Photoluminescence and energy transfer in transparent glass-ceramics based on GdF3:RE3+ (RE = Tb,Eu) nanocrystals

In the present work,the transparent oxyfluoride glass-ceramic samples containing GdF_3:RE~(3+)(RE=Tb,Eu) nanocrystals(nGCs) were fabricated via controlled heat-treatment of precursor xerogels prepared using a sol-gel method.The formation of GdF_3 nanocrystalline phase from gadolinium(III) trifluoroacetate was verified based on XRD measurements.The average crystal sizes calculated from Scherrer formula were estimated to～10 nm as well as～6 nm for Tb~(3+)-and Eu~(3+)-doped samples,respectively.The optical behavior of prepared sol-gel samples was evaluated based on photoluminescence excitation(PLE) and emission spectra(PL) as well as luminescence decay analysis.Obtained samples exhibit the ~5D_4→~7F_J(J=6-3,Tb~(3+))and the ~5D_0→~7F_J(J=0-4,Eu~(3+)) emission bands recorded within the visible spectral area under excitation at near-UV(393 nm(Eu~(3+)),351,369,378 nm(Tb~(3+))) as well as middle-UV illumination(273 nm(Gd~(3+))).Additionally,based on recorded decay curves,the luminescence lifetimes(τ_m) for the ~5D_4(Tb3+) and the ~5D_0(Eu~(3+))excited states were also evaluated.In general,recorded luminescence spectra and double-exponential character of decay curves for nGCs indicate a successful migration of Tb~(3+) and Eu~(3+) dopant ions from amorphous silicate framework to lowphonon energy GdF_3 nanocrystal phase.     

Synthesis and luminescence of β-SrGe(PO_4)_2:RE(RE=Eu~(2+),Eu~(3+),Tb~(3+)) phosphors for UV light-emitting diodes

A new series of β-Sr Ge(PO_4)_2:RE(RE=Eu~(2+),Eu~(3+),Tb~(3+)) phosphors were synthesized and characterized by using X-ray powder diffraction as well as excitation, and emission spectroscopy. The results exhibited that the singly doping Eu2+, Tb~(3+) and Eu~(3+) of β-Sr Ge(PO_4)_2 emit strong blue, green and red light under UV irradiation, respectively. Based on the charge transfer transitions of O~(2–)→RE~(3+), an overlapping excitation band of the as-obtained phosphors could be found in UV region, which made β-Sr Ge(PO_4)_2:RE(RE=Eu~(2+),Eu~(3+),Tb~(3+)) serve as a new series of RGB phosphors. Meanwhile, these phosphors could also be excited by 380 nm excitation simultaneously, and hence the three phosphors mixed physically could achieve the tunable hues from blue to white region by adjusting the mixed ratios.     

Upconversion multicolor tuning of NaY(WO4)2:Tb3+ with Eu3+ doping

A series of Tb~(3+) and Eu~(3+) co-doped NaY(WO_4)_2 phosphors were synthesized by hydrothermal reactions.The crystal structure,morphology,upconversion luminescent properties,the energy transfer from Tb~(3+) to Eu~(3+)ions and the ~5 D_4→ ~7 F_5 transition of the Tb~(3+) ion in NaY(WO_4)_2:Tb~(3+),Eu~(3+) phosphors were investigated in details.The results indicate that all the synthesized samples are of pure tetragonal phase NaY(WO_4)2.Furthermore,the micrometer-sized needle spheres and excellent dispersion of the particles are obtained by adding polyethylene glycol(PEG-2000) as the surfactant.Phosphors of NaY(WO_4)_2:Tb~(3+),Eu~(3+) exhibit the492 nm blue emission peak,546 nm green emission peak,595 nm orange emission peak and 616 nm red emission peak under 790 nm excitation.The energy transfer from Tb~(3+) to Eu~(3+) is a resonant transfer,in which electric dipole-dipole interaction plays a leading role.By adjusting the doping concentration of Eu~(3+) in NaY(WO_4)_2: 1.0 mol%Tb~(3+),xmol%Eu~(3+) phosphors,the emitting color of UC phosphors can be tuned from green to red.     

Influence of reaction parameters on the luminescence properties of monodisperse NaGd(1−x−y)(WO4)2:xEu3+,yTb3+ phosphor by molten salt synthesis

Eu~(3+) activated and Eu~(3+), Tb~(3+) co-activated monodisperse sodium double tungstates NaGd(WO4)2 phosphors were prepared by molten salt method at 750 ℃ for 10 h using NaCl as a flux. The crystal structure and morphology of the as-synthesized phosphors were measured by XRD and SEM, respectively. The photoluminescence properties were characterized by PL spectra, decay lifetime and CIE. The presence of NaCl plays an important role in the morphology and luminescence properties. In this work,NaCl and one of the raw material Na_2 CO_3 in a certain proportion will form a low eutectic salt to decrease the reaction temperature and benefit the formation of monodisperse NaGd(WO_4)_2 crystals. The color of Eu~(3+) and Tb~(3+) co-doped NaGd(WO_4)_2 phosphors can be tuned from creamy white to orange, red and green by adjusting the doping concentration of rare earth ions, since the emission contain the broad blue-green emission origin from NaGd(WO_4)_2 host and characteristic red and green emission origin from Eu~(3+) and Tb~(3+) ions. The electroluminescent spectra and CIE measurement shows that the LED device with NaGd_((1-x))(WO_4)_2:xEu~(3+)(x = 0.24) phosphor can be excited by 365 nm and 380 nm LED chip, and their CIE coordinate is(x = 0.45, y = 0.45) and(x = 0.36, y = 0.37), Ra is 80.3 and 86.3, T_c is 3196 and4556 K, respectively. As a single-component phosphor, NaGd(WO_4)_2:Eu~(3+),Tb~(3+) have potential application in UV-pumped WLEDs.     

Synthesis and optical characterization of Eu2+,Tb3+-codoped Sr3Y(PO4)3 green phosphors

A series of Eu~(2+),Tb~(3+)-codoped Sr_3 Y(PO_4)_3(SYP) green phosphors were synthesized by hightemperature solid-state reaction. Several techniques, such as X-ray diffraction, UV-vis spectrum,and photoluminescence spectrum, were used to investigate the obtained phosphors. The present study investigates in detail photoluminescence excitation and emission properties, energy transfer between the two dopants, and effects of doping ions on optical band gap. SYP:0.05 Eu2+ phosphor shows an intense and broad excitation band ranging from 220 to 400 nm and exhibits a bright green emission band with CIE chromaticity coordinates(0.189, 0.359) under 350 nm excitation. Green emission of SYP:0.03 Tb3+ is intensified by codoping with Eu~(2+), and energy transfer mechanism between them is demonstrated to be a dipole-dipole interaction. Upon 350 nm excitation, SYP:Eu~(2+),Tb~(3+) phosphors exhibits two dominating bands peaking at 466 and 545 nm, which are assigned to 4 f~65 d~1→4 f~7 transition of Eu~(2+) ions and ~5 D_4→~7 F_5 transition of Tb~(3+) ions, respectively. Optimal doping concentrations of Eu~(2+) and Tb~(3+) in the SYP host are 5 mol% and 15 mol%, respectively. Results indicate that SYP:Eu~(2+),Tb~(3+) phosphors are potentially used as green-emitting phosphors for white light-emitting diodes.     

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.     

Structural characterization and temperature-dependent luminescence of CaF_2:Tb~(3+)/Eu~(3+) glass ceramics

Tb~(3+)/Eu~(3+) co-doped transparent glass ceramics containing CaF_2 nanocrystals were successfully synthesized by high temperature melt-quenching method and subsequent heating. The structure and morphology of the samples were investigated by X-ray diffraction(XRD), transmittance electron microscopy(TEM), high resolution TEM(HRTEM) and selected area electron diffraction(SAED). The photoluminescence properties and energy transfer process from Tb~(3+) to Eu~(3+) of CaF_2:Tb~(3+),Eu~(3+) phosphors were also investigated through excitation spectra and decay curves. In addition, the emission spectra of the glass ceramics in a wide temperature range from 21 to 320 K were recorded under the excitation of 485 nm. It was found that the fluorescence intensity ratios of Tb~(3+) at 545 nm(~5D_4→~7F_5) to Eu~(3+) at 615 nm(~5D_0→~7F_2) was highly temperature-dependent with an approximate linear relationship, and the temperature sensitivity was about 0.4%/K. It is expected that the investigated Tb~(3+)/Eu~(3+) co-doped CaF_2 glass ceramics may have prospective application in optical thermometry.     

A hydrometallurgical method of energy saving type for separation of rare earth elements from rare earth polishing powder wastes with middle fraction of ceria

This study described a hydrometallurgical method to investigate the separation of rare earth elements(REEs)from rare earth polishing powder wastes(REPPWs)containing large amounts of rare earth oxides with a major phase of CeO_2 and minor phases of La_2O_3,Pr_2O_3,and Nd_2O_3 using a process devised by the authors.The suggested approach consisted of five processes:the synthesis of NaR E(SO_4)_2·xH_2O from rare earth oxides in Na_2SO_4-H_2SO_4-H_2 O solutions(Process 1),the conversion of NaR E(SO_4)_2·xH_2O into RE(OH)_3 using NaO H(Process 2),and the oxidation of Ce(OH)_3 into Ce(OH)_4 using air with O_2 injection(Process 3),followed by Processes 4 and 5 for separation of REEs by acid leaching using HCl and H_2SO_4,respectively.To confirm the high yield of NaR E(SO_4)_2·xH_2O in Process 1,experiments were carried out under various Na_2SO_4 concentrations(0.4–2.5 mol/L),sulfuric acid concentrations(6–14 mol/L),and reaction temperatures(95–125 oC).In addition,the effect of the pH value on the separation of Ce(OH)_4 in HCl-H_2 O solutions with Ce(OH)_4,La-,Pr-,and Nd(OH)_3 in Process 4 was also investigated.On the basis of above results,the possibility of effective separation of REEs from REPPWs could be confirmed.     

Substituent effects on novel lanthanide(Ⅲ) hydrazides complexes

New lanthanide(Eu~(3+) and Gd~(3+)) complexes were successfully synthesized and the effect of the p-phe nyl substituent on the Eu~(3+)luminescent properties was evaluated.In this sense,benzhydrazide,p-toluic hydrazide,4-hydroxybenzhydrazide and 4-aminobenzoic hydrazide were used as ligands and the complexes were obtained by mixing the lanthanide salts with hydrazides in ethanol at room temperature and keeping the reaction for 2 h under mechanical stirring.Crystal of Gd-amino was obtained and its structure was elucidated by single-crystal X-ray diffraction,revealing that Gd~(3+)centered in a distorted tricapped trigonal-prismatic molecular geometry.IR spectroscopy and the elucidated structure confirm hydrazides acting as bidentate ligands binding to Ln~(3+)ions through the oxygen of carbonyl group and the nitrogen of terminal amine,forming a five-membered ring,CHN analyses confirm the molecular formulas [Gd(amino)4(H_2 O)](NO_3)_3·(C_2 H_5 OH) and [Eu(toluic)3(H_2 O)_3](NO_3)_3.Lower T_1 state energies are observed for ligands p-substituted with higher electron donating capacity groups,such as p-NH_2 and pOH.In contrast,higher lifetimes and quantum efficiencies are obtained for Eu~(3+)complexes with ligands p-H and p-CH_3 substituted,which are not deactivator groups.     

Synthesis and luminescent properties of terbium complex with 2-amino-4-chlorobenzoic acid

A novel complex [Tb(L)_2(H_2O)_3·H_2O](where L=2-amino-4-chlorobenzoic acid) was synthesized and characterized by a series of analysis. The molecular formula of complex was confirmed by Fourier transform infrared(FT-IR) spectroscopy and thermogravimetric/differential thermogravimetric(TG-DTG) measurements. The optical properties of complex was measured by ultraviolet spectroscopy(UV) and fluorescence spectroscopy(FS). The results indicated that Tb~(3+) in the complex was coordinated by ligand, and the complex emitted bright yellow-green luminescence with main peak at 548.8 nm with excitation at 369.4 nm.     

High thermal stability and quantum yields of green-emitting Sr_3Gd_2(Si_3O_9)_2:Tb~(3+) phosphor by co-doping Ce~(3+)

A series of Tb~(3+) mono-doped and Ce~(3+)-Tb~(3+) co-doped Sr_3Gd_2(Si_3O_9)_2 phosphors with high thermal stability and quantum yields were successfully prepared via the solid state reaction. The as-prepared Sr_3Gd_2(Si_3O_9)_2:Tb~(3+) samples showed broad excitation spectrum from 250 to 400 nm and presented characteristic emission transitions ~5D_4→~7F_J(J=6, 5, 4, 3) of Tb~(3+) under 313 nm excitation, which were located at about 488, 541, 584 and 620 nm. The emission intensities of Tb~(3+) rose steadily in Sr_3Gd_2(Si_3O_9)_2 host with the increase of Tb~(3+) concentration even though Gd~(3+) ions were completely replaced by Tb~(3+) ions. The Ce~(3+) ion as a sensitizer could efficiently improve the performance of Tb~(3+) ion. First, with Ce~(3+) co-doping, the excitation spectrum of Tb~(3+) monitored at 541 nm showed a similar band that responds to the violet emission of Ce~(3+) monitored at 416 nm. Second, the quantum yields of Sr_3Gd_2(Si_3O_9)_2:Tb~(3+) phosphors could be enhanced from 26.6% to 80.2% by co-doping Ce~(3+). Finally, the co-doping of Ce~(3+) was also effective to improve the thermal stability of Sr_3Gd_2(Si_3O_9)_2:Tb~(3+). As the temperature rose to 150 oC, the emission intensity of Tb~(3+) remained at about 83.6% of that measured at room temperature, which was better than the commercial YAG:Ce phosphor in terms of their thermal quenching properties. These results indicated that the as-prepared Sr_3Gd_2(Si_3O_9)_2:Tb~(3+),Ce~(3+) samples could be used as green emission phosphors for possible applications in near ultraviolet based WLEDs.     

Luminescent properties and energy transfer mechanism from Tb~(3+) to Eu~(3+) in CaMoO_4:Tb~(3+),Eu~(3+) phosphors

A series of CaMoO_4:Tb~(3+),Eu~(3+) phosphors were prepared by the method of precipitation. The structure and morphology of the phosphors were characterized by the X-ray diffraction(XRD) and field emission scanning electron microscopy(FE-SEM). The photoluminescence properties of the prepared products were researched, and the energy transfer from Tb~(3+) to Eu~(3+) in CaMoO_4 phosphors was studied. By adjusting the doping concentration of Eu~(3+) ions in CaMoO_4:Tb~(3+),Eu~(3+) phosphors, the emitting color of the phosphors could be easily tuned from green to red. With Tb~(3+) doped in the phosphors, the red luminescence of Eu~(3+) by near UV excitation was significantly enhanced. The energy transfer efficiency, rate and average distance between Tb~(3+) and Eu~(3+) in CaMoO_4:5%Tb~(3+),x%Eu~(3+)(mole percent) phosphors(x=0.3–10) were calculated. It was found that the interaction type between Tb~(3+) and Eu~(3+) was electric dipole-dipole interaction in the phosphors.     

Selectively recovering scandium from high alkali Bayer red mud without impurities of iron,titanium and gallium

Experimental results here can give some new insights into the mechanism of selective recovery of scandium and sodium from high alkali Bayer red mud(RM) through sulfation-roasting-leaching process. Effects of roasting and leaching conditions including roasting time, roasting temperature, concentrated H_2SO_4 addition, leaching temperature, leaching time and liquid to RM solid ratio on the leaching rates of calcium, iron, aluminum, silicon, sodium, titanium, scandium and gallium were studied and analyzed, suggesting that roasting temperature and roasting time were the two primary constraints on selective recovery of Sc and Na. High leaching temperature also brought a negative effect on the iron leaching rate. Phase transitions and thermal behaviors of sulfated RM indicated that sodium had an inhibitory action on the liberation of SO_2 or SO_3 from metal sulfates, which should follow the decomposition order of TiOSO_4Ga_2(SO_4)_3Fe_2(SO_4)_3NaFe(SO_4)_2NaAl(SO_4)_2~Al_2(SO_4)_3Na_3Sc(SO_4)_3Na_2SO_4CaSO_4. After water leaching, solid-liquid separation could be carried out extremely smoothly and 95 wt.% Na+, ~60 wt.% Sc in [Sc(H_2O)_x(SO_4)_n]~(3–2n)(x≤6) with impurities of 0 wt.% Fe~(3+), 0 wt.% Ti4+, 0 wt.% Ga~(3+), 7 wt.% Al~(3+), ~29 wt.% Ca~(2+) and ~3 wt.% Si~(4+) could be leached into leachant under the optimized roasting and leaching conditions. The alkali-free residue obtained could then be employed as iron-making or building materials.     

Influence of dysprosium concentration on sensitivity of luminescent thermometers of phosphors Ca_9Tb(PO_4)_5(SiO_4)F_2

Tb~(3+),Dy~(3+)-co-doped Ca_9 Tb_xDy_(1-x)(PO_4)_5(SiO_4)F_2 phosphors were prepared via high-temperature solidphase reaction method and the potential application in optical temperature measurements due to their color-tunable property was investigated in detail.The photoluminescence emission(PL) and photoluminescence excitation(PLE) spectra results show that the as-prepared phosphors exhibit both Tb~(3+) and Dy~(3+) emissions at 546 nm(~5 D_4-~7 F_5 transition of Tb~(3+)) and 587 nm(~4 F_(9/2)-~6 H_(13/2) transition of Dy~(3+)) upon376 nm excitation,respectively.In addition,the fluorescence decay analysis shows that the lifetime of the Tb3+emission rapidly decreases,which confirms the energy transfer existence between Dy~(3+) and Tb~(3+).Under 376 nm excitation,the temperature dependence of the fluorescence intensity ratios for the dualmission bands peaked at 546 and 587 nm was studied in the temperature range from 303 to 573 K.The results show that with the increase of Dy~(3+) concentration,the relative sensitivity first increases and then decreases,what's more,the maximum relative sensitivity is 3.142×10~(-3)%/K for Ca_9 Tb_xDy_(1-x)(PO_4)_5(SiO_4)-F_2(x=0.4).As a consequence,this preliminary study provides a novel method for exploring the novel thermo meters.     

Luminescent properties of Ce~(3+)/Tb~(3+) co-doped glass ceramics containing YPO_4 nanocrystals for W-LEDs

Ce~(3+)/Tb~(3+) co-doped transparent glass ceramics containing YPO_4 nanocrystals were prepared using high temperature melting method,and their structural and luminous properties were investigated.XRD analysis and TEM images confirmed the existence of YPO_4 nanocrystals in glass ceramics.The transmission spectra proved that the glass ceramics specimens still maintained a high transparency.Then the excitation and emission spectra of the Ce~(3+) and Tb~(3+) single-doped and co-doped glass and glass ceramics were discussed,which proved that the glass ceramics had better luminescent properties.Under the near ultraviolet(331 nm)excitation,the broadband emission located at 385 nm was observed which was ascribed to 5d→~2F_(5/2) and ~2F_(7/2) transition of Ce~(3+) ions.Several characteristic sharp peaks centered at 489,543,578 and 620 nm originated from the ~5D_4 to ~7F_J(J=6,5,4,3)of Tb~(3+) ions.The decay time of Tb~(3+) ions at 543 nm and the relevant energy levels of Ce~(3+) ions and Tb~(3+) ions illustrated the transfer process from Ce~(3+) ions to Tb~(3+) ions.The best CIE chromaticity coordinate of the glass ceramics specimen was calculated as(x=0.3201,y=0.3749),which was close to the NTSC standard values for white(x=0.333,y=0.333).All the results suggested that the YPO~4-based Ce~(3+)/Tb~(3+) co-doped glass ceramics could act as potential luminescent materials for white light-emitting diodes.     

Synthesis and luminescence properties of Tb3+/Eu3+ co-doped GdAlO3 phosphors with enhanced red emission

The(Gd_(0.97-x)Eu_xTb_(0.03))AIO_3(x= 0.005-0.07) phosphors were synthesized by the co-precipitation method,using ammonium bicarbonate as a precipitant.The combined technologies of FT-IR,XRD,FESEM,PLE/PL and photo luminescence decay analysis were used to study the phase evolution,morphologies and luminescent properties.The phosphors with good dispersion exhibit strong vivid red emission located at 617 nm(~5 D_0-~7 F_2 transition of Eu~(3+)) under the optimal excitation wavelength of 275 nm(~4 f~8-4 f~75 d~1 transition of Tb~(3+),~8 S_(7/2)→6~I_J transition of Gd~(3+)).The presence of Gd~(3+) and Tb~(3+) excitation bands on the PLE spectra monitoring the Eu~(3+) emission directly gives an evidence of Tb~(3+) → Eu~(3+) and Gd~(3+) → Eu~(~(3+)) energy transfer,The emission intensity varies with the Eu~(3+) amount,and the quenching concentration is ～5 at% which is close to the calculated value.The quenching mechanism is determined to be the exchange reaction between Eu~(3+).The temperature-dependent PL analysis indicates that the best(Gd_(0.92)Eu_(0.05)Tb_(0.03))AlO_3 sample possesses good thermally stable properties.All the(Gd_(0.97-x)Eu_xTb_(0.03))AIO_3 phosphors in this work have similar CIE chromaticity coordinates and color temperatures,which are(0.65 ± 0.02,0.35 ± 0.02) and ～2558 K,respectively.Fluorescence decay analysis shows that the lifetime for～617 nm emission decreases with the content of Eu~(3+) and temperature increasing.Owing to the Tb~(3+)→ Eu~(3+) energy transfer,the luminescent properties of the(Gd_(0.92)Eu_(0.05)Tb_(0.03))AlO_3 phosphors are superior to the single Eu~(~(3+)) doped sample(Gd_(0.95)Eu_(0.05))AlO_3.As a result,the prepared phosphors may be widely used in solid-state display and light emitting devices.     

Dehydration,hydrolysis and oxidation of cerium chloride heptahydrate in air atmosphere

The thermal decomposition of CeCl_3·7 H_2 O was studied from room temperature to 800 ℃. Analysis was performed by applying TG-DTA, XRD, FESEM, EDXS, and TG-MS technologies to investigate the thermal decomposition mechanism of CeCl_3·7 H_2 O in air atmosphere. Multiple forms of hydrated cerium chloride compound were observed in the dehydration products. The CeCl_3 hydrolysis product was separated by a continuous centrifugation method and the phase composition was identified as CeO_2,Ce(OH)_3,and CeCl_3·4 H_2 O by XRD analysis. The evolved gas composition was identified as CI_2 and HCI by TG-MS system. Based on the analysis of the experimental results, the mechanism of thermal decomposition of CeCl_3·7 H_2 O was proposed with completion of the dehydration reaction at 224 ℃,the hydrolysis reaction at 170-480 ℃,and the oxidation reaction of CeCl_3 above 480 ℃.     

VOLTAMMETRIC STUDY ON THE REDUCTION OF RARE EARTHS IN ACETONE

The voltammetric and polarographic behaviours of 14 rare earth elements were investigated in anhydrousacetone.The influence of residual oxygen on their waves was examined.At a concentration lower than 6×10~(-4)mol/L,Eu~(3 ),Yb~(3 )and Sm~(3 ) produce two waves and other rare earth ions exhibit only one wave.When the concentration is greater than 8×10~(-4)mol/L,two waves could be observed on the reductionof Yb~(2 ),Sm~(2 )and other RE~(3 )ions except for Eu~(3 ).By adding 0.6% H_2O(or 1×10~(-4)mol/L NH_4ClO_4)one well-defined wave appears instead of two.The phenomenon is explained that a thin deposit film may beformed at electrode surface owing to the interaction of RE~(3 ) with O_2~-,which is the reduction product of traceoxygen in aprotic solvent.In the presence of a proton donor such as H_2O or NH_4~ ,oxygen reduces directly toH_2O_2 and eliminates the appearance of two waves.     

Energy transfer and 2 μm emission in Tm~(3+)/Ho~(3+) co-doped(Y_(0.87)La_(0.1)Zr_(0.03))_2O_3 nanopowders

(Y_(0.87)La_(0.1)Zr_(0.03))_2O_3 nanopowders doped with various concentrations of Tm~(3+) and Ho~(3+) were prepared by the citrate method. The standard cubic Y_2O_3 phase can be matched in the Tm~(3+)/Ho~(3+) co-doped(Y_(0.87)La_(0.1)Zr_(0.03))_2 O_3 nanopowders. The nanopowders exhibit average particle sizes of 40,60, 80 and 100 nm after calcinated at 900,1000,1100 and 1200℃,respectively. The energy transfer from Tm~(3+) to Ho~(3+) and the optimum fluorescence emission around 2 μm were investigated. Results indicate that the emission bands at around 1.86 and 1.95 μm correspond to ~3 F_4→~3 H_6 transition of Tm~(3+) and ~5 I_7→~5 I_8 transition of Ho~(3+), respectively.Better spectral properties were achieved in Tm~(3+)/Ho~(3+) co-doped(Y_(0.87)La_(0.1)Zr_(0.03))_2O_3 nanopowders with the average size of 100 nm obtained at the conditions of the treatment of precursors calcinated at 1200 ℃ for 2 h doped with 1.5 mol% Tm~(3+) and 1 mol% Ho~(3+).     

Metal-organic frameworks of lanthanide iminodiacetates and tartrates:Synthesis,structural characterization and luminescence properties——Commemorating the 100th anniversary of the birth of Academician Guangxian Xu

Two series of lanthanide-containing metal-organic frameworks(Ln-MOFs) of the general formula{[Ln(HIDA)_2 H_2 O]ClO_4·H_2 O}_n(Ln = La(1),Nd(2),Eu(3),Gd(4),Tb(5),Eu:Tb(6);H_2 IDA=iminodiacetic acid) and [Ln(TT)(HTT)(H_2 O)_3]_n(Ln=Eu(7),Gd(8),Tb(9),Dy(10),and Eu:Tb(11);H_2 TT=tartaric acid)were synthesized by reacting Ln(ClO_4)_3 with iminodiacetic acid and L-tartaric acid,respectively.All compounds were structurally characterized by single-crystal X-ray diffraction.Elemental analyses are co nsistent with the corre sponding crystallographically generated formulas.Mo reover,the luminescence properties of both the single and mixed-lanthanide complexes were studied.Near infrared,red,and green emissions that are characteristic of Nd(Ⅲ),Eu(Ⅲ),and Tb(Ⅲ) are observed for 2,3/7,and 5/9,respectively.For the two mixed-lanthanide complex systems 6 and 11,depending on the relative amount of Eu(Ⅲ) and Tb(Ⅲ),the color of emission can be fine-tuned.It is found that a small amount of Eu(Ⅲ) is adequate for the observation of the most intense transition of Eu(Ⅲ).This is believed to be a result of energy transfer from Tb(Ⅲ) to Eu(Ⅲ) within the same complex-a conclusion supported by the significantly shortened lifetime of Tb(Ⅲ) and the accompanying enhanced lifetime of Eu(Ⅲ) in the mixedlanthanide complex with respect to the corresponding values for the pure Tb(Ⅲ) and Eu(Ⅲ) complexes with the same ligand.