原位漫反射傅里叶变换红外光谱研究锰铁基催化剂上低温选择性催化还原反应机理简

采用自蔓延燃烧法制备了Ti_0.9Mn_0.05Fe_0.05O_2-δ催化剂,运用原位漫反射傅里叶变换红外光谱对该催化剂的NO和NH₃稳态吸附以及NO和NH₃瞬态反应进行了详细地分析与讨论. 结果表明,相比于Lewis酸性位,150℃时Brönsted酸性位吸附的NH₃更具有SCR活性;与双齿硝酸盐和桥式硝酸盐相比,NO吸附产生的单齿硝酸盐是主要的中间物种;该SCR反应遵循Eley-Rideal和Langmuir-Hinshelwood机理,但以后者为主. 另外,O₂的存在有利于NO的氧化和配位态NH₃的活化.     

Mo_8~ⅤW_2~ⅥO_(26)(C_5H_5N)_8·2H_2O: A Novel Mixed-valence Heterometal Polyoxometalate

A new mixed-valence heterometal cluster Mo8VW2VIO26(C5H5N)8·2H2O has been synthesized under solvothermal conditions and characterized by X-ray single-crystal diffraction, IR, UV-vis and XPS spectroscopy. The title compound crystallizes in the triclinic system, space group P1 with a = 11.708(3), b = 12.018(4), c = 13.316(4) , a = 112.184(4), β = 97.844(4), r = 110.043(3)o, V = 1551.9(8) 3 and Z = 1 at 293(2) K. The final full-matrix least-squares refinement converged to R = 0.0414 for 4460 observed unique reflections with I 2σ(I) and w R = 0.1290 for all data(5352) and S = 1.015. In addition, its thermal stability and fluorescent property have also been investigated.     

Tuning of NaTaO_3 Band Structure through Mn~（2＋） Ion Doping and the Enhanced Visible Light Response

Pure and Mn-doped NaTaO3 nanoparticles were synthesized by a simple hydro- thermal method. XRD and XPS results suggested that manganese ions were successfully doped into the NaTaO3 crystalline in Mn2＋ state. UV-vis diffuse reflectance spectra revealed the obvious red-shift in the series of manganese doped NaTaO3 nanoparticles, resulting in a decrease in the band gap of NaTaO3 with the increase of Mn2＋ doping concentration. The photo-degradation experiment indicated that manganese doped NaTaO3 showed good photocatalytic performance and methylene blue（MB） degradation is improved with lower doping concentration of manganese ions under visible light. The simulation of energy band structure by density functional theory unfolded that the substitution of Ta5＋ ions by Mn2＋ ions resulted in an intermediate band（IB） below the bottom of the conduction band（CB）, which was mainly attributed to the state of Mn 3d.     

Hydrolytic Degradation Behaviors of Poly（p-dioxanone） in Ambient Environments

The effects of temperature and relative humidity on the hydrolytic degradation of poly（p-dioxanone）（PPDO） were investigated. The hydrolytic degradation behaviors were monitored by tracing the changes of water absorption, mechanical and crystalline properties, molecular weight and its distribution, surface morphologies, as well as infrared absorption peaks and hydrogen chemical shifts during the degradation. It is found that the water absorption increases whilst the intrinsic viscosity, tensile strength and elongation at break decrease as the temperature or relative humidity increases. With degradation time growing, the molecular weight drops and its distribution broadens. The crystallinity of PPDO has a tendency to increase at first and then to decrease, while the crystalline structure is not significantly changed. At the same time, some cracks are observed on the surface and keep growing and deepening. All results show that temperature plays more significant roles than relative humidity during the degradation. The analyses of Fourier transform infrared spectroscopy and hydrogen nuclear magnetic resonance spectroscopy reveal that the degradation of PPDO is a predominant hydrolysis of ester linkages.     

Electrospinning of nylon-6,6 solutions into nanofibers: Rheology and morphology relationships

The relationship between the rheological properties of nylon-6,6 solutions and the morphology of their electrospun nanofibers was established. The viscosity of nylon-6,6 in formic acid(90%) was measured in the concentration range of 5 wt%-25 wt% using a programmable viscometer. Electrospinning of nylon-6,6 solutions was carried out under controlled parameters. The chemical structure, morphology and thermal properties of the obtained nanofibers were investigated using Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM) and differential scanning calorimetry(DSC), respectively. Entanglement concentration(ce) was found to be 15 wt% and a power law relationship between specific viscosity and solution concentration was observed with exponents of 2.0 and 3.3 for semi-dilute unentangled(c ce) and semi-dilute entangled(c ce) regimes, respectively. The diameter and uniformity of the nanofibers were found to be dependent on the viscosity. Moreover, the average diameter of electrospun nanofibers was found to be dependent on zero shear rate viscosity and normalized concentration(c/ce) in a power law relationship with exponents of 0.298 and 0.816, respectively. For nylon-6,6 solutions, the entanglement concentration(ce = 15 wt%) provides the threshold viscosity required for the formation of a stable polymeric jet during electrospinning and producing uniform beadless fibers. For concentrations less than ce, beaded fibers with some irregularities are formed. DSC analysis showed an increase in crystallinity of all electrospun samples compared to original polymer. Furthermore, Based on FTIR spectroscopy, α phase is dominant in electrospun nanofibers and minor amount of β and γ phases is also available.     

Investigation of Hydrolysis in Poly（ethylene terephthalate） by FTIR-ATR

The hydrothermal aging of poly(ethylene terephthalate)(PET) was investigated at 70 95 °C. A new method to investigate the hydrolysis degree of PET by Fourier transform infrared spectroscopy(FTIR) was proposed. The spectra during the hydrothermal aging were measured using attenuated total reflection accessory(ATR). Peak resolving of carbonyl regions was performed, and the ratio of two groups of bands representing carboxylic acids and esters respectively were calculated to show the hydrolysis degree of ester groups in PET. The acid/ester ratio shows exactly the same trend as the average chain scission number per unit mass at various temperatures and thus can be used as a parameter to characterize the hydrolysis and random chain scission of PET. This method related to the hydrolysis mechanism directly, is simple, fast and convenient compared to the traditional methods such as viscometry, end-group titration and size exclusion chromatography(SEC). It may also be useful in hydrolysis characterization of other polyesters.     

表面增强拉曼光谱在食品安全分析中的应用

拉曼光谱技术具有样品用量少、快速高效、无损分析等特点,表面增强拉曼光谱克服了常规拉曼光谱灵敏度低的缺点,可以获得更多物质结构信息,在现场快速筛查、检测和鉴别农兽残、限用或禁用添加剂分析检测中具有广阔的应用前景。本文综述了表面增强拉曼光谱在食品中农药残留、兽药残留和限/禁用添加剂检测中的研究进展,并展望了其发展前景。     

拉曼光谱在石墨烯结构表征中的应用

石墨烯是sp2碳原子紧密堆积形成的二维原子晶体结构,因其独特的结构与性质引起了科学家们的广泛关注.拉曼光谱是一种快速而又简洁的表征物质结构的方法.主要综述了拉曼光谱技术在石墨烯结构表征中应用的一些最新进展.首先,在系统分析石墨烯声子色散曲线的基础上介绍了石墨烯的典型拉曼特征(G'峰、G峰和D峰),讨论了G'峰、G峰和D峰在石墨烯层数的指认和石墨烯边缘与缺陷态分析中的应用;然后,通过对石墨烯拉曼G峰和G'峰的峰位、峰型以及强度的分析,讨论了石墨烯的层间堆垛方式、掺杂、基底、温度和应力等对石墨烯的电子能带结构的影响;最后,介绍了石墨烯中的二阶和频与倍频拉曼特征以及石墨烯的低频拉曼特征(剪切和层间呼吸振动模),并讨论了其对石墨烯结构的依赖性.     

四种黄酮类化合物与牛血清白蛋白相互作用的光谱分析

在人体生理pH条件下,利用紫外吸收光谱和荧光光谱研究了槲皮素(QUE)、大豆甙元(DAI)、4′,7-二甲氧基-3′-异黄酮磺酸钠(DISS)和3′-大豆甙元磺酸钠(DSS)四种黄酮类化合物与牛血清白蛋白(BSA)的相互作用,结合反应机理对其进行了初步探讨;并计算了结合位点数和结合常数.紫外吸收光谱分析结果表明,在pH=7.4条件下,黄酮类化合物中疏水性的苯环与BSA疏水腔中的氨基酸残基发生作用,从而导致药物分子的吸收峰红移,用Scatchard拟合法可求得DAI及DSS与BSA的结合常数.荧光光谱分析结果表明,BSA对DAI、DISS和DSS均有明显的敏化增强效应,计算得到的增强速率常数分别为1.39×1011,7.72×1011和1.93×1012L·s-1·mol-1,并可求得结合位点数和结合常数.     

两种异马来二氰基二硫烯镍(II)-取代苄基喹啉鎓盐的制备及其光谱性质和晶体结构

以甲醇为溶剂,将异马来二氰基二硫烯酸钾[K2(i-mnt)]和六水氯化镍分别与溴化4-溴苄基喹啉盐([4-BrBzQl]Br)或溴化4-硝基苄基喹啉盐([4-NO2BzQl]Br)直接反应,得到两种新的离子对配合物[4-BrBzQl]2[Ni(i-mnt)2](1)和[4-NO2BzQl]2[Ni(i-mnt)2](2);测定了其红外光谱和紫外-可见光谱,并利用X射线衍射表征了配合物1的晶体结构.结果表明,配合物[4-BrBzQl]2[Ni(i-mnt)2]为三斜晶系,P-1空间群,其每个不对称单元含半个[Ni(i-mnt)2]2-阴离子和1个[4-BrBzQl]+阳离子,晶体中的阴、阳离子通过静电作用和C-H…S、C-H…N氢键作用形成网络结构.