Lanthanide-Sensitized Upconversion Iridium Complex via Triplet Energy Transfer.

Cyclometalated iridium (Ir) complexes demonstrate impressive capabilities across a range of fields, including biology and photocatalysis, due to their tunable optical characteristics and structure flexibility. However, generating upconversion luminescence of Ir complexes under near-infrared light excitation is challenging. Herein, by employing lanthanide-doped upconversion nanoparticles (UCNPs) as the sensitizer, a new strategy is demonstrated to gain upconversion luminescence of Ir complexes via triplet energy transfer. This design relies on a rationally designed hybrid of core-shell structured NaYbF4:Tb@NaTbF4 UCNPs and new Ir phosphonate complexes, in which UCNPs can migrate upconverted energy to the surface of nanoparticles through Tb3+-mediated energy migration and then sensitize the upconversion luminescence of Ir complexes upon 980 nm excitation. Both experimental and theoretical investigations highlight the significance of triplet energy transfer from excited Tb3+ ions to the triplet state of Ir complexes in the sensitization of upconversion luminescence of Ir complexes. These findings may open exciting avenues for fabricating hybrid Ir materials with new functions and driving the development of UCNP-based nanomaterials.

Ecotoxicity of doped zinc oxide nanoparticles: Perspectives on environmental safety.

Studies on the ecotoxicity of doped zinc oxide nanoparticles (ZnO NPs) are recent, with the first publications starting in 2010. In this sense, this is the first study that comprehensively reviews the ecotoxicological effects of ZnO NPs doped with lanthanide elements to fill this literature gap. This research explores a multifaceted question at the intersection of nanotechnology, toxicology, and environmental science. Different types of dopants commonly used for ZnO doping were investigated in this review, focusing on the ecotoxicological effects of lanthanides as dopants. Bacteria were the main class of organisms used in ecotoxicological studies, since antimicrobial activity of these nanomaterials is extensively explored to combat the imminent problem of resistant bacteria, in addition to enabling the safe use of these nanomaterials for biomedical applications. Doping appears to exhibit greater efficacy when compared to undoped ZnO NPs in terms of antimicrobial effects; however, it cannot be said that it has no impact on non-target organisms. An extensive examination of the literature also establishes the importance and need to evaluate the effects of doped ZnO NPs on organisms from different environmental compartments in order to identify their potential impacts. We underscore the dearth of research information regarding the environmental toxicity/ecotoxicity of doped ZnO nanoparticles across various ecological levels, thereby limiting the extrapolation of findings to humans or other complex models. Therefore, we emphasize the urgency of a multi-parameter assessment for the development of sanitary and environmentally safe nanotechnologies.

Investigating the Influence of Impurity Defects on the Adsorption Behavior of Hydrated Sc3+ on the Kaolinite (001) Surface Using Density Functional Theory.

In natural kaolinite lattices, Al3+ can potentially be substituted by cations such as Mg2+, Ca2+, and Fe3+, thereby influencing its adsorption characteristics towards rare earth elements like Sc3+. Density functional theory (DFT) has emerged as a crucial tool in the study of adsorption phenomena, particularly for understanding the complex interactions of rare earth elements with clay minerals. This study employed DFT to investigate the impact of these three dopant elements on the adsorption of hydrated Sc3+ on the kaolinite (001) Al-OH surface. We discerned that the optimal adsorption configuration for hydrated Sc3+ is Sc(H2O)83+, with a preference for adsorption at the deprotonated Ou sites. Among the dopants, Mg doping exhibited superior stability with a binding energy of -4.311 eV and the most negative adsorption energy of -1104.16 kJ/mol. Both Mg and Ca doping enhanced the covalency of the Al-O bond, leading to a subtle shift in the overall density of states towards higher energies, thereby augmenting the reactivity of the O atoms. In contrast, Fe doping caused a pronounced shift in the density of states towards lower energies. Compared to the undoped kaolinite, Mg and Ca doping further diminished the adsorption energy of hydrated Sc3+ and increased its coordination number, while Fe doping elevated the adsorption energy. This study offers profound insights into understanding the role of dopant elements in the adsorption of hydrated Sc3+ on kaolinite.

Frustrated Lewis Pair-Type Reactivity of Intermolecular Rare-Earth Aryloxide and N-Heterocyclic Carbene/Olefin Combinations.

This work reports the cooperative reactivity of rare-earth aryloxide complexes with N-heterocyclic carbene (NHC) or N-heterocyclic olefin (NHO), showcasing their synergistic effect on the activation of H2 and diverse organic substrates. Reactions of RE(OAr)3 (RE=La, Sm, and Y; Ar=2,6-tBu2-C6H3) with unsaturated NHC ItBu (:C[N(R)CH]2, R=tBu) isolated abnormally bound RE metal NHC complexes RE/aNHC. In contrast, no metal-NHO adducts were formed when RE(OAr)3 were treated with NHO (R2C=C[N(R)C(R)]2, R=CH3). Both RE/aNHC and RE/NHO Lewis pairs enabled cooperative H2 activation. Furthermore, RE(OAr)3 were found to catalyze the hydrogenation of the exocyclic C=C double bond of NHO under mild conditions. Moreover, treatment of the La/aNHC complex with benzaldehyde produced a La/C4 1,2-addition product. The La/NHO Lewis pair could react with (trimethylsilyl)diazomethane and α, ß-conjugated imine, affording an isocyanotrimethylsilyl lanthanum amide complex and a La/C 1,4-addition product, respectively.

Rare Earths-The Answer to Everything.

Rare earths, scandium, yttrium, and the fifteen lanthanoids from lanthanum to lutetium, are classified as critical metals because of their ubiquity in daily life. They are present in magnets in cars, especially electric cars; green electricity generating systems and computers; in steel manufacturing; in glass and light emission materials especially for safety lighting and lasers; in exhaust emission catalysts and supports; catalysts in artificial rubber production; in agriculture and animal husbandry; in health and especially cancer diagnosis and treatment; and in a variety of materials and electronic products essential to modern living. They have the potential to replace toxic chromates for corrosion inhibition, in magnetic refrigeration, a variety of new materials, and their role in agriculture may expand. This review examines their role in sustainability, the environment, recycling, corrosion inhibition, crop production, animal feedstocks, catalysis, health, and materials, as well as considering future uses.

Bimetallic Synergy Enables Silole Insertion into THF and the Synthesis of Erbium Single-Molecule Magnets.

The potassium silole K2 [SiC4 -2,5-(SiMe3 )2 -3,4-Ph2 ] reacts with [M(η8 -COT)(THF)4 ][BPh4 ] (M=Er, Y; COT=cyclo-octatetraenyl) in THF to give products that feature unprecedented insertion of the nucleophilic silicon centre into a carbon-oxygen bond of THF. The structure of the major product, [(µ-η8 : η8 -COT)M(µ-L1 )K]∞ (1M ), consists of polymeric chains of sandwich complexes, where the spiro-bicyclic silapyran ligand [C4 H8 OSiC4 (SiMe3 )2 Ph2 ]2- (L1 ) coordinates to potassium via the oxygen. The minor product [(µ-η8 : η8 -COT)M(µ-L1 )K(THF)]2 (2M ) features coordination of the silapyran to the rare-earth metal. In forming 1M and 2M , silole insertion into THF only occurs in the presence of potassium and the rare-earth metal, highlighting the importance of bimetallic synergy. The lower nucleophilicity of germanium(II) leads to contrasting reactivity of the potassium germole K2 [GeC4 -2,5-(SiMe3 )2 -3,4-Me2 ] towards [M(η8 -COT)(THF)4 ][BPh4 ], with intact transfer of the germole occurring to give the coordination polymers [{η5 -GeC4 (SiMe3 )2 Me2 }M(η8 -COT)K]∞ (3M ). Despite the differences in reactivity induced by the group 14 heteroatom, the single-molecule magnet properties of 1Er , 2Er and 3Er are similar, with thermally activated relaxation occurring via the first-excited Kramers doublet, subject to effective energy barriers of 122, 80 and 91 cm-1 , respectively. Compound 1Er is also analysed by high-frequency dynamic magnetic susceptibility measurements up to 106  Hz.

New insights on scandium separation from scandium concentrate with titanium dioxide wastewater.

In this study, a scandium concentrate with Sc2O3 content of 66.24 g/t was obtained from V-Ti magnetite tailings by physical concentration, and the main Sc-bearing minerals were augite and hornblende. A novel process of roasting and leaching was proposed to extract scandium from scandium concentrate with titanium dioxide wastewater. Scandium concentrate was pretreated by roasting, and titanium dioxide wastewater was used to directly leach scandium from the roasted ore. The effects of roasting and leaching parameters such as roasting temperature, roasting time, roasting agents, leaching temperature, leaching time, liquid-to-solid ratio, and leaching agents on scandium separation were thoroughly researched in the experimental procedure. The results show that a scandium leaching efficiency of 85.89% was obtained, and the scandium content of leaching residue decreased to 9.31 g/t under the optimal conditions: a roasting temperature of 1123 K, a roasting time of 120 min, a leaching temperature of 343 K, a leaching time of 120 min, and a m (titanium dioxide wastewater)∶m (roasted ore)∶m (ammonium fluoride) ratio of 8∶1∶0.09. The main findings of the scandium separation mechanism show that Sc-bearing minerals can effectively decompose and release scandium element after roasting, and created favorable conditions for scandium leaching with titanium dioxide wastewater to achieve the purpose of scandium recovery.

Biocompatible Silica-Coated Europium-Doped CsPbBr3 Nanoparticles with Luminescence in Water for Zebrafish Bioimaging.

Cesium lead halide (CsPbX3, X = Br, Cl, and I) nanocrystals (NCs) are widely concerned and applied in many fields due to the excellent photoelectric performance. However, the toxicity of Pb and the loss of luminescence in water limit its application in vivo. A stable perovskite nanomaterial with good bioimaging properties is developed by incorporating europium (Eu) in CsPbX3 NCs followed with the surface coating of silica (SiO2) shell (CsPbX3:Eu@SiO2). Through the surface coating of SiO2, the luminescence stability of CsPbBr3 in water is improved and the leakage of Pb2+ is significantly reduced. In particular, Eu doping inhibits the photoluminescence quantum yield reduction of CsPbBr3 caused by SiO2 coating, and further reduces the release of Pb2+. CsPbBr3:Eu@SiO2 nanoparticles (NPs) show efficient luminescence in water and good biocompatibility to achieve cell imaging. More importantly, CsPb(ClBr)3:Eu@SiO2 NPs are obtained by adjusting the halogen components, and green light and blue light are realized in zebrafish imaging, showing good imaging effect and biosafety. The work provides a strategy for advanced perovskite nanomaterials toward biological practical application.

A comprehensive calibration of integrated magnetron sputtering and plasma enhanced chemical vapor deposition for rare-earth doped thin films.

A new integrated deposition system taking advantage of magnetron sputtering and electron cyclotron-plasma enhanced chemical vapour deposition (IMS ECR-PECVD) is presented that mitigates the drawbacks of each fabrication system. This tailor-made system provides users with highly homogeneous and pure thin films with less undesired hydrogen and well-controlled rare-earth concentration compared to existing methods of rare-earth doping, such as metalorganic powders, sputtering, and ion implantation. We established the first comprehensive report on the deposition parameters of argon flow and sputtering power to achieve desired rare-earth concentrations in a wide composition range of terbium (Tb) doped-silicon oxide (Tb:SiOx) matrices including silicon-rich (x < 2), oxygen-rich (x > 2), and stoichiometric silicon oxide (x = 2). The deposition parameters to fabricate crystalline structure (Tb2Si2O7) in oxygen-rich samples are reported where Tb ions are optically active. IMS ECR-PECVD pushes the solubility limit of the rare-earth dopant in silicon films to 17 at.% for the desired future nanophotonic devices. Supplementary Information: The online version contains supplementary material available at 10.1557/s43578-023-01207-2.

Regulating Electrostatic Interactions toward Thermoresponsive Hydrogels with Low Critical Solution Temperature.

Low critical solution temperature (LCST) of commonly used thermoresponsive polymers in water is basically dominated by hydrophobic interactions. Herein, a novel thermoresponsive system based on electrostatic interactions is reported. By simply loading aluminum chloride (AlCl3 ) into non-responsive poly(2-hydroxyethyl acrylate) (PHEA) hydrogels, PHEA-Al gels turn to have reversible thermoresponsive behavior between transparent and opaque without any volume change. Further investigations by changing metal ion-polymer compositions unravel the necessity of specific electrostatic interactions, namely, cation-dipole bonding interactions between hydroxy groups and trivalent metal ions. The thermoresponsive hydrogel demonstrates high transparency (≈95%), excellent luminous modulation capability (>98%), and cyclic reliability, suggesting great potential as an energy-saving material. Although LCST control by salt addition is widely known, salt-induced expression of thermoresponsiveness has barely been discussed before. This design provides a new approach of easy fabrication, low cost, and scalability to develop stimuli-responsive materials.

Facile Synthesis of Anhydrous Rare-Earth Trichlorides from their Oxides in Chloridoaluminate Ionic Liquids.

Wide applications of anhydrous rare-earth (RE) trichlorides RECl3 in organometallic chemistry, for the synthesis of optical and magnetic materials, and as catalysts require a facile approach for their synthesis. The known methods use or produce toxic substances, are complicated and have limited reliability and upscaling. It has been shown that task-specific ionic liquids (ILs) can dissolve many metal oxides without special reaction conditions at moderate temperature, making the metals accessible to downstream chemistry. Using imidazolium chloridoaluminate ILs, pure crystalline anhydrous RECl3 (RE=La-Nd, Sm-Dy) can be synthesized in one step from RE oxides in high yield. The Lewis acidic IL acts as solvent and reaction partner. The by-product [Al4 O2 Cl10 ]2- , which was detected spectroscopically, remains in solution. The reacted IL can be removed quantitatively by washing. ILs with various imidazolium cations and AlCl3 content and the effect of temperature and reaction time were tested.

Environmental risk of ion-absorbed rare earth ores: concentration of leaching agent and fractionation of Pb.

Rare earth (RE) is an important strategic resource; however, there has been a growing concern about the environmental problems caused by RE mining, such as ammonia nitrogen pollution and heavy metal pollution. There is a limited research about the behavior of leaching agents and the fractionation of RE and heavy metal during the mining process for ion adsorption of rare earth ore (IRE-ore) in the previously available papers. In this study, (NH4)2SO4 solution, which commonly used in the production of mining IRE-ore, was used as a leaching agent. The adsorption behavior of ore soils on ammonium ions was explored by batch experiments. The adsorption process of IRE-ore on ammonium ions followed a pseudo-second-order equation and was controlled by the kinetics of surface adsorption and intra-particle diffusion; the ammonium ion adsorption isotherm conformed to the Freundlich isotherm equilibrium equation, and the higher concentration advantage made the ore soils possess a higher adsorption capacity of ammonium ion. In addition, the fractionation characteristics of lanthanum (La), cerium (Ce), and lead (Pb) in the ore soil during the leaching process were simulated based on the batch and column leaching experiments. The results demonstrated that the exchangeable states of La and Ce in IRE-ore were high, and the exchangeable, carbonate-bound La and Ce were almost all leached out by (NH4)2SO4 leaching agent, while the most of exchangeable Pb flowed out along with leaching agent, and a small amount of leached Pb in the ore soil was converted to iron and manganese oxide-bound Pb and enriched in the direction of migration of the leaching solution, and when the environment (e.g., pH and Eh) changed, this part of Pb may be re-activated. Our research might serve as crucial baseline knowledge for the adsorption of ammonium ions by ore soils, and provide a data reference for reducing the use of leaching agents and developing sustainable technologies for green mining of ion-adsorption RE ores.

Correlation between the particle size, structural and photoluminescence spectra of nano NiCr2O4 and La doped NiCr2O4 materials.

Nano NiCr2O4 undoped and La doped NiCr2O4 nanorods array were successfully prepared by solution based conventional method[sbcm]. The synthesized samples were characterized by the diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) spectroscopy for finding optical properties. Further, the samples structure confirmed by Fourier transforms infrared (FTIR), and X-ray diffraction (XRD)techniques. High-resolution transmission electron microscopy (HRTEM) analysis revealed the attachment of NiCr2O4 nanorods on surface of nanoparticles. From the results, it was found that the reaction time, band gap energy, and particle size strongly influenced by changing the concentration of La in NiCr2O4. This work is notable for its examination of the impact of the precursor on the optical and structural characteristics of samples of La-doped and undoped NiCr2O4. This was the first time the investigation had been done. The average particle size of the La-doped and undoped NiCr2O4 samples is between 16 and 24 nm.

Passive surveillance of wild fauna in northwestern Italy: a possible cognitive approach through geographical district study and fur elementary analysis.

The analysis of animal hair is a useful and non-invasive investigation method for monitoring metal content, whose beginning dates to a few decades ago. This study addresses the issue of wildlife mortality in Piedmont and Aosta Valley by linking the evidence to the characteristics of the territories and to hair elemental profile. The considered animal species were badger, fox, marten, and wolf. The quantitative data for 11 trace metals and 16 lanthanides were evaluated considering animal location and death causes regarding impacts, whose relevant number was confined to the Turin province and to the badger and fox species. The evaluation of the analytical results was performed after the out of bounds sample identification by mean of statistics. For trace metals, some areas have thus been identified, mainly in Turin province, in which the large excess of As, Cd, and Pb was related to district pollution. Moreover, the lower contents of Fe, Mn, and Al in Aosta Valley badgers' hair seem influenced by the different characteristics of the subsoil, in comparison to Piedmont, and a relationship with the living environment and the habits was suggested. Regarding lanthanides, Biella province represents an area in which environmental contamination and abundance of rare-earth elements was recorded.

A review of flotation reagents for bastnäsite-(Ce) rare earth ore.

Given the indispensability and immense value of rare earth elements for scientific and technological advancements in the 21st century, extracting high-quality rare earth resources from nature has become a global priority. Bastnäsite-(Ce) is one of the known rare earth minerals with high rare earth content and wide distribution, which occupies a pivotal position in human life and high-end production activities, making its efficient development and utilization crucial. In recent years, research on separating bastnäsite-(Ce) from gangue minerals has focused on the flotation process, with flotation reagents playing a critical role in achieving effective separation. This paper provides a detailed summary of current research on the behavior of bastnäsite-(Ce) flotation agents on minerals, their interaction with mineral surfaces during flotation separation, and outlines future prospects for further research.

A New Ultrafine Luminescent La2O3:Eu3+ Aerogel.

This paper reports on the synthesis and characterization of La2O3:Eu3+ luminescent aerogels fabricated by the sol-gel method and the supercritical drying technique. The % mol concentration of the Eu3+ ion was varied to study the effects on the luminescent properties of the aerogels. XRD and TEM analysis showed that the La2O3:Eu3+ aerogels exhibited a semi-crystalline behavior regardless of whether the concentration of europium was increased. SEM micrographs revealed a porous structure in the aerogels, which were composed of quasi-spherical nanoparticles that were interconnected and formed coral-shaped agglomerates. Photoluminescence spectroscopy characterization showed that the aerogels had an infrared emission located at λ = 793 nm, and the maximum photoluminescence emission intensity was observed for the aerogel with 50% Eu3+. The results demonstrate that, without heat treatment, it is possible to manufacture luminescent aerogels of rare-earth oxides that can be used in opto-electronic devices.

Environmentally Friendly Approach for Nd2Fe14B Magnetic Phase Extraction by Selective Chemical Leaching: A Proof-of-Concept Study.

The green transition initiative has exposed the importance of effective recycling of Nd-Fe-B magnets for achieving sustainability and foreign independence. In this study, we considered strip-cast, hydrogenated, jet-milled Nd-Fe-B powder as a case study to explore the potential for selective chemical leaching of the Nd-rich phase, aiming to extract the Nd2Fe14B matrix phase. Diluted citric and nitric acids at concentrations of 0.01, 0.1, and 1 M were considered potential leaching mediums, and the leaching time was 15 min. Microstructural investigation, magnetic characterization, and elemental compositional analysis were performed to investigate leaching efficiency and selectivity. Based on SEM analysis, Nd/Fe ratio monitoring via ICP-MS, and the high moment/mass value at 160 emu/g for the sample leached with 1 M citric acid, 1 M citric acid proved highly selective toward the Nd-rich phase. Exposure to nitric acid resulted in a structurally damaged Nd2Fe14B matrix phase and severely diminished moment/mass value at 96.2 emu/g, thus making the nitric acid unsuitable for selective leaching. The presence of hydrogen introduced into the material via the hydrogen decrepitation process did not notably influence the leaching dynamics. The proposed leaching process based on mild organic acids is environmentally friendly and can be scaled up and adopted for reprocessing industrial scrap or end-of-life Nd-Fe-B magnets to obtain single-phase Nd-Fe-B powders that can be used for novel magnet-making.

Electrochemical and Structural Characterization of Lanthanum-Doped Hydroxyapatite: A Promising Material for Sensing Applications.

In the quest to find powerful modifiers of screen-printed electrodes for sensing applications, a set of rare earth-doped Ca10-xREx(PO4)6(OH)2 (RE = La, Nd, Sm, Eu, Dy, and Tm and x = 0.01, 0.02, 0.10, and 0.20) hydroxyapatite (HAp) samples were subjected to an in-depth electrochemical characterization using electrochemical impedance spectroscopy and cyclic and square wave voltammetry. Among all of these, the inorganic phosphates doped with lanthanum proved to be the most reliable, revealing robust analytical performances in terms of sensitivity, repeatability, reproducibility, and reusability, hence paving the way for their exploitation in sensing applications. Structural data on La-doped HAp samples were also provided by using different techniques, including optical microscopy, X-ray diffraction, Rietveld refinement from X-ray data, Fourier transform infrared, and Raman vibrational spectroscopies, to complement the electrochemical characterization.

Thermoluminescence studies of zinc borate (ZnB2 O4 ) phosphor doped with rare earths for dosimetric aspects.

A series of ZnB2 O4 phosphors doped with different concentrations of Eu and Dy (0.05 0.1, 0.2, 0.5, 1.0 mol%) and co-doped with Ce (1, 2, 5, 7, 10 mol%) respectively was prepared via the solid-state reaction technique and the thermoluminescence (TL) behaviour of gamma ray-irradiated samples was studied. The synthesized samples were irradiated with γ-rays for the dose range 0.03-1.20 kGy. The TL intensity variations with dose, dopant concentration, and the effect of co-doping were studied. The TL response curves for ZnB2 O4 :Eu3+ and ZnB2 O4 :Dy3+ , ZnB2 O4 :Eu3 ,Ce3+ and ZnB2 O4 :Dy3+ ,Ce3+ phosphor were observed. It was revealed that ZnB2 O4 :Eu3+ showed a linear TL behaviour for the dose 0.03-1.20 kGy and ZnB2 O4 :Dy3+ showed linearity for the gamma dose range 0.03-0.10 kGy. Furthermore, fading for all the samples was observed to be less than 10% for a storage period of 30 days. In addition to this, the trapping parameters, especially activation energies were evaluated using the Ilich method and the initial rise method. The activation energy values obtained from both methods were in complete agreement with each other.

Dynamics of the Ligand Excited States Relaxation in Novel ß-Diketonates of Non-Luminescent Trivalent Metal Ions.

Complexes emitting in the blue spectral region are attractive materials for developing white-colored light sources. Here, we report the luminescence properties of novel coordination compounds based on the trivalent group 3, 13 metals, and the 1-phenyl-3-methyl-4-cyclohexylcarbonyl-pyrazol-5-onate (QCH) ligand. [M(QCH)3] (M = Al, Ga, and In), [M(QCH)3(H2O)] (M = Sc, Gd, and Lu), [Lu(QCH)3(DMSO)], and [La(QCH)3(H2O)(EtOH)] complexes were synthesized and structurally characterized by a single-crystal X-ray diffraction study. It has been found that the luminescence quantum yields of the ligand increase by one order of magnitude upon metal coordination. A significant correspondence between the energies of the ligand's excited states and the luminescence quantum yields to the metal ion's atomic numbers was found using molecular spectroscopy techniques. The replacement of the central ion with the heavier one leads to a monotonic increase in singlet state energy, while the energy of the triplet state is similar for all the complexes. Time-resolved measurements allowed us to estimate the intersystem crossing (ISC) rate constants. It was shown that replacing the Al3+ ion with the heavier diamagnetic Ga3+ and In3+ ions decreased the ISC rate, while the replacement with the paramagnetic Gd3+ ion increased the ISC rate, which resulted in a remarkably bright and room-temperature phosphorescence of [Gd(QCH)3(H2O)].