Preparation and properties of temperature sensitive paint based on Eu(DBM)3phen as probe molecule

Probe molecule Eu(DBM)3 phen is made up of europium oxide(Eu_2 O_3),dibenzoylmethane(DBM) and1,10-phenanthroline(phen). The temperature sensitive paint(TSP) was compounded by the polymerization of the probe molecule, methyl methacrylate(MMA) and the initiator of benzoyl peroxide(BPO).The structure, morphology, luminescence property of probe molecule and the temperature quenching property of the temperature sensitive paint(TSP) were characterized by infrared spectrometer, UV-vis spectrometer, scanning electron microscopy and fluorescence spectrometer respectively. The infrared spectrum and UV-vis spectra show that Eu and DBM form six membered rings, and Eu-O coordinate bonds form. The nanocrystals are in sphere-like morphology with an average size of approximately100 nm. Fluorescence spectra present that the performance of temperature quenching is excellent,what's more, TSP sample has different temperature sensitivity in various temperature scope. Particularly,under excitation of 286 nm, TSP has a highest temperature sensitivity between 50 and 60 ℃, and the strongest fluorescence emission reaches a peak(615 nm). It indicated that probe molecule(Eu(DBM)_3 phen) has strong luminescent intensity and the temperature quenching properties of Eu(DBM)_3 phen/PMMA is good.     

Emission of Rare Earth Complex Tb0.5Eu0.5 （asprin）3phen

The coprecipitate Tho.sEuo.5(asprin)3phen was synthesized. By doping the rare earth complex into polymer PVK, the EL device was fabricated with the structure of ITO/PVK: RE/PBD/AI. Compared with the device using PVK/Eu (asprin)3phen blend as the light emitting layer, the emission of Eu^3 in the PVK/Th0.5Eu0.5(asprin)3 phen blend is great-ly enhanced along with the quenching of the emission of PVK.     

MCM-41 supported nano-sized CuO-CeO_2 for catalytic combustion of chlorobenzene

In this paper,MCM-41 was synthesized by a soft template technique and MCM-41 supported CuO-CeO_2 nano-sized catalysts with different Cu/Ce molar ratios were prepared by a deposition-precipitation method.N_2 adsorption,HRTEM-EDS,H_2-TPR,XPS characterization,as well as catalytic activity and durability tests for the catalytic combustion of chlorobenzene(CB) were conducted to explore the relationship between the structure and catalytic performance of the catalysts.It is revealed that cuCe(6:1)/MCM-41 has the highest activity and can completely catalyze the degradation of CB at 260℃.The reasons for the high activity of the catalysts are as follows:MCM-41,a type of mesoporous material which has large pore size and large specific surface area,is suitable as a catalyst carrier.The average diameter of nano-sized CuO and CeO_2 particles is about 3-5 nm and adding CeO_2 improves the dispersion of active component CuO,which are highly and evenly dispersed on the surface of MCM-41.Characterization results also explain why MCM-41 supported CuO-CeO_2 with appropriate proportion can highly enhance the catalytic activity.The reason is that CeO_2 acting as an oxygen-rich material can improve the mobility of oxygen species through continuous redox between Ce~(4+)and Ce~(3+),and improve the catalytic performance of CuO for CB combustion.Besides,CuCe(6:1)/MCM-41 also displays good durability for CB combustion,both in the humid condition and in the presence of benzene,making it a promising catalytic material for the elimination of chlorinated VOCs.     

Luminescence study of europium(III) tris(β-diketonato)/phosphonate complexes in chloroform

The extraction of Eu(III) with β-diketone, HA, and monodentate or bidentate Lewis bases, B, into chloroform and the luminescence properties of the extracted species were studied. Pivaloyltrifluoroacetone, Hpta, and 2-thenoyltrifluoroacetone, Htta, were used as the β-diketones. The Lewis bases, B, were tetraethyl methylene diphosphonate, POPO, which was bidentate, and diethyl benzylphosphonate, PhPO which was monodentate. Based on the extraction data, the stability constants, log β of the first complexes between tris(β-diketonato)Eu(III) and the phosphonate, EuA3B, were determined to be 6.0 for the POPO complex and 3.40 for the PhPO complex. The Eu(III) luminescence intensity in the EuA3POPO was larger than EuA3 where A was either pta or tta at similar concentrations of Eu(III), while that in Eu(pta)3PhPO was stronger than EuA3; however, in Eu(tta)3PhPO, it was weaker than Eu(tta)3. The POPO functions as a sensitizer, and the PhPO functions as a quencher for the tta chelate and as a sensitizer for the pta chelate. From the lifetime and quantum yield, φ, of the Eu(III) luminescence in the complexes as well as the observation of the extractability of Eu(III) with the Hpta and the phosphonates and of the luminescence spectra of the complexes, it was confirmed that the extraction of Eu(III) was remarkably enhanced with a β-diketonate and a strong Lewis base, and also the ternary complex that was formed as the extracted species, showed luminescence enhancement. This phenomenon may be due the formation of a strong bond between the Eu(III) and the strong Lewis base leading to more hydrophobicity in the extracted species and also to more effective energy transfer from the Lewis base to the Eu(III). It was not significant whether the donor atoms were N or O.     

Study on Luminescence Properties of a Novel Rare Earth Complex Eu（ TTA）2 （N-HPA） Phen

A novel rare earth complex Eu（TTA）2（N-HPA）Phen （TTA = thenoyltrifluoroacetone, N-HPA = N-phenylanthranilic acid, and phen = 1,10-phenathroline ）, which contains three different ligands, was synthesized. The Eu complex was blended with poly N-vinylcarbazole （PVK） in different weight ratios and spin coated into films. The luminescence properties of films were investigated and energy transfer between PVK and the complex was discussed. Multilayer structural devices consisting of ITO/PVK： Eu （TTA）2 （N-HPA） phen/BCP/Alq3/Al were fabricated with PVK ： Eu （TTA）2（N-HPA） as light-emitting layer. Increasing the concentration of Eu in the PVK thin film would inhibit the emission of PVK to different degrees. Finally, the pure red luminescence of europium（ Ⅲ ） was observed when the doping weight ratio was approximately 1 ： 5, which indicated an effective energy transfer from PVK to rare earth complex.     

Synthesis of novel europium complexes and their photoluminescence properties

Two novel luminescent Eu(III) complexes with the formulas(NIP)Eu(DBM)3 1 and(ENIP)Eu(DBM)3 2(NIP=2-(naphtha-len-1-yl)-1H-imidazo [4,5-f] [1,10] phenanthroline,ENIP=1-ethyl-2-(naphthalen-1-yl)-1H-imidazo [4,5-f] [1,10] phenanthroline,DBM= dibenzoylmethanato) were successfully synthesized and characterized by IR and elemental analysis.The UV-vis absorption spectra and pho-toluminescence properties of the complexes were investigated,and the irradiation at the absorption band between 300-400 nm of europium complexes either in solution or in the solid state led to the emission of a sharp red band at ~610 nm,a characteristic Eu3+ emission due to the transition of 5D0→7F2.Furthermore,the weak emission bands around 587 and 595 nm attributed to 5D0→7F0 and 5D0→7F1 transition were also displayed in the emission spectra.These results demonstrated that the Eu(III) ion was sensitized efficiently by the ligand and displayed photoluminescence with high intensity,narrow half-peak width,and monochromic light.The excited-state lifetimes of 1 and 2 were in the microsecond time scale,but the photoluminescence quantum yield of 2(0.03) was two times higher than that of 1(0.01) which should be at-tributed to the effect of the ethyl substituting in ENIP.     

Synthesis and optical properties of Eu~(3+) ion doped nanocrystalline hydroxya patites embedded in PMMA matrix

Transparent,luminescent and functional nanocomposites demonstrate interesting optical and mechanical properties suitable for many optoelectronic applications.Transparent polymethyl methacrylate(PMMA) polymer nanocomposites modified with thenoyl-trifluoroacetonate(TAA) were fabricated by in situ polymerization and used as hosts for homogenous dispersion of 3 mol.% Eu3+:Ca10(PO4) 6(OH) 2(Eu3+:HA) hydroxyapatite ～20 nm large nanocrystals.The emission,excitation and transmission spectra as well as the fluorescence decay rates of bare Eu3+:HA nanocrystallites,Eu3+:HA embedded in the PMMA and and Eu:HA embedded in the PMMA/TTA nanocomposites were studied.The improvement of transparency was demonstrated with the addition of TTA as well as europium doped hy-droxyapatites in comparison to pure PMMA matrix.The Judd-Ofelt analysis of f-f transitions of Eu3+:HA nanocrystallites,the PMMA/Eu3+:HA and the PMMA+TTA/Eu3+:HA was performed to investigate the optical behavior of the polymeric composites.     

Synthesis and Photoluminescence of Three Europium （ Ⅲ ） Ternary Complexes with New Secondary Ligands of Different Structure

Three new 1,10-phenanthroline derivatives, dipyrido (3,2-f: 2,3-h) quinoxaline (DPQN), imidazo (5,6-f)-( 1,10)-phenanthroline (IP) and 3-phenyl-imidazo (5,6-f)- ( 1,10)-phenanthroline (PIP) were designed and synthesized was a secondary ligand to coordinate with europium (Ⅲ) ion while dibenzoylmethane (DBM) was used as the first ligand. The compositions of the ligands and the europium (Ⅲ) ternary complexes were confirmed by elementary analysis, IR and ^1H-NMR-spectroscopy. The UV-visible absorption spectra, thermal stability, photoluminescence spectra, quantum yield and fluorescence life time of the Eu( Ⅲ) complexes were investigated. The effect of the structure of the secondary ligand on the photoluminescence of the complexes was discussed. The results show that the synthesized Eu(Ⅲ) complexes are good red-emitiing materials for potential application in fabrication of organic electroluminescence devices.     

Separation of Eu（III） with supported dispersion liquid membrane system containing D2EHPA as carrier and HNO3 solution as stripping solution

The Eu(III) separation in supported dispersion liquid membrane (SDLM),with polyvinylidene fluoride membrane (PVDF) as the support and dispersion solution containing HNO3 solution as the stripping solution and Di(2-ethylhexyl) phosphoric acid (D2EHPA) dis-solved in kerosene as the membrane solution,was studied.The effects of pH value,initial concentration of Eu(III) and different ionic strengths in the feed phase,volume ratio of membrane solution and stripping solution,concentration of HNO3 solution,concentration of carrier,different stripping agents in the dispersion phase on the separation of Eu(III) were also investigated,respectively.As a result,the optimum separation conditions of Eu(III) were obtained as the concentration of HNO3 solution was 4.00 mol/L,concentration of D2EHPA was 0.160 mol/L,and volume ratio of membrane solution to stripping solution was 30:30 in the dispersion phase,and pH value was 5.00 in the feed phase.Ionic strength had no obvious effect on the separation of Eu(III).Under the optimum conditions studied,when initial concentration of Eu(III) was 1.00×10–4 mol/L,the separation rate of Eu(III) was up to 94.2% during the separation period of 35 min.The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry.The results were in good agreement with the literature data.     

Preparation and photoluminescence enhancement of Li＋ and Eu3＋ co-doped YPO4 hollow microspheres

Li+ and Eu3+ co-doped YPO4 hollow microspheres were successfully synthesized by a sacrificial template method using polystyrene (PS) as template. Techniques of X-ray diffraction (XRD), scanning electron microscopy (SEM), as well as transmission electron microscopy (TEM) were employed to characterize the as-synthesized sample. Furthermore, the photoluminescence (PL) characterization of the Li+ and Eu3+ co-doped YPO4 microsphere was carried out and the effects of the doping concentration of Li+ and Eu3+ active center concentration as well as calcination temperature on the PL properties were studied in detail. The results showed that the incorporation of Li+ ions into the YPO4 :Eu3+ lattice could induce a remarkable improvement of the PL intensity. The highest emission intensity was observed with the compound of 5%Li+ and 5%Eu3+ co-doped YPO4 , whose brightness was increased by a factor of more than 2.2 in comparison with that of the YPO4 :5%Eu3+.     

Luminescence study of europium（Ⅲ） tris（β-diketonato）/phosphonate complexes in chloroform

The extraction of Eu（Ⅲ） with β-diketone, HA, and monodentate or bidentate Lewis bases, B, into chloroform and the luminescence properties of the extracted species were studied. Pivaloyltrifluoroacetone, Hpta, and 2-thenoyltfifluoroacetone, Htta, were used as the β-diketones. The Lewis bases, B, were tetraethyl methylene diphosphonate, POPO, which was bidentate, and diethyl benzylphosphonate, PhPO which was monodentate. Based on the extraction data, the stability constants, log β, of the first complexes between tfis（β-diketonato）Eu（Ⅲ） and the phosphonate, EuA3B, were determined to be 6.0 for the POPO complex and 3.40 for the PhPO complex. The Eu（Ⅲ） luminescence intensity in the EuA3POPO was larger than EuA3 where A was either pta or tta at similar concentrations of Eu（Ⅲ）, while that in Eu（pta）3PhPO was stronger than EuA3; however, in Eu（tta）3PhPO, it was weaker than Eu（tta）3. The POPO functions as a sensitizer, and the PhPO functions as a quencher for the tta chelate and as a sensitizer for the pta chelate. From the lifetime and quantum yield, φ, of the Eu（Ⅲ） luminescence in the complexes as well as the observation of the extractability of Eu（Ⅲ） with the Hpta and the phosphonates and of the luminescence spectra of the complexes, it was confirmed that the extraction of Eu（Ⅲ） was remarkably enhanced with a β-diketonate and a strong Lewis base, and also the ternary complex that was formed as the extracted species, showed luminescence enhancement. This phenomenon may be due the formation of a strong bond between the Eu（Ⅲ） and the strong Lewis base leading to more hydrophobicity in the extracted species and also to more effective energy transfer from the Lewis base to the Eu（Ⅲ）. It was not significant whether the donor atoms were N or O.     

Effect of gadolinium incorporation on optical characteristics of YNbO_4：Eu~（3＋） phosphors for lamp applications

Eu3+-doped (Y,Gd)NbO4 phosphor was synthesized by solid-state reaction for possible application in cold cathode fluorescent lamps. A broad absorption band with peak maximum at 272 nm was observed which was due to the charge transfer between Eu3+ ions and neighboring oxygen anions. A deep red emission at the peak wavelength of 612 nm was observed which could be attributed to the 5D0→7F2 transition in Eu3+ ions. The highest luminance for Y1-x-yGdyNbO4:Eux3+ under 254 nm excitation was achieved at Eu3+ concentration of 18 mol.% (x=0.18) and Gd3+ concentration of 8.2 mol.% (y=0.082). The luminance of Y0.738Gd0.082NbO4:Eu3+0.18 was higher than that of a typical commercial phosphor Y2O3:Eu3+ and the CIE chromaticity coordinate was (0.6490, 0.3506), which was deeper than that of Y2O3:Eu3+. The particle size of the synthesized phosphors was controlled by the NaCl flux and particle size as high as 8 μm with uniform size distribution of particles was obtained.     

Doped Organic Electroluminescence from a Novel Rare Earth Complex Tb （3-metho） 3 phen

A novel rare earth complex Tb (3-metho)3phen was synthesized and characterized. The complex was doped into PVK to improve the conductivity and film-forming property of Tb(3-metho) 3phen. A device with a structure of ITO/PVK: Tb(3-metho)3phen/Al was fabricated to study the eleetrolumineseent properties of Tb(3-metho) 3 phen. And the optoluminescent and AFM properties of this device were also studied, which proved the existence of energy transfer from PVK to Tb(3-metho)3phen. As a result, a pure green emission with sharp spectral band at 547.5 nm was observed.     

Luminescent properties of Eu³⁺-doped BaZrO₃ phosphor for UV white light emitting diode

A novel orange phosphor Eu3+ doped barium zirconate(BaZrO3) was synthesized by conventional solid state reaction method and its crystal structure and luminescent properties were investigated in this paper.The X-ray diffraction patterns(XRD) showed that simple BaZrO3 phase was obtained.Monitoring at 596 nm,the excitation spectrum consisted of a broad band and a series of narrow bands and the stronger excitation peaks located at 275 and 393 nm,respectively.The emission spectrum excited by 393 nm UV light was composed of four narrow bands.The strongest emission was located at 596 nm.The appropriate concentration of Eu3+ was 0.025(molar fraction) for the highest emission intensity at 596 nm.The H3BO3 and ammonium were added as flux and the results showed that 2 wt.% NH4F ions was the optimal flux for BaZrO3:Eu3+.     

Photoluminescence studies of Eu2+-Yb3+ co-doped BaMgAl10O17 phosphor synthesized by the combustion method

BaMgAl10O17:Eu2+,Yb3+ was investigated as a possible quantum cutting system to enhance solar cells efficiency. Phosphors were synthesized by combustion method and composed of nanorods. Photoluminescence spectra showed that Eu in the sample was reduced to bi-valence while Yb remained trivalence. Through a cooperative energy transfer process, the obtained powders exhibited both blue emission of Eu2+ (around 450 nm) and near infrared emission of Yb3+ (around 1020 nm) under broad band excitation (250-410 nm) originating from 4f→5d transition of Eu2+. Energy transfer phenomenon between the sensitizer Eu2+ and the activator Yb3+ was investigated via the lumines-cent spectra and the decay curves of Eu2+ with different Yb3+ concentrations. Results indicated that energy transfer efficiency from Eu2+ to Yb3+ was not high. The poor efficiency can be explained by the long distance between rare earth ions.     

Cooperative energy transfer in Eu3+,Yb3+ codoped Y2O3 phosphor

Under 980 nm laser excitation,red emission(5D0-7FJ(J=0,1,2)) of Eu3+ was observed in cubic Y2O3 codoped with Eu3+ and Yb3+.The dependence of the upconverted emission on doping concentration and laser power was studied.Yb3+ emission around 1000 nm(2F5/2-2F7/2) was reported upon excitation of Eu3+ ions.The decay curves of 5DJ(J=0,2) emission of Eu3+ under excitation of 266 nm pulse laser were examined to investigate the Eu3+→Yb3+ energy transfer process.Cooperative energy transfer process was discussed as the possible mechanism for the visible up-conversion luminescence of Eu3+ and near-infrared down-conversion emission of Yb3+.     

Synthesis and luminescence properties of rare earth ternary complexes consisting of Eu(III), β-diketones and 1,10-phenanthroline

Three novel β-diketones (HPPP, HTPP, and HFPP) ligands were synthesized by Sonogashira coupling reaction and Claisen con- densation. The structure of β-diketones was confirmed with elemental analysis, IR, NMR and MS spectra. Three new ternary complexes consisting of Eu(III), β-diketones, and 1,10-phenanthroline(phen) were synthesized and characterized as TbL3phen (L=PPP, TPP, FPP) with elemental analysis, chemical analysis, and IR spectra, and their luminescence properties were studied.     

Lanthanum incorporated in MCM-41 and its application as a support for a stable Ni-based methanation catalyst

Herein, lanthanum was incorporated via hydrothermal synthesis into a MCM-41 framework structure with La/Si molar ratios from 0.01 to 0.1. Samples of NiO supported on LaMCM-41 were prepared using the impregnation method. The catalyst performance was evaluated using a fixed bed CO methanation reactor. A Ni/LaMCM-41 catalyst with La/Si = 0.1 shows the best catalytic performance with a CO conversion of almost 100% and a CH4 selectivity of 89.5% at 250 ℃ under a pressure of 1.5 MPa and at an airspeed of 36,000 mL/(g·h). Compared with Ni-La/MCM-41(La/Si = 0.1) and Ni/MCM-41 prepared via the impregnation method, Ni/LaMCM-41(La/Si = 0.1) shows a higher CO conversion and CH4 selectivity.In a 100 h stability test, the Ni/LaMCM-41(La/Si = 0.1) catalyst shows excellent stability; furthermore, the CO conversion is always greater than 98.0%, which is significantly better than the results for Ni/MCM-41.We experimentally demonstrate that elemental La enters the framework of MCM-41. The Ni/LaMCM-41 catalyst performs well because the La reduces the average particle size of the NiO particles and enhances the interaction between NiO and MCM-41; moreover, the introduction of La significantly inhibits the sintering of the catalyst and the formation of carbon deposits.     

Thermochemistry of Ternary Complex Dy(Et_2dtc)_3(phen)

The ternary solid complex was synthesized with sodium diethyldithiocarbamate (NaEt2dtc), 1,10-phenanthroline (phen) and low hydrated dysprosium chloride in absolute ethanol by improved method of reference. The title complex was identified as the general formula of Dy(Et2dtc)3(phen) by chemical and elemental analyses. IR spectrum of the complex shows that the Dy3 coordinated with six sulfur atoms of three NaEt2dtc and two nitrogen atoms of phen. It is assumed that the coordination number of Dy3 is eight.The enthalpy change of liquid-phase reaction of formation, ΔrHθm(l), is determined as (-19.091±0.015) kJ·mol-1 at 298.15 K by a microcalorimeter, and the enthalpy change of the solid-phase reaction of formation, ΔrHθm(s), is calculated as (139.641±0.482) kJ·mol-1 on the basis of a thermochemical cycle. The thermodynamic of reaction of formation was studied by changing the temperature of liquid-phase reaction. The constant-volume combustion energy of the complex, ΔcU, is determined as (-16730.21±9.25) kJ·mol-1 by a precise rotating-bomb calorimeter at 298.15 K. Its standard enthalpies of combustion, ΔcHθm, and standard enthalpies of formation, ΔfHθm, are calculated as (-16749.42±9.25) kJ·mol-1 and (-2019.68±10.19) kJ·mol-1, respectively.     

Synthesis,characterization and thermolysis of lanthanide metal nitrate complexes with 1, 10-phenanthroline,Part-95

The nitrate complexes of cerium, praseodymium and neodymium with 1,10-phenanthroline(phen) of general formula [Ln(phen)2(NO3)2(H2O)2]·NO3(where, Ln=Ce, Pr and Nd) were prepared and characterized by X-ray crystallography. Thermolysis of these complexes was investigated by simultaneous thermogravimetry(TG) and differential thermal analysis(DTA). Isothermal TG was taken to evaluate the kinetic parameters using model fitting as well as model free isoconversional methods. The thermolytic pathways were also suggested, which involves decomposition followed by ignition. All the three complexes had coordination number ten and showed multistep decompositions. In order to evaluate the response of rapid heating, ignition delay(Di) measurements were undertaken. The activation energies for ignition were found to decrease in the order: NdPrCe.