Thermal Stability and Luminescence Properties of Eu^3＋ and Tb^3＋ Complexes with a Silica Matrix by Sol-Gel Method

Ternary complexes of europium and terbium with benzoic acid and 1, 10-phenanthroline [RE(BA)3phen] (BA=benzoate phen=1,10-phenanthroline) were introduced into a silica matrix by sol-gel method. The thermal stability and luminescence behavior of the complexes in silica gels were studied in comparison with the corresponding solid-state complexes by thermal decomposition, excitation and emission spectra. The thermal stability of the complexes is enhanced in silica gel matrix and the luminescence remaines unchanged.     

Fabrication and Luminescence of Rare Earth Complex／SiO2 Hybrid Nanospheres

The organic rare earth complex was embedded in silica spheres to form inorganic-organic hybrid. Photoactiver are earth complexes with various organic ligands exhibit intense narrow emission band, and the silica is an excellent matrix for inorganic-organic structure. The transmission electron microscope image presents the hybrid nanospheres. The diameter of the hybrid is about 100 nm. The europium complex that incorporated into silica sphere is also proved by the IR spectra, the excitation and emission spectra. The lifetimes of the Eu3 ions in the hybrid nanospheres and in the pure europium complex were also detected. This hybrid with inhomogeneous compositions exhibits specifically tailored chemical and optical properties, such as perfect thermal and mechanical stability, colorimetric purity and so on. It can be used as luminescent and optical material in EL and PL fields.     

Electrospinning preparation and luminescence properties of Eu(TTA)3phen/polystyrene composite nanofibers

Efficient luminescent composite nanofibers,composed of polystyrene(PS,Mw=250000) and europium complex Eu(TTA)3phen(TTA=2-thenoyltrifluoroacetone,phen=1,10-phenanthroline) with diameters ranging from 350 nm to 700 nm,were prepared by electrospinning and characterized by scanning electron microscope(SEM),Fourier transform infrared spectroscopy(FT-IR),fluorescence spectroscopy,and thermogravimetric analysis(TG).The room-temperature fluorescence spectra of the composite nanofibers were composed of the typical Eu3+ ion red emission,assigned to the transitions between the first excited state(5D0) and the multiplet(7F0-4).Owing to the incorporation of the europium complex into the PS fiber matrix and the subsequent distortion of the symmetry around the lanthanide ions by the capping PS,the polarization of the Eu3+ ions was enhanced,which increased the probability for electronic dipole allowed transitions.The monochromaticity(5D0→7F2/5D0→7F1) around the Eu3+ ions was also efficiently improved.Judd-Ofelt intensity parameters(Ω2 and Ω4) were determined from the emission spectra based on the 5D0→7F2 and 5D0→7F4 electronic transitions,respectively.The results showed that the Ω2 values of the composite nanofibers were apparently higher than that of the pure complex,indicating an increased covalency degree in the europium first coordination shell due to the modification of PS matrix.The modification of the polymer matrix also resulted in much higher thermal stability of the composite fibers than that of the pure complex.     

Hydrothermal synthesis and luminescence properties of Eu3＋ and Sm3＋ codoped BiPO4

Eu3+/Sm3+codoped BiPO4 phosphors were synthesized via a facile hydrothermal method with surfactant-free environment. The X-ray diffraction analysis demonstrated that the samples possessed the standard BiPO4 monoclinic structure. Scanning electron microscopy images showed that all samples composed of well-dispersed, micrometer-sized crystals with shuttle-like shape. Energy transfer from Sm3+to Eu3+was confirmed by the luminescence spectra and the decay processes of Sm3+ 4G5/2 →6H5/2 emission. Orange-red luminescence could be obtained in Eu3+/Sm3+codoped BiPO4 phosphors. The average lifetime of Sm3+ 4G5/2 →6H5/2 emission decreased from 2.70 ms in BiPO4 :0.03Sm3+to 2.37 ms in BiPO4 :0.03Sm3+,0.05Eu3+. The strong and wide absorption band around 395 nm, originating from both7F0 →5L6 transition of Eu3+and6H5/2 →4K11/2 transition of Sm3+, endowed BiPO4 :Eu3+,Sm3+ phosphors with the potential application in the fields of near UV-excited white-light-emitting diodes.     

Optical Spectroscopy of Er^3＋ and Er^3＋/Yb^3＋ Co-doped Bi2O3-GeO2-B2O3-ZnO Glasses

The （60 - x）Bi2O3 - xGeO2-30B2O3-10ZnO （x = 5, 10, 20, 30 molar percent） glasses doped with Er^3＋ and Er^3＋/Yb^3＋ were fabricated using the melting method. The thermal stability of the glasses was studied with their DTA curves. The results show that the difference between the glass transition temperature and the crystallization onset temperature increases with the increase of GeO2 content, indicating that the thermal stability of the glass has become better. The absorption spectra were recorded and the stimulated emission cross sections were calculated using the McCumber theory. The Ω2, O4, and Ω6 parameters,the transition probability, the radiative lifetime, and the fluorescence branch ratio of Er^3＋ for optical transition were calculated from their absorption spectra in terms of reduced matrix U^（t）（λ = 2, 4, 6） character for optical transitions. The infrared emission of Er^3＋ was measured upon excitation with 970 nm light and the full width at half-maximum （FWHM） was estimated from the emission spectra. The pumping efficiency and the intensity of the emission at the 1.54 μm band of Er^3＋ were enhanced considerably by co-doping Yb^3＋ .     

Intercalation Assembly, Characterization and Luminescent Properties of Novel Supramolecular Composite Materials, Tb （ Ⅲ ） Complex with Tetrapodal Ligand- Montmorillonite

Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.     

Research on poly（styrene-acrylic acid）-supported neodymium complex in catalytic copolymerization of styrene and 4-vinylpyridine

The catalytic activity of poly（styrene-acrylic acid） （PSAA） supported neodymium chloride （NdCl3） complex for the copolymerization of styrene and 4-Vinylpyridine was studied. The influence of various factors, such as Al/Nd molar ratio, reaction time, macromolecular carder （PSAA）, and ratio of styrene to 4-vinypyridine （g/g）, on the copolymerization yield of styrene and 4-Vinylpyridine was investigated. The results showed that the copolymerization of polar monomers with olefins occurred efficiently and the catalytic activity of polymer-supported catalyst was higher than that of the similar small molecular catalysts. The activity of PSAA.Nd complex increased with in- creasing Al/Nd molar ratios and decreased with increasing polymerization time. The highest activity of PSAA＇Nd was observed at 120 min, and the highest yield was found at the ratio of styrene to 4-vinylpyridine of 4：2. DSC analysis presented that the resulted polymer had only one glass transition temperature, and showed very good thermal stability.     

Spectroscopic Properties and Effect of Radiation Trapping of a New Er^3＋/Yb^3＋ Co-Doped Tellurite-Silicate Glasses

A new serials of Er^3＋/Yb^3＋ co-doped tellurite-silicate glasses were prepared by the technique of high-temperature mehing. The thermal stability, absorption spectra, emission spectra and upconversion spectra were measured and investigated. It is found that these kinds of glasses have good thermal stability, broad FWHM and large stimulated emission cross-section. The three upconversion emission at 525, 546, 658 nm, corresponding to the ^2H11/2→^4Ⅰ15/2, ^4S3/2→4^Ⅰ15/2 and ^F9/2→^4Ⅰ15/2 transitions of Dr^3＋ ions,     

Electronic Structure of Hydrogen Storage Compounds, LaNi5 and Its Micro-Hydrogenated Compounds

The electronic structures of LaNi5 hydrogen storage alloys and its micro-hydrogenated compounds with two hydrogen atoms in the center of two octahedral interstices and two tetrahedral interstices, were investigated by the first principles discrete variational method （DVM）. The results of density of states and the difference of charge distribution clearly show that the s electrons of H mainly interact with the s electrons of hydride-non-forming element Ni, despite there being a larger affinity of La for hydrogen than that of Ni in pure metal-hydrogen system. From the cohesive energy of systems, we also found two systems have almost same stability with occupation of H atoms.     

Multiple Energy Transfers in Rare Earth Complex-Doped SiO2 Spheres

Silica spheres doped with Eu （TTFA）3 and/or Sm（TTFA）3 were synthesized by using the modified Stober method. The transmission electron microscope image reveals that the hybrid spheres have smooth surfaces and an average diameter of about 210 nm. Fluorescence spectrometer was used to analyze the fluorescence properties of hybrid spheres. The results show that multiple energy transfer processes are simultaneously achieved in the same samples co-doped with Eu （TTFA）3 and Sm（TTFA）3, namely between the ligand and Eu^3＋ ion, the ligand and Sm^3＋ ion, and Sm^3＋ ion and Eu^3＋ ion. Energy transfer of Sm^3＋→Eu^3＋ in the hybrid spheres leads to fluorescence enhancement of Eu^3＋ emission by approximately an order of magnitude. The lifetimes of the hybrid spheres were also measured.     

Facile sol-gel combustion synthesis and photoluminescence enhancement of CaZrO3：Sm3＋ nanophosphors via Gd3＋ doping

CaZrO3:Sm and CaZrO3:Sm,Gd nanophosphors were synthesized by a facile and efficient sol-gel combustion method. Their structure and optical properties were studied. The photoluminesce (PL) results showed that the phosphor could be efficiently excited by irradiation at wavelengths in the visible light region (350-430nm). The CaZrO3:Sm nanophosphor exhibited strong yellow-green, orange and red emissions with peak wavelength centered at 565nm (4G5/2→6H5/2), 601nm (4G5/2→6H7/2) and 645nm (4G5/2→6H9/2), respectively. The incorporation of Gd3+ ions could greatly improve the luminescence intensity. The highest emission intensity was observed with 2mol.% Gd3+ doped CaZrO3:3mol.% Sm powder. The material had potential application in the development of materials for LED’s and other optical devices in the visible region.     

Luminescence of Terbium Complexes Incorporated into Silica Matrix

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Synthesis, Crystal Structure and Fluorescent Properties of a New One-Dimensional Polymer [Sm（ sal ） 4 （ phen）2 Na ] n

A growing attention has been paid to the investi gation of fluorescence enhancement of the lanthanidessince the lanthanides have low absorptivity and poorquantum yields. Fluorescence enhancement has gener ally been achieved through ligand sensitization in re cent years[1~4]. In emission process, an organic lig and is first excited by absorption of light, followed byenergy transfer from the ligand to the excited levels ofa lanthanide, which then emits. Moreover, the fluo rescence of th…     

Synthesis and Characterization of Quaternary Complex of Sm-CH_3C(CH_2OH)_2COOH-Phen

Asrareearthionshaveexcellentfluorescentproperty ,theirapplicationsandresearcheshavere ceivedunabatedattention .Aseriesofcomplexesofrareearthwithfluorescentpropertyhasbeensynthesized[1～ 4] .Throughorbitaltransitionofrareearthions ,UVlightabsorbedcanbechan…     

Luminescence Properties of Sm^3＋ doped Bi2ZnB2O7

The phosphors of （Bi1- x Smx ） 2ZnB2O7 （ x = 0. 01, 0. 03, 0. 05, 0. 07, and 0. 09） were synthesized by conventional solid state reaction. The purity of all samples was checked by X-ray powder diffraction （XRD）. XRD analysis shows that all these compounds are of a single phase of Bi2ZnB2O7, indicating that the Bi^3＋ in Bi2ZnB2O7 can be partly replaced by the Sm^3＋ without the change of crystal structure. The excitation and emission spectra at room temperature show the typical 4f-4f transitions of Sm^3＋ . The dominant excitation line is around 404 nm due to ^6H5/2→^4K11/2 and the emission spectrum consists of a series of lines at 563, 599, 646, and 704 nm due to ^4G5/2→^6H5/2, ^6H7/2, ^6H9/2, and ^6H11/2, respectively. The optimal concentration of Sm^3＋ in Bi2ZnB2O7 is about 3mol% （relative to lmol Bi^3＋ ） and the critical distance Rc was calculated as 2.1 nm. The temperature dependence of the emission intensity of Bi1.94Sm0.06ZnB2O7 was examined in the temperature range between 100 and 450 K. The quenching temperature where the intensity has dropped to half of the initial intensity is 280 K. The lifetime for Sm^3＋ in Bi1.94Sm0.06ZnB2O7 is fitted as a value of 0.29 and 1.03 ms.     

Hydrothermal synthesis, crystal structure and luminescence of a europium complex with phenylmalonic acid and 1, 10-phenanthroline

A new complex Eu2（PA）6（phen）2 was prepared with hydrothermal reaction using EuCl3.6H2O, phenylmalonic acid （H2phma）, and 1, 10-phenanthroline （phen）, where PA was the decarboxylated product of HEphma, phenylacetate. The crystal structure of the title complex was determined with the X-ray diffraction. The title complex was a binuclear molecule with an inversion center. Each Eu^3＋ ion was nine-coordinated with two nitrogen atoms from one phen molecule and seven oxygen atoms from five PA ligands. The carboxylic groups were bonded to the Eu^3＋ ion in three modes, the chelating bidentate, the bridging bidentate, and the bridging-chelating tridentate. The complex emits intense red fluorescence under ultraviolet light. The luminescence peaks correspond to the characteristic emission 5D0→7FJ （J=0-4） transitions of the Eu^3＋ ion.     

Reddish orange long lasting phosphorescence of Sm3+ in Sr2ZnSi2O7:Sm3+ phosphors

Long lasting phosphorescence phosphors with composition of (Sr1-xSmx)2ZnSi2O7 were prepared by conventional high-temperature solid-state method. Their properties were systematically investigated utilizing XRD, photoluminescence, phosphorescence and thermoluminescence spectra. The results showed that these phosphors emitted reddish orange light that corresponds to the characteristic emission due to the 4G5/2→6H5/2, 6H7/2 and 6H9/2 transitions of Sm3+. After the UV light excitation source was switched off, th...     

Co-Precipitation Synthesis and Spectral Characteristics of Long Afterglow Phosphor Y2O2 S： Sm^3＋, Mg^2＋ , Ti^4＋

Y2O2S：Sm^3＋, Mg^2＋, Ti^4＋ phosphor was synthesized by co-precipitation method. The crystalline structure of all synthesized phosphors was investigated by XRD. The result showed that all synthesized phosphors had a hexagonal crystal structure, which was the same as Y2O2S. The emission spectrum and excitation spectrum were measured, and the effect of Sm^3 ＋ molar ratio on the spectra was discussed. The emission spectra of the phosphors showed three emission peaks due to typical transitions of Sm^3 ＋ （4G5/2→6HJ ,J = 5/2, 7/2, 9/2）, and the emission peaks at 606 nm was stronger than others. With the increase of Sm^3 ＋ molar ratio, the emission intensity was strengthened. The excitation peaks were ascribed to the representative energy transition 4f→4f of Ti^4＋ phosphor prepared by co-precipitation method was Sm^3＋ ions. The results indicated that the Y2O2S ： Sm^3＋ , Mg^2＋ , an efficient long afterglow phosphor.     

Thermochemical studies on complex of [Sm(o-NBA)_3phen]_2

A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔθ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle according to Hess’s Law, the standard molar enthalpy of formation of [Sm(o-NBA)3 phen]2 (s) was estimated to be f mHΔθ=–4109.2±7.3 kJ/mol.