Er~(3+)和Ce~(3+)/Ce~(4+)掺杂β-BaB_2O_4纳米棒的制备、结构与发光性质

以Ba(NO_3)_2、NaBH_4、Er_2O_3和CeO_2为原料,在十六烷基三甲基溴化铵(CTAB)表面活性剂辅助下,采用水热法制备了β-BaB_2O_4(β-BBO)纳米棒,稀土离子Er~(3+)单掺杂的β-BBO(β-BBO:Er~(3+))及Er~(3+)和Ce~(3+)/Ce~(4+)共掺杂的β-BBO(β-BBO:Er(3+)/Ce~(3+)/Ce~(4+))纳米棒.通过X射线粉末衍射(XRD)、傅里叶变换红外(FTIR)光谱、拉曼光谱、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和光致发光(PL)光谱分别对样品的物相、结构、形貌、成分及光致发光性质进行了表征.研究结果表明:微量稀土离子掺杂并不改变β-BBO的结构,制得的纳米棒尺寸均匀,长度在200-500 nm之间,直径在10-20 nm之间;β-BBO:Er~(3+)和β-BBO:Er~(3+)/Ce~(3+)Ce~(4+)纳米棒在400nm光激发下,在可见光范围内都观察到中心波长为515和542 nm的绿光.对发光机理的初步研究表明:发光分别对应于Er~(3+)的~2H_(11/2)→~4I_(15/2),~4S_(3/2)→~4I_(15/2)跃迁,铈离子以Ce~(3+)和Ce~(4+)两种形式存在于体系中,Ce~(3+)对Er~(3+)起敏化作用,可以显著增强β-BBO:Er~(3+)/Ce~(3+)/Ce~(4+)纳米棒的发光强度,存在Ce~(3+)→Er~(3+)的能量传递过程.     

β-Ga2O3:Dy3+ 纳米棒束的制备和光致发光性质

采用水热法及后续热处理制备了β-Ga2O3：Dy^3＋纳米棒束. 利用X射线粉末衍射（XRD）, 场发射电子扫描显微镜（FESEM）、发光光谱等测试手段对β-Ga2O3：Dy^3＋的物相、形貌、发光性质等进行了研究. FESEM等测试表明水热样品是由直径约100 nm, 长约2 μm的纳米棒组成的长径比约为3的羟基氧化镓（GaOOH）纳米棒束. 经过900 ℃高温热处理, 得到了形貌和尺寸基本保持不变的β-Ga2O3：Dy^3＋纳米棒束. 光致发光测试表明, Dy^3＋的发光由分别归属于4F9/2-6H15/2的蓝光（460～505 nm, 491 nm为最强峰）和4F9/2-6H13/2的黄光（570～600 nm, 580 nm为最强峰）组成. Β-Ga2O3基质可以有效地向Dy^3＋传递能量. 与固相法样品相比, 采用水热后续热处理方法制备的样品在分散性、形貌、能量传递和寿命方面明显优于固相法样品.     

Fe3O4纳米棒和Fe2O3纳米线的热氧化制备与表征

以铁单质和草酸溶液为原料,将0.75mol/L的草酸溶液滴在铁片上,于空气中200-600℃范围内加热1h,制备了Fe3O4纳米棒和Fe2O3纳米线,用扫描电镜（SEM）、X射线衍射仪（XRD）和透射电子显微镜（TEM）对产物进行表征,并研究了反应温度对产物形貌的影响.结果表明,在200-500℃下空气中反应1h在铁片上直接生长出矩形截面的多晶的立方相Fe3O4纳米棒,其直径范围约为0.5-0.8μm.当反应温度为600℃,得到的产物为六方相的Fe2O3纳米线.研究表明,C2H2O4对纳米棒的形成起关键作用,并提出了可能生长机理.     

纳米晶ZrO2:Sm3+的制备与发光性质研究

用化学共沉淀法制备了Sm3 掺杂浓度不同、煅烧温度不同的纳米晶ZrO2:Sm3 系列发光粉体,所制备的粉体均具有Sm3 离子特征强室温荧光发射.通过XRD分析发现:经600℃煅烧2 h后制备的纳米晶ZrO2:Sm3 是四方相结构;经800℃煅烧2 h得到的样品,以四方相为主,有少量单斜相;经950℃煅烧2 h后得到的样品,以单斜相为主,四方相的比例较小.不同煅烧温度下样品发光性质研究表明:因经不同温度煅烧制备的样品所处晶体场环境不同,发光中心也不同,经800和950℃煅烧的样品中稀土离子占据两种不同的格位,其一为四方相格位,其二是单斜相格位;ZrO2基质与Sm3 之间有能量传递,单斜相结构更有利于能量传递.荧光强度与掺Sm3 浓度关系研究表明:荧光强度先随Sm3 浓度提高而增强,在浓度达0.7%(摩尔分数)时达到最大,然后又随之降低.     

分子动力学模拟研究β-BAB2O4熔体的结构

The local structure of β-BaB2O4 melt at 1400 K has been studied by using the method of molecular dynamics simulation. The radial functions simulated show agreement with the recent experimental results of X-ray diffraction. The calculation of bond order parameters indicates that the local structure of the melt can be described by the model of linear combination of 0.11 tetrahedrons BO4 and 0.89 planar triangles BO3. In the process of crystal growth the existing of many planar triangles BO3 in the melt maybe favorable for the forming of planar boroxol rings B3O6 near the crystal interface. The statistics of rings and chains have been done and some isolated BO3, pyroborate B2O5,chain（－B－O－）n and isolated B3O6 rings are found in the melt which is in agreement with HTRS experimental results. A large (－B－O－)n network is also found and it is suggested that the planar BO3 units are mainly existed in the network but isolated.     

Li+,Zn2+共掺杂对Gd2O3:Eu3+纳米粉结构和发光性能的影响

采用燃烧法制备出Li^＋,Zn^2＋掺杂的Gd2O3：Eu^3＋纳米荧光粉,研究了掺杂离子对Gd2O3：Eu^3＋的结晶性能、晶粒形貌和光致发光特性的影响.以X射线衍射（XRD）、透射电子显微镜（TEM）、发射光谱和衰减时间谱等手段表征材料性能.结果表明,Li^＋,Zn^2＋掺杂可显著提高Gd2O3：Eu^3＋纳米粉在611 nm处的发光强度,最大可达到未掺杂时的2.5倍.发光增强的主要原因可归结为3个方面： （1）使晶粒由单斜相向更利于发光的立方相转变; （2）氧空位的敏化剂作用; （3）掺杂离子的助熔剂效应,使晶粒的结晶性能提高、粒径增大,从而降低表面态引起的发光猝灭.     

Ce3+和Tb3+掺杂的稀土硼酸盐玻璃的发光性质

报道Ｃｅ＾３＋和Ｔｂ＾３＋掺杂的硼酸盐玻璃的合成及该系列玻璃的激发和发射光谱性质。在紫外光激发下,玻璃中的Ｃｅ＾３＋发射蓝紫光,Ｔｂ＾３＋发射有特征的绿光,在Ｃｅ＾３＋和Ｔｂ＾３＋共掺杂的体系中,可观察到Ｃｅ＾３＋强烈敏化Ｔｂ＾３＋发光的现象。分析表明,Ｃｅ＾３＋和Ｔｂ＾３＋之间存在辐射能量传递稿铲无辐射能量传递。     

Sc3+ 掺杂的尖晶石型LiMn2 O4 正极材料制备及性质

A series of Sc3+-doped spinel lithium manganese oxides Li1+xScyMn2-yO4（y=0.01, 0.02, 0.06, and 0.10）were synthesized by solid state reaction using LiOH·H2O, MnO2, and Sc2O3 as starting materials. The results of powder X-ray diffraction indicated that the doped Li1+xScyMn2-yO4 maintain the cubic structure of spinel phase Fd3m. The electrochemical properties were characterized by electrochemical methods. The initial discharge capacity reached 135 mAh/g and the capacity fading rate was less than 2% after 40 cycles. The spinel phase was well preserved after 40 cycles. The doping of Sc3+ effectively improved the cycleability of spinels, and was a promising way for the improvement of spinel LiMn2O4 cathode materials.     

Y2O3和CeO2复合掺杂ZrO2纳米晶的制备与表征

以ZrOCl2.8H2O,Y2O3,Ce（NO3）3.5.5H2O为原料,NH3.H2O作沉淀剂,少量表面活性剂PE作分散剂,采用反向共沉淀-喷雾干燥法,结合物理、化学分散技术,成功地制备了Y2O3,CeO2复合掺杂ZrO2纳米粉末。通过DSC-TG,XRD,XPS,BET和SEM等方法对所制得粉末进行了表征。结果表明：以Ce0.1Y0.1Zr0.8O1.95化学计量比制备的多元氢氧化物胶体经过喷雾干燥处理后,在500℃基本完成水合氧化物的分解,577℃附近完成由非晶相向立方相的转变;经过580-1000℃煅烧后,CeO2和Y2O3已经完全固溶到ZrO2中,形成类质同相体,该粉末系列均属于立方相萤石结构;掺杂进入ZrO2晶格中的Ce呈＋4价形式存在;比表面积由22.0 m^2.g^-1（580℃煅烧）减至4.97 m^2.g^-1（1000℃煅烧）;SEM结果显示800℃煅烧的该粉末颗粒尺寸分布均匀,多呈类球状,且粒径在50-80 nm。     

β-PbO2纳米棒及Pb3O4纳米晶的制备与表征

利用NaClO在碱性溶液中与Pb(Ac)2进行氧化反应直接合成出直径为10－20nm、长度为400nm、长径比达20以上的纯相β－PbO2纳米棒，对所得β－PbO2在420℃下进行热解，得到晶粒尺寸为20nm左右的Pb3O4。对液相氧化反应的温度、时间、氧化剂浓度、pH等因素的影响进行了详细研究，获得了最佳合成反应条件，所得产物利用粉末X射线衍射和透射电子显微镜分析进行了表征。     

CaF2对CaO-CaF2-B2O3-SiO2：Sm2O3玻璃的光致发光增强效应

用高温熔融法制备了掺杂Sm₂O₃的CaO-CaF₂-B₂O₃-SiO₂(CFBS:Sm)发光玻璃材料, 并借助X射线衍射(XRD)谱、傅里叶变换红外(FTIR)光谱以及光致发光(PL)光谱等分析手段研究了玻璃基体中CaF₂的摩尔分数及其结构、红外透过性能以及荧光性能的关系. XRD和FTIR测试表明, 玻璃基体中引入CaF₂并未引起非晶结构的变化但其红外透过峰发生移动. 光谱学测试表明, CFBS:Sm发光玻璃在404 nm波长激发下出现对应于Sm³⁺离子位于566、603和650 nm的特征荧光峰, 其发光颜色为橙红色(x=0.531, y=0.371). 此外, 随着玻璃基体中CaF₂摩尔分数的增加, CFBS:Sm发光玻璃的荧光发射强度、荧光寿命(Sm³⁺的⁴G_5/2能级)和荧光量子效率也表现出增大的趋势. 这种CFBS:Sm发光玻璃中荧光发射强度和荧光寿命的提高主要是由于玻璃基体中的CaF₂替代CaO引起基体相互作用和声子能量降低、无辐射跃迁减弱造成的.     

Catalytic decomposition of H2O2 on Co3O4 doped with MgO and V2O5

The effects of doping of Co₃O₄with MgO (0.4–6 mol%) and V₂O₅ (0.20–0.75 mol%) on its surface and catalytic properties were investigated using nitrogen adsorption at −196°C and decomposition of H₂O₂ at 30–50°C. Pure and doped samples were prepared by thermal decomposition in air at 500–900°C, of pure basic cobalt carbonate and basic carbonate treated with different proportions of magnesium nitrate and ammonium vanadate. The results revealed that, V₂O₅ doping followed by precalcination at 500–900°C did not much modify the specific surface area of the treated Co₃O₄ solid. Treatment of Co₃O₄ with MgO at 500–900°C resulted in a significant increase in the specific surface area of cobaltic oxide. The catalytic activity in H₂O₂ decomposition, of Co₃O₄ was found to suffer a considerable increase by treatment with MgO. The maximum increase in the catalytic reaction rate constant (k) measured at 40°C on Co₃O₄ due to doping with 3 mol% MgO attained 218, 590 and 275% for the catalysts precalcined at 500, 700 and 900°C, respectively. V₂O₅-doping of Co₃O₄ brought about a significant progressive decrease in its catalytic activity. The maximum decrease in the reaction rate constant measured at 40°C over the 0.75 mol% V₂O₅-doped Co₃O₄ solid attained 68 and 93% for the catalyst samples precalcined at 500 and 900°C, respectively. The doping process did not modify the activation energy of the catalyzed reaction but much modified the concentration of catalytically active constituents without changing their energetic nature. MgO-doping increased the concentration of CO³⁺–CO²⁺ ion pairs and created Mg²⁺–CO³⁺ ion pairs increasing thus the number of active constituents involved in the catalytic decomposition of H₂O₂. V₂O₅-doping exerted an opposite effect via decreasing the number of CO³⁺–CO²⁺ ion pairs besides the possible formation of cobalt vanadate.     

Photoluminescence of samarium-doped TiO2 nanotubes

Samarium (Sm)-modified TiO₂ nanotubes (TNTs) were synthesized by low-temperature soft chemical processing. X-ray powder diffraction analyses of the synthesized Sm-doped and non-doped TNTs show a broad peak near 2θ=10°, which is typical of TNTs. The binding energy of Sm ³d_5/2 for 10 mol% Sm-doped TNT (1088.3 eV) was chemically shifted from that of Sm₂O₃ (1087.5 eV), showing that Sm existed in the TiO₂ lattice. Sm-doped TNTs clearly exhibited red fluorescence, corresponding to the doped Sm³⁺ ion in the TNT lattice. The Sm-doped TNT excitation spectrum exhibited a broad curve, which was similar to the UV–vis optical absorption spectrum. Thus, it was considered that the photoluminescence emission of Sm³⁺-doped TNT with UV-light irradiation was caused by the energy transfer from the TNT matrix via the band-to-band excitation of TiO₂ to the Sm³⁺ ion.     

Er3+/Yb3+共掺纳米In2O3的制备及上转换发光

用低温溶剂热法以乙二醇为溶剂合成了Er3+和Yb3+共掺的In2O3纳米晶。用X射线衍射(XRD)、透射电镜(TEM)、漫反射光谱和上转换发光光谱对样品进行了分析。XRD和TEM结果表明,产物为纯的立方相In2O3结构,粒径约为30 nm;漫反射光谱显示了In2O3∶Er3+,Yb3+纳米晶在522、653和975 nm附近有3个吸收带;在980 nm近红外光激发下,样品发射出中心波长为525及555 nm的绿光和662 nm的红光,分别对应于Er3+的2H11/2→4I15/2、4S3/2→4I15/2和4F9/2→4I15/2跃迁;研究了Er3+和Yb3+离子的不同掺杂浓度对发光强度的影响,确定了Yb3+和Er3+离子的最佳掺杂浓度均为3%;双对数曲线显示绿光和红光的发射过程均为双光子吸收过程,对样品的上转换发光机制进行了初步讨论。     

Hydrothermal synthesis and fluorescence of YF3: Eu3+

<正>Europium(Ⅲ)-doped YF_3 is prepared by a hydrothermal process at 200℃.X-ray diffraction(XRD) pattern identifies the formation of YF_3 phase without detectable impurity.Environment scanning electron microscopy(ESEM) image shows the even size distribution of the samples with cubic morphology.The excitation and emission spectra of the rare earth ions doped YF_3 are investigated by fluorescence spectrophotometer.The excitation spectrum for 591 nm emission has several excitation bands at 320, 365,386,397 and 467 nm,and the main peak value was 397 nm.Typical Eu~(3+) emission peaks at 591 nm(~5D_0→~7F_1) and 612 nm (~5D_0→~7F_2) are observed when excited by 397 nm,and the strongest emission is 591 nm,demonstrating that the rare earth ions occupy the centrosymmetrical sites in YF_3.     

稀土离子掺杂的焦硅酸钇纳米粉末的制备和发光和发光性质

By using metal nitrates as starting materials and citric acid as a complexing agent, Y2Si2O7:Re3+ (Re=Eu, Tb) phosphors were prepared by a sol-gel method. X-ray diffraction was employed to characterize the resulting samples. The results of XRD indicate that the ff-Y2Si2O7 nanocrystal with size of 27 nm is obtained at 1000 oC and the doping ion content does not influence the structure. The excitation spectra in the UV and VUV ranges and the emission spectra of Re3+ doped samples were measured. The excitation spectra in the VUV range is due to absorption of host, that in the UV range is ascribed to absorption transitions from 4f to 5d state of the Tb3+ and the charge transfer in the Eu3+-O2- bond. The spectral energy distribution of the Tb3+ emission depends strongly on the Tb3+ concentration. The dependence of photoluminescence intensity on Re3+ concentration is also discussed in detail. The fluorescent decay curves at room temperature were measured and analyzed.     

Ce3+掺杂La2O3的17O固体核磁共振研究

本文用水热共沉淀法制备Ce³⁺掺杂La₂O₃的前驱体,随后在H₂/N₂气氛下用高温煅烧法合成了不同Ce³⁺浓度的掺杂La₂O₃。由于Ce³⁺的掺杂,¹⁷O固体核磁共振谱图中在698、650和558处出现了新的共振峰;随着Ce³⁺掺杂浓度的增加,这些峰的强度也随之增强。根据谱峰位置和强度,对谱图进行了归属:698、650处的共振峰应源自与Ce³⁺相连的四配位O(OCeLa₃),558处的信号则来自于与Ce³⁺相连的六配位O(OCeLa₅)。通过¹⁷O固体核磁共振能够直接观测与Ce³⁺直接相连的O显示该方法将可能用于研究稀土掺杂氧化物功能材料。     

磁性TiO2/CoFe2O4纳米复合光催化材料的制备

以磁性CoFe2O4为核,采用改进的溶胶-凝胶法,制备了磁性TiO2/CoFe2O4纳米复合光催化材料.利用VSM(振动样品磁强计)技术对其磁性能进行了研究,结果表明:由该法所得的TiO2/CoFe2O4纳米复合光催化材料的饱和磁化强度虽稍弱于纯CoFe2O4纳米材料,但其矫顽力则优于CoFe2O4.TEM、XRD、UV-Vis等的结果表明,该纳米复合材料中的TiO2为锐钛矿结构;与TiO2相比,纳米复合材料对光的吸收拓展到了整个紫外-可见区,且吸收强度大大增强.对染料废水光催化降解的模拟研究表明,该复合材料在紫外光下,6 h可以使亚甲基蓝染料溶液的脱色率达95%,且重复使用3次时染料溶液的脱色率仍能保持在90%,明显优于纯TiO2.     

First Principles Study of Ca3Sc2Si3O12:Ce3+ Phosphors

Charge compensation plays a very important role in modifying the local atomic structure and moreover the spectroscopic property of an isolated luminescent center, and so has been widely adopted in phosphor designs. In this work, we carry out first principles calculations on various cases of Ce³⁺ centers in Ca₃Sc₂Si₃O₁₂ by considering the effects of the charge compensations related to N^3-, Sc³⁺, Mn²⁺, Mg²⁺, and Na⁺. Firstly, the local structures around Ce³⁺ are optimized by using density functional theory calculations with supercell model. The 4f→5d transition energies of Ce³⁺ are then obtained from the CASSCF/CASPT2/RASSI-SO calculations performed on Ce³⁺-centered embedded clusters. The calculated energies support the previous assignments of the experimental spectra. Especially, a previously unclear peak is identified to be caused by Sc³⁺ substituting Si⁴⁺. The results show that the first principles calculations can be used as an effective tool for predicting and interpreting spectroscopic properties of the phosphors.