K2OsO2(OH)4低温拉曼光谱研究

本工作获得了低温下锇酸钾K₂OsO₂(OH)₄的拉曼光谱,并对其声子行为进行了研究。在低温下,K₂OsO₂(OH)₄的拉曼光谱信噪比和展宽都得到改善,由晶胞收缩引起的晶体场扰动使位于高波段的ν₁模分裂为ν′₁和ν″₁两个振动模;而晶体中氢键体系取向的重定向行为使ν₂模在低温下发生了不连续变化。     

基于水内标的NO-3，SO2-4，ClO-4拉曼光谱定量分析研究

拉曼光谱由于重现性差,在进行定量分析时往往需要内标。在水溶液中,水在2 700~3 900 cm-1范围伸缩振动拉曼峰很强,有作为内标的可能性,但水与溶质的相互作用会导致水伸缩振动拉曼峰形状发生变化,此外水的占比也会随着溶质浓度的变化而变化,当溶质浓度较高时需要对水的含量进行校正。将这两点因素考虑在内,研究了以水为内标,采用拉曼光谱法测量水溶液中NO-₃,SO2-₄和ClO-₄浓度的适用性。不同浓度NaNO₃,Na₂SO₄和NaClO₄溶液的拉曼光谱显示随着盐浓度的升高水在2 700~3 900 cm-1范围内的拉曼峰呈现出左肩下降右肩上升的变化趋势。将三种盐溶液拉曼光谱中酸根离子拉曼峰面积（A_盐）和水的拉曼峰面积（A_H2O）的比值（Ｒ_S=A_盐/A_H2O）与溶液中酸根离子和水的含量的比值（c_盐/c_H2O）作图,均呈现出良好的线性关系,拟合得到三条相关曲线的R2分别为0.999 1,0.999 1和0.999 4,说明酸根离子和水的拉曼散射系数均未发生变化或者在同比例变化。虽然水拉曼峰的形状发生了改变,但并不会影响水作为内标的可行性。在引入水的含量修正后,经理论推导c_盐与R_S符合关系式：c_盐=AR_S/(1+BR_S)。在0.1 mol·L-1到近饱和的宽浓度范围内,将R_S对c_盐作图,通过数据拟合获得的NaNO₃,Na₂SO₄和NaClO₄的工作曲线分别为c_NaNO3=18.8R_S/(1+0.6R_S) (R2=0.999 1),c_Na2SO4=20.2R_S/(1+1.0R_S) (R2=0.998 8),c_NaClO4=15.0R_S/(1+0.7R_S) (R2=0.999 8)。NaNO₃,Na₂SO₄和NaClO₄的检出限分别为0.008 0,0.005 2和0.007 3 mol·L-1。在水拉曼峰形状变化不影响其作内标可行性的基础上,当溶液中同时存在两种阴离子时,通过在水含量修正部分加入干扰离子对水含量的影响,可以在单盐溶液定量工作曲线中加入校正项来消除溶液中干扰离子对待测离子分析结果的干扰,但当干扰离子浓度较大而待测离子浓度较小时,干扰离子拉曼峰强度过大会影响到待测离子拉曼峰面积的准确性,从而使得校正的效果下降。     

正磷酸盐晶体Ba3(PO4)2和Sr3(PO4)2高温拉曼光谱研究

测量了碱土金属正磷酸盐Ba₃(PO₄)₂和Sr₃(PO₄)₂常温及高温拉曼光谱, 对拉曼振动模式进行指认, 并分析了晶体拉曼振动光谱及晶体结构在高温下的变化. 在温度升高的过程中, 拉曼振动频率向低频移动且振动峰宽度展宽, 晶体中的P-O平均键长随温度升高而变长, 但O-P-O的键角并未发生变化. 晶体在900 ℃以下无结构相变发生. 关键词： 3(PO₄)₂和Sr₃(PO₄)₂')" href="#">Ba₃(PO₄)₂和Sr₃(PO₄)₂ 高温拉曼光谱 振动模式 高温结构     

基于表面增强拉曼的饮料中山梨酸钾快速定量检测方法

基于实验室自行搭建的拉曼光谱点扫描系统,利用表面增强拉曼技术对橙味饮料中山梨酸钾的含量进行了定量快速检测研究。通过与山梨酸钾标准品拉曼光谱及其水溶液表面增强拉曼光谱等比较分析,确定了山梨酸钾1 648.4,1 389.3和1 161.8 cm-1处的表面增强特征拉曼位移。通过山梨酸钾橙味饮料平行样品的拉曼位移峰强重现性实验并计算其峰强的相对标准偏差证实了该表面增强拉曼方法具有较好的重复性。采集了山梨酸钾浓度范围为1.706～0.180 7 g·kg-1的33个橙味饮料样品的表面增强拉曼光谱,所有原始光谱经S-G 5点平滑及Baseline基线去除荧光背景预处理后分别用一元线性回归分析、多元线性回归分析和偏最小二乘回归分析方法,建立了山梨酸钾的定量预测模型。经比较,选取三个山梨酸钾拉曼特征位移1 161.8,1 389.3和1 648.4 cm-1所建立的多元线性回归模型校正集的相关系数(R2_C)和均方根误差(RMSEC)分别为0.983 7和0.051 7 g·kg-1,验证集的相关系数(R2_P)和均方根误差(RMSEP)分别为和0.969 9和0.052 8 g·kg-1,比一元线性回归模型和偏最小二乘回归模型误差小、精度高。基于表面增强拉曼完全可以实现橙味饮料中山梨酸钾的定量快速预测,为各类食品中山梨酸钾含量的快速监测奠定了技术基础。     

钙钛矿(C6H5CH2NH3)2PbBr4拉曼光谱研究

运用激光拉曼光谱实验和密度泛函理论计算研究了450～1 700 cm-1光谱范围内有机-无机杂化钙钛矿材料(C₆H₅CH₂NH₃)₂PbBr₄的振动模式特性。对比实验所得拉曼光谱和理论计算所得拉曼光谱,发现密度泛函理论计算可以很好的模拟(C₆H₅CH₂NH₃)₂PbBr₄有机部分的分子振动模式。同时通过比较分析密度泛函理论计算和参考文献,对450～1 700 cm-1光谱范围内的拉曼峰的分子振动模式进行了初步的归属,并发现该光谱范围内的拉曼峰主要是由(C₆H₅CH₂NH₃)₂PbBr₄分子中有机部分振动所产生的。     

近红外高光谱成像技术在筛查保健食品中违禁添加抗炎药物双氯芬酸钠的研究

双氯芬酸钠是一种非甾体抗炎药,抗炎症效果较好,抗炎化学药物双氯芬酸钠有可能违禁添加到缓解炎症保健食品中。目前已有一些文献研究水、肉及牛奶等中的药物双氯芬酸钠,主要利用高效液相色谱、表面增强拉曼及电化学等方法,需要相对复杂的预处理过程,操作步骤相对复杂,耗时。为了快速、无损检测保健食品中违禁添加物的成分,探索建立采用1 000～2 524 nm波段或特征最优波段的光谱作为自变量,将近红外高光谱成像技术结合化学计量学分析的方法定量分析缓解炎症保健食品中可能添加的不同浓度的双氯芬酸钠。研究主要运用了8种光谱预处理方法,基于全光谱波长建立了偏最小二乘回归及主成分回归模型,同时,为了提高模型的准确性和稳定性,利用β系数方法选择最优波段1 130～1 147,1 412～1 468,1 658～1 709,2 010～2 055,2 122～2 178和2 395～2 423 nm为自变量建立与双氯芬酸钠浓度的多元线性回归模型。比较了偏最小二乘回归、主成分回归及多元线性回归三种模型。分析结果显示,经标准正态变量预处理方法建立多元线性回归模型,该模型的准确性和和预测能力较好,其预测最低限为0.05%,预测值与实测值的R2为0.992 5,预测均方根误差为0.004 9,标准预测偏差为0.004 9,说明近红外高光谱成像技术为快速定量分析缓解炎症保健食品中违禁添加抗炎药物双氯芬酸钠提供了理论基础。有望进一步开发拓展到其他违禁添加药物的快速定量应用。     

B2O3-Na2O-CaO-SiO2玻璃结构的拉曼光谱研究

制备了B₂O₃-Na₂O-CaO-SiO₂四元系若干玻璃样品,通过实验拉曼光谱和量子化学从头计算相结合的方法,对其微观结构进行了定性定量研究。结果表明,随着B₂O₃的加入,硅酸盐转变为硼硅酸盐结构。当质量比CaO/SiO₂=1时,B主要以[BO₃]的形式参与网络形成,并在B₂O₃含量为6 Wt%时迹象明显。拉曼光谱精细结构解谱的结果表明,B的加入使结构复杂化,体系中Q₁相对含量减少,Q₃相对含量增加,整体由以Q₂为主变为以Q₂、Q₃为主。     

MgO-TiO2二元系熔体结构的原位超高温拉曼光谱研究

利用激光加热超高温气动悬浮熔体和皮秒拉曼光谱测试技术耦合,有效抑制超高温黑体辐射对拉曼光谱的影响,获得了高信噪比的二元镁钛酸盐系列熔体拉曼光谱。定量分析了熔体中团簇结构的分布及其随组分浓度的变化规律。定量分析表明：MgO-TiO₂二元系熔体中存在H₀、Q₀、Q₁、Q₂和Q₃微结构单元,且随TiO₂浓度的增加,熔体中四配位TiO₄四面体逐渐向六配位TiO₆八面体转变。     

CS2在Ｃ6H6中的弱费米共振特性及对Bertran公式修正

通过测量CS₂在C₆H₆中不同浓度的拉曼光谱,观察到了纯CS₂与溶液中的v₁—2v₂费米共振明显不同.用Bertran方程,计算了费米共振特性参数.结果表明,随着CS₂浓度降低,两光谱强度比R=I_v1/I_2v2减小,耦合系数W增加,其他参数 关键词： 拉曼光谱 费米共振 溶剂效应 二硫化碳     

单壁BC3纳米管晶格动力学研究

基于力常数模型计算了一系列扶手椅型、锯齿型和手性单壁BC₃纳米管的声子色散关系.描述了单壁BC₃纳米管结构的表征方式,比较详细地给出了其结构、对称性和晶格动力学分析.基于数值计算结果,讨论了拉曼活性模和红外活性振动模的频率与管径的关系.由分析结果做出推断,BC₃纳米管的拉曼光谱和红外光谱比单壁碳纳米管更为复杂. 关键词： 3纳米管')" href="#">BC₃纳米管 声子色散关系 晶格动力学     

含硼盐卤体系中碳酸根和碳酸氢根分析方法改进

利用甘露醇法测定硼、双指示剂法测定总碱度,同时借鉴血清中HCO-₃的检测方法,建立了一种分光光度-滴定分析联用方法,用于准确测定含硼盐卤体系中硼及CO2-₃和HCO-₃的准确含量。以酚红为显色剂,考察了测定波长、显色剂用量、显色反应温度、pH等测试条件的影响,并从浓度与吸光度的线性关系,检出限及加标回收率等方面进行了系统研究,结果表明：在显色剂用量为1 mL,控制pH 8.4,室温下进行显色反应;在波长558 nm处,CO2-₃在0~10 mmol·L-1内吸光度与浓度有良好线性关系,线性相关系数R2=0.999 8,检出限为2.53×10-3 mmol·L-1。样品加标回收率范围在97.75%~101.76%间,相对误差在-1.67%~-1.95%。该方法简便易行,精密度好,准确度高,优化了共存硼体系中CO2-₃和HCO-₃含量的测定方法,为含硼盐卤体系中体系碳酸根和碳酸氢根含量的准确测定提供了一种新的方法,对于盐湖卤水的基础研究和实际应用提供了新的思路和实验方法。     

10B丰度变化对可溶硼浓度监测计算的影响分析

在机组运行过程中,硼表硼浓度与化学分析硼浓度会出现一定偏差,根据秦山第二核电厂几台机组的实际运行数据整理出该硼浓度偏差的具体数据,并通过对比对应时间内的10B丰度变化情况,分析10B丰度变化对该偏差的影响,得出该偏差主要是受10B变化的影响且在机组寿期中达到最大的结论,并针对该现象对机组运行提出建议。同时采用ORIENT对考虑了10B丰度变化的理论硼浓度进行计算,并通过与化学分析硼浓度的对比得出该计算结果是可靠的,由此可以更加准确地预测、跟踪计算堆芯硼浓度的变化。     

Eu3+/Dy3+共掺Sr3Y2(BO3)4荧光粉的发光性质研究

稀土掺杂发光材料一直是科研领域研究的热点,被广泛应用于白光LED、温度传感、显示显像、新能源和激光等领域。基质的结构对于稀土离子光致发光特性有非常重要的影响,在众多发光基质材料中,硼酸盐具有透光范围宽、光学损伤阈值高、较好的热稳定性和化学稳定性等优点。碱土-稀土金属硼酸盐Sr₃Y₂(BO₃)₄具有出色的光学性能,对其发光性能的研究具有重要意义。稀土离子Eu³⁺具4f⁶电子层,是一种典型的下转换发光中心离子,常被选作红色发光材料的激活剂。Dy³⁺具4f⁹电子层,也是一种典型的下转换发光中心离子,在紫外光激发下,在蓝色光区和橙色光区有较强的荧光发射。采用高温固相法合成了Sr₃Y₂(BO₃)₄∶Eu³⁺/Dy³⁺荧光粉,通过XRD和SEM对样品的结构和形貌进行了表征,XRD结果表明,1 0...     

Synthesis and formation mechanism of pinnoite in sulfated-type boron concentrated brine by dilution method

The synthesis of pinnoite (MgB₂O(OH)₆) in boron-containing brine was established with a novel dilution method. Effects of temperature, precipitation time, boron concentration and mass dilution ratio on the formation of pinnoite were investigated. The products obtained were characterized by X-ray diffraction (XRD), Raman, thermogravimetric and differential scanning calorimeter (TG-DSC), and scanning electron microscopy. The transformation mechanism of pinnoite with different dilution ratios was assumed by studying the crystal growth of pinnoite. The results showed that pinnoite was synthesized above 60 °C in the diluted brine. There were two reaction steps – precipitation of amorphous solid and the formation of pinnoite crystals – during the whole reaction process of pinnoite when the dilution ratio is more than 1.0 at 80 °C. While in the 0.5 diluted brine, only one reaction step of pinnoite crystal formation was observed and its transformation mechanism was discussed based on dissociation of polyborates in brine. Besides, the origin of pinnoite mineral deposited on salt lake bottom was proposed.     

Combustion synthesis and luminescent properties of a new material Li2(Ba0.99,Eu0.01)SiO4:B for ultraviolet light emitting diodes

Using urea as fuel and boric as flux, a novel bluish green emitting phosphor Li₂(Ba_0.99,Eu_0.01)SiO₄:B³⁺ has been successfully synthesized using a combustion method. The material has potential application as the fluorescent material for ultraviolet light-emitting diodes (UV-LEDs). The dependence of the properties of Li₂(Ba_0.99,Eu_0.01)SiO₄:B³⁺ phosphors upon urea concentration, boric acid doping and initiating combustion temperature were investigated. The crystallization and particle sizes of Li₂(Ba_0.99,Eu_0.01)SiO₄:B³⁺ have been investigated by using powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Luminescence measurements showed that the phosphors can be efficiently excited by ultraviolet (UV) to visible region, emitting a bluish green light with peak wavelength of 490 nm. The results showed that the boric acid was effective in improving the luminescence intensity of Li₂(Ba_0.99,Eu_0.01)SiO₄ and the optimum molar ratio of boric acid to barium nitrate was about 0.06. The optimized phosphors Li₂(Ba_0.99,Eu_0.01)SiO₄:B_0.06³⁺ showed 160% improved emission intensity compared with that of the Li₂(Ba_0.99,Eu_0.01)SiO₄ phosphors under UV (λ_ex=350 nm) excitation.     

Vibrational properties of superionic glasses (AgI)x(Ag2O nB2O3)1-x

In this letter we refer on the Raman-scattering measurements in superionic glasses (AgI)_x(Ag₂O nB₂O₃)_1-x where 0 ? x ? 0.5. The behaviour of the low-frequency Raman spectra, Δν < 250 cm^?1, has been interpreted as due to a vibrational density of states mainly due to the silver halide. Nonlinear increase of the Raman efficiency with the increase of AgI concentration has been found: a phenomenological explanation is presented.     

Luminescence optimization of Eu-doped LnAl3(BO3)4 (Ln=Y, Gd) red phosphor using spray pyrolysis

LnAl₃(BO₃)₄:Eu³⁺ (Ln=Y, Gd) red phosphor particles were prepared by spray pyrolysis and the luminescent intensity under vacuum ultraviolet (VUV) excitation was investigated by changing Eu³⁺ content, Y/Gd molar ratio, and boron content. The concentration quenching for Eu³⁺ activator was observed at 5 at%. The highest luminescent intensity at 615 nm due to the ⁵D₀→⁷F₂ transitions of Eu³⁺ was achieved when the ratio of Gd to Y was 0.55. The R/O ratio (obtained by dividing the red emission intensity at 615 nm with the orange one at 592 nm), however, was not influenced by the G/Y ratio. Using excess boron, up to 135% of the stoichiometric quantity, improved the emission intensity of LnAl₃(BO₃)₄:Eu³⁺ red phosphor. According to XRD analysis, the sample prepared using boron of a stoichiometric quantity had YBO₃ phase as a minor phase. Such YBO₃ phase progressively disappeared with an increase in the excess quantity of boron, which was responsible for the enhancement of emission intensity. In addition, the R/O ratio became larger and larger by increasing the excess content of boron due to a reduction in the symmetry of Y site. Consequently, both the emission intensity and the color coordinate of LnAl₃(BO₃)₄:Eu³⁺ red phosphors were successfully optimized in terms of the Y/Gd ratio and the excess quantity of boron in spray pyrolysis.     

Changing emission of divalent samarium doped into barium octoborate as a function of firing time

Barium octoborate has been synthesized by air firing of co-precipitated borates with additional boric acid. During the firing process, samarium ions doped into the matrix are reduced to the divalent state. Two different divalent samarium emission spectra have been observed from the material as a function of the firing history, even though the structure, as identified by powder X-ray diffraction remained consistent. A minor barium pentaborate impurity, in conjunction with significant thermal variability in the strength of the divalent samarium emission generated by the different sites in the two borate materials, appears to give rise to this phenomenon.     

Raman scattering from mixed crystals (HgBr2)1−x(HgI2)x

The behavior of long wavelength optic phonons in mixed system HgBr₂-HgI₂ has been investigated in Raman scattering. Different types of behavior, i.e. ‘persistent type’ and ‘amalgamation type’ were observed. Three strong Raman bands were observed for persistent type mode. These correspond to stretching vibration of HgBr₂, HgBrI, HgI₂ molecules. Intensity of these bands showed striking concentration dependence. A model based on nearly free molecular approximation have been proposed to explain the dependence. The analysis indicated that the distribution of anions on the sublattices is essentially random. For amalgamation (one-mode) type behavior, it is suggested that the intramolecular force relevant to the vibration is comparable to the intermolecular force and that the band width of the corresponding phonon branch in the parent crystal is broad enough to be degenerate with impurity mode at the low concentration limit.