形貌可控纳米SrFe12O19的溶胶-凝胶法制备及磁性能研究

采用柠檬酸法，在加入柠檬酸的同时加入少量有机模板剂(EDTA、熔融的硬脂酸和草酸)作为分散剂，与柠檬酸络合物上多余的羟基形成氢键，使前驱体定向生长，制得了针状、棒状以及纺锤状纳米SrFe₁₂O₁₉粉体，与不加有机模板剂时制得的球状相比，形貌发生极大的变化的。利用XRD﹑IR和TEM等测试手段对煅烧后的纳米SrFe₁₂O₁₉进行表征，并利用VSM对磁性能进行研究，结果表明各向异性越大，矫顽力越大。同时对有机模板剂对形貌的影响机理进行了初步的探究。     

Photoluminescence properties of a novel phosphor, Na3La9O3(BO3)8:RE(RE=Eu,Tb)

The new oxyborate phosphors, Na₃La₉O₃(BO₃)₈:Eu³⁺ (NLBO:Eu) and Na₃La₉O₃(BO₃)₈:Tb³⁺ (NLBO:Tb) were prepared by solid-state reactions. The photoluminescence characteristics under UV excitation were investigated. The dominated emission of Eu³⁺ corresponding to the electric dipole transition ⁵D₀→⁷F₂ is located at 613 nm and bright green luminescence of NLBO:Tb attributed to the transition ⁵D₄→⁷F₅ is centered at 544 nm. The concentration dependence of the emission intensity showed that the optimum doping concentration of Eu and Tb is 30% and 10%, respectively.     

Hydrothermal synthesis and luminescent properties of LuBO3:Tb microflowers

Hexagonal vaterite-type LuBO₃:Tb³⁺ microflower-like phosphors have been successfully prepared by an efficient surfactant- and template-free hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectrometry, transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL) and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The as-obtained phosphor samples present flowerlike agglomerates composed of nanoflakes with thickness of 40 nm and high crystallinity in spite of the moderate reaction temperature of 200 °C. The reaction mechanism has been considered as a dissolution/precipitation mechanism; the self-assembly evolution process has been proposed on homocentric layer-by-layer growth style. Under ultraviolet excitation into the 4f⁸→4f⁷5d transition of Tb³⁺ at 248 nm (or 288 nm) and low-voltage electron beam excitation, LuBO₃:Tb³⁺ samples show the characteristic green emission of Tb³⁺ corresponding to ⁵D₄→⁷F_{6, 5, 4, 3} transitions with the ⁵D₄→⁷F₅ transition (542 nm) being the most prominent group, which have potential applications in fluorescent lamps and field emission displays.     

Fabrication and luminescent properties of the core-shell structured YNbO4:Eu/Tb@SiO2 spherical particles

The core-shell structured YNbO₄:Eu³⁺/Tb³⁺@SiO₂ particles were realized by coating the YNbO₄:Eu³⁺/Tb³⁺ phosphors onto the surface of spherical silica via a sol-gel process. The obtained materials were characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform IR spectroscopy (FT-IR), photoluminescence (PL) spectra, and cathodoluminescence (CL) spectra. The results indicate that 600 °C annealed samples consist of amorphous silica core and crystalline YNbO₄:Re shell, having perfect spherical morphology with uniform size distribution. Upon excitation by UV or electron beam, these phosphors show the characteristic ⁵D₀-⁷F_1-4 emission lines of Eu³⁺ and the characteristic ⁵D₄-⁷F_3-6 emission lines of Tb³⁺. The PL intensities of Eu³⁺ can be tuned by altering the annealing temperature and the coating number of YNbO₄:Eu³⁺ layers.     

Solvothermal synthesis and luminescent properties of monodisperse LaPO4:Ln (Ln=Eu, Ce, Tb) particles

Monodisperse rare-earth ion (Eu³⁺, Ce³⁺, Tb³⁺) doped LaPO₄ particles with oval morphology were successfully prepared through a facile solvothermal process without further heat treatment. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) spectra and the kinetic decays were performed to characterize these samples. The XRD results reveal that all the doped samples are well crystalline at 180 °C and assigned to the monoclinic monazite-type structure of the LaPO₄ phase. It has been shown that all the as-synthesized samples show perfectly oval morphology with narrow size distribution. The possible growth mechanism of the LaPO₄:Ln has been investigated as well. Upon excitation by ultraviolet radiation, the LaPO₄:Eu³⁺ phosphors show the characteristic ⁵D₀−⁷F_1-4 emission lines of Eu³⁺, while the LaPO₄:Ce³⁺, Tb³⁺ phosphors demonstrate the characteristic ⁵D₄−⁷F_3-6 emission lines of Tb³⁺.     

Preparing nanometer scaled Tb-doped Y2O3 luminescent powders by the polyol method

Sub-micrometer Tb-doped Y₂O₃ luminescent powders were prepared from nitrate precursors using the polyol method. Just after precipitation, the powders consist of agglomerates with a spherical shape and a size ranging between 400 and 500 nm. Each agglomerate is composed of ultra-small crystallites (from 3 to 6 nm) of a bcc oxide phase whose luminescence presents original features in comparison with bulk materials. Powders were further calcinated at different temperatures and for annealing below 900 °C, highly crystalline samples with the classical green ⁵D₄→⁷F₅ luminescent transitions of Tb³⁺ ions are obtained. For optimized annealing temperatures, sintering between the agglomerates is avoided and a sub-micrometric powder with a narrow size distribution and a high luminescence is obtained.     

Controlled synthesis and luminescent properties of Eu(Eu), Dy-doped Sr3Al2O6 phosphors by hydrothermal treatment and postannealing approach

In this work, Sr₃Al₂O₆: Eu²⁺ (Eu³⁺), Dy³⁺ phosphors have been prepared by hydrothermal treatment and subsequently postannealing approach, using Sr(NO₃)₂, Al(NO₃)₃·9H₂O, and CO(NH₂)₂ as starting materials. The as-obtained phosphors were characterized by means of XRPD, FESEM, and PL techniques. In addition, many reaction parameters were studied in detail, including the initial mole ratios, hydrothermal reaction temperature, calcination temperature and calcination atmosphere. Remarkably, two scientific merits exist herein: Sr₃Al₂O₆: Eu²⁺ (Eu³⁺), Dy³⁺ phosphors can be selectively obtained in a reducing atmosphere (H₂/Ar, 20%+80%) and in air, respectively; adding certain amount of sodium citrate can alter the shape and size of Sr₃Al₂O₆: Eu²⁺ (Eu³⁺), Dy³⁺ phosphors in essence. Besides, the luminescent properties of Sr₃Al₂O₆: Eu²⁺ (Eu³⁺), Dy³⁺ phosphors were studied by excitation spectra, emission spectra and decay curves.     

Morphology control and luminescence properties of BaMgAl10O17:Eu phosphors prepared by spray pyrolysis

Starting from the aqueous solutions of metal nitrates with citric acid and polyethylene glycol (PEG) as additives, BaMgAl₁₀O₁₇:Eu²⁺ (BAM:Eu²⁺) phosphors were prepared by a two-step spray pyrolysis (SP) method. X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectra were used to characterize the resulted BAM:Eu²⁺ phosphors. The obtained BAM:Eu²⁺ phosphor particles have spherical shape, submicron size (0.5-3 μm). The effects of process conditions of the spray pyrolysis, such as molecular weight and concentration of PEG, on the morphology and luminescence properties of phosphor particles were investigated. Adequate amount of PEG was necessary for obtaining spherical particles, and the optimum emission intensity could be obtained when the concentration of PEG was 0.03 g/ml in the precursor solution. Moreover, the emission intensity of the phosphors increased with increasing of metal ion concentration in the solution. Compared with the BAM:Eu²⁺ phosphor prepared by citrate-gel method, spherical BAM:Eu²⁺ phosphor particles showed a higher emission intensity.     

Sol-gel synthesis of mesoporous CaCu3Ti4O12 thin films and their gas sensing response

A new sol-gel synthesis procedure of stable calcium copper titanate (CaCu₃Ti₄O₁₂—CCTO) precursor sols for the fabrication of porous films was developed. The composition of the sol was selected in order to avoid the precipitation of undesired phases; ethanol was used as solvent, acetic acid as modifier and poly(ethyleneglycol) as a linker agent. Films deposited by spin-coating onto oxidized silicon substrates were annealed at 700 °C. The main phase present in the samples, as detected by X-ray diffraction and Raman spectroscopy, was CaCu₃Ti₄O₁₂. Scanning electron microscopy analysis showed that mesoporous structures, with thicknesses between 200 and 400 nm, were developed as a result of the processing conditions. The films were tested regarding their sensibility towards oxygen and nitrogen at atmospheric pressure using working temperatures from 200 to 290 °C. The samples exhibited n-type conductivity, high sensitivity and short response times. These characteristics indicate that CCTO mesoporous structures obtained by sol-gel are suitable for application in gas sensing.     

Host-sensitized luminescence of Dy, Pr, Tb in polycrystalline CaIn2O4 for field emission displays

CaIn₂O₄:Dy³⁺/Pr³⁺/Tb³⁺ blue-white/green/green phosphors were prepared by the Pechini sol-gel process. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), diffuse reflectance, photoluminescence (PL) and cathodoluminescence (CL) spectra as well as lifetimes were utilized to characterize the samples. The XRD results reveal that the samples begin to crystallize at 800 °C and pure CaIn₂O₄ phase can be obtained after annealing at 900 °C. The FE-SEM images indicate that the CaIn₂O₄:Dy³⁺, CaIn₂O₄:Pr³⁺ and CaIn₂O₄:Tb³⁺ samples consist of spherical grains with size around 200-400 nm. Under the excitation of ultraviolet light and low-voltage electron beams (1-5 kV), the CaIn₂O₄:Dy³⁺, CaIn₂O₄:Pr³⁺ and CaIn₂O₄:Tb³⁺ phosphors show the characteristic emissions of Dy³⁺ (⁴F_9/2-⁶H_15/2 and ⁴F_9/2-⁶H_13/2 transitions, blue-white), Pr³⁺ (³P₀-³H₄, ¹D₂-³H₄ and ³P₁-³H₅ transitions, green) and Tb³⁺ (⁵D₄-⁷F_6,5,4,3 transitions, green), respectively. All the luminescence is resulted from an efficient energy transfer from the CaIn₂O₄ host lattice to the doped Dy³⁺, Pr³⁺ and Tb³⁺ ions, and the corresponding luminescence mechanisms have been proposed.     

Electronic properties and rare-earth ions photoluminescence behaviors in borosilicate: SrB2Si2O8

Undoped and RE ions doped SrB₂Si₂O₈ were successfully synthesized. After the application of UV and VUV spectroscopy measurements, we made a novel discovery that the emission of SrB₂Si₂O₈:Eu prepared in air can be switched between red and blue by the different excitations. The information is that quite a part of Eu³⁺ was spontaneously reduced to Eu²⁺ in air. The PL properties of Eu²⁺ in VUV and Eu³⁺, Ce³⁺ and Tb³⁺ in UV-VUV region in SrB₂Si₂O₈ were evaluated for the first time. The excitation mechanisms of the O²⁻-Eu³⁺ CT, Ce³⁺f-d and Tb³⁺f-d transitions in UV region as well as the Eu³⁺f-d, O²⁻-Ce³⁺ CT, O²⁻-Tb³⁺ CT transitions and the host lattice absorption in VUV region were established. In addition, first principles calculation within the LDA of the DFT was applied to calculate the electronic structure and linear optical properties of SrB₂Si₂O₈ and the results were compared with the experimental data.     

Surface modification of thermoplastics by atomic layer deposition of Al2O3 and TiO2 thin films

Al₂O₃ and TiO₂ thin films were deposited by atomic layer deposition at 80-250 °C on various polymeric substrates such as polymethylmethacrylate (PMMA), polyetheretherketone (PEEK), polytetrafluoroethylene (PTFE) and ethylenetetrafluoroethylene (ETFE). The films were studied with FESEM, EDX, XRD, contact angle measurements and adhesion tests. The film growth rates on the thermoplastics were close to the corresponding growth rates on Si substrates. The adhesion of the films was good on PEEK and poor on PTFE. All coated surfaces showed lower water contact angles than the uncoated thermoplastics. Furthermore, the water contact angles on all TiO₂-coated surfaces decreased upon UV illumination, most efficiently with crystalline TiO₂ coatings.     

ZnAl2O4:Mn材料的制备及发光性能

以共沉淀法与煅烧法联用,成功制备了一系列ZnAl₂O₄:xMn样品。通过扫描电镜和X射线粉末衍射测试研究了样品的形貌和物相特征,结果表明尖晶石结构的ZnAl₂O₄中[AlO₆]的八面体位可以有效被Mn⁴⁺替代。通过荧光激发和发射光谱研究了样品的发光性能,发现Mn⁴⁺在ZnAl₂O₄体系中掺杂可以显示出明亮的红色发光(发射峰值位于680 nm处)。比较不同Mn⁴⁺浓度(Mn与Al的物质的量之比)掺杂样品的发光强度时发现,Mn⁴⁺最佳掺杂浓度为0.06%。通过德克斯特公式分析了发光强度与浓度关系,探究浓度猝灭机制,结果表明最邻近离子之间能量传递造成Mn⁴⁺浓度猝灭的发生。为了提高Mn⁴⁺的发光强度,选择了7种金属离子(Li⁺、Na⁺、K⁺、Ca²⁺、Sr²⁺、Sn²⁺和Ga³⁺)与Mn⁴⁺共掺杂进入ZnAl₂O₄基质中,其中效果较突出的为Li⁺和Ga³⁺,其共掺杂使Mn⁴⁺发光强度分别增强0.6倍和1倍。     

掺杂对棒状纳米SrFe_(12)O_(19)形貌和性能的影响

以FeCl2为原料,利用化学沉淀法制备了针状纳米α-FeOOH中间体,并通过柠檬酸法在针状纳米α-FeOOH表面包裹锶的柠檬酸配合物,煅烧后形成的棒状纳米SrFe12O19并分别在共沉淀和溶胶-凝胶2个不同过程中对纳米SrFe12O19进行镧掺杂。采用XRD,TEM和振动样品磁强计(VSM)对SrFe12O19及掺杂锶铁氧体的结构、形貌及磁性能进行了表征。结果表明:沉淀法和柠檬酸法相结合后制得的针状前驱体于900℃煅烧后可制得平均直径为40nm,长径比为15～20的棒状纳米SrFe12O19。在沉淀过程中对前驱体进行掺杂后制得的SrLaxFe12-xO19较同温度时在溶胶-凝胶过程中进行掺杂制得样品的长径比有所增加,进而使得SrLaxFe12-xO19的各向异性变大,磁性能增加,且在沉淀过程中掺杂镧后,样品的矫顽力和饱和磁化强度达到最大值时,x值明显大于溶胶-凝胶过程中进行掺杂制得的棒状SrLaxFe12-xO19。利用共沉淀法掺杂后,当x=0.15时制备的样品的矫顽力最大为6179.1Oe,此时样品的饱和磁化强度和剩余磁化强度分别65.7和38.4emu·g-1。当x=0.2时制备的样品的饱和磁化强度达到最大值为67.3emu·g-1,样品的矫顽力为5852.7Oe。     

一维纳米Co_3O_4,Ag/Co_3O_4及CuO/Co_3O_4的合成与电催化性能(英文)

采用水热合成法制备了Co3O4及复合Ag/Co3O4、CuO/Co3O4一维纳米产品。用XRD,FE-SEM和TEM手段对产品进行了表征。采用循环伏安法研究了合成产品修饰的玻碳电极在碱性溶液中对对硝基苯酚的电催化还原性能。与裸玻碳电极相比,1mmol·L-1的对硝基苯酚在用Co3O4、特别是CuO/Co3O4修饰的玻碳电极上还原的峰电流明显增大,用Ag/Co3O4(Ag/Co原子比分别为1∶5和2∶5)修饰的玻碳电极催化还原对硝基苯酚时,尽管还原峰电流增大不是太大,但其峰电位明显降低(分别降低0.265和0.371V)。     

Superstructure of a phosphor material Ba3MgSi2O8 determined by neutron diffraction data

Ba₃MgSi₂O₈, a phosphor host examined for use in white-light devices and plant-growth lamps, was synthesized at 1225 °C in air. Its crystal structure has been determined and refined by a combined powder X-ray and neutron Rietveld method (, Z=3, a=9.72411(3) Å, c=7.27647(3) Å, V=595.870(5) Å³; R_p/R_wp=3.79%/5.03%, χ²=4.20). Superstructure reflections, observed only in the neutron diffraction data, provided the means to establish the true unit cell and a chemically reasonable structure. The structure contains three crystallographically distinct Ba atoms—Ba1 resides in a distorted octahedral site with S₆ () symmetry, Ba2 in a nine-coordinate site with C₃ (3) symmetry, and Ba3 in a ten-coordinate site with C₁ (1) symmetry. The Mg atoms occupy distorted octahedral sites, and the Si atom occupies a distorted tetrahedral site.     

Partial Oxidation of Methane to Synthesis Gas over Hexaaluminates LaMAl11O19-δ Catalysts

A series of M-substituted hexaaluminates LaMAl11O19-δ （M=Fe, Co, Ni, Mn, and Cu） were prepared and characterized by XRD, XPS, TPR and TGA techniques, respectively. They exhibited different reducibility and catalytic activity for partial oxidation of methane （POM） to synthesis gas. Among the LaMAl11019-δ samples, LaNiAl11O19-δ showed the best catalytic activity for the topic reaction and selectivity for synthesis gas at 780 ℃ for 2 h. The conversion of CH4 was over 99.2%, and the product selectivity for both CO and H2 was above 90.3%.     

WS2/CuGa2O4复合材料的制备及其气敏性

采用共沉淀法制备了CuGa₂O₄纳米材料,并利用水热法制备了一系列WS₂/CuGa₂O₄复合材料。结合X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等对制备的材料进行了物相组成、表面形貌以及元素价态的分析。研究了WS₂的复合量对 CuGa₂O₄材料检测乙醇气体敏感性能的影响。实验结果表明,当 WS₂与 CuGa₂O₄质量比为 1%时,该复合材料制备的传感器在室温下对 100 μL·L^-1乙醇气体表现出 345.3 的灵敏度,响应时间和恢复时间分别为 184 和 69 s,且最低检测限为 0.1μL·L^-1。     

WS2/CuGa2O4复合材料的制备及其气敏性

采用共沉淀法制备了CuGa₂O₄纳米材料,并利用水热法制备了一系列WS₂/CuGa₂O₄复合材料。结合X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等对制备的材料进行了物相组成、表面形貌以及元素价态的分析。研究了WS₂的复合量对CuGa₂O₄材料检测乙醇气体敏感性能的影响。实验结果表明,当WS₂与CuGa₂O₄质量比为1%时,该复合材料制备的传感器在室温下对100μL·L^-1乙醇气体表现出345.3的灵敏度,响应时间和恢复时间分别为184和69 s,且最低检测限为0.1μL·L^-1。     

静电纺丝结合溶胶-凝胶法制备MgNb2O6陶瓷纤维

以五氧化二铌(Nb2O5)和氧化镁(MgO)为原料,柠檬酸作配位剂,采用静电纺丝结合溶胶-凝胶法制备了铌酸镁(MgNb2O6)陶瓷纤维。在本合成体系中,高质量Nb5+溶液的获得是形成MgNb2O6前驱体溶胶的关键步骤。通过TGA,FTIR,XRD,TEM以及SEM技术对纤维的形貌,微观结构以及组成进行了表征。结果表明,900℃烧结以后得到的MgNb2O6纤维长度约为10 cm,具有中空结构,壁厚约为800 nm。