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Up-Converting Lanthanide Fluoride Core@Shell Nanorods for Luminescent Thermometry in the First and Second Biological Windows - β-NaYF4: Yb3+, Er3+@SiO2 Temperature Sensor
摘要： Up-converting core@shell type β-NaYF4:Yb3+-Er3+@SiO2 nanorods have been obtained by a two-step synthesis process, which encompasses hydrothermal and microemulsion routes. The synthesized nanomaterial forms stable aqueous colloids and exhibits a bright dual-center emission (λex= 975 nm), i.e. up-conversion luminescence of Er3+ and down-shifting emission of Yb3+, located in the first (I-BW) and the second (II-BW) biological windows of the spectral range. The intensity ratios of the emission bands of Er3+ and Yb3+ observed in the Vis-NIR range monotonously change with temperature, i.e. the thermalized Er3+ levels (2H11/2→4I15/2/4S3/2→4I15/2) and the non-thermally coupled Yb3+/Er3+ levels (2F5/2→2F7/2/4I9/2→4I15/2 or 4F9/2→4I15/2). Hence, their thermal evolutions have been correlated with temperature using the Boltzmann type distribution and 2-th order polynomial fits for temperature sensing purposes, i.e. Er3+ 525/545 nm (max Sr = 1.31 %K-1) and Yb3+/Er3+ 1010/810 nm (1.64 %K-1) or 1010/660 nm (0.96 %K-1). Additionally, a fresh chicken breast was used as a tissue imitation in the performed ex vivo experiment, showing the advantage of the use of NIR Yb3+/Er3+ bands, vs. the typically used Er3+ 525/545 nm band ratio, i.e. better penetration of the luminescence signal through the tissue in the I-BW and II-BW. Such nanomaterials can be utilized as accurate and effective, broad-range Vis-NIR optical, contactless sensors of temperature.
关键词： Up-conversion luminescence,Luminescence intensity ratio (LIR),Functional nanomaterials,Rare earth ions,Energy transfer,Optical thermometer
更新于2025-11-25 10:30:42
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Eu-doped layered yttrium hydroxides sensitized by series of benzenedicarboxylate and sulphobenzoate anions
摘要： A number of Eu-doped layered yttrium hydroxides intercalated with various benzenedicarboxylate (phthalate, isophthalate and terephthalate) and sulphobenzoate (2-, 3- and 4-sulphobenzoate) anions was obtained using hydrothermal microwave (HTMW) treatment. For the first time, phthalate, isophthalate and sulphobenzoate anions were intercalated into layered rare-earth hydroxides (LRHs). Two approaches to the synthesis of intercalated layered yttrium hydroxides were used: ion exchange reactions and homogeneous hydrolysis of rare-earth cations in the presence of the intercalated anion. Ion-exchange reactions between layered rare-earth hydroxides and a series of benzenedicarboxylic and sulphobenzoic acid salts were performed under conditions of HTMW treatment, which significantly increased the rate of intercalation. The structure of the first representative of layered rare-earth hydroxides intercalated with sulphobenzoate-type anions, namely layered yttrium hydroxide intercalated with 4-sulphobenzoate of composition Y3(OH)7(C7H4O5S)·H2O, was solved. Intercalation of benzenedicarboxylate and sulphobenzoate anions into Eu-doped layered yttrium hydroxides led to a substantial sensitization of Eu3+ luminescence. The local symmetry of Eu3+ was greatly decreased by intercalation of benzenedicarboxylate and sulphobenzoate anions.
关键词： Layered rare-earth hydroxides,anion exchange,LRH,hydrothermal microwave treatment,luminescence,hybrid materials
更新于2025-11-21 11:20:42
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Extraction of rare earth oxides from discarded compact fluorescent lamps
摘要： Discarded CFL samples are evaluated as a potential source of REEs (Y, Eu, Ce, Tb). The phosphors powder obtained from mechanical separation contains 31% rare earth values. The quantitative XRD analysis of phosphor sample yielded 39.9% red (YOX: Y1.90Eu0.10O3), 14.6% green (CAT: Al11Ce0.67MgO19Tb0.33), and 21.4% blue (BAM: Al10.09Ba0.96Mg0.91O17: Eu2+) phosphor along with 14.1% silica. Planetary ball milling was found promising in the liberation of REEs from given phosphor sample. A short milling of 20–30 min and 3–4 M acid concentration was found adequate for optimal recovery (> 90%) of REEs. Calcination of the precipitates resulted in the formation of REO with Y-Eu purity of > 98% and > 90% recovery rate. Eu, Y phase dissolution behavior was found completely different than Ce, Tb phase due to inert nature of Al11Ce0.67MgO19Tb0.33 till 120 min milling and 6 M acid concentration in leaching. Excessive milling promotes overall dissolution along with impurities dissolution and which further restrict the precipitation process. Based on the complete material balance 13 g of a mixed oxide of Y and Eu can be obtained from 100 units of CFLs.
关键词： Discarded CFL,Phosphor,Rare earth elements,Leaching,Mechanical milling
更新于2025-11-21 11:18:25
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Physical, structural and optical properties of Sm3+ doped lithium zinc alumino borate glasses
摘要： Sm3+ doped lithium zinc alumino borate glasses with composition 15ZnF2–12Li2CO3–10BaO–8Al2O3–(55-x) B2O3–xSm2O3 where x = 0.1, 0.3, 0.5, 0.7 and 1.1 mol% were prepared by conventional melt quenching technique Their optical, physical, structural, mechanical and luminescence properties are investigated. UV–Vis-NIR absorption spectra showed all possible transitions of samarium ion in this glass matrix. Band gap values for all the glass samples were above 3 eV con?rming the insulating nature for the glass. Densities, assessed using the Archimedes rule, were observed to be increasing with increasing samarium concentration. Increase in molar volume with addition of samarium content indicated that the extension of glass network is on account of the increase of number of Non-Bridging Oxygens created by network modi?er samarium ions. Scanning Electron Microscopy (SEM) image showed a smooth surface for the synthezied glass. X-Ray Di?raction (XRD) technique was employed to verify the amorphous nature of the glasses. A Makishima and Mackenzie theoretical model gave acceptable approximation of elasticity constants viz. Young's modulus, shear modulus, bulk modulus and Poisson's ratio. The high Vickers hardness values evaluated with mechanical loads of 50, 100, 300, 500, 1000 g force, proved the stability of the glasses. Emission spectra showed a prominent transition 4G5/2 → 6H7/2 at 598 nm excited with 6H5/2 → 4P3/2 transition at 401 nm. Luminescence quenching e?ect was observed beyond 0.3 mol% Sm2O3 addition. The chromaticity coordinates (x, y) clustered in the orange-red region, making these Sm3+ doped lithium zinc alumino borate glasses suitable candidate for applications in LEDs and solid-state lasers.
关键词： XRD,Photoluminescence,Samarium,Vickers hardness,Radiation shielding,Makishima and Mackenzie,Rare earth
更新于2025-11-21 11:18:25
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Dual-mode luminescent core-shell nanoarchitectures for highly sensitive optical nanothermometry
摘要： Currently, FIR-based luminescent nanothermometry has aroused wide concern for its promising applications in fast-moving objects, harsh environments and microscopic temperature. Synchronously promoting the absolute and relative sensitivities of optical thermometers is one of the significant issues at present. In this work, a new nanothermometry strategy to possess both high absolute and relative sensitivities have been proposed by coupling of thermally-coupled-levels-based technique with non-thermally-coupled-levels method in the core-shell designed nanomaterials. Following this strategy, the core-shell-structured NaGdF4:Yb,Er@ NaYF4:Ce,Tb,Eu nanocrystals have been successfully prepared. Remarkably, the adverse cross-relaxation among different activators is extremely suppressed owing to the spatial separation of Er3+ and Eu3+/Tb3+ activators, being conducive to the realization of both intense green upconverting emissions and yellow downshifting luminescence. Moreover, the temperature-sensitive dual-mode luminescent behaviors of core-shell nanomaterials are systematically studied to probe the possible application in FIR-related luminescent thermometry. Specially, the thermally-coupled-levels-based FIR of Er3+ : 2H11/2 / 4I15/2 to Er3+ : 4S3/2 / 4I15/2 and non-thermally-coupled-levels-based FIR of Eu3+ : 5D0 / 7F2 to Tb3+ : 5D4 / 7F6 are proved to be applicable as temperature probes, leading to the achievement of dual-mode temperature sensing. Using the pre-designed core@shell nanoarchitectures, the absolute sensitivity can reach up to 1.02% K-1 based on Eu3+/Tb3+ Stokes emissions and the relative sensitivity could reach as high as 1.12% K-1 based on Er3+ anti-Stokes luminescence. We believe that this study provides a valid approach for developing high-performance optical nanothermometers.
关键词： Optical nanothermometry,Rare-earth luminescent materials,Dual-mode emission,Core-shell nanoarchitectures
更新于2025-11-20 15:33:11
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Eu3+/Yb3+ co-doped gadolinium oxysulfide upconverting nanorods: Morphological, physicochemical and optical evaluation
摘要： In this study, we introduce a novel route to produce down and upconverting Eu3t/Yb3t co-doped oxysul?de nanorods, which display strong red emission at 620 nm under Vis (460 nm) or NIR (976 nm) wavelength excitation. An in-depth analysis of the synthesis parameters such as lanthanides concentration, type of nucleating agent, reaction temperature, and the reaction pressure was performed to determine their in?uence in the morphology and photoluminescence properties. It was demonstrated that as a nucleating agent, ethanolamine is a good substitute of the commonly used triethylamine providing the advantage of using lower toxicity reagents. The Transmission Electron Microscopy (TEM), Infrared (FTIR) and Zeta Potential analysis showed that the chemical surface of nanorods evolve during thermal and sul?dation processes without producing morphological changes. The intensity of light emission during downconversion (DC) and upconversion (UC) phenomena was found to be doping ions concentration dependent. The highest DC light emission was found at a Yb3t/Eu3t concentration ratio of 0.25, while the most intense UC luminescence was found at 4. Conversely, quenching of DC and UC was observed when using Yb3t/Eu3t concentration ratios of 4 and 0.25 respectively, indicating that luminescent centers are strongly affected in both processes by the chemical environment but also for the ions doping ratio. It was demonstrated that two-photon absorption is the primary mechanism for the red emission in the UC process.
关键词： Nanorods,Rare earth alloys and compounds,Upconversion,Oxysul?de
更新于2025-11-19 16:56:35
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An AND logic gate-based fluorescence probe for the detection of homovanillic acid, an indicator of the tumor
摘要： Homovanillic acid (HVA) is one of the major metabolites of catecholamine in human. An elevated level of HVA in urine and blood has been associated with many diseases, including catecholamine-secreting tumors. Consequently, detection of the biomarker HVA in urine is an effective strategy to detect cancer precursors and early stage cancers. In this study, a fluorescence probe is designed and fabricated by integrating lanthanide ions with metal-organic frameworks (MOFs). The fluorescence probe shows distinguished response toward HVA and exhibits ratiometric detection of HVA, rendering it an excellent candidate for sensing devices. Thus, we have designed logic gate operation integrating the probe with logical operations for the intelligent sensing of HVA. Furthermore, this type of luminesce based sensors integrated with logic gate augur for the further application in real-time early diagnosis of tumors in the future.
关键词： Rare earth,Homovanillic acid,Fluorescent probe,Logic gate,Ratiometric sensing,Metal-organic frameworks
更新于2025-11-19 16:56:35
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Yb/Er/Tm tri-doped Na3ZrF7 upconversion nanocrystals for high performance temperature sensing
摘要： Non-contact optical thermometry based on fluorescence intensity ratio (FIR) technique has been widely researched over the past few decades. However, the reported systems exhibit two important shortcomings including the existence of a few interferential signals in addition to the required spectral bands for FIR and the absence of internal standard for reference signal. Herein, only two emission bands of Er3+: 4F9/2→4I15/2 (~673 nm) and Tm3+: 3H4 → 3H6 (~800 nm) are achieved in Yb/Er/Tm tri-doped Na3ZrF7 nano-system. Moreover, the upconversion (UC) emission intensity of Er3+ keeps unchanged with the rising of temperature, which is applied as reference signal; while that of Tm3+ enhances evidently, which is applied as temperature signal. The calculated maximum absolute temperature sensitivity (Sa) and relative temperature sensitivity (Sr) are 0.17 K-1 at 393 K and 1.76 %K-1 at 313 K, respectively.
关键词： Na3ZrF7 nanocrystals,self-reference,rare earth ions,temperature sensor,upconversion
更新于2025-11-14 17:04:02
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Luminescence Tuning of Layered Rare-Earth Hydroxides (LRHs, R = Tb, Y) Composites with 3-Hydroxy-2-naphthoic Acid and Application to the Fluorescent Detection of Al <sup>3+</sup>
摘要： Tunable luminescence (quenching or blue shift) of HNA/OS-LRH composites (HNA is 3-hydroxy-2-naphthoic acid; OS is the anionic surfactant of 1-octanesulfonic acid sodium; LRHs are layered rare-earth hydroxides, R = Tb3+, Y3+) in the solid state and delaminated state is reported, which is utilized as an effective fluorescent probe for detecting metal ions. HNA/OS species are intercalated into LRH layers to generate composites of HNAxOS1?x-LTbH (x = 0.10, 0.15, 0.20 , 0.25) and HNAyOS1?y-LYH (y = 0.05, 0.10, 0.15, 0.20, 0.25, 0.30). In the solid state, LYH composites exhibit green emissions (from 493 to 504 nm) with a large blue shift in comparison to the 542 nm emission of free HNA? anions, while in the delaminated state in formamide (FM), the composites display blue emission (480 nm) relative to the green emission (512 nm) of an HNA soltuion in FM. However, LTbH composites display coquenched luminescence in both the solid state and delaminated state. Also, HNA0.25OS0.75-1:1-LYH, HNA0.25OS0.75-1:2-LYH, and HNA0.05OS0.95-1:1-LYH (1:1 and 1:2 are HNA:NaOH molar ratios) show significantly elongated fluorescence lifetimes of 15.35, 14.37, and 12.72 ns, respectively, in comparison with free HNA-Na (6.44 ns), and their quantum yields of 23.40%, 21.97%, and 22.31%, respectively, are much larger than that of free HNA-Na (4.86%). The LTbH composite (HNA0.25OS0.75-1:1-LTbH) has also a relatively higher quantum yield of 12.46%. The HNA0.25OS0.75-1:1-LYH colloid exhibits excellent recognition selectivity for Al3+ over other metal ions (Mg2+, Co2+, Ni2+, Cu2+, Zn2+, Pb2+, Cd2+, and Hg2+) with distinct fluorescence sensitization. It shows an intense change in its fluorescence emission when it is bound to Al3+ ions, giving a lower detection limit of 6.32 × 10?6 M. This is novel research on the fluorescence chemosensing of LRH composites.
关键词： Layered rare-earth hydroxides,Fluorescent detection,Chemosensing,Luminescence tuning,Al3+ ions
更新于2025-11-14 15:28:36
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Reversible luminescence modulation and temperature sensing properties of Pr <sup>3+</sup> /Yb <sup>3+</sup> codoped K <sub/>0.5</sub> Na <sub/>0.5</sub> NbO <sub/>3</sub> ceramics
摘要： In this work, we have prepared a novel (K0.5Na0.5)0.99-xPrxYb0.01NbO3 (abbreviated as KNN:xPr3+/0.01Yb3+, x=0.0006, 0.0008, 0.001, 0.002, 0.003 and 0.004) ceramic, which possess visible UC emissions, photochromic (PC) and optical thermometric properties. Under the excitation of a 980-nm diode laser, all the samples show the featured emissions of Pr3+ ions and the UC emission intensity is greatly dependent on the Pr3+ doping content. The optimal UC luminescence intensity is obtained at x=0.001. All the prepared samples show a strong PC reaction, and a large luminescence quenching degree (ΔRt) of 74.94% is found. The optical thermometric properties of both the irradiated and unirradiated KNN:0.001Pr3+/0.01Yb3+ ceramics in the temperature range of 123-573 K have been investigated via measuring the temperature-dependent UC emission spectra of green emissions, which originate from the two 3P1 and 3P0 thermally coupled levels. It has been found that the prepared samples have both excellent PC behaviors and temperature sensing performances. These results suggest that the KNN:xPr3+/0.01Yb3+ ceramics are promising candidates for the applications in PC reaction and thermometers.
关键词： Ferroelectrics,Thermometer,Upconversion,Rare-earth ions,Photochromism
更新于2025-11-14 15:28:36