Wet chemical synthesis and photocatalytic activity of potassium niobate K6Nb10.8O30 powders

The nanometer potassium niobate powders with tungsten bronze (TB)-type structure were synthesized by a wet chemical method and characterized by X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM). X-ray photoelectron spectroscopy (XPS) analysis confirmed the niobium with mixed valence states exists in the crystal structure of the photocatalyst, which may be advantage for increasing the photocatalytic activity. The band gap of K₆Nb_10.8O₃₀ powders was estimated to be about 2.92 eV and shows a markedly blue-shift as compared to that of the sample obtained by the solid-state reaction. The photocatalytic activity of the samples was evaluated by degradation of acid red G under UV irradiation and the photocatalytic reaction follows first-order kinetics. The photocatalytic activity of the as-prepared sample is much higher than that of sample synthesized by solid-state reaction, and slightly higher than that of P25-TiO₂.     

微量元素掺杂对LED用红色荧光粉(Sr,Ca)AlSiN3:Eu2+长期性能的影响

(Sr,Ca)AlSiN₃:Eu²⁺红色荧光粉在热性能和长期使用性能等方面还有一定差距,导致制成的白光LED在长期工作状态下发生光衰和色标漂移,影响了白光LED的品质。为解决这一问题,将微量碱土金属离子和稀土金属离子掺入(Sr,Ca)AlSiN₃:Eu²⁺中,研究其对(Sr,Ca)AlSiN₃:Eu²⁺红色荧光粉热性能和长期使用性能的影响。实验结果表明:Li⁺-Dy³⁺、Li⁺-Ho³⁺等碱土金属-稀土金属离子对(Sr,Ca)AlSiN₃:Eu²⁺红色荧光粉的光衰性能有较明显的提升,同时也显著减小了制灯后长时点亮的色漂移。     

爆轰和燃烧法合成SrAl2O4：Eu2+，Dy3+纳米发光粉

 在低温条件下分别用爆轰法和燃烧法制备出了SrAl₂O₄：Eu²⁺,Dy³⁺ 纳米发光粉。从合成条件、热处理温度等方面详细对比了爆轰法和燃烧法对所制备的SrAl₂O₄：Eu²⁺,Dy³⁺纳米发光粉的晶体生长行为、粒子形貌和光学性质等的影响。研究表明,随着热处理温度的升高,爆轰法制备的纳米发光粉的平均粒径逐渐增大,而燃烧法制备的纳米发光粉的平均粒径先减小后增大,在600 ℃时平均粒径存在一个极小值。在同样热处理温度下,爆轰法制备的纳米发光粉的平均粒径增长明显高于燃烧法合成的纳米发光粉的平均粒径。最后讨论了长余辉的发光机理,并给出了如何改进合成方法的建议。     

三维荧光光谱结合平行因子算法测定两种食品色素的含量

应用英国Edinburgh FLS920P稳态和时间分辨荧光光谱仪测量了12个混合色素样本的三维荧光光谱,将得到的三维荧光光谱数据矩阵(EEMS)与平行因子算法相结合,来建立一种检测食品色素的方法。实验中,使用核一致诊断法(CORCONDIA)确定了混合溶液的组分数为3,然后利用平行因子分析法(PARAFAC),得到胭脂红、诱惑红的平均回收率分别为(99.3%±5.0%)和(102.2%±5.6%),且预测均方根误差(RESEP)分别为(0.054)和(0.205)。结果表明,该法可在干扰物质苋菜红存在的情况下,对混合溶液中胭脂红、诱惑红二种色素同时定量测定,具有简便、快速等优点,可为合成食品色素的检测提供借鉴。     

Sr2+掺杂荧光粉Ca2Nb2O7：Eu3+的发光特性

采用高温固相法制备出Ca_1.97-xSr_xNb₂O₇：3%Eu³⁺（x=0.10,0.50,1.0,1.5,1.97）红色荧光粉,研究了Ca_1.97-xSr_xNb₂O₇：3%Eu³⁺的发光特性及Sr²⁺的浓度对该荧光粉发光性质的影响。随着Sr²⁺浓度的改变,Ca_2-xSr_xNb₂O₇：Eu³⁺的XRD呈现不同的相。Ca_1.97Nb₂O₇：3%Eu³⁺（x=0）的激发光谱中,302 nm附近的强宽带来自于O^2-→Eu³⁺电荷转移跃迁,272 nm附近的肩峰来自于NbO^7-₆基团的电荷转移跃迁,350~600 nm范围内的锐锋属于Eu³⁺的特征4f-4f组内跃迁。在398 nm激发下,发射光谱的最强峰位于616 nm,属于Eu³⁺的⁵D₀→⁷F₂电偶极跃迁,发射出强烈的红光。当Ca²⁺逐渐被Sr²⁺取代时,Ca_2-xSr_xNb₂O₇：Eu³⁺的各激发峰的强度先提高后降低,且O^2-→Eu³⁺电荷转移跃迁发生明显红移。少量Sr²⁺的掺杂可以有效提高Ca_2-xSr_xNb₂O₇：Eu³⁺ 的红光发射强度,当x=0.01时该荧光粉的红光发射达到最强,可以被紫外LED芯片激发。     

An azine-linked 2D porphyrinic covalent organic framework for red light photocatalytic oxidative coupling of amines

The construction of two-dimensional covalent organic frameworks (2D COFs) with robust stability for photocatalysis has gained intensive attention recently. Herein, we report the design and synthesis of a highly crystalline azine-linked porphyrinic 2D COF (Por-HZ-COF). Our results clearly show that Por-HZ-COF adopts an eclipsed AA stacking structure with a high Brunauer-Emmett-Teller (BET) specific surface area of 1586 m²/g. In addition, Por-HZ-COF is chemically stable under various conditions, even in 12 M sodium hydroxide aqueous solution or 9 M hydrochloric acid. Moreover, Por-HZ-COF can be used for the photocatalytic aerobic oxidative coupling of benzylamines under red light irradiation with high activity and good reusability. This study demonstrates a novel robust 2D COF with azine linkage that has promising applications in photocatalysis.     

白光LED用红色荧光粉Cs2SiF6:Mn4+的软化学法制备及性能

采用了一种软化学制备方法合成了Cs_2SiF_6:Mn~(4+)红色荧光粉。通过粉末X射线衍射XRD、扫描电镜SEM对样品的物相和形貌进行了表征。并测试了不同Mn4+掺杂浓度下的样品的荧光光谱、变温光谱、荧光寿命、量子效率等来评估其性能。同时,进行了LED器件封装并完成了光电性能测试。结果表明,所合成的纯相红色荧光粉Cs_2SiF_6:Mn~(4+)表面呈现不规则的形貌。激发光谱中,位于360和460 nm的宽带激发峰分别归属于4A2g→4T1g和4A2g→4T2g跃迁。发射光谱中,位于630 nm处的窄带发射峰可归结为2Eg→4A2g跃迁。温度从25℃升高到150℃,发光强度基本保持不变,150℃时的发光强度是25℃时的100.03%。不同Mn4+掺杂浓度下的样品的发光寿命均在8.0 ms以上。最佳样品Cs2Si F6∶0.06Mn4+的量子效率是88%。此外,采用Cs2SiF6∶0.06Mn4+作为红色组份封装成的LED器件,当Cs2SiF6∶0.06Mn4+的添加量为24%(质量分数)时,器件的色坐标是(0.411 3,0.412 9),色温CCT=3899 K,显色指数Ra=88,R9=84.2,流明效率为123.84 lm·W-1,同时器件发出暖白光。     

绿色荧光粉NaCaPO4：Tb3+的制备与发光特性

采用高温固相法合成了适用于UVLED芯片激发的NaCaPO₄:Tb³⁺绿色荧光粉并对其发光性质进行了研究。该荧光粉的发射峰位于418,440,492,545,586,622nm,分别对应Tb³⁺的⁵D₃→⁷F₅、⁵D₃→⁷F₄、⁵D₄→⁷F₆、⁵D₄→⁷F₅、⁵D₄→⁷F₄、⁵D₄→⁷F₃能级跃迁。其中位于492,545nm的发射峰最强,样品发射很好的绿光。主要激发峰位于380~400nm之间,属于4f→4f电子跃迁吸收,与UVLED芯片的发射相匹配。考察了Tb³⁺掺杂浓度和Li⁺,Na⁺和K⁺作为电荷补偿剂对样品发光性能的影响:Tb³⁺的最佳掺杂浓度为10%,以Li⁺的补偿效果最好。NaCaPO₄:Tb³⁺是一种适用于白光LED的绿色荧光材料。     

A precise self-built secondary mass database for identifying red dyes and dyeing techniques with UPLC-MS/MS

Dyes on ancient silks have been a worth studying field through human's history, although current reports ignore the connection between natural dyes origin and relevant colour reduction methods, which poses an insurmountable obstacle for restoration of historical silks. In this paper, a series of 12 red hue silks from six natural dyes (sappanwood, Chinese madder, safflower, lac, cochineal, dragon's blood) via three different dyeing techniques were used to establish a self-built precise tandem mass spectrometry (MS/MS) database. With organic solvent extracting on those manual-dyed silks, ultraperformance liquid chromatography - electrospray ionization - quadrupole time of flight mass spectrometry (UPLC-ESI-QTOF-MS) was utilized to form preliminary MS database for screening and identifying of the potential dyes compounds without standard references. Furthermore, combining the targeted MS/MS mode and the matching threshold of 70.00, a self-built secondary MS/MS database was successfully established, which contains 33 compounds, 32 chromatograms and 32 MS/MS fragments. As for real sample application, the self-built precise MS/MS database had revealed that the dyes on two historical silks (Shanghai Museum, China) belong to Chinese madder just with different mordant dyeing ordinal. Additionally, by experimental restoration, visually indistinguishable silks (ΔE_ab* < 1.5 NBS) were successfully restored. This explorative methodology can further inspire the traceability of biological dyestuffs, which lays instructive foundation on protection and restoration of artefacts, connecting the archaeological science and human art.