Electroanalytical tools to investigate the divalent state of Eu（III） and Nd（III） ions in non-aqueous medium

The divalent state of Ln(Ⅲ) ions has attracted much interest because of their ability to serve isomorphously in many biological sys-tem of divalent Ca(II) ion. Therefore, present paper deals with the study of divalent state of Eu(Ⅲ) and Nd(Ⅲ) ions in non-aqueous medium. In present study, cyclic voltammetry and chronopotentiometry were utilized to establish the divalent state of Eu(Ⅲ) and Nd(Ⅲ) ions. The cy-clic voltammetric technique showed two-step reduction process at cathode for both Ln(Ⅲ) ions under specified experimental conditions and chronopotentiometric method also showed two different transition times (). Looking to the shape of cyclic voltammogram we calculated het-erogeneous forward rate constant (K0fh, cm/s) and diffusion coefficient (D, cm2/s) for both ions, which suggested that sweep rate had great ef-fect on the shape of cyclic voltammogram of Eu(Ⅲ) and Nd(Ⅲ) ions. The result of chronopotentiometry also suggested that stable divalent states of Eu(Ⅲ) and Nd(III) ions existed with chronopotentiogram with two distinct transition times. The diffusion coefficients (D, cm2/s) were calculated from Sand equation. The diffusion coefficients of both techniques were compared and the results suggested that the system at electrode surface was changing from being reversible to irreversible.     

Progresses in electroluminescence based on europium（III） complexes

The research on electroluminescence based on europium(III) complexes has come to an important phase. This article reviewed the progresses in photoluminescence and electroluminescence of Eu(III) complexes in recent years from the views of the design of Eu(III) complexes and optimization of device structures, and discussed some important factors influencing electroluminescence performance. The problems existing in the practical application such as the volatility and thermal stability of Eu(III) complexes in this area were discussed, and the possible corresponding solutions were briefly prospected.     

Synthesis, characterization and thermostability of tris（2,2,6,6-tetramethyl-3,5- heptanedionato）yttrium（III）

The metal-organic chemical vapor deposition (MOCVD) technique is a promising process for high temperature superconductor YBa2Cu3O7-δ(YBCO) preparation. In this technique, the purity, evaporation characteristics and thermostability of adopted precursors will decide the quality and reproducible results of YBCO film. In the present report, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)yttrium(III)(Y(TMHD)3) was synthesized by the interaction of yttrium nitrate hydrate with TMHD in methanol solution, and its structure was identified by FTIR, 1 H NMR, 13C NMR and EI-MS spectroscopy. Subsequently, the thermal property and the kinetics of decomposition were systematically investigated by non-isothermal thermogravimetric analysis methods (TGA) at different heating rates in streams of N2,and the average apparent activation energy of evaporation process was evaluated by the Ozawa, Kissinger and Friedman methods. The possible conversion function was estimated through the Coats-Redfern method to characterize the evaporation patterns and followed a phase boundary reaction mechanism by the contracting area equation with average activation energy of 88.9kJ/mol.     

Synthesis and luminescence characteristics of terbium（III） activated NaSrBO3

The thermoluminescence (TL) and photoluminescence (PL) properties of the phosphor NaSrBO 3 :Tb 3+ were reported and discussed. The combustion technique was used for the synthesis of polycrystalline samples of NaSrBO 3 :Tb 3+ . The TL glow curve of the compound had a simple structure with a single peak at 434 K. TL sensitivity of the phosphor was found to be more than that of (LiF:Mg,Cu,P). The TL glow curve was studied as a function of concentration of dopant and dose of gamma ray irradiation. The kinetic parameters of the thermoluminescence of NaSrBO 3 : Tb 3+ were calculated employing the peak shape method. The photoluminescence (PL) properties of Tb 3+ doped in NaSrBO 3 were studied over the 200-400 nm excitation range. The excitation spectra of NaSrBO 3 :Tb 3+ consisted of single narrow band peaking at about 236 nm. The emission spectra monitored at 236 nm excitation consisted of a series of sharp lines peaking at 489, 544, 586 and 622 nm corresponding to the 5 D 4 → 7 F j (j=3,4,5,6) transitions within the 4f 8 configurations of Tb 3+ .     

Synthesis and fluorescent properties of a novel europium（III） complex with terpyridine-capped poly（ethylene glycol）

Terpyridine-capped poly(ethylene glycol) (PEG) was synthesized as a novel polymeric ligand and rare earth complex was prepared from Eu(NO3)3 and the telechelic macromolecules. The structure of the complex was characterized by 1H NMR, FT-IR, UV-vis and fluores-cence spectroscopy. Strong fluorescent emission of the complex was observed at 593 and 616 nm upon the excitation of 300 nm. The fluo-rescent emission was quenched upon addition of trace amount of diethyl chlorophosphate (DCP). And the observed Ksv values for DCP were measured to be 0.568×103 and 0.89×103 L/mol for quenching at 593 and 616 nm, which indicated the detection limit for DCP was about 0.014 mmol/L. These results showed that the terpyridine-lanthanide complex could be an effective chemosensor with a potential application in the detection of organophosphates.     

Ionic liquids as novel spectroscopic solvents for Eu（III）-containing complex

Novel soft materials,Eu(III)-containing complex dissolved in [C8mim][X](X=Cl-,PF6-and Tf2N-) ionic liquids,were synthesized.FT-IR and elementary analysis of complex proved that the molecular formula is [C8mim][Eu(TTA)4].The complex and ionic liquids had highthermal stability according to TGA.The photoluminescence spectra showed that the [C8mim][Eu(TTA)4] exhibited typical red emission deriving from 5D0-7F2 transition.After dissolving the complex in [C8mim][X](X=Cl-,PF6-and Tf2N-) ionic liquids,the luminescence intensitydecreased in the following order:[C8mim][Tf2N]≈[C8mim][PF6 ]>[C8mim][Cl].This was because Tf2N-and PF6-anions had larger molecularvolume and weaker coordination ability than Cl-.     

Study on transport of Dy（III） by dispersion supported liquid membrane

The transport of Dy(III) through a dispersion supported liquid membrane (DSLM) consisting of polyvinylidene fluoride membrane (PVDF) as the liquid membrane support and dispersion solution including HCl solution as the stripping solution and 2-ethyl hexyl phosphonic acid-mono-2-ethyl hexyl ester (PC-88A) dissolved in kerosene as the membrane solution, was studied. The effects of pH value, initial concentration of Dy(III) and different ionic strength in the feed phase, volume ratio of membrane solution and stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on transport of Dy(III) were also investigated, respectively. As a result, when the concentration of HCl solution was 4.0 mol/L, concentration of PC-88A was 0.10 mol/L, and volume ratio of membrane solution and stripping solution was 40:20 in the dispersion phase, and pH value was 5.0 in the feed phase, the transport effect of Dy(III) was the best. Ionic strength had no obvious effect on transport of Dy(III). Under the optimum condition studied, when initial concentration of Dy(III) was 0.8 × 10^?4 mol/L, the transport rate of Dy(III) was up to 96.2% during the transport time of 95 min. The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry. The diffusion coefficient of Dy(III) in the membrane and the thickness of diffusion layer between feed phase and membrane phase were obtained and the values were 1.99 × 10^?7 m²/s and 15.97 μm, respectively. The results were in good agreement with experimental results.     

La（III）-loaded bentonite/chitosan beads for defluoridation from aqueous solution

Developing low-cost and effective materials for excess fluoride removal is important for providing safe water. A novel ad- sorbent, La（IlI）-loaded bentonite/chitosan beads （La-BCB） was prepared for defluoridation from aqueous solution. The effects of various parameters such as dosage of La（III）, pH, temperature, contact time, initial fluoride concentration and presence of co-existing anions were investigated to examine the defluoridation behavior. The maximum defluoridation capacity of La-BCB was 2.87 mg/g at pH 5, 30 ℃. Scanning electron microscopy （SEM）, energy dispersive spectroscopy （EDX） and Fourier transform infrared spectros- copy （FTIR） were employed to analyze the characteristics of La-BCB. The equilibrium fluoride adsorption data fitted well with both Langmuir and Freundlich isotherm models. The RL value revealed that the defluoridation process using La-BCB was favorable. The adsorption kinetics followed pseudo-second order kinetic as well as particle and intraparticle diffusion models. The presence of car- bonate and bicarbonate reduced defluoridation capacity of La-BCB while sulphate, nitrate and chloride showed slight effect. The ex- hausted La-BCB was regenerated using sodium hydroxide with only 17% loss. The reasonable defluoridation mechanism could be interpreted as adsorption and ion exchange.     

Electrochemical behavior of Ce（III） in LiF-BaF2 melts

The electrochemical behavior of Ce(III) was investigated in the molten LiF-BaF2 (81 mol.%-19 mol.%) on a molybdenum elec-trode in the temperature range of 1098-1188 K using cyclic voltammetry and chronopotentiometry. It was observed that CeF3 could be re-duced into cerium metal in a reversible one-step process exchanging three electrons (Ce(III)+3e-→Ce(0)) at the operating temperatures on a molybdenum cathode. The electrochemical reduction process was controlled by the diffusion of Ce(III) in the solution. The Ce(III) diffusion coefficients were calculated at different temperatures and the values obeyed the Arrhenius law with an activation energy of 87.5 kJ/mol.     

Solvent extraction of La（III） with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester （EHEHPA） by membrane dispersion micro-extractor

The conventional rare earth solvent extraction equipments have many problems such as long mixing time, low processing capacity, large factory area occupation, high energy consumption and so on. In order to solve the problems, many types of equipments were brought out. In this work, studies were carried out on the La（III） extraction process with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester （EHEHPA） by membrane dispersion micro-extractor. Equilibrium studies showed that the initial aqueous pH value 4.15 with the saponification rate 40%was the optimal operation condition. The effects of membrane dispersion micro-extractor operational conditions such as dispersion mode, bulk flow rate and organic phase flow rate on the extraction efficiency were studied. The results showed that when the organic solution was the dispersed phase, the extraction efficiency was higher than that of others. Increasing bulk flow ratio could enhance the extraction efficiency greatly. When the ratio of organic phase flow rate to that of aque-ous phase was 80：80, the extraction efficiency was over 95%. The effect of stripping phase acidity on the La（III） recovery was studied. The results showed that when the stripping phase pH was 2.0, organic phase flow rate to stripping phase flow rate was 20：80;the re-covery efficiency of La（III） can reach 82%.     

Solvent extraction of neodymium（III） from acidic nitrate medium using Cyanex 921 in kerosene

The extraction of neodymium(Ⅲ) from acidic nitrate medium was investigated using Cyanex 921 as extractant in kerosene. The metal concentration in the aqueous phase before and after extraction was determined spectrophotometrically by Arsenazo Ⅲ method. The complete equilibration was achieved in 15 min. The effects of shaking time, nitric acid concentration, nitrate concentration, extractant concentration, and temperature on the extraction were studied. The extraction of Nd(Ⅲ) was found to increase very slowly with increase in concentration of HNO3 in the range of 0.001-0.008 mol/L and then decreased when 0.01 mol/L HNO3 was used. The percentage of extraction was increased with increase in nitrate concentration from 0.01-0.45 mol/L and then decreased when nitrate concentration increased to 0.5 mol/L. Quantitative extraction of Nd(Ⅲ) (98%) was obtained from the aqueous phase containing 0.001 mol/L HNO3 and 0.1 mol/L KNO3 using 0.5 mol/L Cyanex 921. On the basis of slope analysis, the extracted complex in the organic phase was proposed to be Nd(NO3)3.2Cyanex 921. The extraction of Nd(III) was found to increase with increase in concentration of metal ion in the range of 0.001-0.05 mol/L from 0.001 mol/L HNO3 and 0.1 mol/L KNO3 with 0.1 mol/L Cyanex 921. The percentage of extraction of neodymium was found to decrease with increase in temperature. From temperature variation studies, the negative value of △H indicated the extraction reaction to be exothermic and the negative value of △S indicated the formation of a stable complex. Almost 100% Nd(Ⅲ) was recovered from the fully loaded organic phase using 0.002 mol/L H2SO4 and 0.01 mol/L HCl.     

Synthesis, fluorescence properties of Eu（III） complexes with novel carbazole functionalized β-diketone ligand

A novel carbazole functionalized β-diketone, methyl 6-(9-ethylcarbazole-3-yl)-oxoacetyl-2-pyridinecarboxylate (MEP), and its corresponding binary Eu(III) complexes Eu(MEP)₃·2H₂O and ternary complex Eu(MEP)₃Phen with 1,10-Phenanthroline (Phen) were prepared. The ligand was characterized based on elemental analysis, FT-IR, and ¹H NMR, and the complexes were characterized with elemental analysis, FT-IR and thermogravimetric and differential thermal analysis (TG-DTA). The investigation of fluorescence properties of the complexes Eu(MEP)₃·2H₂O and Eu(MEP)₃Phen showed that the Eu(III) ion could be sensitized efficiently by the ligand to some extent, in particular, in the ternary system, the secondary ligand Phen acting as a light-harvesting center was involved in the highly efficient energy transfer process, and the emission was stronger than the binary complex. In addition, the introduction of the carbazole moiety enlarged the π-conjugated system of the ligand and enhanced the luminescent intensity of the complexes.