Search Results (58)

Triethylamine (TEA), a volatile organic compound (VOC), has important applications in industrial production. However, TEA has an irritating odor and potential toxicity, making it necessary to develop sensitive TEA gas sensors with high efficiency. This study focused on preparing LaFeO₃ nanoparticles modified by SnS₂ nanosheets (SnS₂/LaFeO₃ composite) using a hydrothermal method together with sol–gel technique. According to the comparison results of the gas-sensing performance between pure LaFeO₃ and SnS₂/LaFeO₃ composite with varying composition ratios, 5% SnS₂/LaFeO₃ sensor had a sensitivity for TEA that was 3.2 times higher than pure LaFeO₃ sensor. The optimized sensor operates at 140 °C and demonstrates strong stability, selectivity, and long-term durability. Detailed analyses revealed that the SnS₂ nanosheets enhanced oxygen vacancy (O_V) content and carrier mobility through heterojunction formation with LaFeO₃. This study provides insights into improving gas-sensing performance via p-n heterostructure design and proposes a novel LaFeO₃-based material for TEA detection. Full article

High-entropy ceramics have gained wider attention due to their structural integrity and stability, which can be used in various functional applications. Especially, high-entropy oxides exhibit excellent thermal stability, particularly at high temperatures. Thermal barrier coating materials must demonstrate good thermal stability without any phase transformation or phase separation, which is critical in aerospace and energy conversion applications. To address this, we have prepared new high-entropy stannate pyrochlore oxide nanoparticles with the composition (Gd_0.2Nd_0.2La_0.2Pr_0.2Sm_0.2)₂Sn₂O₇ through a simple glycine-assisted sol–gel synthesis. The phase evolution was probed at different heat-treatment temperatures from 1000 °C to 1500 °C. Among the temperatures investigated, a single-phase pyrochlore oxide was formed from 1300 °C without any impurity or phase separation. The obtained nanoparticles were characterized using various techniques, including X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), nanoindentation, and dilatometry to investigate their physiochemical and mechanical properties. The Vickers hardness of high-entropy oxides is 4.2 ± 0.33 GPa, while a thermal expansion coefficient (TEC) of 8.7 × 10⁻⁶ K⁻¹ at 900 °C is calculated. The results show that the prepared high-entropy pyrochlore oxide can be a suitable candidate for thermal barrier coating. Full article

A Pt@CeLaCoNiOx/Co@SnO₂ laminated MOS sensor was prepared using Co@SnO₂ as the gas-sensitive film material and Pt@CeLaCoNiOx as the catalytic film material. The sensor was verified to exhibit good sensing performances for dimethyl methylphosphonate, a simulant of Sarin, under a temperature modulation, and characteristic peaks appeared in the resistance response curves only for dimethyl methylphosphonate. The Article Swarm Optimization-Backpropagation Neural Network had a good ability to identify the resistance response data of dimethyl methylphosphonate. The identification accuracy increased as the concentration of dimethyl methylphosphonate increased. This scheme can effectively identify whether the test gas contained dimethyl methylphosphonate or not, which provided a reference for achieving the high selectivity of the MOS sensor for Sarin. Full article

In the western Tarim Basin, Carboniferous granular dolostones deposited on a carbonate platform contain a small amount of terrigenous materials of sand-size fraction, agglomerated clay minerals, or similar phases. However, the role of terrigenous materials on dolomitization is still unclear. The aim of this study was to reveal the dolomitization mechanism. The granular dolomites have small crystal size, earthy yellow color, and fabric-retentive texture, with relatively good order. These features indicate dolomites precipitated during early diagenesis. The ratio of rare earth elements (RREs) abundance of the stable isotopes ⁸⁷Sr/⁸⁶Sr relative to Post-Archean Australian Shale (PAAS) normalized patterns was used to study the source of the dolomitizing fluids. The composition of REEs is characterized by heavy rare earth (HREE) enrichment (average Nd_SN/Yb_SN = 0.83). There is a positive (La/La*)_SN anomaly and slightly positive (Gd/Gd*)_SN and (Y/Y*)_SN anomaly; δ¹⁸O of seawater in fractionation equilibrium with granular dolostones was from −2.8‰ to 1.7‰ PDB, implying the dolomitizing fluid was contemporary, slightly evaporated seawater. The granular dolostones on the relatively thick shoals were subject to subaerial exposure before pervasive dolomitization, with evidence that the input of detrital kaolinite predated the formation of dolomites. Higher ⁸⁷Sr/⁸⁶Sr values and ∑REE in granular dolostones than the values in equivalent limestones indicate that dolomitization was related to terrigenous materials. Within the terrigenous materials, the negative-charged clay minerals may have catalyzed the dolomitization, resulting in dramatically decreased induction time for precipitation of proto-dolomites. A greater amount of terrigenous materials occurred on the shoals at the sea level fall, resulting from enhanced river entrenchment and downcutting. As a result, after subaerial exposure, the penesaline water flow through the limy allochems sediments lead to dolomitization, with the catalysis of illite on relatively thick shoals. Full article

As one of the representative transparent conducting oxides, perovskite-typed La-doped BaSnO₃ (LBSO) films could be integrated with other perovskite materials to create all-perovskite oxide devices exhibiting exotic physical properties. To overcome the intricate trade-off between conductivity and transmittance in LBSO-based devices, understanding the structural modulating mechanisms of transmittance is definitely crucial. In this paper, the influences of the prevailing Ruddlesden–Popper faults (RP faults) on the transmittance of LBSO films were systematically illuminated, whose density were regulated by the oxygen partial pressures during film growth. High-angle annular dark field (HAADF) STEM and X-ray diffraction (XRD) were employed to characterize the microstructures of the films growing under various oxygen partial pressures and annealing under different oxygen partial pressures. A decrease in RP fault density was observed in the films grown and annealed at high oxygen partial pressures, which displayed improved visible light transmittance. Atomic-scale energy-dispersive spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) analyses revealed the different electronic structure at RP faults compared with the bulk material, including the double concentration of La and increased M5/M4 white line ratio, which is modulative by the oxygen deficiency in LBSO film. It is revealed that the RP defaults in LBSO films annealed at low oxygen pressures displayed larger changes in electronic structure compared with the counterparts with low oxygen deficiency. This work suggests that the oxygen deficiency in LSBO films plays a crucial role in changing the density of RP faults and their electronic structures, thereby regulating the transmittance of LBSO films, which would provide guidance for fabricating high-performance LBSO films. Full article

Molybdenite Re–Os and zircon U–Pb isotopic data are first obtained from the stockwork and disseminated-style gold-bearing ores and the fine-grained granite hosting these ores in the Xiawolong gold mine, respectively, which is located within the Muping–Rushan gold metallogenic belt, eastern Jiaodong Peninsula, so as to illustrate the genesis of gold mineralization and its implication for exploration. Four molybdenite samples yield a well-defined Re–Os isochron age of 118.4 ± 2.5 Ma (2σ), which is identical to the weighted average Re–Os model age of 118 ± 1.7 Ma (2σ). Integration of the new geochronologic data with those reported recently from the other gold mines in the Muping–Rushan gold metallogenic belt suggests that a discrete gold event occurred in Xiawolong ca. 4 m.y. older than that for the other gold mineralization at ca. 114 Ma in eastern Jiaodong. In addition, two fine-grained granite samples, measured using the LA-ICP-MS zircon U–Pb method, produce the first precise ages of 118 ± 2 to 117 ± 2 Ma (2σ), identical to the molybdenite Re–Os ages, within the margin of error and obtained in this study. The fine-grained granite has a similar lithology and emplacement age as those of the medium-grained monzogranite consisting of the marginal facies of the Sanfoshan batholith, and is considered to be the crystallization products of Sanfoshan granitic magma in the late stage. Combined with the previous S-Pb-D-O isotope, fluid inclusion and geological studies, which suggest that the ore-forming fluid of Xiawolong gold mineralization is from magmatic water, and the identification that the magnetite coexists with the gold-bearing pyrite and molybdenite in the gold ores, which indicates a high oxygen fugacity (fO₂) of both the magma and resultant hydrothermal fluids, it is logical to infer that the Xiawolong gold deposit is genetically in relation to the Sanfoshan granitic magmatism, which is high in fO₂ and rich in Au at the magmatic–hydrothermal transition stage, and the change in fO₂ mostly likely makes a significant contribution to the precipitation of Au. This result reveals that the late-stage granitic magma with high fO₂, which is crystallized into the fine-grained granite, probably is also rich in Au, except the W–Mo–Cu–Zn–U–Be–Li–Nb–Ta–Sn–Bi-elements. Therefore, based on the extensional tectonic regime for the early Cretaceous Jiaodong gold deposits, we propose that gold exploration in the Jiaodong should not only focus on the fault-hosted Au but also on the fine-grained granite-hosted Au around the apical portions of the late Early Cretaceous small-granitic intrusions with high fO₂. This model could also be important for prospecting in other gold ore districts, which have a similar tectonic setting. Full article

A series of high-entropy pyrochlore ceramics, specifically (La_1/3Nd_1/3M_1/3)₂(Zn_1/2Sn_1/2)₂O₇ (M = Sm, Eu, Gd, or Dy), have been synthesized using the solid-state reaction method. Their potential as high-temperature thermistors was investigated by analyzing electrical and aging properties at elevated temperatures. Characterization using X-ray diffraction, scanning electron microscopy, and Raman spectroscopy confirms that these ceramics are dense, single-phase solid solutions with a pyrochlore structure. Electrical analysis demonstrate that these ceramics maintain high resistivity and resistance stability, exhibiting typical negative temperature coefficient features and high B values across a wide temperature range. These characteristics make (La_1/3Nd_1/3M_1/3)₂(Zn_1/2Sn_1/2)₂O₇ promising candidates for the development of high-sensitivity, long-life high-temperature thermistors suitable for applications within the temperature range of 400–1200 °C. Full article

Porous pure SnO₂ nanofibers (NFs) and La₂O₃ nanoparticles (NPs)-embedded porous SnO₂ NFs were successfully synthesized via electrospinning followed by calcination. These materials were systematically evaluated as gas-sensing elements in metal-oxide-semiconductor (MOS) sensors. The La₂O₃ NPs embedded in porous SnO₂ NFs demonstrated superior gas-sensing performance compared to pure SnO₂ NFs. Specifically, the incorporation of La₂O₃ resulted in a 12-fold enhancement in gas-sensing response towards ethanol, significantly improving both sensitivity and selectivity by tuning the carrier concentration and modifying oxygen deficiencies and chemisorbed oxygen levels. Thus, La₂O₃ NPs embedded in SnO₂ NFs present a promising strategy for the development of high-performance ethanol gas sensors. Full article

Energy storage efficiency (η) and large recoverable energy density (W_re) are necessary for antiferroelectric materials in order to develop antiferroelectric-based dielectric capacitors with exceptional energy storage capacity. In the present paper, the effect of doping La³⁺ on the energy storage capacity of Pb_1−xLa_x(Hf_0.45Sn_0.55)_0.995O₃ antiferroelectric ceramics was studied. Adjusting the content of La and changing the phase structure of PLHS from antiferroelectric to relaxor ferroelectric gradually, which narrowed its hysteresis loop, yielded a high energy storage efficiency of 81.9% and the maximum breakdown field strength of 200 kV/cm when x = 2 mol%. In addition, the recoverable energy density and energy storage efficiency both showed excellent temperature stability and frequency stability in the temperature range of 10–110 °C and the frequency range of 10–100 Hz, suggesting that Pb_0.98La_0.02(Hf_0.45Sn_0.55)_0.995O₃ are favorable materials candidates for the preparation of pulsed-power capacitors that can be used in a wide range of conditions. Full article

Titanites can be excellent markers of element transfer in medium-temperature retrograde metamorphism. Euhedral titanites from several alpine fissures from Mont Blanc, particularly those of Périades and Courtes, crystallised at the end of the main quartz stage and are synchronous with the formation of green biotites and albite before chlorite formation. Micro-XRF, SEM, electron probe, and LA-ICP-MS analyses show that these titanites have a wide range of Al₂O₃ content from 1 to 8%, are dominated by -OH versus F, and have a wide range of Nb (up to 4500 ppm), Y (up to 3000 ppm), Zr (up to 1800 ppm), and Sn (up to 1400 ppm) concentrations. The allanite from the granite, partly destabilised into epidote, is the most likely source of Nb, Y, Zr, Sn, and REE. Titanites are enriched in HREE and show variations in LREE depending on the studied sites. Like quartz, they formed at around 400 ± 20 °C, which is compatible with the formation of green biotites after the destabilisation of granite Fe-Mg silicates. This early stage of fluid circulation, synchronous with the Mont Blanc massif uplift, is therefore marked by the titanite formation at the transition between the biotite and chlorite stability fields. Full article

The Shuangjianzishan silver polymetallic deposit is located in the copper–tin–lead–zinc–silver polymetallic metallogenic belt in the Southern Great Xing’an Range, with silver resources of more than 18,000 t, which is the largest silver polymetallic deposit in Asia. Early studies concluded that the Shuangjianzishan deposit is typically an epithermal Ag-Pb-Zn deposit that lacks a high-temperature mineralization stage. In recent years, with the deepening of research, a large amount of Cu-Sn mineralization has been found in the deep part of the Shuangjianzishan deposit, but it is less studied. The laser-ablation inductively coupled mass spectroscopy (LA-ICP-MS) technique is used to investigate the distribution and substitution of trace elements in chalcopyrite and cassiterite. In this paper, the trace element study of chalcopyrite and cassiterite from the Shuangjianzishan deposit reveals that Sn, In, As, Se, Sb, and Tl mainly exist in chalcopyrite in isomorphic form, while Pb, Bi, and Ni mainly exist in chalcopyrite in the form of mineral inclusions. The enrichment of the high-temperature elements Sn and Se in chalcopyrite, and the deficit of the middle- and low-temperature elements Ga, Sb, etc., reflect that the chalcopyrite in the Shuangjianzishan deposit was formed in a middle- and high-temperature environment, and it also indicates that the early ore-forming hydrothermal solution may be rich in Sn. Fe, In, Co, and Ni mainly exist in cassiterite in isomorphic form, and the content of W in cassiterite is high. There are two main forms, one is isomorphic and the other is wolframite inclusion. Cassiterite has Fe-rich and W-U-poor characteristics, indicating that cassiterite from the Shuangjianzishan deposit was formed under relatively oxidized conditions, and the relative enrichment of elements such as Fe, W, Zr, and Hf indicates that the temperature of cassiterite formation was high. The elemental content and inter-ionic coupling relationships suggest that the cassiterite from the Shuangjianzishan deposit may have an elemental replacement mechanism of W⁶⁺ + Fe²⁺ ↔ 2Sn⁴⁺ or Fe³⁺ + OH⁻ ↔ Sn⁴⁺ + O²⁻. The trace elements in cassiterite of the Shuangjianzishan deposit are rich in Fe and Mn and depleted in Nb and Ta, according to the Fe-W diagram, and the tin mineralization of the Shuangjianzishan deposit belongs to cassiterite–sulfide-type tin mineralization. Chalcopyrite Co/Ni ratios >1 are consistent with the characteristics of chalcopyrite genesis in hydrothermal deposits. Full article

Solid-state lithium metal batteries (LMBs) have been extensively investigated owing to their safer and higher energy density. In this work, we prepared a novel elastic solid-state polymer electrolyte based on an in situ-formed elastomer polymer matrix with ion-conductive plasticizer crystal embedded with Li_6.5La₃Zr_1.5Ta_0.5O₁₂ (LLZTO) nanoparticles, denoted as LZT/SN-SPE. The unique structure of LZT/SN-SPE shows excellent elasticity and flexibility, good electrochemical oxidation tolerance, high ionic conductivity, and high Li⁺ transference number. The role of LLZTO filler in suppressing the side reactions between succinonitrile (SN) and the lithium metal anode and propelling the Li⁺ diffusion kinetics can be affirmed. The Li symmetric cells with LZT/SN-SPE cycled stably over 1100 h under a current density of 5 mA cm⁻², and Li||LiFePO₄ cells realized an excellent rate (92.40 mAh g⁻¹ at 5 C) and long-term cycling performance (98.6% retention after 420 cycles at 1 C). Hence, it can provide a promising strategy for achieving high energy density solid-state LMBs. Full article

In this work, a reliable and robust in situ non-matrix-matched calibration method is proposed for element composition determination in scheelite samples. With external calibration against the silicate glass standard reference material NIST SRM 610, the concentrations of both major elements (Ca and W) and trace elements (Si, Fe, Mo, Y, rare earth elements, etc.) in scheelite are determined using an ArF 193 nm excimer nanosecond laser ablation-inductively coupled plasma mass spectrometer (LA-ICP-MS). Here, the ablation was performed by hole drilling under a helium (He) environment using a laser spot size of 35 μm and a laser repetition of 5 Hz, and the aerosols were then transported to a quadrupole ICP-MS by a mixture of He and make-up gas argon (Ar) with a total gas flow rate of 1.6 L/min. Results showed that there was no apparent matrix effect between the NIST SRM 610 and scheelite by this proposed method. With internal standardization against W, the obtained concentrations of CaO and WO₃ were found to yield an average matrix CaO/WO₃ mass fraction ratio of 0.245 (2σ = 0.003, n = 19), which agreed well with the value of 0.243 (2σ = 0.002, n = 15) from electron probe microanalysis (EPMA). Furthermore, the accuracy of trace element analyses with this proposed non-matrix-matched calibration in situ method was evaluated by comparing the concentration results with those from bulk analysis by solution nebulizer ICP-MS (SN-ICP-MS). It was found that the quantification results from LA-ICP-MS and SN-ICP-MS were comparable, in particular showing a relative concentration bias of the total ∑REE+Y contents of less than 2%. This confirmed that scheelites can be accurately analyzed in situ by LA-ICP-MS without matrix-matched calibration standards. By using this developed in situ method, the element compositions in a series of scheelite samples from different W-associated deposits in China were successfully quantified, promising further genetic process investigation and associated geologic activities of the polymetallic resources. 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

Different classes of solid electrolytes for all-solid-state batteries (ASSB) are currently being investigated, with each of them suitable for a different ASSB concept. Their combination in hybrid battery cells enables the use of their individual benefits while mitigating their disadvantages. The cubic stuffed garnet Li₇La₃Zr₂O₁₂ (LLZO), for example, is stable in contact with metallic lithium but has only moderate ionic conductivity, whereas the thiophosphate Li₁₀SnP₂S₁₂ (LSPS) is processable using conventional battery manufacturing technologies and has an excellent lithium-ion conductivity but an inferior electrochemical stability. In this work, we, therefore, present a layered hybrid all-solid-state full-cell concept that accommodates a lithium metal anode, a LiNi_0.8Co_0.1Mn_0.1O₂-based composite cathode with an LSPS catholyte (LSPS/NCM811) and a sintered monolithic LLZO separator. The electrochemical stability of LLZO and LSPS at cathodic potentials (up to 4.2 V) was investigated via cyclic voltammetry in test cells, as well as by cycling half cells with LSPS or a mixed LSPS/LLZO catholyte. Furthermore, the pressure-dependency of the galvanostatic cycling of a Li | LLZO | LSPS/NCM811 full cell was investigated, as well as the according effect of the Li | LLZO interface in symmetric test cells. An operation pressure of 12.5 MPa was identified as the optimal value, which assures both sufficient inter-layer contact and impeded lithium penetration through the separator and cell short-circuiting. Full article