Search Results (39)

Organometallic rare-earth complexes have attracted considerable attention in recent years due to their unique structures and exceptional magnetic properties. In this study, we report the synthesis and magnetic characteristics of a family of monopentamethylcyclopentadienyl-coordinated trinuclear rare-earth hepta-chloride clusters [(Li(THF)(Et₂O))(Cp^*RE)₃(μ-Cl)₄(μ₃-Cl)₂(μ₄-Cl)] (RE₃: RE =Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Cp* = pentamethylcyclopentadienide). These clusters were synthesized by reacting LiCp* with RECl₃ in a 1:1 molar ratio within a mixed solvent system (THF: Et₂O = 1:9), resulting in high solubility in common organic solvents such as DCM, THF, and Et₂O. Magnetic studies conducted on these paramagnetic clusters reveal the coexistence of ferromagnetic and antiferromagnetic superexchange interactions in Gd₃. Additionally, Dy₃ exhibits both ferromagnetic and antiferromagnetic intramolecular dipolar interactions. Notably, slow magnetic relaxation was observed in Dy₃ below 23 K under a zero DC applied field with an energy barrier of 125(6) cm⁻¹. Full article

A variety of variables, such as organic matter input, redox conditions, depositional rates, and terrigenous input, affect the deposition of black shale. Furthermore, because of the significant regional variations in paleodepositional environments, these factors have a complex role in organic matter enrichment. Global geological events influenced sedimentary conditions, organic enrichment, and the development of organic-enriched shales during the Late Ordovician to Early Silurian. The Wufeng–Longmaxi Formation black shales in Southeastern Chongqing were analyzed for X-ray diffraction (XRD), major and trace element geochemistry, and total organic carbon (TOC) data; this led to further analysis of the relationship between the depositional environment and organic matter aggregation and rock type evolution. The primary minerals found in the Wufeng–Longmaxi shale are quartz, feldspar, carbonatite (calcite and dolomite), and clay. The high index of compositional variability (ICV) values (>1) and the comparatively low chemical index of alteration (CIA) values (52.6–72.8) suggest that the sediment source rocks are juvenile and are probably experiencing weak to moderate chemical weathering. The selected samples all show negative Eu anomalies, flat heavy rare earth elements, and mildly enriched light rare earth elements. The ratios of La/Th, La/Sc, Th/Sc, ΣREE-La/Yb, TiO₂-Ni, and La/Th-Hf suggest that acidic igneous rocks were the main source of sediment, with minor inputs from ancient sedimentary rocks. The correlations of paleoclimate proxies (Sr/Cu, CIA), redox proxies (V/Cr, V/Ni, V/(V + Ni), Ni/Co, U/Th), paleoproductivity proxies (Ba_xs, Cu_EF, Ni_EF), and water mass restriction proxies (Mo/TOC, U_EF, Mo_EF) suggest a humid–semiarid, anoxic, moderate–high paleoproductivity, and moderate–strongly restricted environment. On the basis of the aforementioned interpretations, the paleoenvironment of the Wufeng–Longmaxi Formations was established, with paleoredox conditions and restricted water masses likely being the primary factors contributing to organic matter enrichment. Full article

Europium(III) β-diketone and organic carboxylic acid complexes are designable, easy to prepare, and easy to modify and have excellent fluorescence properties (narrow emission spectral band, high colour purity, long fluorescence lifetime, high quantum yield, and a spectral emission range covering both the visible and near-infrared regions). These complexes play important roles in popular fields such as laser and fibre-optic communications, medical diagnostics, immunoassays, fluorescent lasers, sensors, anticounterfeiting, and organic light-emitting diodes (OLEDs). In the field of light-emitting materials, europium complexes are especially widely used in OLED lamps, especially because of their high-efficiency emission of red (among the three primary colours); accordingly, these complexes can be mixed with blue and green phosphors to obtain high-efficiency white phosphors that can be excited by near-ultraviolet light. This paper reviews the red-light-emitting europium complexes with β-diketone and organic carboxylic acid as ligands that have been studied over the last five years, describes the current problems, and discusses their future application prospects. Full article

Ionic rare earth ore (IREO) has a high abundance of medium and heavy rare earth elements (REEs), making it a vital strategic resource for China. In this work, two typical microorganisms, Aspergillus niger and Acidithiobacillus ferrooxidans, were used to study the interaction mechanism during the bioleaching of IREO under acidic conditions. The results revealed some differences in the interaction and leaching effects of A. niger and A. ferrooxidans on ionic rare earth minerals. A. niger mainly forms rare earth complexes with rare earth ions in IREO by secreting metabolites such as organic acids, thereby promoting the release of REEs, and it has a strong adsorption capacity for Yb. A. ferrooxidans promotes the release of REEs from rare earth minerals, primarily through iron–sulfur oxidation. The differential expression of metabolic genes (e.g., gpmL, FabF, FASN) associated with major metabolite secretion indicates their correlation with the leaching process. The above results reveal the role of the typical acid-producing microorganisms A. niger and A. ferrooxidans and their metabolites in the leaching of IREO, which is valuable for understanding the interaction mechanisms between microorganisms and IREO under acidic conditions. Full article

Polydentate ligands with nitrogen donor atoms have possibly given rise to the largest group of coordination complexes described. Among these ligands, amidinates represent a nitrogenated version of carboxylates and allow the formation of complexes with most elements in the periodic table, adopting chelate or bridge coordination modes. The precursors of these ligands, amidines, can present an alkynyl group as the substituent of their central atom, R′N=C(C≡CR)NHR′, which provides an additional point of reactivity for these molecules, as well as a different electronic behavior compared to conventional amidines with alkyl groups on the central carbon atom of the amidine group. These propiolamidines have been obtained through classical stoichiometric organic synthesis procedures or, with greater atomic economy, through catalytic procedures based on Main Group, Transition, or Rare Earth metals. This work reviews these synthesis methods, as well as the reactivity in the obtention of new, more complex heterocyclic organic molecules. Full article

Strategic breakthroughs have been made in the exploration and evaluation of Gulong shale oil in the Songliao Basin. However, the Heiyupao Depression, located near the Gulong Depression, hosts a thick section of the Qingshankou Formation shale that has not been extensively studied. This paper presents novel insights into the lithofacies characteristics, depositional environment, and reservoir features of the Qingshankou Formation shale in the Heiyupao Depression, with a specific focus on the origin and maturation of organic-rich shale. Four core wells were drilled, and 152 core samples were analyzed through a variety of techniques, including rock type classification, mineral composition, TOC content, rare earth elements, rock pyrolysis, organic matter type determination, and CT scanning. Results indicate that the Qingshankou shale is dominated by felsic compositions and Type I kerogen, with organic maturity varying across the section. Based on lithology, sedimentary structures, mineralogy, and organic matter abundance, five distinct lithofacies are identified: high-organic mud-rich felsic shale, high-organic sand-rich felsic shale, medium-organic sand-rich felsic shale, medium-organic massive shale, and low-organic sand-rich felsic shale. Notably, the Type A lithofacies (high-organic mud-rich felsic shale) is identified as a primary source rock due to its intergranular and organic matter pores, albeit with low porosity and poor connectivity. In contrast, the Type E lithofacies (low-organic sand-rich felsic shale) have high porosity, well-developed micro- and nano-scale pores, and strong connectivity, marking them as the primary reservoirs. The characteristics of this region differ significantly from those of Gulong shale oil, requiring different extraction strategies. The mineral composition of such shale is predominantly felsic rather than mixed. The findings not only provide theoretical support for the exploration of complex lacustrine shale in the Songliao Basin but also offer valuable insights for the resource development of similar non-marine shale systems worldwide. Full article

Arid desert regions are among the harshest ecological environments on Earth. Halophytes, with their unique physiological characteristics and adaptability, have become the dominant vegetation in these areas. Currently, research on halophytes in this region is relatively limited, particularly concerning studies related to their root endophytic fungi, which have been rarely reported on. Therefore, investigating the diversity and composition of endophytic fungi in halophytes is crucial for maintaining ecological balance in such an arid environment. This study focuses on eight representative angiosperm halophytes from the West Ordos Desert in China (including Nitraria tangutorum, Salsola passerina, Suaeda glauca, Reaumuria trigyna, Reaumuria kaschgarica, Limonium aureum, Apocynum venetum, and Tripolium vulgare), utilizing Illumina MiSeq high-throughput sequencing technology combined with soil physicochemical factor data to analyze the diversity, composition, and ecological functions of their root-associated fungal communities. Ascomycota dominated the fungal composition in most halophytes, particularly among the recretohalophytes, where it accounted for an average of 88.45%, while Basidiomycota was predominant in Suaeda glauca. A Circos analysis of the top 10 most abundant genera revealed Fusarium, Dipodascus, Curvularia, Penicillium, and other dominant genera. Co-occurrence network analysis showed significant differences in fungal networks across halophyte types, with the most complex network observed in excreting halophytes, characterized by the highest number of nodes and connections, indicating tighter fungal symbiotic relationships. In contrast, fungal networks in pseudohalophytes were relatively simple, reflecting lower community cohesiveness. Redundancy analysis (RDA) and Mantel tests demonstrated that soil factors such as organic matter, available sulfur, and urease significantly influenced fungal diversity, richness, and evenness, suggesting that soil physicochemical properties play a critical role in regulating fungal–plant symbiosis. Functional predictions indicated that endophytic fungi play important roles in metabolic pathways such as nucleotide biosynthesis, carbohydrate degradation, and lipid metabolism, which may enhance plant survival in saline–alkaline and arid environments. Furthermore, the high abundance of plant pathogens and saprotrophs in some fungal communities suggests their potential roles in plant defense and organic matter decomposition. The results of this study provide a reference for advancing the development and utilization of halophyte endophytic fungal resources, with applications in desert ecosystem restoration and halophyte cultivation. Full article

The phenomenon of high-temperature oxidation in magnesium alloys constitutes a significant obstacle to their application in the aerospace field. However, the incorporation of active elements such as alloys and rare earth elements into magnesium alloys alters the organization and properties of the oxide film, resulting in an enhancement of their antioxidation capabilities. This paper comprehensively reviews the impact of alloying elements, solubility, intermetallic compounds (second phase), and multiple rare earth elements on the antioxidation and flame-retardant effects of magnesium alloys. The research progress of flame-retardant magnesium alloys containing multiple rare earth elements is summarized from two aspects: the oxide film and the matrix structure. Additionally, the existing flame-retardancy models for magnesium alloys and the flame-retardant mechanisms of various flame-retardant elements are discussed. The results indicate that the oxidation of rare earth magnesium alloys is a complex process determined by internal properties such as the structure and properties of the oxide film, the type and amount of rare earth elements added, the proportion of multiple rare earth elements, synergistic element effects, as well as external properties like heat treatment, oxygen concentration, and partial pressure. Finally, some issues in the development of multi-rare earth magnesium alloys are raised and the potential directions for the future development of rare earth flame-retardant magnesium alloys are discussed. This paper aims to promote an understanding of the oxidation behavior of flame-retardant magnesium alloys and provide references for the development of rare earth flame-retardant magnesium alloys with excellent comprehensive performance. Full article

Rare earth elements (REEs) have recently been classified as critical and strategic metals due to their importance in modern society. Research on the geochemical behaviors and mineralization of REEs not only provides essential guidance for mineral exploration but also holds great significance in enhancing our understanding of Earth’s origin and evolution. This paper reviews recent research on the occurrence characteristics, deposit types, and hydrothermal behaviors of REEs, with a particular focus on comparing the complexation and transport of REEs by F, Cl, S, C, P, OH, and organic ligands in fluids. Due to the very weak hydrolysis of REE ions, they predominantly exist as either hydrated ions or free ions in low-temperature and acidic to weakly basic fluids. As the ligand activity increases, the general order of transporting REEs is Cl⁻ ≈ ${\mathrm{S}\mathrm{O}}_4^{2-}$ > F⁻ ≈ ${\mathrm{P}\mathrm{O}}_4^{3-}$ > ${\mathrm{C}\mathrm{O}}_3^{2-}$ > OH⁻ under acidic conditions or OH⁻ > ${\mathrm{S}\mathrm{O}}_4^{2-}$ ≈ Cl⁻ > F⁻ under alkaline conditions. In acidic to neutral hydrothermal systems, the transport of REEs is primarily dominated by ${\mathrm{S}\mathrm{O}}_4^{2-}$ and Cl⁻ ions while the deposition of REEs could be influenced by F⁻, ${\mathrm{C}\mathrm{O}}_3^{2-}$, and ${\mathrm{P}\mathrm{O}}_4^{3-}$ ions. In neutral to alkaline hydrothermal systems, REEs mainly exist in fluids as hydroxyl complexes or other ligand-bearing hydroxyl complexes. Additionally suggested are further comprehensive investigations that will fill significant gaps in our understanding of mechanisms governing the transport and enrichment of REEs in hydrothermal fluids. Full article

This paper presents an overview of approaches proposed in the scientific literature for the voltammetric determination of rare earth elements (mainly cerium and europium individually, as well as various lanthanides simultaneously) in manifold kinds of samples. The work is divided into chapters describing the most important aspects affecting the sensitivity of the proposed methods: the technique adopted (AdSV, ASV, CSV), complexing agents used, the kind of working electrode (mercury-based, noble metal or carbon electrodes) and the most popular electrode modifiers (e.g., metal film, carbon nanotubes, molecularly imprinted polymers). Analytical parameters of the procedures presented in the paper are collected in tables. The subsequent chapters are devoted to a detailed discussion of potential inorganic and organic interfering factors. The possibilities of simultaneous determination of several lanthanides in one sample and the influence of other lanthanides on the determined rare earth element were also discussed. Finally, the applications of the voltammetric procedures to the determination of rare earth metals in real samples with miscellaneous matrix is described. All analytical results were tabulated in order to compare the analytical suitability of the proposed procedures. Full article

During the Late Permian period, the coal from the Jiashun Mine in Xingren City, Guizhou Province, China, is characterized by a high sulfur (5.84%) and lithium (Li) (94.5 μg/g) content. Lithium is a critical metal in the context of global energy transition. Considering the importance of environmental protection and resource utilization, the mode of occurrence and distribution of trace elements in different coal preparation products were investigated. The obtained results indicated the following: (1) The minerals in Jiashun coal were mainly composed of veined and epigenetic pyrite, quartz, and kaolinite. Most of the minerals could be effectively removed from the cleaned coal through gravity separation. (2) The mode of occurrence of rare earth elements and yttrium (REY) in the coal was relatively complex, and they were mainly found in middlings from gravity separation and in flotation tailings. (3) The mode of occurrence of the trace elements in the coal significantly influenced their removal rate. The removal rate was significantly higher for trace elements removed through gravity separation compared to those removed using flotation. The trace elements mainly found in fine-grained minerals wrapped by organic matter or combined with organic portions had better removal results through flotation. The trace elements that occurred both in the minerals and organic matters had low removal rates (<25%) using two coal preparation methods. (4) Li was more enriched in the middlings from gravity separation (98 μg/g) and in flotation tailings (102 μg/g), reaching the marginal grade (80 μg/g) of Li in coal. (5) Li in Jiashun coal may be derived from intermediate-felsic rocks at the top of the Kangdian Upland and late hydrothermal solutions. Full article

Microbialite textures, such as microbial mats and biofilms, were observed in the Middle Triassic dolomite in the Sichuan Basin, western China, using core examination, thin section petrography, scanning electron microscopy (SEM), and geochemical analyses. The dolomite texture, consisting of fibrous and spherulitic structures, is similar in morphology and size distribution to those observed in microbial culture experiments. Extracellular polymeric substances (EPS) were identified based on the occurrence of fibers forming a reticular pattern and nanometer-sized spheroids. The rare earth element (REE) and stable isotope (C, O, and Sr) compositions of the Middle Triassic dolomite were measured to determine their geochemical characteristics. Using seawater as a standard, the dolomitic microbialites (MD) exhibited significantly positive La and Eu anomalies and higher REE concentrations and (Nd/Yb)_sn values than associated limestones, and these patterns are inferred to be related to initial complexation on organic ligands in the biofilm, as proposed by previous researchers. The ambient temperature during dolomite precipitation was estimated to be within the 23 °C to 50 °C range, as indicated by the δ¹⁸O values of the dolomite. This study suggests that various microbial effects can significantly affect diagenetic processes in the Middle Triassic dolomite. Full article

The luminescent metal-organic complexes of rare earth metals are advanced materials with wide application potential in chemistry, biology, and medicine. The luminescence of these materials is due to a rare photophysical phenomenon called antenna effect, in which the excited ligand transmits its energy to the emitting levels of the metal. However, despite the attractive photophysical properties and the intriguing from a fundamental point of view antenna effect, the theoretical molecular design of new luminescent metal-organic complexes of rare earth metals is relatively limited. Our computational study aims to contribute in this direction, and we model the excited state properties of four new phenanthroline-based complexes of Eu(III) using the TD-DFT/TDA approach. The general formula of the complexes is EuL₂A₃, where L is a phenanthroline with –2–CH₃O–C₆H₄, –2–HO–C₆H₄, –C₆H₅ or –O–C₆H₅ substituent at position 2 and A is Cl⁻ or NO₃⁻. The antenna effect in all newly proposed complexes is estimated as viable and is expected to possess luminescent properties. The relationship between the electronic properties of the isolated ligands and the luminescent properties of the complexes is explored in detail. Qualitative and quantitative models are derived to interpret the ligand-to-complex relation, and the results are benchmarked with respect to available experimental data. Based on the derived model and common molecular design criteria for efficient antenna ligands, we choose phenanthroline with –O–C₆H₅ substituent to perform complexation with Eu(III) in the presence of NO₃¯. Experimental results for the newly synthesized Eu(III) complex are reported with a luminescent quantum yield of about 24% in acetonitrile. The study demonstrates the potential of low-cost computational models for discovering metal-organic luminescent materials. Full article

To reveal the regularity of variation in the rare earth occurrence states of weathered crust elution-deposited rare earth ores, ore samples from different weathering crust layers were obtained by performing the sequential extraction procedure. The order of rare earth contents firmly obeyed the following sequence: the weathered layer > humic layer > partly weathered layer. The occurrence states of rare earth elements were mainly the ion exchange state, carbonate bound state, iron–manganese oxide state, organic binding state and residual state. The proportions of rare earth elements found in the rare earth ion exchange state of the weathered layer, humic layer and partly weathered layer were 78.55%, 73.53% and 53.88%, respectively. The light rare earth elements (LREEs) found in the rare earth ion exchange state were enriched in the upper part of the weathering crust, while the heavy rare earth elements (HREEs) were enriched in the lower part. There were also obvious negative anomalies in the content of cerium in the ion exchange state. The content of rare earth elements found in the carbonate bound state was small, and the rare earth partition pattern was basically consistent with that of the ion exchange state, which had little effect on the differentiation of the rare earth elements. The iron–manganese oxide state was mainly enriched with cerium, and the content of cerium increased with the depth of the weathering crust. The iron–manganese oxide state was the main factor causing the phenomenon of the anomaly in the cerium content. Meanwhile, the iron oxides in the iron–manganese oxide state were mainly hematite and goethite. The organic binding state mainly beneficiated yttrium and cerium by complexation and certain adsorption. The content of elements found in the rare earth residual state was related to the degree of weathering and reflected the release sequence of rare earth elements in the mineralization process. Clarifying the rare earth occurrence states is conducive to better revealing the metallogenic regularity of weathered crust elution-deposited rare earth ores. In addition, the results can provide a valuable reference for expanding the available rare earth resources and the efficient comprehensive utilization of rare earth ore. Full article

A number of alkali organometallic complexes with suitable thermodynamic properties and high capacity for hydrogen storage have been synthesized; however, few transition metal–organic complexes have been reported for hydrogen storage. Moreover, the synthetic processes of these transition metal–organic complexes via metathesis were not well characterized previously, leading to a lack of understanding of the metathesis reaction. In the present study, yttrium phenoxide and lanthanum phenoxide were synthesized via metathesis of sodium phenoxide with YCl₃ and LaCl₃, respectively. Quasi in situ NMR, UV-vis, and theoretical calculations were employed to characterize the synthetic processes and the final products. It is revealed that the electron densities of phenoxides in rare-earth phenoxides are lower than in sodium phenoxide due to the stronger Lewis acidity of Y³⁺ and La³⁺. The synthetic process may follow a pathway of stepwise formation of dichloride, monochloride, and chloride-free species. Significant decreases in K-band and R-band absorption were observed in UV-vis, which may be due to the weakened conjugation effect between O and the aromatic ring after rare-earth metal substitution. Two molecular structures, i.e., planar and nonplanar, are identified by theoretical calculations for each rare-earth phenoxide. Since these two structures have very close single-point energies, they may coexist in the materials. Full article