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。     

Sol-Gel法合成锂离子筛前驱体LiMn2O4的研究

采用溶胶-凝胶法、用柠檬酸和乙二醉作为聚合反应的单体合成了正尖晶石结构LiMn2O4的前驱体,研究了反应物摩尔比、pH值及焙烧温度对材料性能的影响,并通过XRD、IR和SEM等方法研究了柠檬酸螯合法合成正尖晶石结构LiMn2O4的溶胶-凝胶过程,探讨了反应机理.研究表明,在Li/Mn摩尔比为0.6、pH值为3.0及焙烧温度为600℃时,合成的正尖晶石结构LiMn2O4的前驱体具有较好的晶粒结构,其一次粒子直径大多在100nm以内.     

溶胶-凝胶法制备CuCo2O4催化剂及性能研究

采用溶胶一凝胶技术，在不同络合剂体系中制备CuCo2O4催化剂，用XRD、BET法、TPR、二甲苯完全氧化等技术和手段研究了催化剂的晶相、还原性能及催化活性。结果表明加入络合剂对提高催化剂比表面积，降低晶粒尺寸至纳米量级有明显作用，对二甲苯的催化氧化表现出优良的反应活性。     

ZnAl2O4：Cu,Mn纳米晶的光学性能研究

采用溶胶凝胶法制备了铜锰共掺的ZnAl2O4纳米晶,使用X射线衍射和光致发光对晶体的结构和光学性能进行了研究。结果表明样品具有单一的尖晶石结构,在309 nm波长光的激发下,具有438 nm、511 nm、530 nm和617nm的光发射。随退火温度的升高,红光发射强度变强,蓝光发射随Cu2＋掺杂浓的增加而变强,CIE坐标显示纳米晶的发光在白光区域。     

Y2O3：Eu^3＋薄膜的制备及发光性能的研究

以稀土氧化物为原料，用溶胶-凝胶法制备前驱液，加入适量的聚乙烯醇做成膜物质，用浸渍拉提法在石英玻璃表面上得到均匀的薄膜，然后经过适当的干燥和热处理得到Y2O3：Eu^3＋发光薄膜．讨论了Eu^3＋的掺杂浓度和热处理温度对薄膜发光性能的影响．试验表明：Eu^3＋的最佳掺杂浓度为8％（摩尔分数），薄膜的发光性能随热处理温度提高而增强，当热处理温度达到700℃后，薄膜的发光性能基本上稳定．同时用原子力显微镜和X射线衍射分析了薄膜的表面形貌和结构．     

水系镁离子电池正极材料MgMn2O4的制备

采用溶胶-凝胶法制备得到了主相为四方结构的MgMn2O4。研究了煅烧温度对产物的相演化和表面形貌的影响,比较了电化学循环稳定性。结果表明,550℃烧结得到了表面呈现多孔通道和孔洞的MgMn2O4 (MMO550),在40 mA/g电流密度下,最大放电比容量为54.0 mAh/g; 与碳纳米管于400℃复合2 h后,CNT形成的导电网格有效地将MgMn2O4颗粒连接起来,得到MMO/CNT样品的首次放电比容量可达118.0 mAh/g,是未复合MMO550最大放电比容量的2.2倍,循环30周后容量保持在88.1 mAh/g。     

溶胶-胶水热合成法制备纳米CoAl2O4粉体

以仲丁醇铝和硝酸钴为原料,用溶胶-凝胶水热合成法制备了纳米CoAl2O4粉体,探讨了水热合成中前驱体的制备工艺条件,并用X射线衍射和扫描电镜等手段分析了水热系统中反应温度、反应时间对纳米CoAl2O4粉体的形成以及形貌的影响.结果表明:前驱体在250℃的水热系统中反应24 h,能制备出较纯净、结晶完整、粒度均匀、粒径小、尖晶石结构的纳米CoAl2O4粉体,其平均粒度约为50～60nm.     

Nb2O5薄膜的制备及性能研究

以NbCl5作为前驱物,用微波催化的溶胶-凝胶法制备了Nb2O5薄膜,并在不同温度下进行热处理。经透过率测试及用X射线衍射分析仪和原子力显微镜对薄膜的相结构和表面形貌进行测试分析,测试结果表明：制得的薄膜主晶相为假六方Nb2O5晶相（TT-Nb2O5晶相）。薄膜厚度具有良好的透光率、良好的空架结构。     

溶胶-凝胶法制备红色荧光粉NaEu(MoO_4)_2的发光性能研究

利用溶胶-凝胶法制备出红光纳米NaEu(MoO4)2荧光粉。通过X-射线粉末衍射(XRD)、扫描电镜(SEM)、固体荧光对所制备出的荧光粉的结构、形貌以及发光性能进行表征。结果表明在700℃煅烧下的样品的粒径约300 nm,形貌均一,并且红光发射最强。它的CIE(Commission Inter-nationale de l'Eclairage,International Commission on Illumination)坐标值为:x=0.66,y=0.34),色纯度很高。它有可能成为近紫外-紫光InGaN芯片用的红色荧光粉。     

YVO4:Eu3+,Bi3+荧光粉的制备及荧光性能研究

用溶胶凝胶法在较低温度下制备了YVO4:Eu3+,Bi3+荧光粉,采用X射线衍射仪(XRD),扫描电子显微镜(SEM)及荧光分光光度计测试,研究了合成产物的结构、表面形貌,分析了在Eu3+含量一定的情况下掺杂Bi3+的浓度的变化对发光性能的影响.结果表明,溶胶凝胶法合成的YVO4:Eu3+,Bi3荧光粉为单相结构、粒径在1 μm左右、无团聚现象;Bi3+对Eu3+离子有敏化作用,在一定浓度下使荧光粉的发射强度增加.     

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.     

Enhanced photoluminescence property of Dy co-doped BaAl2O4:Eu green phosphors

Eu²⁺-doped BaAl₂O₄ green phosphors were prepared by a conventional solid-state reaction and the effects of Dy³⁺ co-doping on the photoluminescence property were investigated. The phosphors were characterized by X-ray powder diffraction (XRD), fluorescence spectroscopy, field-emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS). XRD showed that all prepared samples exhibited a hexagonal BaAl₂O₄ phase. Fluorescence spectroscopy showed that the photoluminescence efficiency increased with increasing Eu²⁺ concentration until 3 mol% then decreased at higher concentrations due to concentration quenching effect. Moreover, Dy³⁺ co-doping increased the photoluminescence efficiency of the Eu²⁺-doped BaAl₂O₄ phosphor.     

NO reduction by CH4 in the presence of O2 over La2O3 supported on Al2O3

Dispersing La₂O₃ on δ- or γ-Al₂O₃ significantly enhances the rate of NO reduction by CH₄ in 1% O₂, compared to unsupported La₂O₃. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La₂O₃ precursor used, the pretreatment, and the La₂O₃ loading. The most active family of catalysts consisted of La₂O₃ on γ-Al₂O₃ prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m²) occurred between the addition of one and two theoretical monolayers of La₂O₃ on the γ-Al₂O₃ surface. The best catalyst, 40% La₂O₃/γ-Al₂O₃, had a turnover frequency at 700°C of 0.05 s⁻¹, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La₂O₃/Al₂O₃ catalysts exhibited stable activity under high conversion conditions as well as high CH₄ selectivity (CH₄ + NO vs. CH₄ + O₂). The addition of Sr to a 20% La₂O₃/γ-Al₂O₃ sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO⁼₄ to the latter Sr-promoted La₂O₃/Al₂O₃ catalyst decreased activity although sulfate increased the activity of Sr-promoted La₂O₃. Dispersing La₂O₃ on SiO₂ produced catalysts with extremely low specific activities, and rates were even lower than with pure La₂O₃. This is presumably due to water sensitivity and silicate formation. The La₂O₃/Al₂O₃ catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.     

The mechanism of SO2 effect on NO reduction with propene over In2O3/Al2O3 catalyst

An In₂O₃/Al₂O₃ catalyst shows high activity for the selective catalytic reduction of NO with propene in the presence of oxygen. The presence of SO₂ in feed gas suppressed the catalytic activity dramatically at high temperatures; however it was enhanced in the low temperature range of 473–573 K. In TPD and FT-IR studies, the formation of sulfate species on the surface of the catalyst caused an inhibition of NO_X adsorption sites, and the absorbance ability of NO was suppressed by the presence of SO₂, and the amount of ad-NO₃⁻ species decreased obviously. This leads to a decrease of catalytic activity at higher temperatures. However, addition of SO₂ enhanced the formation of carboxylate and formate species, which can explain the promotional effect of SO₂ at low temperature, because active C₃H₆ (partially oxidized C₃H₆) is crucial at low temperature.     

ZrO2/SiO2- and La2O3/Al2O3-supported platinum catalysts for CH4/CO2 reforming

Surface-phase ZrO₂ on SiO₂ (SZrOs) and surface-phase La₂O₃ on Al₂O₃ (SLaOs) were prepared with various loadings of ZrO₂ and La₂O₃, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH₄/CO₂ reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al₂O₃ and Pt/SiO₂ catalysts. CO₂ or CH₄ pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO₂ to form a stable surface-phase oxide. The lanthana cannot be spread well on Al₂O₃, but it forms a stable amorphous oxide with Al₂O₃. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO₂ and Pt/Al₂O₃ by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO₂ and Pt/Al₂O₃ catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO₂ adsorbed on the basic sites of SZrOs and SLaOs.     

Synthesis and photoluminescence enhancement of Ca3Sr3(VO4)4:Eu3+ red phosphors by co-doping with La3+

In this study, a series of red-emitting Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphors co-doped with La³⁺ was prepared using the combustion method. The microstructures, morphologies, and photoluminescence properties of the phosphors were investigated. All Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ samples synthesized at temperatures greater than 700 ℃ exhibited the same standard rhombohedral structure of Ca₃Sr₃(VO₄)₄. Furthermore, the Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ phosphor was effectively excited by near-ultraviolet light of 393 nm and blue light of 464 nm. The strong excitation peak at 464 nm corresponded to the ⁷F₀→⁵D₂ electron transition of Eu³⁺. The strong emission peak observed at 619 nm corresponded to the ⁵D₀→⁷F₂ electron transition of Eu³⁺. Co-doping with La³⁺ significantly improved the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺ red phosphors. The optimum luminescence of the phosphor was observed at Eu³⁺ and La³⁺ concentrations of 5% and 6%, respectively. Moreover, co-doping with La³⁺ also improved the fluorescence lifetime and thermal stability of the Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphor. The CIE chromaticity coordinate of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ was closer to the NTSC standard for red phosphors than those of other commercial phosphors; moreover, it had greater color purity than that of all the samples tested. The red emission intensity of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ at 619 nm was ~1.53 times that of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺ and 2.63 times that of SrS:Eu²⁺. The introduction of charge compensators could further increase the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ red phosphors. The phosphors synthesized herein are promising red-emitting phosphors for applications in white light-emitting diodes under irradiation by blue chips.     

硫掺杂ZnFe2O4/蒙脱石复合材料的铀酰吸附研究

为获得铀酰(UO2²⁺)吸附性能高的吸附剂,以蒙脱石(Montmorillonite,MMT)和铁酸盐(ZnFe₂O₄)为原材料与L-半胱氨酸通过水热反应制备了硫掺杂ZnFe₂O₄(S-ZnFe₂O₄)和ZnFe₂O₄/MMT(S-ZnFe₂O₄/MMT),采用XRD、FTIR和SEM对S-ZnFe₂O₄和S-ZnFe₂O₄/MMT进行了结构表征,研究了pH、接触时间和UO2²⁺初始质量浓度对UO2²⁺吸附效果的影响,结果表明:S-ZnFe₂O₄呈高分散的纳米颗粒状,并且均匀分布于蒙脱石片层结构表面;S-ZnFe₂O₄与蒙脱石复合后能明显提高其UO2²⁺吸附性能,最佳吸附pH为6.0;S-ZnFe₂O₄和S-ZnFe₂O₄/MMT复合材料对UO2²⁺的最大吸附量分别为51.44 mg/g和68.45 mg/g;吸附符合Langmuir等温吸附模型和伪二阶动力学模型,说明吸附过程属于表面单分子层化学吸附。     

Design and synthesis of ZnCo2O4/CdS for substantially improved photocatalytic hydrogen production

In this study, the hydrogen evolution performance of CdS nanorods is improved using ZnCo₂O₄. ZnCo₂O₄ nanospheres are synthesized using the hydrothermal and calcination methods, and CdS nanorods are synthesized using the solvothermal method. From the perspective of morphology, numerous CdS nanorods are anchored on the ZnCo₂O₄ microspheres. According to the experimental results of photocatalytic hydrogen evolution, the final hydrogen evolution capacity of 7417.5 μmol∙g^–1∙h^–1 is slightly more than two times that of the single CdS, which proves the feasibility of our study. Through various characterization methods, it is proved that the composite sample has suitable optoelectronic properties. In addition, ZnCo₂O₄ itself exhibits good conductivity and low impedance, which shortens the charge-transfer path. Overall, the introduction of ZnCo₂O₄ expands the adsorption range of light and improves the performance of photocatalytic hydrogen evolution. This design can provide reference for developing high-efficiency photocatalysts.     

Catalytic decomposition of N2O over CeO2 promoted Co3O4 spinel catalyst

A series of CeO₂ promoted cobalt spinel catalysts were prepared by the co-precipitation method and tested for the decomposition of nitrous oxide (N₂O). Addition of CeO₂ to Co₃O₄ led to an improvement in the catalytic activity for N₂O decomposition. The catalyst was most active when the molar ratio of Ce/Co was around 0.05. Complete N₂O conversion could be attained over the CoCe0.05 catalyst below 400 °C even in the presence of O₂, H₂O or NO. Methods of XRD, FE-SEM, BET, XPS, H₂-TPR and O₂-TPD were used to characterize these catalysts. The analytical results indicated that the addition of CeO₂ could increase the surface area of Co₃O₄, and then improve the reduction of Co³⁺ to Co²⁺ by facilitating the desorption of adsorbed oxygen species, which is the rate-determining step of the N₂O decomposition over cobalt spinel catalyst. We conclude that these effects, caused by the addition of CeO₂, are responsible for the enhancement of catalytic activity of Co₃O₄.