Sm3+离子激活的Ba3ZnNb2O9荧光粉的制备及发光性能

利用高温固相法合成了不同Sm³⁺掺杂浓度的Ba₃ZnNb₂O₉荧光粉,并利用X射线粉末衍射(XRD)、漫反射光谱(DRS)、荧光发射光谱及荧光寿命等表征手段对样品的结构与发光性能进行了研究。XRD结果显示纯样Ba₃ZnNb₂O₉与Ba₃ZnNb₂O₉:Sm³⁺荧光粉的衍射图完全吻合,表明Sm³⁺离子的少量引入并未对晶体结构产生影响。漫反射光谱显示样品可以被近紫外光有效激发。发射光谱表明存在基质向Sm³⁺离子的能量传递过程,Sm³⁺离子的最佳掺杂浓度为x=0.1。     

白光SrMoO4:Eu3+,K+@g-C3N4荧光粉的合成及其性能研究

为了获得单一基质白光荧光粉，以三聚氰胺为原料，采用热分解法制备g-C₃N₄蓝色荧光粉，采用高温固相法制备了Sr_0.92Mo O₄:0.08Eu³⁺(SMO:E)和Sr_0.82Mo O₄:0.08Eu³⁺,0.10K⁺(SMO:EK)红色荧光粉，通过沉淀吸附反应制备了Sr_0.82Mo O₄:0.08Eu³⁺,0.10K⁺@0.013g-C₃N₄(SMO:EK-CN)复合荧光粉。利用X射线粉末衍射、红外光谱、荧光光谱、热猝灭分析对荧光粉进行表征，分别探讨了Eu³⁺单掺杂和Eu³⁺、K⁺共掺杂以及Eu³⁺、K⁺、g-C₃N₄     

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。     

基于第一性原理计算的Sr2MgSi2O7:Eu2+,Dy3+长余辉材料持续发光机理

长余辉材料应用广泛,但种类繁多、发光机理难以被普遍阐释。针对发光–余辉性能好的Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺硅酸盐长余辉材料,构建Sr₂MgSi₂O₇基质、Eu掺杂及(Eu,Dy)共掺杂Sr₂MgSi₂O₇的分子模型,进行第一性原理计算。从电子结构角度解译电子跃迁俘获路径,并阐释Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺的持续发光机理。结果表明：Eu、Dy离子的掺入使Sr₂MgSi₂O₇由间接带隙半导体转变为直接带隙半导体;Dy 5d态主要位于Fermi能级与Eu 5d态之间,并与Eu 5d态存在能量重叠,这证实了Dy³⁺作为电子陷阱的合理性。S...     

双激发波长响应的Sr2Gd1–xNbO6:x Eu3+的荧光性能与热稳定性

针对目前钙钛矿型红色荧光粉热稳定性较差的问题,以带隙和结构可调变的双钙钛矿型 Sr₂Gd Nb O₆为基质、Eu³⁺为激活离子,采用高温固相法成功制备双钙钛矿型 Sr₂Gd_1–xNb O₆: x Eu³⁺(x=0.04～0.12)红色荧光粉,通过 X 射线衍射、紫外–可见分光光度和荧光光谱分析对目标产物进行表征。结果表明：合成的荧光粉具有单斜晶体结构,其空间群为 P2₁/c。结构分析表明：掺杂的铕以 Eu³⁺的化合态取代了基质 Sr₂Gd Nb O₆中的 Gd³⁺,形成了单一晶体结构的荧光粉。Sr₂Gd_1–xNb O₆: x Eu³⁺荧光粉在蓝光λ_ex=468 nm 和近紫外 λ_ex=395 nm...     

硫元素掺杂的超窄带零热猝灭蓝光荧光粉：Rb Na3(Li12Si4O16–ySy):Eu2+

采用传统的高温固相法合成出了硫元素掺杂的具有473 nm和525 nm双发射的UCr₄C₄型Rb Na₃(Li₁₂Si₄O_16–yS_y):Eu²⁺窄带蓝光荧光粉,并在UCr₄C₄结构中实现零热猝灭发光性能,其发光积分强度在250℃下提升至室温的107%。Eu²⁺离子的格位占据分析及缺陷表征揭示了对应的发光调控和零热猝灭机理。采用阳离子取代策略(Ti⁴⁺部分取代Si⁴⁺)成功消除了荧光粉位于525 nm的肩带峰,将蓝光色纯度从61.1%提升至83.7%,使Rb Na₃(Li₁₂Si₃Ti O_16–yS_y):Eu²⁺荧光粉有望成为应用于液晶显示背光的蓝色发光候选材料,为UCr     

Eu3+掺杂Ba2LaZrO5.5基荧光粉的制备及发光研究

以溶胶凝胶法制备了Ba₂LaZrO_5.5:Eu³⁺荧光粉，探讨溶液的pH值、焙烧温度和掺杂Eu³⁺的量对荧光粉的结构和发光的影响。证实了当pH=3、焙烧温度为800℃时Ba₂LaZrO_5.5:21%Eu³⁺荧光粉为立方体钙钛矿结构；在280nm激发下基质Ba₂LaZrO_5.5在468nm处有较强的蓝光发射，而Ba2LaZrO_5.5:21%Eu³⁺荧光粉在612nm处有Eu³⁺的红光发射峰最强。     

Sm3+掺杂双钙钛矿结构Sr3Sn2O7的应力发光特性

Sr₃Sn₂O₇:Sm³⁺是一种被广泛研究的应力法光材料,但关于Sm³⁺掺杂量的研究仍然存在缺失。本工作采用高温固相法制备Sr_3–xSn₂O₇:x Sm³⁺。在Sr₃Sn₂O₇中掺入少量Sm³⁺后,样品仍然保持着非中心对称的双钙钛矿结构。样品在受到紫外灯激励或应力施加之后,能展现出稳定的光致发光、长余辉和应力发光性能,且这三者的光谱显示出一致性。应力发光来源于Sm³⁺的⁴G_5/2激发态向⁶H_J (J=5/2,7/2,9/2)基态的电子跃迁。通过调控x值对其发光性能进行优化,在x=0.020时性能最好。Sm³⁺掺杂量的变化对应力发光性能的影响,既对现有的相关工作进行了补充,同时...     

SiO2:Eu3+荧光粉的制备及其发光性能的研究

采用stober溶胶-凝胶法制备以SiO₂为基质,Eu³⁺为激活剂的红色荧光粉。研究了退火温度,稀土Eu³⁺掺杂量对荧光粉发光性能的影响。研究表明：制备出了分散度高,形貌好的球形SiO₂粒子,粒径分布单一,几乎均在613 nm左右,SiO₂粒子为非晶态,稀土离子的掺杂并未改变SiO₂的结构。稀土离子掺杂量与退火温度仅影响发射峰的强度,并未影响发射峰的位置。SiO₂:Eu³⁺最佳退火温度为600℃、最佳掺杂量为6 mol%,位于橙红光区。     

TiO2-SiO2∶Eu3+荧光粉的制备及发光性能的研究

采用溶胶凝胶法制备TiO₂-SiO₂∶Eu³⁺发光材料，通过XRD, FTIR,荧光光谱仪的测试表征材料的结构和发光性能。结果表明，通过溶胶凝胶法成功的制备了TiO₂-SiO₂复合氧化物荧光粉。FTIR证明1070cm^-1为Si-O-Si的反对称伸缩振动，795cm^-1为Si-O-Si的对称伸缩振动，937cm^-1为Ti-O-Si特征峰。荧光光谱表明以465nm为激发波长，Eu³⁺在612nm(⁵D₀→⁷F₂)红色发光最强。Ti/Si为1∶1时，Eu³⁺掺杂浓度为4mol%时发光强度最佳。     

Fabrication and thermoelectric properties of heavily rare-earth metal-doped SrO(SrTiO3)n (n = 1, 2) ceramics

To clarify the effect of substitutional electron doping on the thermoelectric figure of merit (ZT = S²σTκ⁻¹) of Ruddlesden–Popper phase SrO(SrTiO₃)_n (or Sr_n+1Ti_nO_3n+1), measurements were conducted for several thermoelectric parameters, e.g. electrical conductivity (σ), Seebeck coefficient (S) and thermal conductivity (κ), of (Sr_1−xRE_x)_n+1Ti_nO_3n+1 (n = 1 or 2, RE (rare earth): La or Nd, x = 0.05 and 0.1) dense ceramics prepared by a conventional solid-state reaction and hot-pressing technique. Crystal structures of the resultant ceramics were represented as (Sr_1−xRE_x)_n+1 Ti_nO_3n+1 evaluated by powder X-ray diffraction followed by the Rietveld analysis. All the ceramics exhibited electrical conductivity and the σ values simply depended on the dopant concentration, indicating that both La³⁺ and Nd³⁺ ions act as electron donors. The |S| values increased with temperature due to decrease in the chemical potential. Significant reduction of the κ values was observed as compared to cubic-perovskite SrTiO₃. The ZT value increased with temperature and reached 0.15 at 1000 K for (Sr_0.95La_0.05)₃Ti₂O₇.     

Ta、Ba共掺杂石榴石型Li7La3Zr2O12电解质的制备及性能研究

传统锂离子电池采用有机电解液体系,能量密度难以进一步提升,同时存在一定的安全隐患。采用无机固体电解质构建全固态锂电池,在提高电池能量密度同时可兼顾安全性问题。在众多无机固体电解质中,Li₇La₃Zr₂O₁₂(LLZO)石榴石电解质具有离子电导率高、与金属锂接触稳定等优势,成为受人关注的材料。为了进一步提高该材料的导电性,采用固相法合成Ta、Ba共掺杂LLZO(Li_7-x+yLa_3-yBa_yZr_2-xTa_xO₁₂)电解质,采用X射线衍射、扫描电子显微镜和电化学阻抗法分析样品的物相结构、微观形貌及离子电导率。结果表明,Ta⁵⁺掺杂能够稳定立方相结构,Ba²⁺作为掺杂剂和烧结剂,促进晶粒生长和陶瓷致密化,从而降低总电阻。其中,Li_6.45La_2.95Ba_0.05Zr_1.4Ta_0.6O₁₂样品在室温下的总电导率为1.07×10^-3 S·cm^-1,活化能为0.378 eV。Ta⁵⁺/Ba²⁺共掺杂有利于制备高致密度和高电导率的石榴石型电解质材料。     

TayNb1−yVO5 (0<y<1) mixed oxides synthesized by sol–gel method: electrochemical Li-insertion

Mixed oxides of general formulae Ta_yNb_1−yO₅ (0<y<1) have been synthesized by a modified sol–gel method. Characterization of the samples has been carried out by x-ray diffraction, SEM/EDX, FTIR spectroscopy and thermal analysis. The electrochemical properties have been studied in a lithium cell. The first discharge capacity decrease from 206 (y=0.25) to 136 mA h g⁻¹ (y=0.75). Ta_yNb_1−yO₅ samples undergo an irreversible structural changes induced by electrochemical Li⁺-insertion. For all compositions, the new compounds formed after the first discharge has a very high cyclability, as shown the low capacity loss <1% per cycle.     

离子对(Nb5+-Cr3+)掺杂对0.93Bi0.5Na0.5TiO3-0.07BaTiO3陶瓷微观结构和电学性能的影响

采用固相烧结法制备(Bi_0.5Na_0.5)_0.93Ba_0.07Ti_1-x(Nb_0.5Cr_0.5)_xO₃(摩尔分数x=0%、0.5%、1%、2%、2.5%、5%)(简称BNBT-xNC)无铅压电陶瓷,研究离子对(Nb⁵⁺-Cr³⁺)对0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃(简称BNT-7BT)陶瓷微观结构、介电、铁电和应变性能的影响。结果表明,所有组分为伪立方相。随着离子对(Nb⁵⁺-Cr³⁺)含量增加,BNBT-xNC陶瓷的铁电弛豫特性明显改变,在较低掺杂浓度下(0%≤x≤1%)为非遍历弛豫态,随含量增加(1%≤x≤2%),出现非遍历-遍历弛豫态共存,最后转变为遍历弛豫态(2.5%≤x≤5%);陶瓷从铁电态向弛豫态转变,应变性能先增加后降低,最大应变S_max和逆压电常数d^*₃₃在x=2%时达到最大,分别为0.22%和431 pm/V。     

Effect of codoping LiNbo3:Eu3 crystal with Mg2 ions on the Eu3 optical absorption spectrum

In this work the optical absorption spectra of Eu³⁺ doped LiNbO₃ measured as a function of Li/Nb ratio are presented. Two Eu³⁺ sites, dealing with the Nb⁺⁵ and Li⁺ lattice sites, have been characterized by their corresponding ⁷F_o -⁵D₂ optical transitions. A doubly doped sample (LiNbo³: Mg, Eu) has been used to study the influence of Mg²⁺ ions on the Eu³⁺ optical absorption spectrum. The main effect is a shifting of the relative occupation of the two Eu³⁺ sites.     

K+掺杂LiNi1/3Co1/3Mn1/3O2材料的制备及电化学性能研究

锂离子电池正极材料LiNi_1/3Co_1/3Mn_1/3O₂具有放电比容量大、热稳定性好、成本低、安全性能好等优点,但其倍率性能有待进一步提升。本文采用水热法制备了K⁺掺杂LiNi_1/3Co_1/3Mn_1/3O₂材料LNCM-xK。通过X射线衍射谱、场发射扫描电镜和X射线光电子能谱表征LNCM-xK的形貌和结构,通过电化学工作站和蓝电测试系统测试其电化学性能。结果表明:K⁺掺杂能有效降低阳离子混排程度,改善LiNi_1/3Co_1/3Mn_1/3O₂材料的电化学性能,其中当x=0.125时K⁺掺杂LiNi_1/3Co_1/3Mn_1/3O₂样品(LNCM-0.125K)阳离子混排程度最低;LNCM-0.125K样品电化学性能最佳,0.2 C下50次循环后容量保持率为96.15%;在不同电流密度(0.2 C,0.5 C,1 C,2 C,5 C)下进行倍率性能测试,连续充放电30次后LNCM-0.125K样品容量保持率为97.00%。     

AFeO3 (A=La, Nd, Sm) and LaFe1−xMgxO3 perovskites as methane combustion and CO oxidation catalysts: structural, redox and catalytic properties

Catalytic methane combustion and CO oxidation were investigated over AFeO₃ (A=La, Nd, Sm) and LaFe_1−xMg_xO₃ (x=0.1, 0.2, 0.3, 0.4, 0.5) perovskites prepared by citrate method and calcined at 1073 K. The catalysts were characterized by X-ray diffraction (XRD). Redox properties and the content of Fe⁴⁺ were derived from temperature programmed reduction (TPR). Specific surface areas (SA) of perovskites were in 2.3–9.7 m² g⁻¹ range. XRD analysis showed that LaFeO₃, NdFeO₃, SmFeO₃ and LaFe_1−xMg_xO₃ (x·0.3) are single phase perovskite-type oxides. Traces of La₂O₃, in addition to the perovskite phase, were detected in the LaFe_1−xMg_xO₃ catalysts with x=0.4 and 0.5. TPR gave evidence of the presence in AFeO₃ of a very small fraction of Fe⁴⁺ which reduces to Fe³⁺. The fraction of Fe⁴⁺ in the LaFe_1−xMg_xO₃ samples increased with increasing magnesium content up to x=0.2, then it remained nearly constant. Catalytic activity tests showed that all samples gave methane and CO complete conversion with 100% selectivity to CO₂ below 973 and 773 K, respectively. For the AFeO₃ materials the order of activity towards methane combustion is La>Nd>Sm, whereas the activity, per unit SA, of the LaFe_1−xMg_xO₃ catalysts decreases with the amount of Mg at least for the catalysts showing a single perovskite phase (x=0.3). Concerning the CO oxidation, the order of activity for the AFeO₃ materials is Nd>La>Sm, while the activity (per unit SA) of the LaFe_1−xMg_xO₃ catalysts decreases at high magnesium content.     

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。     

Performance of La1−xSrxAl1−y−y′FeyMgy′O3−δ perovskites in methane combustion: effect of aluminum and magnesium content

Perovskites of different La_1−xSr_xAl_1−y−y′Fe_yMg_y′O_3−δ compositions (x=0, 0.1, 0.15, 0.2 and y=0.1, 0.3, 0.5, 0.8) were prepared from a reactive precursor slurry of hydrated oxides. Each sample was aged between 16 and 26 h up to 1473 K. Activity in methane combustion (1%/air) was determined in a plug-flow reactor, with 1 g catalyst and 24 l/h flowrate. Gradual decrease in activity due to thermal aging was observed, the degree of activity loss being composition dependent. Nevertheless, activity of samples aged at 1370 K was nearly independent of composition. The best thermal stability showed LaAl_0.65Fe_0.15Mg_0.2O₃ perovskite. None of the magnesium substituted perovskites performed better than a La_0.85Sr_0.15Al_0.87Fe_0.13O₃ reference sample.