Fluorescence properties and application of doping complexes Eu_(l-x)L_x(TTA)_3Phen as light conversion agents

1　INTRODUCTIONRecently ,theinvestigationonlightconversiona gentsmainlycoversorganicluminescentpigments ,in organicluminescentmaterialsandrareearthcomplex esluminescentmaterials[1 4 ] .Organicfluorescentpig mentsforlightconversionagentshavegoodlumines centintensity ,howevertheirstabilityispoor .Inor ganicluminescentmaterialshavegoodstability ,buttheirfluorescentintensityislowandhaspoorcompat ibilitywithresin .Rareearthcomplexesluminescentmaterialshavehighfluorescentintensityandgoodsta bil…     

Fluorescence properties and application of doping complexes Eu1-xLx (TTA)3Phen as light conversion agents

Light conversion agents Eu1-x Lx (TTA)3 Phen (L denotes La3+ , Gd3+ , Y3+ ) complexes were prepared,and the influence of doping ions on fluorescence properties was investigated by elementary analysis, FTIR and fluorescent spectra. The results show that FTIR spectra of Eu1_x Lx (TTA)3 Phen complex system are identical with that of EuTTA3 Phen, which indicates that the complexes Eu1 xLx(TTA)3Phen are similar in structure to Eu (TTA)3Phen. For the above doping elements, co-fluorescence enhancement has the following order: Gd3+ ＞Y3+ ＞La3+ , and the optimum mole fractions of doping elements are 0.4, 0.2 and 0.5 respectively for Gd3+ , Y3+ ,La3+. Among all the complexes, Eu0.6 Gd0.4 (TTA)3 Phen complex has the strongest fluorescent intensity. Applying Eu0.6 Gd0.4 (TTA)3 Phen complex to plastic and printing inks, bright red fluorescence plastic and printing inks are obtained when the content of europium reaches 0.1% (mass fraction).     

Syntheses and applications of Eu（Ⅲ） complexes of 2-thienyltrifluoroacetonate, terephthalic acid and phenanthroline as light conversion agents

A series of europium(Ⅲ) complexes of 2-thienyltrifluoroacetonate (HTTA), terephthalic acid (TPA) and phenanthroline (Phen) were synthesized. The new complexes Eu(TPA)(TTA)Phen and Eu2(TPA)(TTA)4Phen2 were characterized by elemental analysis, IR spectrum, scanning electron microscope and thermal stability analysis. The results show that the thermal stability of the Eu( Ⅲ ) complexes increases in the following order: the mononuclear complex Eu(TTA)3Phen, the binuclear complex Eu2(TPA)(TTA)4Phen2, the chain polynuclear complex Eu(TPA)(TTA)Phen. And the formation of the binuclear/polynuclear structure of the new complexes appears to be responsible for the enhancement of their thermal and optical stability. In addition, The fluorescence excitation spectra of these new complexes show more broad excitation bands than that of the complex Eu(TTA)3Phen corresponding to their formation. The enhancement of Eu3 fluorescence in the new complexes can be observed by the addition of Gd3 . The bright red luminescent plastics can be obtained when the complex EuGd(TPA)(TTA)4Phen2 is added above 0.5% (mass fraction).     

稀土铕配合物在荧光防伪油墨中的应用

以铕离子（Eu^3＋）为中心,以苯甲酰丙酮（BZA）、苯甲酸（BA）、邻菲咯啉（Phen）为配体,在无水乙醇中合成了三元配合物Eu（BZA）3Phen与Eu（BA）3Phen．配合物的紫外可见光谱与红外光谱分析表明配体与铕离子发生配位,合成了三元配合物．研究配合物的荧光性能,发现Eu（BZA）3Phen的相对荧光强度大于Eu（BA）3Phen．将荧光强度高的Eu（BZA）3Phen作为荧光剂制备了荧光防伪油墨．荧光防伪油墨的荧光性能显示,油墨与配合物Eu（BZA）3Phen发射波长相同,均为612nm．荧光防伪油墨在可见光下无色,在紫外灯下呈现红色,可用于防伪包装印刷．     

铕/钬-苯甲酸-邻菲罗啉混合稀土配合物的合成与表征及荧光性质

在无水乙醇溶液中合成了铕/钬-苯甲酸(BA)-邻菲罗啉(Phen)混合稀土配合物,通过元素分析、红外光谱、摩尔电导等实验,确定配合物化学组成为RE(BA)3Phen(RE=Eu3+/Ho3+)。在310 nm紫外光激发下,研究了稀土配合物的荧光光谱。结果表明,铕和钬之间存在相互作用,钬对铕具有显著的敏化作用,这些混合配合物可以发出强度更高的红色荧光。当配合物中铕与钬物质的量之比为1∶1时,其荧光发射强度约为未引入钬时的2.2倍。     

锂离子电池正极材料Li0.97Re0.01FePO4的合成及性能

采用固相反应法合成了锂离子电池正极材料Li0.97Re0.01FePO4(Re=Er,Y,Gd,Nd,La),采用X射线衍射、恒电流充放试验对掺杂试样的微观结构和电化学性能进行测试。试验结果表明:掺杂稀土金属离子对LiFePO4的晶体结构没有影响,与LiFePO4相比,掺杂Er3+,Y3+,Gd3+的试样具有优良的循环性能和倍率性能,而掺杂Nd3+,La3+的试样的循环性能和倍率性能较差。掺杂试样中,Li0.97Gd0.01FePO4的电化学性能最佳,在C/10和1C(1C=120 mA.g-1)倍率下放电容量均最大。     

Sensitization and intra-molecular energy transfer of Eu<Superscript>3+</Superscript> by Tb<Superscript>3+</Superscript> in Eu-Tb binuclear complexes/PMMA

A series of Eu0.5Tb0.5(TTA)3Phen/PMMA (TTA=thenoyltrifluoroacetone,Phen=phenanthroline) and Eu0.5Tb0.5(TTA)3Dipy/PMMA (Dipy=2,2’-dipyridyl) were prepared by in-situ polymerization.The structures of the composites were characterized by IR spectra and electron spectrum.Photoluminescence properties were investigated by UV-Vis spectra and fluorescence spectra.Meanwhile,the energy transfer models were set up.The results indicated that polymer parts were attached with the rare-earth molecular parts in the composi...     

双核稀土配合物Gd_xSm_(1-x)(TTA)_3phen的制备及发光性能

合成了系列钆钐双核稀土有机配合物GdxSm1-x(TTA)3phen(x=0~0.9).红外光谱(IR)、X射线衍射(XRD)、热重(TG)结果推测了配合物可能的分子结构;紫外可见光谱(UV/vis)结果表明,该系列稀土有机配合物能有效的吸收紫外光,吸收峰主要来自于有机配体TTA和phen(270nm和351nm处);荧光光谱(FS)结果表明,Gd3+对于Sm3+具有荧光增效,当Gd3+的摩尔分数为0.6时,Gd0.6Sm0.4(TTA)3phen类配合物的特征荧光(562nm,596nm和643nm处)强度均达到最大.     

单分散铕掺杂氧化钇空心微球的荧光性能研究

以单分散三聚氰胺-甲醛微球为模板,通过煅烧除去模板,制备出粒径均一的铕掺杂氧化钇空心微球荧光材料. 利用扫描电子显微镜、透射电子显微镜、傅立叶变换红外光谱仪、X射线衍射仪、荧光分度计对氧化物空心微球荧光材料进行表征. 结果表明:成功地制备了铕掺杂氧化钇单分散空心微球,铕元素掺杂进入氧化钇晶体后对氧化钇晶型没有影响,随着铕元素含量的增加,晶格常数逐渐增大. 铕掺杂氧化钇空心球在613 nm处均表现出强烈的发射峰,当铕元素掺杂量为原分子数x=5%时,荧光强度最强;随着铕元素含量的增多,电荷迁移带红移,表明铕-氧键共价性逐渐减弱、离子性逐渐增强.     

Y_2O_3:Eu~(3+)纳米粉体的制备及其性能研究

以Y2O3,Eu2O3为原料,NH3?H2O和NH4HCO3为沉淀剂,采用共沉淀法,在700至1200℃下煅烧2h制备出Y2O3:Eu3+纳米粉体,通过X射线衍射分析(XRD)、扫描电镜(SEM)和荧光分光光度计等表征样品的性能,研究不同掺杂浓度,不同烧结温度及不同沉淀剂对粉体各项性能的影响。结果表明,以两种沉淀剂制备的纳米粉体均为纯相,与Y2O3标准PDF卡片41-1105相吻合。以NH3?H2O为沉淀剂制备出来的前驱体在1100℃下煅烧2h获得的粉体分布均匀,近似球形,粒径分布在50~80nm,以NH4HCO3为沉淀剂制备出来的前驱体在1100℃下煅烧2h获得的粉体分布均匀,纯度高,具有良好的分散性,粒径分布在60~80nm。制备出来的粉体在波长为254nm的紫外光激发下发出611nm的红光。     

光致发光稀土铕高分子配合物的合成研究初探

目的　合成稀土高分子配合物并研究其光致发光的光物理过程 .方法以 4-乙烯基吡啶 (4 VP)与甲基丙烯酸甲酯 (MMA)的共聚物为配体 ,并与邻菲洛啉 (Phen)小分子配体协同反应 ,与 Eu( )配位 ,合成了稀土高分子配合物 ;通过紫外光谱与荧光光谱的测定 ,研究稀土高分子配合物光致发光的机理 .结果4-乙烯基吡啶共聚物通过吡啶环上的氮原子与稀土离子可直接配位 ;小分子配体具有协同配位效应 .结论稀土配合物具有很强的荧光强度 .     

Y2O3：Eu超细粉体的制备及其在聚丙烯中的应用

利用微波辅助溶胶凝胶法得到纳米Y2O3：Eu红色荧光粉。对前驱体和试样进行了红外（FTIR）微结构分析,从试样显微结构分析了微波辐射加热机制。借助X射线衍射仪（XRD）、透射电镜（TEM）和荧光光谱（PL）,对所得粉体进行了表征。结果表明,在700℃的温度下保温2h所得Y2O3：Eu粉体具有较佳的综合性能,96．3％的颗粒分布在15～27nm,且具有较好的荧光强度。扫描电镜（SEM）照片表明,Y2O3：Eu粉体呈疏松状分布,其表现软团聚尺寸小于100nm。考察了Y2O3：Eu粉体在聚丙烯（pp）中的成核、荧光和分散效果。结果表明,所添加的微量的Y2O3：Eu粉体具有成核作用,有利于粉体在pp中均匀分散,但pp样品荧光强度随着粉体添加量的增加而提高。     

Synthesis and photoluminescence property of red phosphors LiEu_(1-x)Y_x(WO_4)_(0.5)(MoO_4)_(1.5) for white LED

A series of novel red phosphors LiEu1-xYx(WO4)0.5(MoO4)1.5 (x=0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8) were synthesized by conventional solid state reaction method with the starting materials: WO3, MoO3, Eu2O3, Li2CO3 and Y2O3. The spectrum and the crystal structure of the phosphors were characterized by F-4500 and XRD respectively. Meanwhile the effects of flux and Y3+ concentration on the crystal structure and luminescent properties of the phosphors were investigated. The results showed that the optimal cont...     

溶胶沉淀法合成修饰氧化铕溶胶与特性表征

以噻吩甲酰三氟丙酮（TTA）、1,10-邻菲罗啉（phen）作为修饰剂,采用溶胶沉淀法制备得到修饰纳米氧化铕甲醇溶胶。采用荧光光谱、紫外可见光谱（UV-Vis）和高分辨率透射电镜（HRTEM）等方法研究了NaOH浓度对修饰氧化铕有机溶胶荧光特性的影响和修饰氧化物纳米粒子的结构及性能。结果表明,用phen和TTA作为修饰剂得到的修饰氧化铕溶胶都能发出了Eu^3＋的特征红色荧光,NaOH浓度对修饰纳米氧化铕甲醇溶胶的荧光强度具有很大的影响;HRTEM和选区衍射实验表面纳米粒子的核心为氧化铕微晶,其平均粒径小于10nm。由于修饰氧化铕溶胶能发出很强的红色荧光,是一种潜在的优质发光材料。     

Synthesis and luminescence properties of Eu3＋, Sm3＋ doped （YxGd1-x）2O3： Si4＋, Mg2＋ long-lasting phosphor

A novel red long-lasting phosphor,(Y1-xGdx)2O3:Eu3+,Sm3+,Si4+,Mg2+,was synthesized by the co-precipitation method using oxalate precipitation as the precursor.X-ray diffraction(XRD),scanning electronic microscopy(SEM),integrated thermal analyzer(TG),and photoluminescence spectra(PL) as well as the ST-900PM weak light photometer were used to study the synthesis conditions,morphology,luminescence properties,and the decay time of the phosphor.The XRD results show that the products synthesized at 1400°C for 4 h...     

1，3-丙二胺缩邻香兰素Ni—Gd配合物的合成及表征

文章用乙酸镍和1,3-丙二胺缩邻香兰素得到的配体（H2L）,以及硝酸钆在无水甲醇体系中合成Ni—Gd配合物。用红外光谱对邻香兰素、1,3-丙二胺缩邻香兰素（H2L）、[LNi]·H2O金属配合物和Ni—Gd配合物进行了表征,并用荧光光谱仪对异核双金属配合物做荧光性能表征。结果表明：金属元素成功的配合到Schiff碱上,成功地合成了1,3-丙二胺缩邻香兰素Ni—Gd配合物。     

曙红/铕-MCM-41介孔材料组装体的制备与发光性能

室温下制备出介孔材料MCM-41,将稀土离子铕和荧光染料曙红Y作为客体组装到MCM-41主体孔道中,制得Eosin Y/Eu-MCM-41复合型介孔材料组装体。采用XRD、RTIR、N2吸附和激发与发射光谱等技术对样品结构和性能进行了表征。结果表明,制备出的复合型介孔材料组装体仍保持MCM-41的六方有序结构,客体分子主要存在于主体介孔材料孔道中。激发与发射光谱显示曙红Y为发光中心,Eosin Y/Eu-MCM-41组装体的发光强度与Eosin Y-MCM-41比较呈规律性变化,当Eosin Y/Eu摩尔比为1∶1时其发光强度最强。     

杂多元配合物Eu-NTA-POBA-DBSO的 分子设计、合成及发光性能研究

为了实现具有特定配位方式的Eu（Ⅲ）杂多元配合物的靶向合成,首先采用稀土硝酸盐与β-萘酰三氟丙酮（NTA）和二苯基亚砜（DBSO）配体反应合成先导化合物,然后利用对甲氧基苯甲酸（POBA）取代先导化合物中的硝酸根实现羧基与稀土离子配位,并通过利用先导化合物中β-萘酰三氟丙酮和二苯基亚砜配体形成的较大空间位阻阻禁羧基桥式配位,实现了羧基双齿螯合配位的靶向合成。运用元素分析、红外光谱、扫描电镜、热重与荧光光谱等手段对相关配合物进行了系统的表征,并根据表征结果推测了它们的化学结构。研究结果表明,双齿螯合型配合物Eu（NTA）2（POBA）（DBSO）2比混合配位型配合物Eu（POBA）（NTA）2（DBSO）2具有更好的分散性能与更高的能量传递效率,并出现主发射峰劈裂弱,发射峰半高宽变锐的特征;而混合配位型配合物Eu（POBA）（NTA）2（DBSO）2比双齿螯合型配合物Eu（NTA）2（POBA）（DBSO）2具有稍好的热稳定性。得到了2种鲜艳红色的高效荧光材料。     

BCPDA的合成及其在玻片表面的修饰

合成了4，7-二氯磺基苯．1，10-菲罗啉-2，9-二羧酸(BCPDA)，产物和中间产物均用红外光谱、核磁共振谱、元素分析进行了表征，并将BCPDA联接到经过修饰的玻片表面，结果表明BCPDA能够较好地与玻片表面的氨基偶联，而且与Eu^3 形成了稳定的螫合物Eu^3 BCPDA，表明其可对固相表面的分子进行标记，通过捕获液相中的Eu^3 离子，实现表面的可寻址定量时间分辨荧光分析．     

Compatible hybrid 3D printing of metal and nonmetal inks for direct manufacture of end functional devices

The currently available 3D printing still cannot simultaneously deal with the metal and nonmetal inks together due to their huge difference in the melting points and poor compatible printability between each other. Here through introducing the low melting point alloy Bi₃₅In_48.6Sn₁₆Zn_0.4 and silicone rubber as functional inks, we proposed a compatible hybrid 3D printing method for manufacturing the desired device, the supporting substrate and the allied package structure together. The principle of pneumatic-typed 3D printing of multiple inks was described and typical physical properties of the ink Bi₃₅In_48.6Sn₁₆Zn_0.4 were measured. Several key factors dominating the printing quality such as the temperature of the printing head, the air pressure exerted upon the liquid metal ink in the syringe, the moving velocity and the height of the printing head etc. were clarified. A general way of directly printing out 3D structured electronic devices consisting of both metal and nonmetal materials was demonstrated. Such hybrid objects were patterned and formed up layer by layer with Bi₃₅In_48.6Sn₁₆Zn_0.4 alloy and silicone rubber which would become solidified after standing for a period of time under room temperature. To illustrate the compatible printability of these printing inks, a three-layer tricolor LED stereo circuit with controlled lighting capability was further manufactured and evaluated. The present study opens an important hybrid 3D printing way for directly manufacturing functional and structural end devices in an easy and low cost way.