Trivalent Lanthanide Ions Research Articles

Achieving Bright Up‐Conversion Luminescence of Eu3⁺ and Tb3⁺ Ions within Coordination Polymers

AbstractAchieving the up‐conversion luminescence (UCL) centered around trivalent lanthanide (Ln3+) ions in coordination polymers (CPs) is extremely challenging. Herein, Yb3⁺‐doped Ln‐CPs of [Eu1‐xYbx(pfbz)2(phen)Cl] (x = 0.3, namely 3; x = 0.5, namely 4; x = 0.7; namely 5), and [Tb1‐xYbx(pfbz)2(phen)Cl] (x = 0.2, namely 6; x = 0.5, namely 7; x = 0.6, namely 8) are reported by doping Yb3⁺ into Ln‐CPs of [Ln(pfbz)2(phen)Cl] (Ln = Eu, 1; Ln = Tb, 2). Both 5 and 8 visually exhibit excellent cooperative sensitization UCL of Eu3⁺ and Tb3⁺ ions, while 5 represents the first instance of an Ln‐CP where the UCL of Eu3⁺ ion is visually observable. Investigations into the UCL of these CPs reveal that the energy transfer is achieved through direct energy transfer from two individual Yb3⁺ ions, marking the first time such a mechanism has been employed in UCL in Eu/Tb‐CPs.

Photoluminescence and scintillation properties of rare earth doped Lu2O3 single crystal grown by floating zone method

A series of Lu2O3 single crystals doped with rare earth (RE) ions (RE = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb, dopant concentrations are 1 %) was synthesized by the floating zone method. Their photoluminescence (PL) and scintillation properties were evaluated. In PL, emissions due to 4f-4f transitions of trivalent rare earth ions were observed, and those doped with Nd3+, Eu3+, Tb3+ and Er3+ showed the highest emission intensities among the samples. As a scintillation property, those doped with Eu, Gd, and Dy showed a clear photoabsorption peak under 137Cs 662 keV γ-ray irradiation. Among them, the Eu3+-doped Lu2O3 showed the highest scintillation light yield of 67000 photons/MeV. The current work conducted the first systematic study of rare earth doped Lu2O3 single crystals grown by the floating zone method.

Efficient separation of Chromium(III) from Lanthanide(III) via reductive boronization in molten chloride

It is an easy way to recover metals in molten salt by the precipitation-based method, but the selectivity yet remains challenging. Herein, a new separation method employing reductive boronization is proposed, and it is validated by the separation of trivalent chromium and lanthanide ions in molten LiCl-KCl. Although no Cr(III) and La(III) separation was achieved by using NaBH4, Cr(III) was successfully removed via the formation of insoluble CrB2 when B powder was used as the boronization reagent with La(III) remaining entirely in the melt. More than 97% Cr(III) can be removed from the CrCl3-LaCl3-LiCl-KCl melt after a reaction time of 300 min, and the removal rate was retained when the La/Cr ratio varied from 0.1:1 to 10:1. Such reductive boronization method is also valid in other Ln(III)/Cr(III) systems. The boronization process involves the reduction of Cr(III) and the reaction between zero valent metal and boron rather than the simple combination of anions and cations to give precipitates as evidenced by the XPS analyses. The difference in reactivity between Cr(III) and La(III) toward B can be rationalized in terms of their significant difference in the ΔG values of the boronization reactions that mainly correlates with the much lower reduction potential of La(III)/La(0), which makes B an ideal boronization reagent for the separation of trivalent chromium and lanthanide ions in molten chloride.

Wide Range Near-Zero Thermal Quenching of Orange-Yellow Phosphor via Impeding Self-Oxidation of Eu2+ for Versatile Optoelectronic Applications.

Li2SrSiO4:Eu2+ is a promising substitute for traditional Y3Al5O12:Ce3+ (YAG:Ce3+) owing to its strong orange-yellow emission of 4f-5d transition originating from Eu2+ dopant, covering the more red-light region. However, its inevitable luminescence thermal quenching at high temperatures and the self-oxidation of Eu2+ strongly impede their applications. Their remediation remains highly challenging. Herein, an anti-self-oxidation(ASO) concept of Eu2+ in Li2SrSiO4 substrate by adding trivalent rare-earth ions (A3+: A = La, Gd, Y, Lu) for highly efficient and stable orange-yellow light emission have been proposed. A significantly increased orange-yellow emission (202% improvement) from Li2Sr0.95A0.05SiO4:Eu2+ with a wide range near-zero thermal quenching is obtained, superior to other Eu2+ activated phosphors. The presence of A3+ ions with various radii modifies the ASO degree of Eu2+ ions, achieving the tunable chemical state, composition, electronic configuration, crystal-field strength, and luminescent characteristics of the developed phosphors. For the proof of the concept, a W-LED device and a PDMS (Polydimethylsiloxane) luminescent film are fabricated, endowing excellent luminescence performance and thermal stability and the huge application prospects of Li2SrSiO4:Eu2+ in lighting and display fields.

6-(6-Methyl-1,2,4,5-Tetrazine-3-yl)-2,2'-Bipyridine: A N-Donor Ligand for the Separation of Lanthanides(III) and Actinides(III).

Here, we report the synthesis of the 6-(6-methyl-1,2,4,5-tetrazine-3-yl)-2,2'-bipyridine (MTB) ligand that has been developed for lanthanide/actinide separation. A multimethod study of the complexation of MTB with trivalent actinide and lanthanide ions is presented. Single-crystal X-ray diffraction measurements reveal the formation of [Ce(MTB)2(NO3)3], [Pr(MTB)(NO3)3H2O], and [Ln(MTB)(NO3)3MeCN] (Ln = Nd, Sm, Eu, Gd). In addition, the complexation of Cm(III) with MTB in solution was studied by time-resolved laser fluorescence spectroscopy. The results show the formation of [Cm(MTB)1-3]3+ complexes, which occur in two different isomers. Quantum chemical calculations reveal an energy difference between these isomers of 12 kJ mol-1, clarifying the initial observations made by time-resolved laser fluorescence spectroscopy (TRLFS). Furthermore, quantum theory of atoms in molecules (QTAIM) analysis of the Cm(III) and Ln(III) complexes was performed, indicating a stronger covalent contribution in the Cm-N interaction compared to the respective Ln-N interaction. These findings align well with extraction data showing a preferred extraction of Am and Cm over lanthanides (e.g., max. SFAm/Eu = 8.3) at nitric acid concentrations <0.1 mol L-1 HNO3.

Newly synthesised diglycolamide functionalised silica gel with terminal 2-ethylhexyl alkyl chain, Silica-DGA (2EH) having high ligand density for adsorption of trivalent actinide and lanthanide from acidic medium

A novel diglycolamide resin with 2-ethylhexyl terminal alkyl chain functionalised to silica gel was synthesised and characterised by ATR-FTIR, SEM, TG/DSC, &13C (CP/MAS) solid state NMR techniques. Effective functionalization of the organic ligand upon silica gel was confirmed from the two carbonyl stretching frequencies at 1735 cm−1 and 1619 cm−1 in the FTIR spectrum and carbonyl carbon atom signal at 170 ppm in 13C (CP/MAS) solid state NMR spectrum. Thermo gravimetric measurement showed 17.3 ± 0.2 % (W/W) weight loss corresponding to the ligand loading value of 425 µmol/g. The resin showed very high uptake of trivalent lanthanide and actinide ions from 4.0 M HNO3 medium and very low distribution of Cs & Sr; Kd ∼ 1.1×103 mL/g for Am(III), ∼ 1.41×103 mL/g for Eu(III), ∼2.5 mL/g for Sr and 1.53 mL/g for Cs. FTIR spectroscopic study of the Eu3+ adsorbed resin showed single carbonyl stretching frequency at 1654 cm−1, instead of the two carbonyl stretching frequencies in fresh silica-DGA(2EH) resin indicating complexation through carbonyl oxygen. Very low Kd of ∼1.2–5.1 mL/g for lanthanides/actinides from 4.0 M HNO3 containing water soluble DGA namely N, N, N, N, Tetraethyldiglycolamide (TEDGA) in the concentration range 0.3–0.1 M indicates 99 % back adsorption feasibility.

Facile sol–gel synthesis of trivalent Al3+-Gd3+ ions co-doped nanoscale cobalt spinel ferrite for magneto-electronic applications

The magnetic spinel ferrites nanomaterials simultaneously doped with multivalent cations have gained a lot of interest from many researchers during the last decade. Also, the doping of trivalent rare-earth ions in spinel ferrites is promising for many technological applications. Considering these facts, in this work we investigated the trivalent Al3+-Gd3+ ions co-doped cobalt ferrite nanoparticles with nominal composition as CoFe2-2xAlxGdxO4 (x = 0.00, 0.03, 0.05, 0.07, 0.10). The sol–gel auto ignition route assisted by citric acid as a chelating agent was utilized to synthesize the series of nanoparticles. The Rietveld refined X-ray diffraction (XRD) patterns were analyzed to ensure the single-phase formation of nanoparticles with spinel cubic structure. The spherical-shaped grain morphology of the nanoparticles was indicated by scanning electron microscopy (SEM) images. The elemental analysis obtained by energy dispersive X-ray analysis (EDAX) revealed stoichiometric formation of the samples along with high purity. The two prominent frequency modes analogous to the spinel ferrite structure were noted in the infrared spectra assuring the successful formation of all the samples. The soft magnetic behaviour with a lower coercivity of the prepared nanoparticles was confirmed by the vibrating sample magnetometer (VSM) technique. The DC electrical resistivity plots indicated that resistivity decreases with an increase in Al3+-Gd3+ co-doping. The dielectric studies of all the samples showed increasing behaviour with an increase in Al3+-Gd3+ co-doping. All the results suggest that the Al3+-Gd3+ co-doped cobalt ferrite nanoparticles can be useful for real-world applications, specifically in nanoelectronics devices.

Rare Earth Element Binding and Recovery by a Beta Roll-Forming RTX Domain.

The Block V of the RTX domain of the adenylate cyclase protein from Bordetella pertussis is disordered, and upon binding eight calcium ions, it folds into a beta roll domain with a C-terminal capping group. Due to their similar ionic radii and coordination geometries, trivalent lanthanide ions have been used to probe and identify calcium-binding sites in many proteins. Here, we report using a FRET-based assay that the RTX domain can bind rare earth elements (REEs) with higher affinities than calcium. The apparent disassociation constants for lanthanide ions ranged from 20 to 75 μM, which are an order of magnitude higher than the affinity for calcium, with a higher selectivity toward heavy REEs over light REEs. Most proteins release bound ions at mildly acidic conditions (pH 5-6), and the high affinity REE-binding lanmodulin protein can bind 3-4 REE ions at pH as low as ∼2.5. Circular dichroism (CD) spectra of the RTX domain demonstrate pH-induced folding of the beta roll domain in the absence of ions, indicating that protonation of key amino acids enables structure formation in low pH solutions. The beta roll domain coordinates up to four ions in extreme pH conditions (pH < 1), as determined by equilibrium ultrafiltration experiments. Finally, to demonstrate a potential application of the RTX domain, REE ions (Nd3+ and Dy3+) were recovered from other non-REEs (Fe2+ and Co2+) in a NdFeB magnet simulant solution (at pH 6).

Manipulating and investigating the room-temperature magnetic memory phenomenon: The impact of rare-earth ion doping on nickel oxide nanoparticles

This study investigates the relationship between point defect density and magnetic properties in nickel oxide (NiO) nanoparticles (NPs). Specifically, we explore the effects of 0.5 % trivalent rare-earth ion (RE3+: Ce3+, Pr3+, Nd3+, Sm3+, and Dy3+) doping on NiO NPs, considering the influence of RE3+ ionic radius on structural modulation and magnetic properties. Our findings reveal important trends: increased microstrain (0.08 %–0.17 %) and decreased crystalline size (36–17 nm) with increasing ionic radius (r = 0.91 to 1.01 Å), along with a preference for growth along the (1 1 1) plane over (2 0 0). Additionally, multivalent point defects increase with the increase of ionic radius. Substituting Ni2+ site with RE3+ ion promotes nearest-neighbor weak ferromagnetic interaction over next-nearest-neighbor strong antiferromagnetic (AF) interaction. This leads to a redshift of two magnons (2 M) frequency by 50 cm−1 and enhanced room temperature (RT) magnetization (0.23–0.43 emu/g) with increasing ionic radius. Ce-doped NiO (r = 1.01 Å) shows the smallest crystalline size (17 nm), maximum 2 M redshift, and enhanced RT magnetization (0.43 emu/g) based on interacting bound magnetic polaron model. Ce-, Pr-, Nd-, and Sm-doped NiO NPs exhibit RT magnetic memory effects, while Dy-doped NiO NPs (r = 0.912 Å) display AF properties. Our analysis provides valuable insights for designing RT magnetic memory materials with tailored properties through suitable RE3+ ion substitutions.

Mass Transfer Process by Diffusion of RE(III) (RE=La, Pr) in Eutectic LiCl-KCl Salt

Mass transfer is an important link in the entire electrode process. To investigate mass transfer process by diffusion of trivalent rare Earth ions in molten LiCl-KCl system, the electroreduction mechanism, mass transfer kinetics and diffusion layer thicknesses of RE(III) (RE = La and Pr) were studied by a series of electrochemical methods. It was found that RE(III) underwent one-step reduction reaction with the exchange of 3-electron and reversible processes. The diffusion coefficients (D) of RE(III) and limiting current densities (j l ) for RE(III)/RE pair were measured at different temperatures and concentrations by cyclic voltammetry and chronoamperometry, respectively. Based on the results of D and j l , the diffusion layer thickness (δ) of RE(III) was calculated using the simplified Nernst-Planck formula. Furthermore, the impacts of temperature and concentration on δ were explored. The results indicated that as the temperature declined and ions concentration increased, δ decreased. Meanwhile, the relationships between δ and temperature and concentration were also obtained.

Investigation of the sensitization effect of Yb3+ in Yb, Er co-doped Sr5(PO4)3F transparent ceramics: From single-band red upconversion to temperature sensing behavior

Lanthanide-ion-doped red upconversion (UC) fluorescent materials with excellent signal-to-noise ratio, stability, and red-green luminous intensity ratio have proven of tremendous research importance for biomedical, three-dimensional (3D) displays, sensors, and other sectors. In this study, xYb, 1Er: Sr5(PO4)3F (S-FAP) (x=0–5 at%) transparent ceramics with outstanding optical quality were fabricated by hot pressing the co-precipitation powder with high sintering activity. The energy dispersive X-ray (EDX) results showed that the trivalent lanthanide ions were evenly doped into the S-FAP ceramic lattice. Increased Yb3+ doping considerably restricted the growth of ceramic grain size, which should be attributable to a decrease in sintering activity under high Yb doping conditions. The co-doping of Yb3+ successfully resulted in a significant improvement in up/down conversion efficiency via effective energy transfer mechanisms and the optimization of the electron population at the energy level of red-green emission. Furthermore, single-band red upconversion luminescence with the greatest red-green upconversion luminescence integral intensity ratio of 125.74 was discovered under 980 nm laser pumping at room temperature. The energy transition process involved in the phenomenon of the up-conversion luminescence intensity shift of red-green emission has been thoroughly examined. Finally, the noncontact optical thermometric ability based on fluorescence intensity ratio (FIR) technology showed that the maximum absolute sensitivity (Sa) of the 5Yb1Er sample in the temperature range of 320–556 K is 1.1×10−3 K−1, implying the possible use of Yb/Er-doped S-FAP transparent ceramics in the field of optical thermometers.

S+E+O-band luminescence and enhancement in Nd3+/Tm3+/Ce3+ doped tellurite glass

A new, to our knowledge, doped combination of Nd3+, Tm3+, and Ce3+ ions was developed in tellurite glass with a fundamental composition of TeO2-ZnO-WO3-Bi2O3, and the structural, thermal, and especially near-infrared (NIR) luminescent properties in O-, E-, and S-bands were explored. The XRD pattern confirmed the amorphous nature of synthesized tellurite glass, the Raman spectrum disclosed different structural units that make up the glass network, the DSC curve confirmed good host thermal stability, while XPS measurement revealed that cerium mainly exists in the trivalent form in a glass network. Upon being pumped with an 808 nm laser, a 1.34 µm band fluorescence from Nd3+:4F3/2level→4I13/2 level transition and a 1.46 µm band fluorescence from Tm3+:3H4level→3F4 level transition were observed, which in turn formed a wide luminescence band from 1260 to 1560 nm in the tellurite glass containing both Nd3+ and Tm3+ ions owing to their spectral overlapping. The measured full width at half maximum (FWHM) for the aforementioned wideband luminescence was about 203 nm with Nd2O3 and Tm2O3 concentrations of 0.015 mol. % and 0.5 mol. %, respectively, and exhibited a further ∼60% increase in peak intensity after the incorporation of 0.4 mol. % amount of CeO2, which arises from the phenomena of cross relaxation and energy transfer among the three trivalent rare earth ions. The experimental evidence presented in this work shows that tellurite glass containing Nd3+, Tm3+, and Ce3+ has potential as an active material for S-, E-, and O-band wideband luminescence.

From Dopant to Host: Solution Synthesis and Light‐Emitting Applications of Organic‐Inorganic Lanthanide‐Based Metal Halides

The rich and unique energy level structure arising from 4fn inner shell configuration of trivalent lanthanide ions (Ln3+) renders them highly attractive for light‐emitting applications. Currently, research primarily focuses on Ln3+ doping in either traditional garnets or the recently developed perovskite phosphors. However, there have been few reports on stable phosphors crystallized with pure lanthanide elements. Herein, a universal solution‐based route to eight Ln3+‐based metal halides from the organic‐inorganic A4LnX7 family is described, where A+ = 4,4‐difluoropiperidinium (DFPD+), Ln3+ = Nd3+, Eu3+, Ho3+, Sm3+, Tm3+, Tb3+, Yb3+, Er3+, and X− = Cl−, Br−. Visible photoluminescence (PL) is observed from Tb3+‐, Eu3+‐, Ho3+‐, and Sm3+‐based compounds with Tb and Eu compositions exhibiting high PL quantum yields of 90–100%; Nd3+‐, Tm3+‐, Yb3+‐, and Er3+‐based crystals show fascinating near‐infrared emission. Light‐emitting diodes (LEDs) fabricated with (DFPD)4TbCl7 yield characteristic emission of Tb3+, representing the first demonstration of electroluminescence from these organic‐inorganic Ln3+‐based metal halides. Moreover, these materials exhibit distinct excitation wavelength‐dependent emission after alloying with different Ln3+ ions, making them interesting for multicolor display and multilevel information encryption applications. It is foreseen that this study will open up the way to a possible design of robust optoelectronic devices based on lanthanide metal halides.

Identification of rare earth elements in synthetic and natural monazite and xenotime by visible-to-shortwave infrared reflectance spectroscopy

To support the role of proximal and remote sensing in geological rare earth element (REE) resource exploration, we studied the reflectance spectroscopy of synthetic single- and mixed-REE phosphate phases. Synthesis yielded monazite for the elements La to Gd, and xenotime for Dy to Lu and Y. Visible-to-shortwave infrared (350–2500 nm) reflectance spectra of synthetic single-REE monazites and xenotimes can be used to identify the ions responsible for the absorption features in natural monazites and xenotimes. Nd3+, Pr3+ and Sm3+ produce the main absorption features in monazites. In natural xenotime, Dy3+, Er3+, Ho3+ and Tb3+ ions cause the prevalent absorptions. The majority of the REE-related absorption features are due to photons exciting electrons within the 4f subshell of the trivalent lanthanide ions to elevated energy levels resulting from spin-orbit coupling. There are small (< 20 nm) shifts in the wavelengths of these absorptions depending on the nature of the ligands. The energy levels are further split by crystal field effects, manifested in the reflectance spectra as closely spaced (∼ 5–20 nm) multiplets within the larger absorption features. Superimposed on the electronic absorptions are vibrational absorptions in the H2O molecule or within [OH]−, [CO3]2− and [PO4]3− functional groups, but so far only the carbonate-related spectral features seem usable as a diagnostic tool in REE-bearing minerals. Altogether, our study creates a strengthened knowledge base for detection of REE using reflectance spectroscopy and provides a starting point for the identification of REE and their host minerals in mineral resources by means of hyperspectral methods.

HfTiO4 transparent thick film phosphors activated with Eu3+, Dy3+, and Tb3+ ions

Hafnium (Hf)-based double oxides show promise as high-efficiency scintillators due to large effective atomic numbers and high relative density. However, the preparation of these scintillation crystals is challenging due to their high melting points and incongruent melting behavior. In the present study, we demonstrated that the chemical vapor deposition (CVD) of single-phase HfTiO4 films on quartz glass substrate was successfully deposited at temperatures ranging from 973 to 988 K, with a TiO2 molar ratio in the precursor vapor of 25–45 mol% TiO2. The deposition rate of HfTiO4 reached 36 µm h−1. The films exhibited an in-line transmittance of 78 % relative to the raw glass substrate at a wavelength of 600 nm. When activated with Eu3+, Dy3+, and Tb3+ ions, the HfTiO4 films displayed red, yellow, and green photoluminescence emissions originated from the 4f–4f transitions of each trivalent rare-earth ion under ultraviolet light irradiation. HfTiO4 exhibited no intrinsic background emission, suggesting that the addition of a selected activator could yield a phosphor with the desired emission color range.

Optical and photoluminescence properties of trivalent rare earth ions doped LiMgPO4

Trivalent rare-earth-activated luminescent materials have attracted a lot of attention due to their fascinating optical properties and broad range of applications. In this study, polycrystalline Sm and Eu-doped LiMgPO4 luminescent materials were synthesized using a solid-state reaction technique. The crystalline structures, morphological features, and optical characteristics of the synthesized materials were thoroughly investigated using x-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Field-Emission Scanning Electron Microscopy (FE-SEM) and UV–vis spectroscopy. The Rietveld refinement analysis confirmed the phase purity of synthesized phosphors. In addition, the strain induced owing to the incorporation of trivalent rare-earth ions and crystallite sizes of each synthesized material was estimated using the Williamsons-Hall (W-H) and modified Debye-Sherrer equations. The estimated results of the microstrain were reported to be 0.0010, 0.0023 and 0.0020. Subsequently, as a consequence of distinct peak profile options, the projected average crystallite size by both approaches was distinct. The UV–vis spectroscopy analysis reveals that Sm and Eu doped materials exhibit absorption bands around 402 nm and 396 nm and depicts the declining band gap values. The Photoluminescence (PL) spectra at 402 nm and 395 nm excitation wavelengths exhibited the distinctive emissions of both Sm3+ (4G5/2 → 6H7/2) and Eu3+ (5D0 → 7F2) ions emanating due to the intra-configurational f - f and 4 f − 4 f transitions. Finally, the CIE diagram explicitly demonstrates that the Sm and Eu-modified materials reveal their exceptional color purity. McCamy’s approach was used to determine various parameters of trivalent rare-earth doped materials. The correlated color temperature ( TCCT ) and their coordinates TCCT (ζ, β) was found to be 2287 K, 1900 K, 0.281, 0.632, and 0.302, 0.681 respectively. Temperature-dependent emission spectra exhibit excellent color and thermal stability at high temperatures. The obtained results in this study indicate that the synthesized luminescent materials can potentially be used in white light-emitting diode applications.

Understanding the separation of trivalent lanthanides and actinides using multiple diglycolamide-containing ligands: a review

Abstract The complexation and separation behaviour of trivalent actinides and lanthanides with various multiple diglycolamide (DGA) group-containing ligands are compiled in the present review. The DGA arms are anchored on various scaffolds, viz., C- and N-pivot tripodal backbones, benzene-centred tripodal backbones, calix[4]arene, pillar[5]arene and azamacrocycle scaffolds. Dendrimers of different generations having DGA arms were also evaluated for the extraction and complexation studies of trivalent actinide and lanthanide ions. The extraction efficiency of the DGA units increases significantly when they are grouped together on a single backbone/scaffold. Furthermore, the selectivity was found to improve in many cases, particularly with respect to the UO2 2+ ion. This is very important for the development of suitable ligands for the extraction/separation of the actinide and lanthanide ions. Combined experimental, luminescence and DFT studies on the complexation of trivalent actinides and lanthanides with these DGA-based ligands are quite useful to understand their extraction and separation behaviour and this review article gives a critical analysis of the results available in the literature.

Study on the leaching behavior differences of rare earth elements from coal gangue through calcination-acid leaching

Critical metals in coal-based byproducts have been gradually regarded as one of the most important alternative resources due to the market parameters, strategic perspective, and advanced technology. In this study, the mechanism of calcination-acid leaching for rare earth elements (REY) recovery from coal gangue of Jungar coalfield was proposed based on the results of sample characteristics, extraction law, kinetic analysis, and typical mineral leaching. The micro-particles of bastnaesite and monazite were found and embedded in the kaolinite via micro-observation with SEM-EDS. Kaolinite in coal gangue calcined at 600 ℃ was transformed into highly positively reactive metakaolinite, enhancing the dissolution of aluminum (Al) and exposing the rare earth minerals encapsulated within the particles. Meanwhile, bastnaesite was thermally decomposed into rare earth oxides and rare earth fluorides. Rare earth oxides are more easily dissolved by acid, and the fluoride ions and the aluminum ions form a stable complex ion [AlF6]3-, which promotes the dissolution of rare earth fluoride. In addition, a high REY and Al recovery (78.8% of REY, and 88.5% of Al) came true from calcined coal gangue at optimal conditions. The leaching kinetics showed that REY leaching followed the hybrid control model of interfacial transfer and diffusion through solid layer, while Al leaching is controlled by chemical reaction. The leaching test of monazite shows that the leaching efficiency of LREY is higher than that of HREY indicating the leaching difference of LREY (82.3%) and HREY (61.3%) in coal gangue is mainly influenced by monazite. This may be related to the crystal structure and the radius of trivalent rare earth ions. This study provides a useful reference for the extraction of REY from coal gangue.

Preparation of trivalent rare-earth element-substituted bioactive glass robocast scaffolds for osteosarcoma treatment: structural, morphological, mechanical, drug delivery, and biological properties

In this study, trivalent rare-earth ion (Eu3+, Gd3+, and Yb3+)-substituted silicate-based bioactive glass scaffolds were prepared by robocasting method using sol–gel-derived bioactive glass powders for tissue engineering applications and cancer therapy. The structural, morphological, and mechanical properties of the prepared scaffolds as well as their in vitro bioactivity in simulated body fluid (SBF) were investigated in detail. In addition, an anticancer drug (5-FU) adsorption and release behavior of the scaffolds was studied as a function of time. In vitro, cytotoxicity and alkaline phosphatase activity were investigated using human skin fibroblast BJ and osteosarcoma SaOS-2 cells. Results showed that using lanthanide ion-containing (0.5, 1, 3, and 5 wt%) sol–gel-derived bioactive glass powders it was possible to successfully fabricate periodic, mesh-like patterned robocast glass scaffolds. All of the scaffolds prepared in the study sintered at 675 °C showed an amorphous structure. The compressive strength of scaffolds was in the range of 8.8 MPa to 13.6 MPa and the highest strength values were obtained in the Yb3+-containing scaffolds. Hydroxyapatite formation was obtained for the scaffolds immersed in SBF for 28 days. The fluorouracil adsorption amount was calculated to be ~ 25% for all types of scaffolds and the cumulative drug release was in the range of 20–25% depending on the dopant concentration. Results of the in vitro cell culture experiments revealed that all of the scaffolds fabricated in the study were not cytotoxic to fibroblast and osteosarcoma cells for up to 7 days under in vitro conditions. An increase was obtained for the ALP activities for both types of cells as the incubation time was increased.

Energy transfer from Ce3+ to Eu3+ in the spinel structure of ZnAl2O4 phosphor for optoelectronic applications

Zinc aluminate (ZnAl2O4), with a spinel structure is known for its versatile applications as catalyst, ceramic material, and optoelectronic device. ZnAl2O4 is an excellent host for trivalent rare-earth ions such as Dy3+ , Tb3+, Eu3+ and Sm3+ has been extensively investigated for application in display devices. The focus of this work is on Ce3+ and Eu3+ co-dopants aiming to address issues such as multistage combustion synthesis routes, the formation of secondary phases, that often impact luminescence intensity. Through a systematic approach, we synthesized the ZnAl2O4 host with consistent cerium concentration and varying europium ions using one-step combustion synthesis route. The findings reveal that the synthesized material exhibits efficient energy transfer, mitigates concentration quenching and demonstrates favorable color chromaticity. The crystal structure analysis confirms phase purity and addresses concerns related to secondary phase formation. The simplified and cost-effective approach of one-step combustion synthesis method for synthesizing Ce3+ and Eu3+ co-doped ZnAl2O4 suggests that this phosphor has potential applications in ultraviolet photo-electronic technology and other opto-electronic devices.