宽带发射Ca2KMg2V3O12:Eu3+荧光粉的制备及其发光性能研究

本文通过高温固相法合成了新型的宽带发射Ca2KMg2V3O12:Eu3+荧光粉,并利用X射线粉末衍射仪,荧光光谱仪等表征手段对荧光粉的晶体结构及其发光性能进行了分析;探讨了Ca2KMg2V3O12荧光粉的自激活发光机理和Eu3+掺杂浓度对发光性能的影响.结果表明:所制备的样品为立方晶系Ca2KMg2V3O12晶体.在紫外光的激发下,Ca2KMg2V3O12:Eu3+既表现出[VO4]基团的宽带发射,又表现出Eu3+的特征发射,同时两者之间存在能量传递.Ca2KMg2V3O12:Eu3+荧光粉是一种良好的自激活发光材料,在紫外光激发的白光LED上具有潜在的应用前景.     

稀土Tm3+/Yb3+共掺杂氟氧化物上转换可见发光

制备了稀土Tm3+/Yb3+共掺杂氟氧化物上转换发光材料(60TeO2-10AlF3-10PbF2-10NaF-2Tm2O3-8Yb2O3),在980nm红外光泵浦激发下,测量了样品的吸收谱、上转换荧光发射谱和上转换发光强度与激光泵浦功率的对数关系.观察到峰值为477nm蓝光和651nm红光可见发射,分别是稀土Tm3+的激发态1G4→3H6,1G4→3F4跃迁;在806nm附近,观察到较强的红外发射(3H4→3H6),分析了稀土Tm3+/Yb3+共掺杂氟氧化物上转换可见发射机制,证实了稀土Tm3+上转换发射是在稀土Yb3+的敏化作用下,通过能量传递(ET)和激发态吸收(ESA),实现了激发态1G4向基态3H6、激发态3F4跃迁的三光子吸收过程和激发态3H4→3H6的双光子吸收过程.     

新型稀土发光材料Sr3-xMgSi3O10:Tb3+x的合成及性质

采用凝胶-燃烧法,在活性炭弱还原气氛下合成了新型荧光粉Sr3-xMgSi3O10: Tb3+x,通过热分析仪、红外光谱、X射线粉末衍射、X射线能量色散谱仪及荧光分光光度计等对产物的形成过程、结构、组成及发光性质进行了分析和表征.结果表明:干凝胶起火燃烧得前驱物,经900 ℃还原热处理即可得目标产物,其晶体结构与Sr2MgSi2O7相似,同属四方晶系.Sr3-xMgSi3O10: Tb3+x的激发光谱为一位于200～300 nm的宽带,主激发峰在249 nm左右;发射光谱由491 nm, 544 nm, 586 nm, 624 nm等一系列窄带发射峰组成,归属于Tb3+的5D4到7FJ (J=6,5,4,3)的跃迁.主发射峰位于544 nm,对应于Tb3+的5D4→7F5的能级跃迁,导致一种黄绿光发射.研究发现:还原温度及Tb3+掺杂浓度对发光强度有着重要的影响,并对浓度猝灭机制进行了探讨.     

水热法合成Gd2O3∶Dy3+纳米棒及发光性能

以氢氧化钠为沉淀剂,采用水热方法制备了Gd2O3∶Dy3+纳米棒.通过红外光谱、扫描电镜及X射线衍射对前驱体及目标产物的物相结构、微观形貌进行了分析表征,通过荧光分光光度计测试了所得Gd2O3∶Dy3+的发光性能.结果表明:水热前驱体为六方相氢氧化钆(镝),经900℃焙烧得立方相的Gd2O3∶Dy3+.所得G d2O3∶Dy3为直径约100 nm,长度约500 nm～1μm的纳米棒.其激发光谱由一系列激发峰组成,峰值分别位于239 nm、279 nm、314 nm、353 nm,最强峰位于279 nm处;发射光谱主要由两部分组成,分别为460 ～500 nm的蓝光和560～590nm的黄绿光发射峰(带),均属于Dy3+的特征发射,且后者的强度远高于前者,因此,在紫外光激发下呈黄光发射.     

稀土Tm^3＋/Yb^3＋共掺杂氟氧化物上转换可见发光

制备了稀土Tm^3＋/Yb^3＋共掺杂氟氧化物上转换发光材料（60TeO2-10AlF3-10PbF2-10NaF-2Tm2O3-8Yb2O3）,在980nm红外光泵浦激发下,测量了样品的吸收谱、上转换荧光发射谱和上转换发光强度与激光泵浦功率的对数关系.观察到峰值为477nm蓝光和651nm红光可见发射,分别是稀土Tm^3＋的激发态^1G4→^3H6,^1G4→^3F4跃迁;在806nm附近,观察到较强的红外发射（^3H4→^3H6）,分析了稀土Tm^3＋/Yb^3＋共掺杂氟氧化物上转换可见发射机制,证实了稀土Tm^3＋上转换发射是在稀土Yb^3＋的敏化作用下,通过能量传递（ET）和激发态吸收（ESA）,实现了激发态^1G4向基态^3H6、激发态^3F4跃迁的三光子吸收过程和激发态^3H4→^3H6的双光子吸收过程.     

新型稀土发光材料Sr_(3-x)MgSi_3O_(10)∶Tb_x~(3+)的合成及性质

采用凝胶-燃烧法,在活性炭弱还原气氛下合成了新型荧光粉Sr3-xMgSi3O10∶Tb3x+,通过热分析仪、红外光谱、X射线粉末衍射、X射线能量色散谱仪及荧光分光光度计等对产物的形成过程、结构、组成及发光性质进行了分析和表征。结果表明:干凝胶起火燃烧得前驱物,经900℃还原热处理即可得目标产物,其晶体结构与Sr2MgSi2O7相似,同属四方晶系。Sr3-xMgSi3O10∶Tb3x+的激发光谱为一位于200～300nm的宽带,主激发峰在249nm左右;发射光谱由491nm,544nm,586nm,624nm等一系列窄带发射峰组成,归属于Tb3+的5D4到7FJ(J=6,5,4,3)的跃迁。主发射峰位于544nm,对应于Tb3+的5D4→7F5的能级跃迁,导致一种黄绿光发射。研究发现:还原温度及Tb3+掺杂浓度对发光强度有着重要的影响,并对浓度猝灭机制进行了探讨。     

Ba0.955Al2Si2-xTixO8∶Eu2+荧光粉晶体结构和光谱特性

由高温固相反应制得Ba0.955Al2Si2-xTixO8∶Eu2(x=0～1.0)系列试样,通过XRD和荧光光谱测试,研究各试样的晶体结构和光谱特性.XRD分析结果表明,当Ti4+置换Si4+的量逐渐增至1.0时,各试样均为单斜晶系,空间群为C2/m(12),其晶胞参数a,b,c,β和晶胞体积V呈线性递增,其中晶胞参数c变化幅度最大,a最小,试样的晶粒尺寸略微减小.荧光光谱分析结果表明,试样的荧光激发谱为宽带,位于230 ～ 400 nm,可264 nm、303 nm、341nm和367 nm四个峰拟合成,表观峰值位于340 nm;试样的发射光谱为370～600 nm一宽带不对称峰,峰值为434nm,可拟合成419 nm和453 nm两峰,两拟合峰峰位随Ti4+置换量增加线性红移;利用试样荧光光谱和Van Uitert经验公式,得出BaAl2 Si2O8∶Eu2+中Ba2+的配位数为9.     

近紫外激发Ca2 NaMg2 V3 O12:Sm3+荧光粉的制备及发光性能

近紫外激发单一基质白光发射荧光粉是当前LED用荧光转换材料的研究热点.采用高温固相反应制备了Ca2 NaMg2 V3 O12:Sm3+荧光粉,并利用X射线粉末衍射仪和荧光光谱仪等测试手段,对其物质结构和荧光性能进行了表征.探讨了(VO4)3-基团的发光机理,及其与Sm3+离子之间的能量传递机制.结果表明:Ca2 NaMg2 V3 O12:Sm3+荧光粉属于立方相晶体结构.在340 nm紫外线激发下,样品发射蓝绿光,发射最强峰位于500 nm,发射光谱覆盖整个可见光区.Sm3+离子的最佳掺杂浓度为0.03,同时(VO4)3-基团与Sm3+离子之间的能量传递主要是通过电四偶极-电四偶极相互作用来实现的.     

SrCO3∶Eu2+荧光粉的制备及其发光性能研究

首先采用微波辅助共沉淀制备SrCO.∶Eu3+前驱物,然后高温还原得到SrCO3∶Eu2+样品.通过X射线衍射仪(XRD)和荧光光度仪分析样品的结构和发光性能,确定样品的最佳煅烧温度为1100℃,助熔剂硼酸的最佳用量为15;.研究表明,样品的激发图谱由220 ～ 320 nm和400 ～580 nm两个宽带光谱组成;发射图谱位于550～700 nm宽带吸收峰,其特征发射峰值位于610 nm(λex =475 nm),属于红色发光.这种宽带激发和发射的碳酸锶基质的稀土荧光粉可望用于制造荧光玻璃.     

Dy3+掺杂对CaLaAl3O7晶体结构和发光性能的影响

采用高温固相法制备了CaLa1-xAl3O7∶ xDy3+(0≤x≤0.15)发光粉体,利用X射线衍射分析了材料的物相,计算发现:随Dy3+掺杂浓度的增加,晶胞体积线性减小.在348 nm光激发下,该系列样品发射谱为Dy3+的4f9组态内的特征发射峰,峰值波长分别为478 nm、577 nm和667 nm,总的发射呈现白色,色坐标计算值几乎相同,而且都处于白光区域内(色坐标(0.33,0.33)).CaLa1-xAl3 O7∶xDy3+材料发光强度随Dy3+浓度的增大呈现先增大后减小的趋势,在x=0.04时达到峰值.分析了材料在577 nm发射强度与Dy掺杂浓度的关系,并根据D.L.Dexter的相关理论得到:Dy3自身猝灭机理是电偶极-偶极相互作用.     

Triethyl ammonium salt of O,O′-bis(p-tolyl)dithiophosphate, [Et3NH]+[(4-MeC6H4O)2PS2]−

Triethyl ammonium Salt of O,O′-bis(p-tolyl)dithiophosphate and O,O′-bis(m-tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively with P₂S₅ in toluene and have been characterized by elemental analysis, IR, ¹H and ³¹P NMR spectroscopy. The molecular structure of O,O′-bis(p-tolyl)dithiophosphate has been determined. Crystal data: [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻: Monoclinic, P2₁/c, a=15.2441(9) ?, b=10.415(2) ?, c=3.9726(9) ?, β=91.709(7)°, V=2217.5(1) ?⁻³, Z=4.Supplementary materials Additional material available from the Cambridge Crystallographic Data Centre (CCDC no. 600927 for [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻ comprises the final atomic coordinates for all atoms, thermal parameters, and a complete listing of bond distances and angles. Copies of this information may be obtained free of charge on application to The Director, 12 Union Road, Cambridge CB2 2EZ, UK (fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).     

First-principles coexistence simulations of supercooled liquid silicon

We perform first-principles coexistence simulations of the low-density and the high-density phases of supercooled liquid silicon and find a negative slope for the coexisting line in the temperature-pressure plane. Electron density maps and electron-localization function plots of the two phases of silicon show marked differences. The calculated differences suggest more localized electrons in the low-density liquid compared to the high-density liquid, coming from an increased population of covalent bonds, which further explain the calculated negative slope in the two phase coexistence regime. This is consistent with the presence of a pseudo-gap in low-density liquid silicon, absent in the high-density liquid which shows a metallic behavior.     

Crystal structures of thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane

Structures of both thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane, ?C₆H₄?CH₂SCH₂?C₆H₁₀?CH₂SCH₂?, have been determined, wherecis andtrans refer to the attachments to the cyclohexane ring. Thecis form crystallizes in the monoclinic space groupP2₁/c witha=8.4299(11)Å,b=21.772(2)Å,c=8.9724(13)Å, β=116.574(11)^o, andZ=4. Thetrans isomer packs into the monoclinic space groupP2₁ witha=8.159(16)Å,b=10.185(5)Å,c=9.558(2)Å, β=112.435(18)^o, andZ=2. The cyclohexane ring of thecis isomer is in the chair conformation, while the cyclohexane of thetrans isomer is found in a twisted boat conformation.     

CTAB与SDBS对碳酸锶粒子生长形态调控及机理研究

以表面活性剂CTAB和SDBS为化学添加剂,采用化学共沉淀法对碳酸锶晶体的生长形态进行调控,成功地制备出了实心的树枝状和花瓣为空心的花状碳酸锶粉体,并用X射线衍射(XRD)、扫描电子显微镜(SEM)和傅里叶变换红外光谱(FT-IR)等分析手段对样品进行了表征;最后重点对化学添加剂可能产生的影响机理进行了初步的探讨.结果表明,CTAB和SDBS在晶体生长的过程中能起到显著的影响作用,两者对粒子分散性能的作用效果相反,而且后者对晶体(013)和(213)晶面表面能降低的贡献明显大于前者.     

Crystal structure of Zn4Na(OH)6SO4Cl·6H2O

The structure of Zn₄Na(OH)₆SO₄Cl·6H₂O, a secondary mineral from Hettstedt, Germany, was determined by single-crystal X-ray diffraction. The crystals are hexagonal,a=8.413(8),c=13.095(24) Å, space group $P\bar 3$ , Z=2. The structure was refined to R=0.0554 and R_w=0.0903 for 970 reflections with I≥3σ(I). The structure can be described as zinc hydroxide layers perpendicular toc, from which sulfates and chlorides extend. The layers are held together by a system of hydrogen bonds involving hexaaquo Na⁺ ions which occupy the interlayer space.     

Synthesis and Crystal Structure of 5-[2-(6-bromonaphthalenyloxymethyl)]-3-(4-morpholinomethyl)-1,3,4-oxadiazole-2(3<Emphasis Type="Italic">H</Emphasis>)-thione

Abstract  The title compound, C₁₈H₁₈BrN₃O₃S, a derivative of 1,3,4-oxadiazole, crystallizes in the triclinic space group P-1 with unit cell parameters a = 6.8731(3), b = 8.9994(4), c = 15.7099(6) ?, α = 92.779(3)°, β = 130.575(3)°, γ = 107.868(4)°, Z = 2. The dihedral angle between the mean planes of the planar naphthyl and morpholine (chair) rings with the planar oxadiazol ring is 50.1(8) and 76.8(6)°, respectively. The planar naphthyl ring is twisted 52.2(5)° with the mean plane of the morpholine ring. A group of four intermolecular close contacts are observed between a bromine atom and hydrogen atoms from the closely packed naphthyl, morpholine and oxy–methyl groups in the unit cell. These molecular interactions in concert with an additional series of π–π stacking interactions that occur between the center of gravity of the two 6-membered rings of the naphthalene group influence the twist angles of each of these three groups. A MOPAC AM1 calculation of the conformation energy of the crystal structure [226.0128(9) kcal] compared to that of the minimum energy structure after geometry optimization [29.9744(1) kcal] reveals a significantly reduced value. The twist angles of the three groups above also change after the AM1 calculation giving support to the influence of both intermolecular C–H···Br short-range interactions and Cg π–π stacking interactions on these angles which therefore play a role in stabilizing crystal packing. Graphical Abstract  Crystal structure of 5-{[(6-bromonaphthalen-2-yl)oxy]methyl}-3-(morpholin-4-ylmethyl)-1,3,4-oxadiazole-2(3H)-thione, C₁₈H₁₈BrN₃O₃S, is reported and its geometric and packing parameters described and compared to a MOPAC computational calculation. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal structure of irisolidone from the flowers of Pueraia lobata

Irisolidone (5,7-dihydroxy-6,4′-dimethoxyisoflavone) was isolated from the flowers of Pueraia lobata and its crystal structure was examined by X-ray single crystal diffraction. The crystal structure of irisolidone is monoclinic, space group P2₁/c with a = 15.491(9) ?, b = 7.895(4) ?, c = 13.321(7) ?, β = 110.546(9)° and Z = 4. Hydrogen bonding and aromatic π–π stacking assemble the title compound into a three-dimensional networking structure.     

Synthesis of spinacine and spinacine derivatives: crystal and molecular structures of Nπ-hydroxymethyl spinacine and Nα-methyl spinaceamine

The natural amino acid L-Spinacine (4,5,6,7-tetrahydro-1H-imidazo[4,5-c]pyridine-6-carboxylic acid) has been synthesized following a new pathway which gives a chemically and optically pure product with an excellent yield. The crystal structures of a synthetic intermediate, N^π-hydroxymethyl-spinacine, and a spinacine derivative, N^α-methyl-spinaceamine, have been investigated through X-ray diffraction: Spi(πMeOH)·H₂O, monoclinicP2 _i,a=8.571(1),b=6.682(1),c=8.588(1) Å, and β=94.67(1)^o. Spm(αMe)·2HCl·H₂O, triclinicP l,a=7.492(4),b=10.799(3),c=7.040(2) Å, α=91.88(2), β=98.36(3) and γ=73.34(3)^o. Spi(πMeOH) crystallizes with a water molecule and displays a zwitterionic character. The carboxylate group is in equatorial position and forms a short electrostatic interaction of 2.618(2) Å between one of its oxygens and the protonated nitrogen of the tetrahydropyridine ring. The crystal packing is assured by strong O?H???O, O?H???N, N?H???N intermolecular hydrogen bonds and C?H???O close contacts. The biprotonated compounds Spm(αMe) crystallizes with two Cl^? anions and a water molecule. The positive charge on the imidazole ring is delocalized on the conjugated moiety N=C?N. The crystal is built up by clusters formed by two biprotonated Spm(αMe) molecules, four Cl^? anions and two water molecules linked together by hydrogen bonds.