Search Results (63)

Lanthanide coordination polymers have been developed at a fast rate during the past two decades due to their appealing applications in the modern field of materials science and emerging technologies like luminescence, magnetism, sensing, gas adsorption, and catalysis. The role of lanthanides in imparting specific properties to the coordination polymers has been fully documented in extensive studies carried out by numerous research groups. It has been shown that because lanthanide(III) ions possess a variable coordination number, they readily build two-dimensional and three-dimensional architectures with definite channels, permanent pores, and distinct surface areas. Due to their strong oxophilic propensity and hard Lewis acid character, lanthanides favor the construction of stable coordination polymers and MOF configurations by strongly binding the coordinating groups of the organic linkers. Associated with palladium complexes, the lanthanide ions provide synergistic effects with Lewis acid sites, beneficial to the catalytic activity. These attractive characteristics of lanthanides enabled them to be fruitfully applied in Pd-Ln coordination polymers with catalytic properties. This review covers an array of Pd-Ln coordination polymers applied as heterogeneous catalysts in Suzuki–Miyaura C(sp²)-C(sp²) cross-coupling reactions. The activity and chemoselectivity of Pd(II) ions and Pd nanoparticles associated in coordination polymers with different lanthanides from a selected array of rare earth elements (Eu, Sm, Eu, Gd, Pr, Nd, Ce, La, or Tb) is discussed. High yields (>99%) are attained under optimized reaction conditions. The specific role of lanthanides and organic ligands in creating sustainable and recyclable heterogeneous Pd catalysts is evidenced. Mechanistic aspects of the C(sp²)-C(sp²) cross-coupling reactions are considered. The synergistic interaction between lanthanides and palladium as well as with the organic ligands is highlighted. Full article

The escalating prevalence of counterfeiting and forgery has imposed unprecedented demands on advanced anti-counterfeiting technologies. Traditional luminescent materials, relying on single-mode or static emission, are inherently vulnerable to replication using commercially available phosphors or simple spectral blending. Multimode luminescent materials exhibiting excitation wavelength-dependent emission offer significantly higher encoding capacity and forgery resistance. Herein, we report the colloidal synthesis of lanthanide-doped Cs₂ZrCl₆ nanocrystals (Ln³⁺ = Tb, Eu, Pr, Sm, Dy, Ho) via a robust hot-injection route. These nanocrystals universally exhibit efficient host-to-guest energy transfer from self-trapped excitons (STEs) under 254 nm, yielding sharp characteristic Ln³⁺ f–f emission alongside the intrinsic broadband STE luminescence. Critically, Tb³⁺ enables direct 4f → 5d excitation at ~275 nm, while Eu³⁺ introduces a low-energy Eu³⁺ ← Cl⁻ LMCT band at ~305 nm, completely bypassing STE emission. Due to their multimode luminescent characteristics, we fabricate a triple-mode anti-counterfeiting label displaying different colors under different types of excitation. These findings establish a breakthrough excitation-encoded multimode platform, offering potential applications for next-generation photonic security labels, scintillation detectors, and solid-state lighting applications. Full article

Long persistent phosphors are widely used in many fields, such as LED, bioimaging, urgent lighting, temperature sensors, etc. Although green and blue long persistent phosphors are well developed, efficient orange-yellow long persistent phosphors are still relatively rare. In this work, a novel orange-yellow long-persistent phosphors Ca₂LuScGa₂Ge₂O₁₂:xPr³⁺ (CLSGGO:xPr³⁺, x = 0.003, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05) are prepared and systematically investigated through its crystal structural information, photoluminescence, and persistent luminescence properties. Under ultraviolet light excitation, these phosphors exhibit orange-yellow emission stemming from the ³P₀ and ¹D₂ multiple electron transitions in the 4f level of Pr³⁺ ion. In addition, the material exhibits bright persistent luminescence. The complex garnet matrix structure of Ca₂LuScGa₂Ge₂O₁₂ provides excellent conditions for the formation of traps. Through the testing of thermoluminescence curve and function fitting, the density and depth of traps are studied; also, the storage and release process of carriers in the material are calculated in detail. A reasonable persistent luminescence mechanism is proposed for CLSGGO:0.01Pr³⁺. This work enriches the research content of photoluminescence and long persistent luminescence of Pr³⁺-doped garnet-based phosphors and paves the way for the future research of long persistent luminescent materials doped with rare earth ions. Full article

Solution combustion-synthesized BaAl₂O₄: Eu²⁺, Nd³⁺, and Pr³⁺ blue–green long-afterglow phosphors are prepared and systematically investigated. First, XRD confirms the BaAl₂O₄ host and screens for trace residual features. SEM reveals the agglomerated granular morphology typical of combustion products. XPS verifies the valence states (Eu²⁺, Nd³⁺, Pr³⁺) and the chemical environment of the host lattice. UV-Vis diffuse reflectance spectra, transformed via the Kubelka–Munk function and analyzed using Tauc plots (indirect-allowed), indicate a wide band gap of the BaAl₂O₄ host with small, systematic shifts upon Nd³⁺/Pr³⁺ co-doping. PL measurements show Eu²⁺ 4f–5d emission and co-dopant-assisted excitation/defect pathways without altering the Eu²⁺ emission band shape. Afterglow lifetime and decay analyses correlate trap depth/distribution with the extended persistence. Finally, we demonstrate anti-counterfeiting by (i) snowflake printing and (ii) a binary 3 × 3 grid printed with two afterglow inks of different lifetimes to realize multi-level authentication. The sequential evidence links structure, chemistry, optical absorption, carrier trapping, and practical readout, providing a coherent basis for performance enhancement and application. Full article

Ce-doped Lu₂Si₂O₇ has a high density, high luminescence efficiency even at high temperatures, and a high effective atomic number, making it a promising candidate for use as a radiation detector in medical devices and resource exploration equipment. In this study, we grow and characterize Pr³⁺ and Ce³⁺-doped Lu₂Si₂O₇ single crystals by systematically varying the Ce³⁺ to Pr³⁺ ratio to further improve scintillation properties. The optical characterization results show a bidirectional energy transfer: from the Pr³⁺ 5d levels to the Ce³⁺ 5d levels and from the Ce³⁺ 5d levels to the Pr³⁺ 4f levels. Consistently with this result, the PL decay time of emission from the Pr³⁺ 5d–4f transition tends to become faster as the Ce³⁺/Pr³⁺ ratio increases, due to the energy transfer from the Pr³⁺ 5d levels to the Ce³⁺ 5d levels. Additionally, (Ce_0.0022 Pr_0.0016 Lu_0.9962)₂Si₂O₇ exhibits a high light yield comparable to Ce-doped Lu₂Si₂O₇ and a slightly faster decay time than Ce-doped Lu₂Si₂O₇. Full article

The method of measuring temperature using luminescence by analyzing the emission spectra of Pr³⁺-doped YF₃ using principal component analysis is presented. The Pr³⁺-doped YF₃ is synthesized using a solid-state technique, and its single-phase orthorhombic crystal structure is confirmed using X-ray diffraction. The emission spectra measured within the 93–473 K temperature range displays characteristic Pr³⁺ f-f electronic transitions. The red emission from the ³P_0,1→³H₆,³F₂ electronic transition mostly dominates the spectra. However, at low temperatures, the intensity of the green emissions from the ³P_0,1→³H₅, deep-red ³P_0,1→³F₄, and the deep-red emissions from the ³P_0,1→³F₄ transitions are considerably lower compared to the intensity of the red emissions. Temperature variations directly impact the photoluminescent spectra, causing a notable increase in the green and deep-red emissions from the ³P₁ excited state. We utilized the entire spectrum as an input for principal component analysis, considering each temperature as an independent group of data. The first principal component explained 99.3% of the variance in emission spectra caused by temperature and we further used it as a reliable temperature indicator for luminescence thermometry. The approach has a maximum absolute sensitivity of around 0.012 K⁻¹. The average accuracy and precision values are 0.7 K and 0.5 K, respectively. Full article

Seven new lanthanide coordination polymers, namely [Ln(cpt)₃H₂O)]n(Ln = La (1), Pr (2), Sm (3), Eu (4), Gd (5), Dy (6), and Er (7)), which were synthesized under hydrothermal conditions using 4′-(4-(4-carboxyphenyloxy)phenyl)-4,2′:6′,4′-tripyridine (Hcpt) as the ligand. The crystal structures of these seven complexes were determined using single-crystal X-ray diffraction, and they were found to be isostructural, crystallizing in the triclinic P$\stackrel{-}{1}$ space group. The Ln(III) ions were nine-coordinated with tricapped trigonal prism coordination geometry. The Ln(III) cations were coordinated by carboxylic and pyridine groups from (cpt)⁻ ligands, forming one-dimensional ring-chain structures. Furthermore, the luminescent properties of complexes 1–7 were investigated using fluorescent spectra in the solid state. The fluorescence sensing experiments demonstrated that complex 4 exhibits high selectivity and sensitivity for detecting Co²⁺, Cu²⁺ ions, and nitrobenzene. Moreover, complex 3 shows good capability for detecting Cu²⁺ ions and nitrobenzene. Additionally, the sensing mechanism was also thoroughly examined through theoretical calculations. Full article

The thermal stability of oxyfluorotellurite glass systems, (65-x)TeO₂-20ZnF₂-12PbO-3Nb₂O₅-xPr₂O₃, doped with praseodymium was examined. The different concentrations of praseodymium oxide (x = 0.5 and 2 mol%) were applied to verify the thermal, optical and luminescence properties of the materials under study. The relatively high values of the Dietzel (ΔT) and Saad–Poulain (S or H′) thermal stability factors determined using a differential thermal analysis (DTA) indicate the good thermal stability of the glass matrix, which gradually improves with the content of the active dopant. The temperature dependence of optical spectra in the temperature range 300–675 K for the VIS–NIR region was investigated. The involved Pr³⁺ optical transition intensities and relaxation dynamic of the praseodymium luminescent level were determined. The ultrashort femtosecond pulses were utilized to examine a dynamic relaxation of the praseodymium luminescent levels. Although the measured emission of the Pr³⁺ active ions in the studied glass encompasses the quite broad spectral region, the observed luminescence may only be attributed to ³P_J excited states. As a result, the observed decrease in the experimental lifetime for the ³P₀ level along with the increasing activator content was identified as an intensification of the Pr–Pr interplay and the associated self-quenching process. The maximum relative sensitivities (S_r) estimated over a relatively wide temperature range are ~0.46% K⁻¹ (at 300 K) for FIR (I₅₃₀/I₄₉₇) and 0.20% K⁻¹ (at 600 K) for FIR (I₆₃₀/I₄₉₇), which seems to confirm the possibility of using investigated glasses in optical temperature sensors. Full article

The disadvantage of chalcogenide glasses containing rare earth ions as luminescent materials for the IR optical range is the strong concentration quenching of luminescence due to the non-uniform distribution of rare earth ions in the glass matrix. This study investigates the effect of grinding chalcogenide glass containing Pr³⁺ ions in a planetary ball mill on its luminescent properties in the near-IR range, as well as its optical properties and structure. The results indicate that milling, under certain conditions, leads to a decrease in the concentration quenching of the luminescence of Pr³⁺ ions. This finding suggests that milling can be used in the development of glassy materials with the increased efficiency of luminescence of rare earth ions. However, it is essential to consider that high-energy milling may result in the formation of areas with increased pressure in the obtained material, leading to structural changes in the glass. Full article

The recent COVID-19 pandemic has made everyone aware of the threat of viruses and the growing number of antibiotic-resistant bacteria. It has become necessary to find new methods to combat these hazards. One tool that could be used is UVC radiation, i.e., 100–280 nm. Currently, the available sources of this light are mercury vapor lamps. However, the modern world requires more compact, mercury-free, and less energy-consuming light sources. This work presents the results of our research on a new material in which efficient UVC radiation was obtained. Here, we present the results of research on Ca₉Y(PO₄)₇ polycrystals doped with Pr³⁺ ions prepared using the solid-state method. The absorption, excitation, emission, and emission decay profiles of praseodymium(III) ions were measured and analyzed. The upconversion emission in the UVC region excited by blue light was observed. Parameters such as energy bandgap, refractive index, and thermal stability of luminescence were determined. The studied phosphate-based phosphor possesses promising characteristics that show its potential in luminescent applications in future use in medicine or for surface disinfection. Full article

The application of ultraviolet-C light in the field of surface treatment or photodynamic therapy is highly prospective. In this regard, the stable fluorescent silicate SrO-CaO-MgO-SiO₂-Pr₂O₃ glasses able to effectively convert visible excitation on the ultraviolet praseodymium emission were fabricated and examined. An unusual wide-range visible-to-UVC up-conversion within 240–410 nm has been achieved in Pr³⁺-doped glasses, revealing their potential advantage in different sophisticated disinfection technologies. The integrated emission intensity was studied as a function of light excitation power to assess a mechanism attributed to UVC luminescence. Especially, it was revealed that the multicomponent silicate glass qualities and praseodymium ³P_J excited state peculiarities are favorable to obtaining useful broadband ultraviolet up-converted luminescence. The glass dispersion qualities were determined between 450–2300 nm. The impact of praseodymium concentration on Vis-NIR spectroscopic glass qualities was evaluated employing absorption spectra, emission spectra, and decay curves of luminescence associated with two involved praseodymium excited states. Especially, efficient interionic interactions can be inferred by investigating the decrease in ¹D₂ state experimental lifetime in the heavily doped samples. Examination of absorption spectra as a function of temperature implied that excitation at 445 nm should be quite effective up to T = 625 K. Contrary to this, temperature elevation gives rise to a moderate lowering of the visible praseodymium luminescence. Full article

In this research, a comprehensive series of Pr³⁺-doped lithium niobate and sodium niobate materials were obtained at different temperatures via solid-state sintering, and their structures and properties were compared. NaNbO₃: 0.75% Pr³⁺ phosphors were synthesized by sintering at 1150 °C for 2 h and emitted red persistent luminescence for more than 1200 s, peaking at 612 nm under UV excitation, which was a typical long persistent luminescence phenomenon. Furthermore, the sample glowed when pressurized, and a red bright luminescence which lasted for several seconds was visible to the naked eye. This was a typical mechanical luminescence phenomenon of samples under mechanical stress, directly converting mechanical energy into light energy. It was determined that NaNbO₃:Pr³⁺ and LiNbO₃:Pr³⁺ both possess multimode luminescence. Owing to their red long persistent luminescence (LPL) and mechano-luminescence (ML) properties, Pr³⁺ phosphors can be employed in fields, such as display technologies, stress sensing, structural damage detection, and other complex applications. Full article

China’s rare earth reserves and consumption are the highest in the world. Rare earth metals and alloys play a pivotal role in the domains of permanent magnetic materials, hydrogen storage materials, luminescent materials, abrasive materials, etc. The molten salt electrolysis process is the most widely used method for producing light rare earth metals and alloys in China, with distinct advantages such as continuous production and short process flow. This article focuses on the process technology of preparing rare earth metals and alloys by electrolyzing rare earth oxides in fluoride systems. This article summarizes the effects of process parameters such as cathode and anode structures, electrolysis temperature, and current density on the direct recovery and current efficiency of the preparation of light rare earth metals (La, Ce, Pr, Nd), RE–Mg (RE for rare earth) alloys, RE–Al alloys, RE–Ni alloys, and other rare earth alloys. Meanwhile, the disadvantages of the electrolytic cells and electrode configurations that are currently used in industrial production are discussed. Accordingly, the future prospects of molten salt electrolysis technology in the preparation of rare earth metals and alloys are clarified. Full article

Fluorides have a wide bandgap and therefore, when doped with the appropriate ions, exhibit emissions in the ultraviolet C (UVC) region. Some of them can emit two photons in the visible region for one excitation photon, having a quantum efficiency greater than 100%. In a novel exploration, praseodymium (Pr³⁺) ions were introduced into KLaF₄ crystals for the first time. The samples were obtained according to a high-temperature solid-state reaction. They exhibited an orthorhombic crystal structure, which has not been observed for this lattice yet. The optical properties of the material were investigated in the ultraviolet (UV) and visible ranges. The spectroscopic results were used to analyze the Pr³⁺ electronic-level structure, including the 4f5d configuration. It has been found that KLaF₄:Pr³⁺ crystals exhibit intense luminescence in the UVC range, corresponding to multiple 4f → 4f transitions. Additionally, under vacuum ultraviolet (VUV) excitation, distinct transitions, specifically ¹S₀ → ¹I₆ and ³P₀ → ³H₄, were observed, which signifies the occurrence of photon cascade emission (PCE). The thermal behavior of the luminescence and the thermometric performance of the material were also analyzed. This study not only sheds light on the optical behavior of Pr³⁺ ions within a KLaF₄ lattice but also highlights its potential for efficient photon management and quantum-based technologies. Full article

Multi-band emission luminescence materials are of great significance owing to their extensive application in diverse fields. In this research, we successfully prepared a series of Pr³⁺-doped Ca₃Al₂O₆ multi-band emission phosphors via a high-temperature solid-state method. The phase structure, morphology, luminescence spectra and decay curves were investigated in detail. The Ca₃Al₂O₆:Pr³⁺ phosphors can absorb blue lights and emit lights in the 450–750 nm region, and typical emission bands are located at 488 nm (blue), 525–550 nm (green), 611–614 nm (red), 648 nm (red) and 733 nm (deep red). The influence of the Pr³⁺ doping concentration was discussed, and the optimal Pr³⁺ doping concentration was determined. The impacts of charge compensator ions (Li⁺, Na⁺, and K⁺) on the luminescence of Pr³⁺ were also investigated, and it was found that all the charge compensator ions contributed positively to the emission intensity. More importantly, the emission intensity of the as-prepared phosphors at 423 K can still maintain 65–70% of that at room temperature, and the potential application for pc-LED was investigated. The interesting results indicate that the prepared phosphors may serve multifunctional and advanced applications. Full article