Synthesis and photoluminescence properties of Er3+ and Dy3+ doped Na2NbAlO5 phosphors

A series of Ln³⁺ (Ln³⁺ = Er³⁺/Dy³⁺) ions doped Na₂NbAlO₅ (NNAO) phosphors were synthesized by solid-state method. The Er³⁺ and Dy³⁺ ions doped phosphors were characterized by XRD, photoluminescence (PL) and decay profiles. The Ln³⁺-doped samples are consistent with the pure NNAO phase which is analyzed by the X-ray diffraction result. The PL graphs show that the intensity of luminescence increases with the increasing doping concentrations up to their critical certain values and then decreases at higher concentrations due to the concentration quenching effect of Er³⁺/Dy³⁺ ions. The energy level diagrams containing the positions of 4f and 5d energy levels of Er³⁺ and Dy³⁺ ions have been established and studied. In addition, under the ultraviolet light, the prepared NNAO:xLn³⁺ (Ln³⁺ = Er³⁺/Dy³⁺) phosphors show the characteristic green (Er³⁺), cyan (Dy³⁺) emission, respectively. Under the excitation of 365 nm, the quantum efficiencies of NNAO:0.01Er³⁺ and NNAO:0.03Dy³⁺ phosphors are measured to be 61.7% and 72.2%, respectively. The obtained results indicate that the new NNAO:xLn³⁺ (Ln³⁺ = Er³⁺/Dy³⁺) phosphors are promising applications in white-light emitting diodes field.     

Photocatalytic activity of Lu3+/TiO2 prepared by ball milling method

Ball milling method was applied to prepare Lu~(3+)/TiO_2 photocatalysts. The catalysts were characterized with X-ray powder diffraction(XRD), X-ray photoelectron spectroscopy(XPS), UV-visible diffuse reflectance spectra(UV-vis DRS), energy dispersive X-ray spectrometer(EDS), transmission electron microscopy(TEM) and Brunauer-Emmett-Teller(BET) method. The photocatalytic activities were determined by the degradation of methylene blue(MB) equipped with a 300 W medium pressure mercury lamp. Results show that the first order reaction rate constants of Lu~(3+)/TiO_2 and pure TiO_2 are0.0565 and 0.0263 min-1, respectively, which both were evaluated under the condition of catalysts loading of 0.2 g/L,initial concentration of 25 mg/L for MB, mole ratio of Lu~(3+)/TiO_2 of 1.5% and milling time of 4 h. The average crystal sizes of 1.5 mol% Lu~(3+)/TiO_2 and pure TiO_2 are 18.7 and 19.3 nm, respectively.     

Behavior of sulfate in preparation of single light rare earth carbonate by Mg(HCO_3)_2 precipitation method

The precipitation of the water-leaching solution of Baotou mixed rare earth(RE) concentrate roasted with sulfuric acid using ammonium bicarbonate for producing RE carbonate produces a mass of ammonia-nitrogen wastewater because of the relatively low solubility of rare earth sulfate.To solve the serious problem of ammonia-nitrogen pollution,new precipitators need to be developed urgently so as to meet the requirements of environmental protection and impurities content of the product(SO_4~(2-)1.8 wt% in RE carbonates products).In this paper,we studied the effects of feeding modes on the behavior of SO_4~(2-) during the preparation of light RE carbonate(RE=La,Ce,Pr,Nd) from their sulfate solutions using Mg(HCO_3)_2 as a precipitant.The results indicate that the contents of SO_4~(2+) in the La and Ce precipitates using positive feeding mode exceed 16 wt% because of the formation of La2(CO_3)_(2.15)(-SO_4)_(0.85)·4 H_2 O and Ce2(CO_3)_(2.15)(SO_4)_(0.85)·3 H_2 O,while those of the Pr and Nd precipitates are 4 wt%-5 wt%since they exist in the form of n-carbonate.The precipitates prepared using synchronous feeding mode are all RE carbonate with only 4 wt%-5 wt% of SO_4~(2-) enclosed in the precipitation.The content of SO_4~(2-) in the RE carbonate obtained using reverse feeding mode is the lowest.Among them,the content of SO_4~(2-) in La precipitate is only 1.40 wt%.Both synchronous and reverse feeding modes can effectively reduce the content of SO_4~(2-)in RE carbonate,which provides theoretical guidance for the preparation of qualified light RE carbonate products by Mg(HCO_3)_2 precipitation method.     

Multi-component assembly of luminescent rare earth hybrid materials

This review focuses on the recent research progress in the multi-component assembly of luminescent rare earth hybrid materials, which is based on the luminescent rare earth compounds and two or more other building units, including the other photoactive species. It covers the multi-component luminescent rare earth hybrids which was assembled with different (a) organic-inorganic polymeric units, (b) nanoporous units, (c) nanoparticle composites or (d) other developing special units. Finally, future challenges and opportunities in this field are discussed. Herein it mainly focuses on the work of Yan's group in recent years.     

Bi_2WO_6 doped with rare earth ions:Preparation,characterization and photocatalytic activity under simulated solar irradiation

Rare-earth modification Bi_2 WO_6 composites(RE/Bi_2 WO_6) were studied by experimental performance and theory computation based on the different 4 f orbits of selected rare earth elements(La,Ce,Gd,and Yb).The prepared RE/Bi_2 WO_6 was characterized by XRD,SEM/TEM,XPS,UV-vis DRS,and N_2 adsorption to learn their physical-chemical properties.Azo dye Rhodamine B(RhB) was photodegraded as a target pollutant to investigate the photocatalytic activity of prepared RE/Bi_2 WO_6 composites.The results of experiment and computation show that four rare earth elements with different electron configurations retain the phase and morphology of Bi_2 WO_6 and enhance the removal efficiency of RhB under simulated solar irradiation.The optimum doping contents are 0.01%,0.05%,0.05% and 0.01% for La-,Ce-,Gd-,and Yb-doped Bi_2 WO_6,respectively.However,light rare earth La and Ce doped composites indicate some difference in visible light adso rption capacity and mineralization on RhB co mpared with heavy rare earth Gd and Yb doped composites.Both La/Bi_2 WO_6 and Ce/Bi_2 WO_6 possess larger pore size and higher mineralization ability than Gd/Bi_2 WO_6 and Yb/Bi_2 WO_6 under the same experimental conditions while Gd/Bi_2 WO_6 and Yb/Bi_2 WO_6 show stronger red shift to the visible light due to the more 4 f electrons.The hole oxidation plays a major role in the photodegradation of RhB by all RE/Bi_2 WO_6.     

VUV photoluminescence properties of KSrPO4:Dy3+ phosphor

White-light-emitting phosphors based on phosphate host matrix, KSrPO_4 doped with Dy~(3+), were prepared by solid state reaction and their VUV luminescent properties were firstly investigated. The excitation band peaking at 125-153 nm corresponding to the absorption of PO_4~(3-) group exhibits very strong absorption. The phosphors emit warm-white luminescence under vacuum ultraviolet excitation of 147 nm, which consists of three main emission peaks located at 475, 570 and 662 nm, respectively.According to the luminescence and color chromaticity of the optimal sample KSrPO_4:1 mol%Dy~(3+),1.3 mol%Li~+, it can be a potential candidate for mercury-free fluorescent lamps.     

Enhanced photocatalytic activity of Gd~(3+) doped TiO_2 and Gd_2O_3 modified TiO_2 prepared via ball milling method

Gd~(3+)/TiO_2 and Gd_2O_3/TiO_2 nanoparticles were prepared by ball milling method.The effects of Gd~(3+)ion and Gd_2O_3 on the structure and optical property of TiO_2 were studied by XRD and UV-vis DRS.Specific surface area was determined by Brunauer-Emmett-Teller(BET)method.The morphology and elemental composition were characterized by SEM-EDS.XPS was used to determine the surface compositions and chemical character of elements.The sample sizes and microstructures were observed by TEM.The photocatalytic activities of TiO_2 nanoparticles modified with rare earth metal gadolinium(Gd~(3+)ion or Gd_2O_3)were evaluated by degradation of methylene blue(MB)under UV light.Experimental results indicate that 2,5 mol%Gd~(3+)/TiO_2 shows the best photocatalytic activity compared with Gd_2O_3/TiO_2 and pure TiO_2.The existence of gadolinium can exhibit the aggregation and induce lattice distortion of TiO_2 obtained from XRD,SEM and TEM results.The band gap energy of 2.5 mol%Gd~(3+)/TiO_2 decreases to3.07 eV and it leads to visible light absorption response which can be seen from UV-vis absorption spectra.The surface area of 2.5 mol%Gd~(3+)/TiO_2 equals to 85.8 m~2/g and average crystal size is 21.1 nm.EDS and XPS analyses reveal that gadolinium can be introduced either into TiO_2 lattice or adsorbed on the surface of TiO_2.The content of surface OH groups in 2.5 mol%Gd~(3+)/TiO_2 is 50,88%(1.55 times higher than that of pure TiO_2)and the content of lattice oxygen decreases to 11.26%.The MB(25 mg/L)degradation reaction rate constants of 2,5 mol%Gd~(3+)/TiO_2,0.5 mol%Gd_2O_3/TiO_2 and pure TiO_2 were0.0713,0.0588 and 0.0263 min~(-1),respectively.The degradation rates of rhodamine B(30 mg/L)in 60 min are 97,9%,90.1%and 84.6%for 2,5 mol%Gd~(3+)/TiO_2,0.5 mol%Gd_2O_3/TiO_2 and pure TiO_2,respectively.     

Growth and optical properties of ytterbium and rare earth ions codoped CaF_2-SrF_2 eutectic solid-solution(RE=Y~(3+),Gd~(3+),La~(3+))

Ytterbium and rare earth ions(RE=Y,Gd,La)codoped CaF₂-SrF₂single crystals(3 at%Yb,6 at%RE:CaF₂-SrF₂)were fabricated by temperature gradient technology(TGT).All the space groups remain the same Fm3m as that of Yb:CaF₂-SrF₂.The lattice parameter a,unit cell volume V,as well as bond length of Ca/Sr-F and F-F increase in the sequence of rare-earth ions radius Y³⁺3+3+.The segregation coefficients of Yb ions are 0.87 in Yb,La:CaF₂-SrF₂and Yb,Gd:CaF₂-SrF₂,which are larger than 0.85 in Yb,Y:CaF₂-SrF₂and 0.80 in Yb:CaF₂-SrF₂.Absorption spectra in the range of 200 and 400 nm were analysed with Yb²⁺contents.The absorption and emission cross-sections in the range of 900-1100 nm were determined together with fluorescence lifetime.The saturation pump density/Sat,minimum pump density/m in and gain cross-section were analysed.Yb,La:CaF₂-SrF₂has a relatively higher optical parameter(δem×t,0.52×10²⁰cm²·ms),lower Isat(3.68 kW/cm²)and^min(0.50 kW/cm²)at 1038 nm indicating the potential application in high power laser.Low phonon energy of CaF₂-SrF₂is 302 cm^-1which is located between those of CaF₂and SrF₂as measured by Raman spectra.It is believed that ytterbium and rare earth ions(RE=Y³⁺,Cd³⁺,La³⁺)codoped CaF₂-SrF₂eutectic solid-solution is promising for high-power and wavelength-tunable solid-state lasers.     

Application status and development prospect of rare earth in electrical steels

Rare earth(RE) plays a unique and irreplaceable important role in iron and steel.The developments in both basic research and application of RE steel are rapid in recent years.Especially, RE electrical steels attracts more and more attention.However, the relevant research is still in the exploration stage, and it is urgent to carry out systematic and in- depth research work. Based on the recent research results about the application of RE in electrical steels, the research status of RE in electrical steels under modern technical conditions and the effect mechanism of RE in electrical steels were summarized. The application of RE in conventional non- oriented electrical steels, grain- oriented electrical steels and Fe- 6. 5 mass% Si high- silicon electrical steels were discussed respectively. A large number of studies show that the addition of RE in electrical steels can significantly improve the magnetic properties, mechanical properties and texture of electrical steels.There is a broad application prospect of RE in the improvement of magnetic and mechanical properties for electrical steels, and the development of RE electrical steels with Chinese resources?? characteristics has an important academic value and a practical significance.     

Process mineralogy of Weishan rare earth ore by MLA

Mineral liberation analyser (MLA) was applied to quantitatively analyze the rare earth ore from Weishan in Shandong. Mineralogy parameters, such as mineral composition, occurrence states of rare earth elements (REEs) and valuable elements, mineral embedded grain size distribution, mineral association and liberation, are obtained. Results show that the contents of REEs and other valuable elements mainly contained in the ore were La 1.02 wt%, Ce 4.29 wt%, Pr 0.34 wt%, Nd 0.84 wt%, Sr 3.4 wt% and Ba 26.53 wt%, respectively. The REEs mainly occur in bastnaesite and carbocernaite in the form of independent mineral and the contents of bastnaesite and carbocernaite in the ore were 5.96 wt% and 12.30 wt%, respectively. 67.34% of strontium occurs in carbocernaite and the rest occurs in celestobarite and strontianite mineral. 92.71% of barium occurs in barite. Liberation of main rare-earth minerals such as bastnaesite and carbocernaite is more than 80% when the grinding fineness is 78.42% passing 74 μm. The research results could be employed to provide detailed basic theoretical data for further improvement of the beneficiation process flow and the processing index of rare earth ore, the recycling of other valuable minerals and the comprehensive utilization of tailings.     

Synthesis,characterization and cell imaging properties of rare earth compounds based on hydroxamate ligand

Six binuclear rare earth compounds were synthesized through the ligand of 4-Bromo-N-hydroxy-N-methyl-benzamide (sH₂bha). Compounds 1–3 are isomorphous, and compound 1 is crystallized in the monoclinic system with the P2₁/c space group. Compounds 4 and 5 are isomorphous, and compound 4 is crystallized in the triclinic system with the P-1 space group. Compound 6 is crystallized in the triclinic system with the P-1 space group. The compounds were characterized by thermogravimetric analysis (TGA) and IR spectroscopy. The fluorescence spectrum in the visible area shows characteristic peaks of Eu, Tb, and Dy compounds. The efficiency of Eu compound on the viability of PC3 cells was assessed using CCK8 assays. From the CCK8 results, ionic concentration may have a great effect on PC3 cells' proliferation. Eu compound shows red fluorescence in the cytoplasm of PC3 cell. As for Eu compound, it might have potential application in cell imaging technology.     

Luminescence enhancement of rare earth ions by metal nanostructures

Well-ordered metal structures, i.e. arrays of nanosized tips on silver surface for studies of the luminescence enhancement of absorbed media with rare earth ions were used. These arrays were prepared by the metal evaporation on track membranes. Calculations of resonance frequencies of tips regarded as semispheroids were done taking into account the interaction between dipoles of tips. They were used to discuss experimental results for media with Eu(NO₃)₃·6H₂O salt basing on data for bulk silver dielectric function.     

Synthesis and luminescence of Eu3+ doped nanocrystalline TiO2 spheres

Eu~(3+) doped TiO_2 anatase spheres were obtained by modified sol-gel approach.Spheres(110—250 nm) are composed of smaller(5-15 nm) nanocrystals and exhibit red emission under UV light excitation.Materials were synthesized by multi-step method from glycolated titania alkoxides.Europium doped(1.0 mol%) and non-doped spheres were synthesized.Their optical and structural properties were compared by materials characterization methods,such as X-ray powder diffraction,transmission electron microscopy and PL spectroscopy.Doped TiO_2 spheres are crystalline phase pure and exhibit high luminescence intensity.     

Luminescent properties of Eu~(3+) doped Gd_2WO_6 and Gd_2(WO_4)_3 nanophosphors prepared via co-precipitation method

Eu3+ doped Gd2WO6 and Gd2(WO4)3 nanophosphors with different concentrations were prepared via a co-precipitation method. The structure and morphology of the nanocrystal samples were characterized by using X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM), respectively. The emission spectra and excitation spectra of samples were measured. J-O parameters and quantum efficiencies of Eu3+ 5D0 energy level were calculated, and the concentration quenching of Eu3+ luminescence in dif...     

Synthesis of high quality Ce:YAG nanopowders by graphene oxide nanosheet-assisted co-precipitation method

(Ce_(0.04)Y_(2.96))Al_5O_(12) phosphor nanoparticles were prepared by a modified co-precipitation method with graphene oxide(GO) nanosheets used as dispersing agent. The GO concentration is controlled at 0.0.005,0.01, 0.02, and 0.03 g/L. The addition of lamellar GO nanosheets in the precipitant solution possibly enhances both the dispersity of precursor particles and the crystallinity of phosphor nanoparticles. Pure Ce-doped YAG phase is obtained by calcining the precipitate at 1000 ℃ for 3 h. The(Ce_(0.04)Y_(2.96))Al_5 O_(12)phosphor nanoparticles have an average size of 64 nm and there is no significant change on particle size with increase of the GO concentration in precipitant solution. The luminescence property of(Ce_(0.04)Y_(2.96))Al_5O_(12) phosphor nanoparticles varies with different concentrations of GO. The photoluminescence emission intensity of the optimum sample with 0.02 g/L GO is about 1.6 times higher than the sample without using GO.     

Enhancement of low-temperature toughness of Fe-Mn-C-Al alloy by rare earth Ce-modified inclusions

Fe-Mn-C-Al alloys have been recognized as promising materials for certain low-temperature applications due to their exceptional mechanical properties and cost-effectiveness.However,their limited low-temperature toughness restricts their large-scale applications in specific scenarios.The influence of trace amounts of rare earth cerium(Ce)on the low-temperature toughness of Fe-18Mn-0.6C-1.8Al alloys was investigated.The addition of Ce effectively alters the inclu-sions in the alloy,transforming large-sized irregular inclusions into fine ellipsoidal rare earth inclusions.This leads to a significant reduction in both the proportion and average size of the inclusions,resulting in their effective dispersion throughout the matrix and improved cryogenic performance.The presence of Ce-containing inclusions within the matrix reduces stress concentration,thereby inhibiting microcrack formation and improving impact absorption energy.Specifi-cally,the addition of rare earth Ce alters the fracture behavior of the material at room temperature and low temperature,changing from brittle cleavage fracture to a more ductile failure mode.The impact toughness of the Fe-Mn-C-Al alloy is significantly improved by the addition of 0.0048 wt.％Ce,particularly at-196 ℃ where the impact toughness reaches 103.6 J/cm2,representing an impressive improvement of 87.3％.     

Precipitation-dissolution behaviors of rare earth ions in H_3PO_4-Ca(H_2PO_4)_2 solutions

In order to achieve deeper understanding of rare earth elements(REEs) behaviors during phosphate rock processing with H_3PO_4. The solubility of REEs in Ca(H_2PO_4)_2-H_3PO_4 solutions with various concentrations of Ca(H_2PO_4)_2 at different temperatures were tested. The results demonstrate that REEs solubility decreases sharply with the increasing concentration of Ca(H_2PO_4)_2. Equations between [REE~(3+)] and [H~+],[H~+] and [Ca~(2+)] in Ca(H_2PO_4)_2-H_3PO_4 solutions were built based on the precipitation-dissolution equilibrium of rare earth phosphates and the ionization equilibrium of H_3PO_4. According to the equations, the decreasing mechanism of REEs solubility caused by elevated concentration of Ca(H_2PO_4)_2 was determined. The mechanism can be illustrated as that the elevated concentration of [H_2 PO_4~-] decreases the concentration of hydrogen ion by retarding the ionization process of H_3PO_4 and directly promotes the precipitation of rare earth phosphates. Furthermore, it can be easy deduced that similar effect would be caused by the other cation impurities(Fe~(3+), Al~(3+), etc.) on REEs solubility based on the mechanism. In addition, superimposed reduction effect on REEs solubility caused by the elevated concentration of Ca(H_2PO_4)_2 and the elevated temperature is found. This superimposed effect leads to a super low solubility of REEs in Ca(H_2PO_4)_2-H_3PO_4 solution. On the basis of the experimental study, outlooks and suggestions for further development of REEs recovery method are given.     

Extraction of selected rare earth elements from anthracite acid mine drainage using supercritical CO_2 via coagulation and complexation

Rare earth elements(REEs) are valuable raw materials which are in great demand in modern high technology industries.Developing methods to produce/recover REEs from waste is significant to the national security of any developed country.This study was focused on investigating the use of supercritical CO2(sCO_2) to extract REEs from anthracite acid mine drainage(AMD).Four different mine drainage water source locations at Blaschak Coal Corp.in Pennsylvania,USA were selected for sample collection.An extraction process was developed and demonstrated for two of those water sources containing the highest concentration of REEs.A method involving metal ion coagulation,their dissolution from the sludge into a concentrated aqueous HNO_3 solution,complexation with organic ligands and sCO_2 extraction was developed to recover REEs from AMD.Specifically,sodium aluminate(NaAlO_2) was used as the coagulant to concentrate REEs from the AMD into a solid precipitate.Consequently,over 99%of the REEs in AMD is concentrated in the remaining sludge.During the coagulation process,the effects of pH and NaAlO_2 concentration on REE precipitation were investigated.Fuming nitric acid(HNO_3) was used to digest the pre-concentrated sludge and tributyl phosphate(TBP) was used to form REE/TBP/HNO_3,a non-polar complex with selected REEs,specifically,cerium(Ce),lanthanum(La) and neodymium(Nd).HNO_3 concentration and organic/aqueous phase ratio were considered as the variables to improve complexation efficiency.Dynamic extraction experiments using sCO_2 and REE/TBP/HNO_3 solutions were then conducted at optimal conditions of 60℃ and 20 MPa.The overall REE extraction efficiencies are found to increase with the atomic number of the REE.As a result,the average overall REE extraction efficiencies of 41.8%,40.1% and 58.2% for Ce,La and Nd,respectively,are obtained.The potential improvements in the overall extraction efficiency are also discussed.     

Structural and photoluminescence studies of Eu3+ doped zinc oxide nanorods prepared by precipitation method

Trivalent europium doped zinc oxide (ZnO:Eu3+) nanocrystals were synthesized via room temperature chemical co-precipitation and they were systematically characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and photoluminescence (PL) spectroscopy. The as-synthesized samples were found to have hexagonal wurtzite coexisted with the intermediate Zn5(OH)8Cl2·H2O phase, while the single hexagonal phase was facilitated due to the calcinations. The as obtained samples were broadly composed of nanoflakes while the highly crystalline nanorods were formed due to low temperature annealing of the as-synthesized samples. The crystallite size of the nanoflakes and nanorods (40-90 nm) were extracted from the XRD pattern which was found to be consistent with scanning electron microscopy (SEM) measurements. The photolumi-nescence (PL) spectra of nanophosphors showed bright red and orange emissions at 618 and 594 nm respectively with efficient broad blue green emission spectrum due to ZnO lattice. Further, a good energy transfer process from ZnO host to Eu3+ was observed in PL emission and excitation spectra of Eu3+ doped ZnO ions. In all, the present nanophosphors were found to have great potentiality for bio-applications.     

氯离子选择性电极-标准加入法测定碳酸稀土中氯

采用HNO₃(1+ 2)溶解样品,氯则全部以Cl^—形式溶解于溶液中,通过测定溶液中Cl^—质量浓度,即可计算出碳酸稀土中氯含量。试验探讨了在以硝酸钾和柠檬酸三钠为总离子强度调节缓冲溶液(TISAB)体系中,主要以EDTA溶液络合稀土离子,采用氯离子选择性电极-标准加入法测定碳酸稀土中氯含量的方法。结果表明:溶液中Cl^—质量浓度在2.0～40.0 mg/L范围内,EDTA溶液和TISAB溶液用量均为10 mL,Cl^—质量浓度的负对数与相应电极电位(E)呈良好线性关系,线性相关系数为0.999 9;为保证测试结果的准确性,样品和电极响应斜率S值的测定须在同一恒温体系下进行;方法检出限为0.947 mg/L;对于5 mg/L的Cl^—,大量K⁺、Na⁺、NO₃^— 不干扰Cl^—的测定,RE³⁺、Ca²⁺、Fe²⁺、Na⁺最大允许量分别为10.0、4.0、5.5、23 g/L。按照实验方法测定碳酸镧和混合碳酸稀土中氯,结果的相对标准偏差(RSD,n=5)均小于5%;测定值与氯化银比浊法的测定值基本一致。