MgAl2O4:Ce荧光粉辐照合成及发光机理研究

通过伽马射线辐照辅助聚丙烯酰胺凝胶法合成了MgAl₂O₄和MgAl₂O₄:Ce荧光粉。通过X射线粉末衍射仪（XRD）、透射电子显微镜（TEM）、紫外可见分光光度计和荧光分光光度计研究了MgAl₂O₄:Ce荧光粉的晶体结构、表面形貌、光学性质和发光性质;基于实验所获得的结果,分析了纳米级MgAl₂O₄:Ce荧光粉的发光机理。实验结果表明:采用伽马射线辐照辅助聚丙烯酰胺凝胶法制备纯相MgAl₂O₄和MgAl₂O₄:Ce荧光粉的结晶温度要比传统聚丙烯酰胺凝胶法低100 ℃左右;MgAl₂O₄:Ce荧光粉的平均颗粒尺寸为14 nm,Ce离子掺杂后导致样品颗粒细化;Ce离子的掺入,降低了MgAl₂O₄的能带值,改善了其颜色性质和发光性质;当采用275 nm的光去激发MgAl₂O₄:Ce荧光粉时,获得了425 nm和464 nm的蓝光发射。通过能量传递原理分析认为,杂质缺陷（Ce³⁺）在整个发光过程中扮演了重要角色。MgAl₂O₄:Ce作为一种抗辐射能力强的荧光粉,在空间照明领域具有很好的应用前景。     

BaFe2O4/BaSO4复合光催化剂的制备及降解罗丹明B废水的活性研究

采用化学法、传统溶胶凝胶法和低温烧结技术合成了BaSO₄、BaFe₂O₄和BaSO₄/BaFe₂O₄复合物光催化剂。X射线粉末衍射和傅里叶红外光谱分析表明,BaSO₄和BaFe₂O₄复合后未改变主晶格相的结构。表面形貌分析发现,BaSO₄颗粒细小均匀,BaFe₂O₄颗粒较大且形貌不规则;当二者复合后颗粒尺寸变化较为明显。紫外可见吸收谱分析表明,5%BaSO₄/BaFe₂O₄复合物光催化剂具有强的紫外可见光吸收能力;BaSO₄、BaFe₂O₄、5%BaSO₄/BaFe₂O₄和10%BaSO₄/BaFe₂O₄复合物光催化剂的E_g值分别为3.23、2.89、2.74、2.26 eV。光催化结果表明,5%BaSO₄/BaFe₂O₄光催化剂在降解罗丹明B染料方面比其他几种催化剂显示出了更高的光催化活性。光催化机理分析发现,空穴、羟基自由基和超氧自由基在染料降解过程中扮演了至关重要的角色。     

Ba2+、MoO42-掺杂对NaCaPO4：Eu3+荧光粉发光性能的影响研究

为提高红色荧光粉的发光强度和色纯度,以硝酸钙、硝酸钠、硝酸铕、磷酸二氢铵、钼酸铵、硝酸钡为原料,采用高温固相法合成了NaCa_1-xPO₄：xEu³⁺、NaCa_1-x（PO₄）_1-y（MoO₄）_y：xEu³⁺、NaCa_1-x-zPO₄：xEu³⁺,zBa²⁺系列红色荧光粉。探讨了Eu³⁺单掺杂和Eu³⁺/MoO₄^2-、Eu³⁺/Ba²⁺共掺杂对荧光粉发光性能的影响。用X射线衍射（XRD）、荧光分光光度计、色坐标等对荧光粉的结构进行表征。研究结果表明：掺杂Eu³⁺、MoO₄^2-、Ba²⁺后NaCaPO₄晶系没有发生变化,但是晶胞参数发生了变化,说明Eu³⁺、MoO₄^2-、Ba²⁺进入NaCaPO₄晶格中。在393 nm紫外光激发下,荧光粉发射光谱图出现两个Eu³⁺比较强的特征发射峰,分别属于Eu³⁺的⁵D₀→⁷F₁和⁵D₀→⁷F₂跃迁。与单掺杂16%Eu³⁺荧光粉相比,共掺杂16%Eu³⁺/3%MoO₄^2-或16%Eu³⁺/6%Ba²⁺荧光粉的发射光谱中⁵D₀→⁷F₂跃迁产生的发射峰强度均高于单掺杂16%Eu³⁺荧光粉的发射峰强度,其⁵D₀→⁷F₂与⁵D₀→⁷F₁发射光强度之比（R）分别为1.76（R_Mo）和1.28（R_Ba）,都大于单掺杂16%Eu³⁺荧光粉的R_Eu（0.99）,共掺杂Eu³⁺/MoO₄^2-荧光粉的色纯度比单掺杂Eu³⁺和共掺杂Eu³⁺/Ba²⁺荧光粉的色纯度更好。     

花状与颗粒状NiMn2O4纳米材料的制备及其超级电容性能

分别以尿素和氨水为沉淀剂，采用热溶剂法制备了多孔的花状NiMn₂O₄和颗粒状NiMn₂O₄纳米电极材料，采用 X射线衍射仪、扫描电镜、透射电镜和N₂ 吸附-脱附等手段对NiMn₂O₄材料的物相、形貌结构和孔径分布进行了表征，并通过循环伏安、恒电流充放电、交流阻抗等方法测试了所制备材料的电化学性能。研究了沉淀剂对NiMn₂O₄材料形貌、微观结构及电化学性能的影响。结果表明：以尿素为沉淀剂的NiMn₂O₄是由纳米片组成的花状结构，纳米片厚度为50～60nm，比表面积为104m²/g。在 1A/g 电流密度下比电容为1614F/g，在5A/g电流密度下，尿素为沉淀剂的花状NiMn₂O₄材料经1000次恒电流充放电后其比电容可达初始值的89%。以氨水为沉淀剂的多孔NiMn₂O₄为直径约30nm的纳米颗粒结构，颗粒间团聚严重，比表面积为91m²/g。在1A/g电流密度下比电容为1147F/g，在5A/g电流密度下，氨水为沉淀剂的颗粒状NiMn₂O₄材料经1000次恒电流充放电后其比电容可达初始值的80%。尿素为沉淀剂的花状NiMn₂O₄具有优越的超级电容性能。     

Nb2O5对Nd3+掺杂锗酸盐玻璃光谱性能的影响

蓝光激光器在彩色激光显示、高密度光储存、海洋资源探测、水下通信以及生物科技等领域具有广泛的应用前景。目前较为成熟的Yb³⁺掺杂光纤激光器倍频后仅能获得~490 nm蓝绿光,因此如何得到接近450 nm的纯蓝光激光器是目前急需解决的问题。Nd³⁺:⁴F_3/2→⁴I_9/2能级跃迁产生的0.9 μm光经倍频后可获得~450 nm光,并可应用于蓝光激光器,但该跃迁产生的光所占荧光分支比较低。本文系统研究了1%(质量分数)Nd₂O₃掺杂50GeO₂-(20-x)PbO-15BaO-15ZnO-xNb₂O₅(x%=0%,2.5%,5%,10%,15%,摩尔分数)玻璃的吸收光谱、荧光光谱和荧光寿命,计算了相应的Judd-Ofelt强度参数以及增益带宽。研究发现,Nb₂O₅的加入会使Nd³⁺在900 nm荧光峰的吸收截面、发射截面、有效线宽和荧光分支比增加。当Nb₂O₅浓度为10%(摩尔分数)时,Judd-Ofelt强度参数Ω₂=5.91×10^-20 cm²,光谱质量参数χ=1.01,荧光分支比为42.9%。综上所述,Nb₂O₅能提高Nd³⁺ 0.9 μm的荧光分支比,从而倍频获得纯蓝光(450 nm),有利于蓝光激光器的发展及应用。     

磁性纳米Fe3O4@TiO2可见光下光催化还原Cr(Ⅵ)

通过溶胶-凝胶法、水热法和煅烧法,成功制备出具有光催化活性的Fe₃O₄@TiO₂磁性纳米复合材料,将超顺磁性的Fe₃O₄与TiO₂复合,实现材料的快速回收与可见光响应能力的结合。进一步将Fe₃O₄@TiO₂磁性纳米复合材料应用于Cr(Ⅵ)的去除,实验结果表明,在可见光照射下Fe₃O₄@TiO₂对Cr(Ⅵ)的去除能力是P25的1.96倍。并深入探究了Fe₃O₄@TiO₂中TiO₂含量、Cr(Ⅵ)溶液的pH以及空穴去除剂对Fe₃O₄@TiO₂可见光下光催化还原Cr(Ⅵ)能力的影响,实验表明当Fe₃O₄@TiO₂中TiO₂含量为1.0 g/g,添加甲酸作为空穴去除剂并且溶液pH=2时Fe₃O₄@TiO₂对Cr(Ⅵ)的去除能力最佳,此条件下Cr(Ⅵ)的去除率达到99.85%,重复使用4次,催化能力依然保持较高水平。此外,Fe₃O₄@TiO₂对5~500 mg/L浓度范围内的Cr(Ⅵ)都具有良好的去除能力。Fe₃O₄@TiO₂磁性纳米复合材料对Cr(Ⅵ)具备优异的去除能力,具有良好的应用前景。     

燃烧法制备铝酸铜色料的研究

以三水合硝酸铜、九水合硝酸铝和甘氨酸为原料,采用燃烧法制备了铝酸铜(CuAl₂O₄)棕色色料。采用SEM、XRD、FT-IR、TG-DTA和UV-Vis等测试手段,研究了煅烧制度和铜铝摩尔比(Cu/Al)对色料物相组成、微观结构、呈色性能的影响。结果表明,当Cu/Al摩尔比为1∶2.4,煅烧温度为1 100 ℃(不进行保温)时,可以得到呈色性能最佳的CuAl₂O₄色料,其色度值为L^*=46.22、a^*=24.43、b^*=27.09。     

环烷基NiFe2O4磁流体的制备及有磁场沉降稳定性

目前,磁流体的制备方法多为化学共沉淀法,关于磁流体微乳化制备工艺及有磁场沉降稳定性的研究较少。采用单因素和均匀实验设计方法,判定分散剂及其质量分数对环烷基NiFe₂O₄磁流体沉降稳定性的影响。本文采用微乳化法制备环烷基NiFe₂O₄磁流体,通过样品沉降系数和黏度特性,研究分散剂种类与其质量分数、NiFe₂O₄纳米磁性颗粒质量分数、乳化剂种类及温度对磁流体有磁场沉降稳定性的影响,得到制备环烷基NiFe₂O₄磁流体的较佳参数值。研究结果表明：当十二烷基苯磺酸钠（SDBS）、十二烷基硫酸钠（SDS）与油酸（OA）的质量分数在1%～6%范围内,环烷基NiFe₂O₄磁流体的沉降稳定性较好,并且SDBS与OA的含量对其稳定性的影响大于SDS;当分散剂定量时,随着NiFe₂O₄纳米磁性颗粒质量分数的增加,磁流体先表现出较好的稳定性,后逐渐出现团聚;在一定温度时,乳化剂Surf CA20有利于磁流体内部形成液晶相,减小液珠间吸引势能并且降低磁性颗粒的聚结速度,提高磁流体的有磁场沉降稳定性。     

Co3O4-Bi2O2CO3催化剂的制备及其光催化性能

以Bi(NO₃)₃·5H₂O、Co(CH₃COO)₂·4H₂O为原料,采用化学沉淀-水热法制备了Co₃O₄-Bi₂O₂CO₃异质结构复合半导体光催化剂,并通过X射线衍射仪（XRD）、扫描电镜（SEM）、X射线光电子能谱（XPS）、紫外可见漫反射光谱（DRS）、荧光光谱（PL）等手段对所合成的复合型催化剂进行了理化性能表征。研究结果表明：引入Co₃O₄没有改变Bi₂O₂CO₃物相结构,但促进了Bi₂O₂CO₃ 对可见光的吸收能力,提高了Bi₂O₂CO₃表面吸附氧物种的数量,抑制了光生载流子复合。复合光催化剂对罗丹明B（RhB）的光催化脱色实验显示引入Co₃O₄能够明显提高Bi₂O₂CO₃催化剂的光催化脱色能力。尤其是Co₃O₄引入量为0.6%的Co₃O₄-Bi₂O₂CO₃样品对罗丹明B染料的光催化脱色率可达到97%（模拟日光照射30min）。本文为复合型光催化剂制备提供了简单易行的技术路线,制备的新型半导体复合光催化剂Co₃O₄-Bi₂O₂CO₃在环境净化方面表现出了较好的应用前景。     

La3+对MgAl2O4透明陶瓷致密化过程、光学及力学性能的影响

镁铝尖晶石(MgAl₂O₄)透明陶瓷具有优异的光学和力学性能,在防弹装甲窗口、高马赫整流罩等方面得到了大量的应用。为实现MgAl₂O₄透明陶瓷的致密化,一般需要相对较高的烧结温度,然而高的烧结温度会导致陶瓷晶粒生长过大,影响其性能。因此通过引入合适的烧结助剂降低烧结温度,对于提升陶瓷性能和降低成本均具有很大的意义。本文以高纯商业MgAl₂O₄粉体为原料,La(OH)₃为烧结助剂,采用真空烧结结合热等静压后处理的方式,成功制备MgAl₂O₄透明陶瓷,并采用XRD、SEM等对透明陶瓷的微结构和相组成的演变以及性能进行表征。结果表明,La³⁺在烧结早中期可有效提高陶瓷致密化速率,在烧结后期可抑制陶瓷晶粒生长。掺入0.01%(质量分数)La₂O₃后,MgAl₂O₄光学和力学综合性能优异,所需...     

纳米CoFe2O4的制备及其对PLA结晶性能的影响

为了实现聚乳酸(PLA)的功能化改性,将其进行改性探究PLA的结晶行为,采用了化学共沉淀法制备了油酸包覆的CoFe2O4纳米粒子,同时采用溶液浇铸法制备了PLA/CoFe2O4复合材料.使用傅里叶变换红外光谱(FTIR)、透射电子显微镜(TEM)和X射线衍射仪(XRD)对CoFe2O4粒子及其复合材料的组成和结构进行分...     

Surface properties and reactivity of Cu/γ-Al2O3 catalysts for NO reduction by C3H6: Influences of calcination temperatures and additives

The influences of calcination temperatures and additives for 10 wt.% Cu/γ-Al₂O₃ catalysts on the surface properties and reactivity for NO reduction by C₃H₆ in the presence of excess oxygen were investigated. The results of XRD and XPS show that the 10 wt.% Cu/γ-Al₂O₃ catalysts calcined below 973 K possess highly dispersed surface and bulk CuO phases. The 10 wt.% Cu/γ-Al₂O₃ and 10 wt.% Mn–10 wt.% Cu/γ-Al₂O₃ catalysts calcined at 1073 K possess a CuAl₂O₄ phase with a spinel-type structure. In addition, the 10 wt.% La–10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K possesses a bulk CuO phase. The result of NO reduction by C₃H₆ shows that the CuAl₂O₄ is a more active phase than the highly dispersed and bulk CuO phase. However, the 10 wt.% Mn–10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K possesses significantly lower reactivity for NO reduction than the 10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K, although these catalysts possess the same CuAl₂O₄ phase. The low reactivity for NO reduction for 10 wt.% Mn–10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K is attributed to the formation of less active CuAl₂O₄ phase with high aggregation and preferential promotion of C₃H₆ combustion to CO_x by MnO₂. The engine dynamometer test for NO reduction shows that the C₃H₆ is a more effective reducing agent for NO reduction than the C₂H₅OH. The maximum reactivity for NO reduction by C₃H₆ is reached when the NO/C₃H₆ ratio is one.     

白光LED用红色荧光粉Gd2-xMo3O9:Eux3+制备和研究

用高温固相法成功制备了Gd2-xMo3O9:Eux3+,用XRD荧光光谱仪对其物相以及粉体的激发和发射光谱进行表征和研究;结果表明:在395和464nm两主激发峰均可得到616nm处红光发射峰,属于Eu3+典型的5D0→7F2的跃迁所致。由464nm激发得到的发射峰为单峰,峰宽较窄且发射强度较强。     

Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions

Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions were studied for potential applications in water decontamination technology and their capacity to induce an oxidation process under VIS light. UV–vis spectroscopy analysis showed that the junctions-based Cu₂O, Bi₂O₃ and ZnMn₂O₄ are able to absorb a large part of visible light (respectively, up to 650, 460 and 1000 nm). This fact was confirmed in the case of Cu₂O/TiO₂ and Bi₂O₃/TiO₂ by photocatalytic experiments performed under visible light. A part of the charge recombination that can take place when both semiconductors are excited was observed when a photocatalytic experiment was performed under UV–vis illumination. Orange II, 4-hydroxybenzoic and benzamide were used as pollutants in the experiment. Photoactivity of the junctions was found to be strongly dependent on the substrate. The different phenomena that were observed in each case are discussed.     

DMF effect on the morphology and the luminescence properties of Y2O3:Eu red phosphor prepared by spray pyrolysis

N,N-Dimethylformamide (DMF) was used as a drying control chemical additive (DCCA) in spray pyrolysis in order to improve the luminous properties of Y₂O₃:Eu particles. It was found that the addition of DMF to the spray solution containing citric acid (CA) and ethylene glycol (EG) greatly enhances the photoluminescence intensity as well as the morphology of Y₂O₃:Eu particles. According to BET analysis, the surface area of Y₂O₃:Eu particles prepared from the solution containing only the organic additives was not reduced, whereas, the surface area of the Y₂O₃:Eu particles prepared from the solution containing both DMF and organic additives was decreased gradually as increasing the concentration of DMF. From these results, it was concluded that the adding of DMF to the spray solution containing the organic additives is a very effective way to reduce the porosity of phosphor particles, keeping the spherical morphology. As a result, the densification of porous structure led to greatly improve the photoluminescence intensity of Y₂O₃:Eu particles under ultraviolet (254 nm) excitation. Finally, the prepared Y₂O₃:Eu particles with dense structure showed about 208% improved photoluminescence intensity compared with the particles which have a spherical shape but porous structure.     

Preparation of P2O5-SiO2 hollow microspheres in the presence of phosphoric acid

Silica hollow microspheres containing phosphorous have been prepared by a sol-gel/emulsion method which uses tetraethoxysilane (TEOS) as the precursor for the SiO₂ and phosphoric acid (H₃PO₄) as the precursor for P₂O₅. The hollow structure forms an emulsion system which is composed of an oil phase (kerosene, sorbitan monooleate (Span 80)) and an aqueous phase (a viscous sol solution of ethanol, TEOS and H₃PO₄). Some of the phosphorous remains in the final silica shell structure even after calcination at 650°C. The hollow structure of the P₂O₅-SiO₂ (silicophosphate) was characterized by X-ray diffraction (XRD), polarized optical microscopy (POM), scanning electron microscopy (SEM), nitrogen adsorption measurement and Fourier transform infrared spectroscopy (FTIR).     

Characterizations and activities of the nano-sized Ni/Al2O3 and Ni/La–Al2O3 catalysts for NH3 decomposition

A series of nano-sized Ni/Al₂O₃ and Ni/La–Al₂O₃ catalysts that possess high activities for NH₃ decomposition have been successfully synthesized by a coprecipitation method. The catalytic performance was investigated under the atmospheric conditions and a significant enhancement in the activity after the introduction of La was observed. Aiming to study the influence of La promoter on the physicochemical properties, we characterized the catalysts by N₂ adsorption/desorption, XRD, H₂-TPR, chemisorption and TEM techniques. Physisorption results suggested a high specific surface area and XRD spectra showed that nickel particles are in a highly dispersed state. A combination of XRD, TEM and chemisorption showed that Ni⁰ particles with the average size lower than 5.0 nm are always obtained even though the Ni loading ranged widely from 4 to 63%. Compared with the Ni/Al₂O₃ catalysts, the Ni/La–Al₂O₃ ones with an appropriate amount of promoter enjoy a more open mesoporous structure and higher dispersion of Ni. Reduction kinetic studies of prepared catalysts were investigated by temperature-programmed reduction (TPR) method and the fact that La additive partially destroyed the metastable Ni–Al mixed oxide phase was detailed.     

Enhanced cycling stability of LiMn2O4 by surface modification with melting impregnation method

The surface of as-prepared LiMn₂O₄ was modified with Al₂O₃ by a melting impregnation method. X-ray diffraction, field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) studies indicated that Al₂O₃ nano-particles are distributed around the spinel. X ray absorption fine structure analysis (XAFS) further demonstrated that Al atoms were also doped to the surface of LiMn₂O₄ particles. The nano-Al₂O₃ particle coating improves the capacity retention of spinel LiMn₂O₄ efficiently at both room temperature and 55 °C. The mechanism of improvement for surface modified LiMn₂O₄ can be attributed to the inhibition of a surface Jahn-Teller distortion and the decrease of manganese dissolution, leading to good electric contact among particles.     

Processing of hot pressed Al2O3–Cr2O3/Cr-carbide nanocomposite prepared by MOCVD in fluidized bed

Nanosized particles dispersed uniformly on Al₂O₃ particles were prepared from the decomposition of precursor Cr(CO)₆ by metal organic chemical vapor deposition (MOCVD) in a fluidized chamber. These nanosized particles consisted of Cr₂O₃, CrC_1−x, and C. A solid solution of Al₂O₃–Cr₂O₃ and an Al₂O₃–Cr₂O₃/Cr₃C₂ nanocomposite were formed when these fluidized powders were pre-sintered at 1000 and 1150 °C before hot-pressing at 1400 °C, respectively. In addition, an Al₂O₃–Cr₂O₃/Cr-carbide (Cr₃C₂ and Cr₇C₃) nanocomposite was formed when the particles were directly hot pressed at 1400 °C. The interface between Cr₃C₂ and Al₂O₃ is non-coherent, while the interface between Cr₇C₃ and Al₂O₃ is semi-coherent.