Mesoporous SiO_2 Nanoparticles:A Unique Platform Enabling Sensitive Detection of Rare Earth Ions with Smartphone Camera

Fast and sensitive detection of dilute rare earth species still represents a challenge for an on-site survey of new resources and evaluation of the economic value. In this work, a robust and low-cost protocol has been developed to analyze the concentration of rare earth ions using a smartphone camera. The success of this protocol relies on mesoporous silica nanoparticles(MSNs) with large-area negatively charged surfaces, on which the rare earth cations(e.g., Eu^(3+)) are efficiently adsorbed through electrostatic attraction to enable a ‘‘concentrating effect''. The initial adsorption rate is as fast as 4025 mg(g min)^(-1), and the adsorption capacity of Eu^(3+)ions in the MSNs is as high as 4730 mg g^(-1)(equivalent to ～41.2 M) at 70 °C. The concentrated Eu^(3+)ions in the MSNs can form a complex with a light sensitizer of 1,10-phenanthroline to significantly enhance the characteristic red emission of Eu^(3+)ions due to an ‘‘antenna effect'' that relies on the efficient energy transfer from the light sensitizer to the Eu^(3+)ions.The positive synergy of ‘‘concentrating effect'' and ‘‘antenna effect'' in the MSNs enables the analysis of rare earth ions in a wide dynamic range and with a detection limit down to ～80 nM even using a smartphone camera. Our results highlight the promise of the protocol in fieldwork for exploring valuable rare earth resources.

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 reso- nanee 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.

SPECTRAL VARIATION AND CHARACTERISTICS OF LOW VALENCY RARE EARTH IONS IN COMPLEX OXIDESⅢ.EFFECT OF THE CRYSTAL ENVIRONMENT AND CHEMICAL FACTORS ON LUMINESCENCE PROPERTIES OF EUROPIUM (Ⅱ) ION

In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond distance is given.Quantum chemistry calculation shows that the splitting extent of 4f^65d energy band in cubic or in octahedral fields will be inversely proportional to R^5,where R is the distance of Eu^(2+) to oxygen ligand.The value of R affects slightly the location of the centre of 4f^65d energy band.According to the exper- imental spectrum data,we have discussed the influence of the host chemical composition,the replaced sites of Eu^(2+) and degree of covalency of Eu-O bond on luminescence properties of Eu^(2+).Some regularity of fluorescence spectrum was observed. In alkali-alkaline earth-phosphates,the splitting extent of 4f^65d band (△E) becomes smaller as the Eu-O bond distance (R) increases.In Na_(3-x)(PO_4)_(1-x)(SO_4)_x and Na_(2-x)CaSi_(1-x)P_xO_4 hosts,d-d emission peak of Eu^(2+) will shift to shorter wavelength with the increase of x's value. The crystal structure data show that Eu^(2+) in K_2Mg_2(SO_4)_3 is affected more strongly by crystal-field and covalancy than in KMgF_3,so K_2Mg_2(SO_4)_3:Eu^(2+) emits blue light (E_(em)~m=400nm) and KMgF_3:Eu^(2+) produces ultraviolet fluorescence.

Synthesis and Photocatalytic Activity of TiO_2/V_2O_5 Composite Catalyst Doped with Rare Earth Ions

TiO2/V2O5 catalyst doped with rare earth ions was prepared by sol-gel method. Titanium tetrapropoxide and vanadium pentoxide were used as precursor of the composite catalyst and rare earth ions were used as dopant. The crystal phases, crystalline sizes, microstructure, absorption spectra of doped composite catalyst were studied by XRD, EDS, FT-IR and UV-Vis. Photoactivity of the prepared catalyst under ultraviolet irradiation were evaluated by degradation of methyl orange （MO） in aqueous solution. It is shown that the prepared catalyst is composed of anatase and futile. The rare earth ions are highly dispersed in composite catalyst. All the doped catalysts appear higher photocatalytic activity than TiO2/V2O5 catalyst and catalyst doped with Ce^4＋ present the best activity to MO.

A Theoretical Model of Energy Transfer between Rare Earth Ions in Crystals

The limitation of the random walk theory of energy transfer between rare earth ions in crystals published in literatures is pointed out in this paper. A modified model, which can be used in any level of rare earth ion concentration when the interaction between donor and acceptor is different from that between donors, is introduced. measured fluorescence lifetimes of Yb^3＋：YAl3（BO3）4 This model has been applied to analyze the with a series of Yb^3＋ concentrations.

Improved anti-Stokes energy transfer between rare earth ions in Er(0.5)Yb(9.5):FOV oxyfluoride vitroceramics explains the strong color reversal

The widely used energy transfer theory is a foundation of luminescence, in which the rates of Stokes and anti-Stokes processes have the same calculation formula. An improvement on the anti-Stokes energy transfer to explain the fluorescence intensity reversal between the red and green fluorescence of Er（0.5）Yb（9.5）：FOV is reported in the present article. The range of the intensity reversal Z was measured to be 877. Dynamic processes for 16 levels were simulated. A coefficient, the improvement factor of the intensity ratio of Stokes to anti-Stokes processes in quantum Raman theory compared to classical Raman theory, is introduced to successfully describe the anti-Stokes energy transfer. A new method to calculate the distance between the rare earth ions, which is critical for the energy transfer calculation, is proposed. The validity of these important improvements is also proved by experiment.

Enhancing leaching efficiency of ion adsorption rare earths by ameliorating mass transfer effect of rare earth ions by applying an electric field

Improving the seepage of leaching solution in the ore body and strengthening the mass transfer process of rare earth ions during in-situ leaching are two critical methods to improve the leaching efficiency of rare earth.In this study,2 wt%MgSO_(4)solution was used for the indoor simulated column leaching experiment on rare earth samples and an electric field was applied at both ends of the samples.Then the effects of different intensities,initial application time and duration of the electric field on the rare earth leaching system and its mechanism were investigated.The results show that compared with the single MgSO_(4)solution leaching,applying an electric field with a strength of 6 V/cm can save the leaching time of 30 min and increase the flow velocity of the rare earth leachate by 26.98%.Under the optimal conditions of applying an electric field with a strength of 6 V/cm for 20 min to the leaching system after10 min of the rare earth leachate flowing out,the leaching efficiency of sample increases from 81.20% to 86.05% with the increase of 4.85%.The mechanism analysis shows that when a direct current electric field is applied to the rare earth leaching system,rare earth ions rapidly change from disorderly movement with the seepage into faster and directional movement.In addition,the seepage of the leaching solution is also improved due to the increase of the cross-sectional area of the seepage channel,the polarized water molecules migrate directionally by force from the negative pole,and the movement of the hydrogen is generated by the electrolytic water.More impo rtantly,based on the principle of in-situ leaching process,the layout of injection holes and deflector holes in this process provides a natural site for the electrode layout of the electric field.With the simple equipme nt and the ope ration,the rare earth leaching process with the applied electric field has high feasibility in industrial application.

Multiferroic and in-plane magnetoelectric coupling properties of BiFeO_3 nano-films with substitution of rare earth ions La^(3+) and Nd^(3+)

Single-phase multiferroic BiFeO3 and Bi（0.9）（La/Nd）（0.1）FeO3（doped with rare earth ions La-（3＋） and Nd-（3＋）） films grown on（111）-Pt/Ti/SiO2/Si substrate were prepared via sol-gel method and a subsequent rapid thermal process. The phase composition, microstructure, ferroelectric, dielectric, ferromagnetic properties were investigated, and meanwhile, the in-plane magnetoelectric（ME） coupling effects of the films were reported and studied for the first time in this work. Structural characterization by X-ray diffraction and scanning electron microscopy showed that both BiFeO3 and Bi（0.9）（La/Nd）（0.1）FeO3 exhabited a rhombohedral structure with（111） preferred orientation. The results of the physical properties indicated that the introduction of rare earth ions improved significantly the polarization, magnetization and dielectric properties than the undoped BiFeO3 crystals, and it enhanced effectively the in-plane ME coupling（the ME coupling coefficient αE increased from 0.13 in the pure BiFeO3 to 0.21 in Bi（0.9）La（0.1）FeO3 and 0.34 V/（Oe·cm） in Bi（0.9）Nd（0.1）FeO3）. The mechanism of these phenomena was investigated systematically.

Photocatalytic activity of perovskite SrTiO_(3)catalysts doped with variable rare earth ions

In this work,15 types of rare earth(Re)ions,including Y^(3+),La^(3+),Ce^(3+),Pr^(3+),Nd^(3+),Sm^(3+),Eu^(3+),Gd^(3+),Tb^(3+),Dy^(3+),Ho^(3+),Er^(3+),Tm^(3+),Yb^(3+)and Lu^(3+)doped perovskite SrTiO_(3)powders were synthesized by solgel method.The influence of Re ions doping on the crystal structure,morphology and optical property as well as the photocatalytic activity for the photodegradation of rhodamine B(RhB)was investigated in detail when the synthesized Re ions doped SrTiO_(3)powders were served as catalysts.The presented results revealed that the crystal structure is invariable,whereas the morphology and the optical bandgap are variable for the resultant SrTiO_(3)powders when different Re ions were incorporated into the SrTiO_(3)lattice.The relatedness between the morphology,optical property and photocatalytic activity of the synthesized SrTiO_(3)catalysts doped with variable Re ions were analyzed deeply,providing an insight into the influence factors on the photocatalytic activity of catalysts.

Growth and optical properties of ytterbium and rare earth ions codoped CaF2-SrF2 eutectic solid-solution(RE=Y^(3+),Gd^(3+),La^(3+))

Ytterbium and rare earth ions(RE=Y,Gd,La)codoped CaF_(2)-SrF_(2)single crystals(3 at%Yb,6 at%RE:CaF_(2)-SrF_(2))were fabricated by temperature gradient technology(TGT).All the space groups remain the same Fm3m as that of Yb:CaF_(2)-SrF_(2).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 Y^(3+)<Gd^(3+)<La^(3+).The segregation coefficients of Yb ions are 0.87 in Yb,La:CaF_(2)-SrF_(2)and Yb,Gd:CaF_(2)-SrF_(2),which are larger than 0.85 in Yb,Y:CaF_(2)-SrF_(2)and 0.80 in Yb:CaF_(2)-SrF_(2).Absorption spectra in the range of 200 and 400 nm were analysed with Yb^(2+)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:CaF_(2)-SrF_(2)has a relatively higher optical parameter(δem×t,0.52×10^(20)cm^(2)·ms),lower Isat(3.68 kW/cm^(2))and^min(0.50 kW/cm^(2))at 1038 nm indicating the potential application in high power laser.Low phonon energy of CaF_(2)-SrF_(2)is 302 cm^(-1)which is located between those of CaF_(2)and SrF_(2)as measured by Raman spectra.It is believed that ytterbium and rare earth ions(RE=Y^(3+),Cd^(3+),La^(3+))codoped CaF_(2)-SrF_(2)eutectic solid-solution is promising for high-power and wavelength-tunable solid-state lasers.

Rare earth doped CaCu_3Ti_4O_(12) electronic ceramics for high frequency applications

Ca1-xRxCu3Ti4O12(R=La,Y,Gd;x=0,0.1,0.2,0.3) electronic ceramics were fabricated by conventional solid-state reaction method.The microstructure and dielectric properties as well as impedance behavior were carefully investigated.XRD results showed that the secondary phases with the general formula R2Ti2O7 existed at grain boundaries of rare earth doped ceramics,which inhibited abnormal grain growth.The dielectric constant decreased from 4×105 in pure CaCu3Ti4O12(CCTO) ceramics to 2×103 with rare earth doping....

Up-conversion processes of rare earth ions in heavy metal glasses

Heavy metal lead germanate glasses doubly doped with Yb^3＋ and Ln^3＋ ions （Ln=Er, Tin） were investigated. Up-conversion spectra of Er^3＋ and Tm^3＋ were registered under diode-laser excitation of Yb^3＋. Up-conversion luminescence bands corresponded to ^4S3/2→^4I15/2 （green） and ^4F9/2→^4I15/2 （red） transitions of Er^3＋ as well as ^1G4→^3H6 （blue） and ^3Ha→^3H6 （N]R） transitions of Tm^3＋, respectively.

Effect of rare earth ions doping on properties of LiFePO_4/C cathode material

LiFe0.99RE0.01PO4/C cathode material was synthesized by solid-state reaction method using FeC2O4-2H2O, Li2CO3, NH4H2PO4, RE（NO3）3·nH2O as raw materials and glucose as a carbon source. The doping effects of rare earth ions, such as La3＋, Ce3＋, Nd3＋, on the structure and electrochemical properties of LiFePO4/C cathode material were systematically investigated. The as-prepared samples were characterized by means of X-ray diffraction （XRD）, scanning electron microscopy （SEM） and particle size analysis. The electrochemical properties were investigated in terms of constant-current charge/discharge cycling tests. The XRD results showed that the rare earth ions doping did not change the olivine structure of LiFePO4, and all the doped samples were of single-phase with high crystallinity. SEM and particle size analysis results showed that the doping of La3＋, Ce3＋ and Nds＋ led to the decrease of particle size. The electrochemical results exhibited that the doping of La3＋ and Ce3＋ could improve the high-rate capability of LiFePO4/C cathode material, among which, the material doped with 1% Ce3＋ exhibited the optimal electrochemical properties, whose specific discharge capacities could reach 128.9, 119.5 and 104.4 mAh/g at 1C, 2C and 5C rates, respectively.

A novel polystyrene-poly(hydroxamic acid)interpenetrating polymer network and its adsorption towards rare earth ions

A novel polystyrene-poly(hydroxamic acid)interpenetrating network resin(PS-PHA IPNs)was successfully synthesized by suspension polymerization and interpenetrating network technology.The effects of various experimental parameters,including pH,contact time and initial concentrations of rare earth ions on the adsorption capacity were discussed in detail.Under the condition of pH 4.0(La^(3+)),1.0(Ce^(3+))and 3.0(Y^(3+)),respectively,PS-PHA IPNs can reach equilibrium adsorption in 6 h and get maximum adsorption capacities(1.08,1.43 and 1.36 mmol/g).The adsorption process of PS-PHA IPNs for La(Ⅲ),Ce(Ⅲ)and Y(Ⅲ)ions can be described by liquid membrane diffusion,particle diffusion and chemical reaction.The adsorption process is a spontaneous and endothermic process and can be better simulated by Langmuir adsorption isotherm.The studies of SEM-EDS indicate that rare earth ions are adsorbed on the surface of PS-PHA IPNs.Fourier transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS)analysis further prove that rare earth ions are chemisorbed on the surface of PS-PHA IPNs.These results reveal that the as-prepared PS-PHA IPNs is a promising adsorbent for adsorption of rare earth ions due to their higher adsorption capacity than other adsorbents.

Localization of rare earth ions in an inhomogeneous magnetic field toward their magnetic separation

Efficient extraction and recycling methods are an important issue for rare earth elements(REE). The significant differences in their magnetic moments make magnetic separation a promising step. Although the magnetic field gradient manipulation of ions seemed to be impossible, the robust enrichment of some paramagnetic RE ions was found in the vicinity of the magnet. The studies in recent years resolved the physical paradox of why, despite the Brownian motion of the ions, there is a reproducible enrichment of RE ions in magnetic field gradients. The existence of trigger process and energy barrier was proved.However, these studies usually used only high paramagnetic ions, e.g., Dy(Ⅲ) or Ho(Ⅲ). This work verifies the theory of the possible magnetic separation for 8 different rare earth ions, respectively. For this purpose, concentration distribution in rare earth chloride solutions were measured using a MachZehnder interferometer. The magnetic field was assured by a Halbach configuration to enhance the effect. The results show the classification of RE solutions into 2 classes: Class I contains the REs with low magnetic moment, whereas Class II includes the REs of high magnetic moment. Only the latter group shows the enrichment of ions in the vicinity of the magnet which encourages the implementation of magnetic separation into existing hydrometallurgical technology to enhance the selectivity of REE.

Local structure and luminescent properties of lead phosphate glasses containing rare earth ions

Local structure and luminescent properties of lead phosphate glasses containing rare earth ions were studied. Optically active ions such as Eu^3＋, Dy^3＋, Tb^3＋ and Er^3＋ were chosen as dopants. The local structure was verified using X-ray diffraction and Fourier transform inflared （FT-IR） spectroscopy. The visible luminescence bands recorded for the studied samples corresponded to ^5D0→^7Fj （J=0÷4） transitions of Eu^3＋, ^4F9/2→^6Hj/2 （J=11÷15） transitions of Dy^3＋, ^5D3→^7FJ, （J＇=1÷6） and ^5Da→^7FJ （J=3÷6） transitions of Tb^3＋, and ^4S1/2→^4I15/2 transitions of Er^3＋.

Highly efficient enrichment and adsorption of rare earth ions(yttrium(Ⅲ))by recyclable magnetic nitrogen functionalized mesoporous expanded perlite

A magnetic mesoporous expanded perlite-based(EPd-APTES@Fe3 O_(4))composite was designed and synthesized as a novel adsorbent for enrichment of rare earth ions in aqueous solution.Effect of various factors including the pH of solution,contact time and adsorbent dosage on the adsorption behaviors of yttrium(Ⅲ)by the EPd-APTES@Fe3 O_(4) nano-material composites from aqueous solution was investigated.The maximum adsorption capacity of the as-prepared materials for yttrium(Ⅲ)ions was 383.2 mg/g.Among the various isotherm models,the Freundlich isotherm model could well described for the adsorption of the rare ea rth ions at pH 5.5 and 298.15 K.The kinetic analysis indicated that the adsorption process followed the pseudo-second order kinetics model,and the rate-determining step might be chemical adsorption.Thermodynamic parameters declared that the adsorption process was endothermic.In addition,Fourier transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS)and the quantum chemical calculation indicated that the yttrium(Ⅲ)ions were captured on the EPd-APTES@Fe3 O_(4) surface mainly by coordination with functional group of-NH2.More importantly,the adsorption-desorption studies indicated that the EPd-APTES@Fe3 O_(4) nano-material composites had a high stability and good recyclability.

PERVAPORATION SEPARATION OF WATER-ACETIC ACID MIXTURES THROUGH AN-co-AA MEMBRANES TREATED WITH RARE EARTH METAL IONS

Pervaporation separation of water-acetic acid mixtures through Poly(AN-co-AA) membranes and rare earth metal ions treated Poly(AN-co-AA)membranes was investigated for the first time. The results showed that the treatment with rare earth metal ions could greatly improve the characteristics of the separation of water-acetic acid mixtures.

~1H and ^(13)C NMR studies of TTHA complexes with diamagnetic rare earth ions

TTHA complexes with diamagnetic rare earth ions (La3+, Y3+ and Lu3+) were studied by 1H and 13C NMR spectroscopy. A symmetric structural model was suggested for La(TTHA) complex and an asymmetric model for Y(TTHA) and Lu(TTHA) complexes. The complex formation was dependent on the pH value of the solution. The interactions of La(TTHA) with the additional metal ions (La3+, Y3+ and Ca2+) were relatively weak, but relatively strong for that of Lu(TTHA) with the additional Lu3+.

Correlation Evaluation of Ion Adsorption-Based Rare Earth Leaching Performance Based on Zeta Potential Drop Leaching

Rare earth elements are indispensable raw materials for advanced aero-engines, special optical materials, and high-performance electronic products. With the development of the social economy, the global demand for rare earth resources is increasing, and rare earths have become a key metal for the development of new industries and frontier technologies that are highly valued both at home and abroad. Ion-adsorbed rare earth ores are an important source of rare earths, so the efficient green leaching of ion-adsorbed rare earths is important. Researchers found that the selection of an efficient green leaching agent for ion-adsorbed rare earths is based on the zeta potential of tailing clay minerals in addition to leaching efficiency, and both zeta potential and leaching ion concentration are related to mineral acidity and alkalinity, and the pH of tailing water suspension is a direct indicator of environmental water quality requirements. Therefore, the efficiency of the leaching process is closely integrated with the environmental evaluation, and the characteristics and correlation of the changes in zeta potential, pH, conductivity and pollutant concentration of the pulp of clay mineral content during the leaching process of ore leaching and tailings aqueous electrolyte solution leaching are studied by evaluating the leaching system, and a set of correlation leaching efficiency and environmental impact evaluation method is established based on the results of the above analysis, which is of scientific development of ion adsorption rare earth resources. It has important theoretical significance and practical application value.