this purpose, samples were synthesized using the Pechini method and then infiltrated with an iron nitrate solution. The reduction process in dry H₂ forced the topotactic ion exchange exsolution, leading to the formation of additional round-shape structures on the surfaces of grains. EDS scans and XRD analysis confirmed the formation of bimetallic alloys, which suggests that these materials have great potential for further use as anode materials for Solid Oxide Fuel Cells (SOFCs). Full article

Solid oxide fuel cells are characterized by a high efficiency for converting chemical energy into electricity and fuel flexibility. This research work focuses on developing durable and efficient anodes for solid oxide fuel cells (SOFCs) based on exsolving nickel from the perovskite structure. A-site-deficient La- and Ni-doped strontium titanates (La_0.2Sr_0.7Ti_0.95Ni_0.05O_3−δ, LSTN) were synthesized using four different techniques and mixed with Ce_0.8Gd_0.2O_2−δ (GDC) to form the SOFC anode. The synthesis routes of interest for comparison included solid-state, sol-gel, hydrothermal, and co-precipitation methods. LSTN powders were characterized via XRD, SEM, TPR, BET and XPS. In situ XRD during reduction was measured and the reduced powders were analyzed using TEM. The impact of synthesis route on SOFC performance was investigated. All samples were highly durable when kept at 0.5 V for 48 h at 800 °C with H₂ fuel. Interestingly, the best performance was observed for the cell with the LSTN anode prepared via co-precipitation, while the conventional solid-state synthesis method only achieved the second-best results. Full article

There is a magmatic lull period in the East Kunlun orogen (EKO) during the Jurassic to the Cretaceous. However, due to the lack of records of magmatic activity restricts our understanding of the late Mesozoic magmatic-tectonic evolution of the EKO. Herein, an integrated study of geochronology, whole-rock geochemistry and Sr-Nd isotopes were conducted for the Cretaceous mafic dykes in the EKO, Northern Tibet Plateau, to reveal their petrogenesis and geodynamic implications. LA-ICP-MS Zircon U-Pb dating reveals that the studied mafic dykes comprising diabase and diabase porphyry emplaced at ca. 80.9 ± 0.8 Ma. The Cretaceous mafic dykes have low contents of SiO₂ (46.36 wt.%~47.40 wt.%) but high contents of MgO (6.79 wt.%~7.38 wt.%), TiO₂ (1.91 wt.%~2.13 wt.%), Nb (12.4~18.3 ppm) and Nb/U ratio (31~39), resembling Nb-enriched mafic dykes. They exhibit chondrite-normalized rare earth element (REE) and primitive mantle-normalized trace element patterns, remarkably similar but not identical to the oceanic island basalts (OIB). The moderate REE fractionation ((La/Yb)_N = 3.55~5.37), weak negative Eu anomalies (δEu = 0.87~0.97) and relative enrichment of Rb, Ba, K, as well as high contents of Cr and Ni and slightly depleted Sr-Nd isotopes (εNd(t) = −0.18~1.33), suggest that the studied dykes originate from a partial melting of spinel lherzolite and a little of garnet which was previously modified by subducted sediments. Combined with other evidence, we propose that the studied Cretaceous Nb-enriched mafic dykes in the Northern Tibet Plateau were formed in the intraplate setting, which may be a partial melting of the enriched mantle in the lower lithosphere caused by the activity of the East Kunlun strike-slip fault. 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

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

In this work, we report a systematic study of the influence of film thickness on the structural and magnetic properties of epitaxial thin films of Pr_2−δNi_1−xMn_1+xO_6−y (PNMO) double perovskite grown on top of two different (001)-SrTiO₃ and (001)-LaAlO₃ substrates by RF magnetron sputtering. A strong dependence of the structural and magnetic properties on the film thickness is found. The ferromagnetic transition temperature (T_C) and saturation magnetization (Ms) are found to decrease when reducing the film thickness. In our case, the thinnest films show a loss of ferromagnetism at the film-substrate interface. In addition, the electronic structure of some characteristic PNMO samples is deeply analyzed using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) measurements and compared with theoretical simulations. Our results show that the oxidation states of Ni and Mn ions are stabilized as Ni²⁺ and Mn⁴⁺, thus the ferromagnetism is mainly due to Ni²⁺-O-Mn⁴⁺ superexchange interactions, even in samples with poor ferromagnetic properties. XMCD results also make evident large variations on the spin and orbital contributions to the magnetic moment as the film’s thickness decreases. Full article

The Tanshan area is located in the southern section of the west margin of the Ordos basin. The Middle Jurassic Yan’an Formation is relatively thick and rich in coal and oil shale layers, having positive potential for energy development. In order to explore the sedimentary environment of oil shale and the controlling factors of organic matter accumulation, 18 oil shale samples collected from two boreholes (Guyou-3 and Guyou-4) in the Tanshan area were selected as the research objects, and organic geochemical and elemental geochemical tests were carried out systematically. The results show that oil shales have the characteristics of medium oil content, medium ash, high calorific value, low sulfur and low maturity stage, which constitutes good hydrocarbon generation potential. The organic matter is mainly humic type, resulting from terrigenous debris and higher plant debris. The indictors of C-value (mean 81.90), Th/U ratio (mean 3.44), CaO/(MgO·Al₂ O₃) ratio (mean 0.07), δEu (mean 0.71), δCe (mean 1.15), V/(V + Ni) ratio (mean 0.79), Ce_anom index (mean −0.04), Ba_bio index (mean 488.97 μg/g), P/Ti ratio (mean 0.08), TOC/S ratio (mean 59.80), Sr/Ba ratio (mean 0.57) and (La/Yb)_N ratio (mean 14.71) indicate that Tanshan oil shales were formed in a warm–humid climate and anoxic-reducing environment, with a low-salinity water body and a low deposition rate but also a relatively low initial paleoproductivity. Paleoclimate conditions, organic matter sources and redox properties of paleowater are the main controlling factors affecting the accumulation of organic matter in oil shales. Although low paleoproductivity and deposition rates are not conducive to the preservation of organic matter, under the conditions of warm and humid climate and a reducing water environment, the continuous and stable input of terrigenous debris and higher plant debris can also cause the enrichment of organic matter. Full article

Abundant Early Cretaceous magmatism is conserved in the central and southern Great Xing’an Range (GXR) and has significant geodynamic implications for the study of the Late Mesozoic tectonic framework of northeast China. In this study, we provide new high-precision U–Pb zircon geochronology, whole-rock geochemistry, and zircon Hf isotopic data for representative intrusive rocks from the northern part of the Ulanhot area to illustrate the petrogenesis types and magma source of these rocks and evaluate the tectonic setting of the central-southern GXR. Laser ablation inductively coupled plasma–mass spectrometry (LA-ICP-MS) zircon U–Pb dating showed that magmatism in the Ulanhot area (monzonite porphyry: 128.07 ± 0.62 Ma, quartz monzonite porphyry: 127.47 ± 0.36, quartz porphyry: 124.85 ± 0.34, and granite porphyry: 124.15 ± 0.31 Ma) occurred during the Early Cretaceous. Geochemically, monzonite porphyry belongs to the metaluminous and alkaline series rocks and is characterized by high Al₂O₃ (average 17.74 wt.%) and TiO₂ (average 0.88 wt.%) and low Ni (average 4.63 ppm), Cr (average 6.69 ppm), Mg^# (average 31.11), Y (average 15.16 ppm), and Yb (average 1.62 ppm) content with enrichment in Ba, K, Pb, Sr, Zr, and Hf and depletion in Ti, Nb, and Ta. The granitic rocks (e.g., quartz monzonite porphyry, quartz porphyry, and granite porphyry) pertain to the category of high-K calc-alkaline rocks and are characterized by high SiO₂ content (>66 wt.%) and low MgO (average 0.69 wt.%), Mg^# (average 31.49 ppm), Ni (average 2.78 ppm), and Cr (average 8.10 ppm) content, showing an affinity to I-type granite accompanied by Nb, Ta, P, and Ti depletion and negative Eu anomalies (δEu = 0.57–0.96; average 0.82). The Hf isotopic data suggest that these rocks were the product of the partial melting of juvenile crustal rocks. Notably, fractionation crystallization plays a crucial role in the process of magma emplacement. Combining our study with published ones, we proposed that the Early Cretaceous intrusive rocks in the Ulanhot area were formed in an extensional tectonic background and compactly related to the subduction of the Paleo-Pacific Ocean plate. Full article

Perovskite derived Ni catalysts offer the remarkable benefit of regeneration after catalyst poisoning or Ni particle growth through the reversible segregation of Ni from the perovskite-type oxide host. Although this property allows for repeated catalyst regeneration, improving Ni catalyst stability towards sulfur poisoning by H₂S is highly critical in solid oxide fuel cells. In this work Mn, Mo, Cr and Fe were combined with Ni at the B-site of La_0.3Sr_0.55TiO_3±δ to explore possible benefits of segregation of two transition metals towards sulfur tolerance. Catalytic activity tests towards the water gas shift reaction were carried out to evaluate the effect of the additional metal on the catalytic activity and sulfur stability of the Ni catalyst. The addition of Fe to the Ni perovskite catalyst was found to increase sulfur tolerance. The simultaneous segregation of Fe and Ni from La_0.3Sr_0.55Ti_0.95-xNi_0.05Fe_xO_3±δ (x ≤ 0.05) was investigated by temperature programmed reduction, X-ray diffraction and X-ray absorption spectroscopy and catalytic tests after multiple redox cycles. It is shown that catalytic properties of the active phase were affected likely by the segregation of Ni/Fe alloy particles and that the reversible segregation of Ni persisted, while it was limited in the case of Fe under the same conditions. Full article

In solid oxide fuel cells, doped strontium titinates have been widely studied as anode materials due to their high n-type conductivity. They are used as current conducting backbones as an alternative to nickel-cermets, which suffer degradation due to coking, sulphur poisoning, and low tolerance to redox cycling. In this work, anode backbone materials were synthesized from La_0.2Sr_0.25Ca_0.45TiO_3−δ (LSCT_A-), modified with 5 wt.% Zn, and infiltrated with nickel (Ni)/ceria gadolinium-doped cerium oxide (CGO), Fe, and Co. The electrodes were further studied for their electrochemical performance using electrochemical impedance spectroscopy (EIS) at open circuit voltage (OCV) in different hydrogen to steam ratios and at various operating temperatures (850–650 °C). Infiltration of electrocatalysts significantly reduced the polarization resistance and among the studied infiltrates, at all operating temperatures, Ni-CGO showed excellent electrode performance. The polarization resistances in 3% and 50% H₂O/H₂ atmosphere were found to be 0.072 and 0.025 Ω cm², respectively, at 850 °C, and 0.091 and 0.076 Ω cm², respectively, at 750 °C, with Ni-CGO. These values are approximately three orders of magnitude smaller than the polarization resistance (25 Ω cm²) of back bone material measured at 750 °C. Full article

Sr(Ti_1−xFe_x)O_3−δ (0 ≤ x ≤ 0.2) thin films were grown on Si(100) substrates with LaNiO₃ buffer-layer by a sol-gel process. Influence of Fe substitution concentration on the structural, ferroelectric, and magnetic properties, as well as the leakage current behaviors of the Sr(Ti_1−xFe_x)O_3−δ thin films, were investigated by using the X-ray diffractometer (XRD), atomic force microscopy (AFM), the ferroelectric test system, and the vibrating sample magnetometer (VSM). After substituting a small amount of Ti ion with Fe, highly enhanced ferroelectric properties were obtained successfully in SrTi_0.9Ti_0.1O_3−δ thin films, with a double remanent polarization (2P_r) of 1.56, 1.95, and 9.14 μC·cm⁻², respectively, for the samples were annealed in air, oxygen, and nitrogen atmospheres. The leakage current densities of the Fe-doped SrTiO₃ thin films are about 10⁻⁶–10⁻⁵ A·cm⁻² at an applied electric field of 100 kV·cm⁻¹, and the conduction mechanism of the thin film capacitors with various Fe concentrations has been analyzed. The ferromagnetic properties of the Sr(Ti_1−xFe_x)O_3−δ thin films have been investigated, which can be correlated to the mixed valence ions and the effects of the grain boundary. The present results revealed the multiferroic nature of the Sr(Ti_1−xFe_x)O_3−δ thin films. The effect of the annealing environment on the room temperature magnetic and ferroelectric properties of Sr(Ti_0.9Fe_0.1)O_3−δ thin films were also discussed in detail. Full article