焙烧条件对Ce离子价态影响的XPS研究

在均相沉淀法制备含铈化合物的过程中,利用XRD和IR尤其是XPS研究了含Ce化合物在不同焙烧温度条件下产物的结构、铈离子的价态变化、化合物表面性质及其内核电子构型。XRD结果表明,焙烧温度的不同可产生不同的铈基化合物,导致产物中Ce离子价态的变化,IR结果也证实了这一点。单纯均相沉淀法得到的产物为三价的斜方晶系的单晶Ce_2O(CO_3)_2·H_2O(Ⅲ)微粒;将三价的Ce_2O(CO_3)_2·H_2O加热到200℃,产物转化成高价态六价化合物CeO(CO_3)_2·H_2O(Ⅵ);加热温度再升高到250℃,产物转化为稳定的四价化合物CeO_2(Ⅳ)。XPS通过对3种不同价态化合物的O(1s),Ce(3d),Ce(4d)峰进行精细扫描,研究了产物的表面性质及其内部电子构型,比较结果证实了不同价态铈化合物的形成是由于内核价电子构型的差异引起的。     

新型Schiff碱及其铈(Ⅲ)配合物的合成与表征

在无水乙醇溶剂中,合成双对二甲氨基苯甲醛缩邻苯二胺(L)新型Schiff碱配体,并且在丙酮溶液中合成了它的Ce()配合物。经元素分析、摩尔电导、IR、UV、TG-DTA、1HNMR等分析表明:配合物的可能组成是[CeL2(NO3)2](NO3).2H2O,为1:2(Ce:L)型、含两个结晶水的紫红色固体配合物,电解质类型为1:1型,即配合物外界有1个NO3-,另2个NO3-在配合物的内界以螯合双齿形式参与了配位,中心Ce(Ⅲ)离子的配位数为8。     

两种新型电荷转移盐的合成和光谱研究

合成了两种新的有机盐[NO₂BzPy]Cl(1)和[NO₂BzPyNH₂]Cl(2),(1)[或(2)]与K[TCNQ]₂进一步反应生成[NO₂BzPy] [TCNQ]₂ (3)和[NO₂BzPyNH₂] [TCNQ]₂(4)。光谱数据表明：TCNQ盐中存在TCNQ0和TCNQ-,并形成了一维TCNQ分子柱,且TCNQ₀和TCNQ-之间存在相互作用,部分电荷从[TCNQ]-₂向阳离子([NO₂BzPy]+和[NO₂BzPyNH₂]+)转移。     

Fabrication and Optimization of Poly(vinyl alcohol)/Zirconium Acetate Electrospun Nanofibers Using Taguchi Experimental Design

This paper presents an investigation regarding poly(vinyl alcohol)/zirconium acetate (organic–inorganic) (PVA/Zrace) nanofibers prepared by electrospinning which could be used as a precursor for fabricating ceramic metal oxide nanofibers. The effect of some processing variables, including polymer solution concentration, tip to collector distance and applied voltage of electrospinning, and the amount of Zrace and their interactions, on the diameter of the nanofibers were studied. Taguchi experimental design and a statistical analysis (ANOVA) were employed and the relationship between experimental conditions and yield levels determined. It was concluded that to obtain a narrow diameter distribution as well as maximum fiber fineness, a polymer concentration of 10 wt%, tip to collector distance of 18 cm and applied voltage of 20 kV variables were the optimum. Furthermore, it was also concluded that the ratio of Zrace (6 g) to PVA solution (10% wt) played an important role for achieving the minimum fiber diameter. Under these optimum conditions, the diameters of the electrospun composite fibers ranged from 86 nm to 381 nm with a diameter average of 193 nm. The experiments were done with Qualitek-4 software with “smaller is better” as the quality characteristics. The optimized conditions showed an improvement in the fibers diameter distribution and the average fibers diameter showed good resemblance with the result predicted using the Taguchi method and the Qualitek-4 software. The ANOVA results showed that all factors had significant effects on the fibers diameter and distribution, but the effect of PVA concentration and zirconium acetate were more significant than the other factors.     

酶电极上葡萄糖氧化酶的活性的X射线微区分析

利用X射线微区分析, 对二氧化硅溶胶-凝胶包埋于普鲁士蓝修饰玻碳电极上的葡萄糖氧化酶的活性进行了分析; 以Ce(NO₃)₃为捕捉剂, 底物葡萄糖经葡萄糖氧化酶作用产生过氧化氢,后者与捕捉剂反应生成沉淀于酶的活性部位。从X射线微区分析结果表明： 酶电极表面固定化酶的分布均匀,且保存较高的酶活,从微观的角度说明了酶电极的性能与酶电极表面酶活分布的关系。此法制备的葡萄糖氧化酶电极具有较高的灵敏度,稳定性,这与电化学测试结果是一致的。     

Effect of carbon nanotubes dispersion on morphology, internal structure and thermal stability of electrospun poly(vinyl alcohol)/carbon nanotubes nanofibers

The current work reports the effect of multi walled carbon nanotubes and single walled carbon nanotubes dispersion on morphological, structural and thermal degradation of electrospun poly(vinyl alcohol) (PVA)/carbon nanotubes (CNTs) dispersed in sodium dodecyl sulfate (SDS) (PVA/CNTs–SDS) composites nanofibers. (PVA/CNTs–SDS) nanocomposites fibers were elaborated using the traditional electrospinning process to disperse and align CNTs into the fibers, especially for low CNTs loading fraction: 0.3 and 0.7 wt%. The morphology of the electrospun fibers was studied using the scanning electronic microscopy. The average diameter of the fibers changes significantly after the incorporation of the CNTs in the PVA. Furthermore, Fourier transform infrared spectroscopy elucidated the effect of CNTs on the crystallization of the PVA which was confirmed by X-ray diffraction analysis. Thermogravimetric analysis showed that the thermal stability of the composite fibers depends on the loading fraction and on the type of carbon nanotubes.     

Electrospun cerium nitrate/polymer composite fibres: synthesis, characterization and fibre-division model

Cerium (Ⅲ) nitrate/poly(vinylpyrrolidone) (Ce(NO3)3/PVP) composite fibres have been prepared by electrospinning. After calcining the composite fibres in air at 500℃,CeO2 nanowires were obtained. The characterizations of the as-spun composite fibres and resultant nanowires have been carried out by a scanning electron microscope (SEM),an infrared spectrometer,an x-ray diffractometer and a fluorescence spectrophotometer. Interestingly,some unusual ribbon-like or twin fibres were observed besides the common fibres with circular or elliptic cross sections. We developed a fibre-division model resulting from Coulomb repulsion and solvent vaporization to interpret the formation of the ribbons or twin fibres,which has been confirmed by the SEM studies. Our results also indicate that the formation of the ribbons or twin fibres is less dependent on operation voltage and work distance.     

纳米棒状长余辉材料BaAl_2O_4:Eu~(2+),Dy~(3+)的制备与发光性能

利用硝酸铝、硝酸钡、尿素为原料,以一定比例H_2O/正丁醇及H_2O/正丁醇/SBS的混合液作传递压力的介质,进行反应,然后将得到的前驱体在还原气氛下高温煅烧,得到亮度高,余辉时间长的BaAl_2O_4:Eu~(2+),Dy~(3+)纳米棒状长余辉发光材料。TEM和SEM测试表明高温煅烧后得到的BaAl_2O_4:Eu~(2+),Dy~(3+)为棒状结构,其激发光谱和发射光谱均为宽带,主发射峰分别为498 nm,是典型的Eu~(2+)5d→4f跃迁。该方法的特点在于:采用水热法合成的BaAl_2O_4:Eu~(2+),Dy~(3+)长余辉发光材料一般需经过高温煅烧,容易结块,而在合成制得的产品经1 300℃高温煅烧后仍呈现分散性良好的棒状结构,不需球磨,且发光性能良好,可直接应用。同时将2种不同的实验条件进行比较,发现在不使用表面活性剂的条件下依然可得到分散性良好的棒状BaAl_2O_4:Eu~(2+),Dy~(3+)长余辉发光材料。该制备方法有望在其他铝酸盐和硅酸盐系长余辉发光材料的制备中得到应用。     

Fabrication and characterization of bismuth oxide–holmia nanofibers and nanoceramics

In this article, a novel and simple method to produce both boron doped and undoped holmia stabilized bismuth oxide nanoceramic materials has been put forward. Boron doped and undoped poly (vinyl alcohol)/bismuth–holmia acetate nanofibers were produced using the electrospinning technique and were calcined at 850 °C afterward in order to obtain nanopowder. The characteristics of the nanofibers were investigated with FT-IR, XRD, and SEM. XRD analyses showed that boron undoped holmia stabilized bismuth oxide nanopowders have the face-centered cubic structure (δ-phase), and that the incorporation of boron atoms into the composite prevents the nucleus formation and turns the structure into a more amorphous glassy form. The SEM micrographs of the fibers showed that the addition of boron results in the formation of cross-linked bright-surfaced fibers. The average fiber diameters for electrospun boron doped and undoped PVA/Bi–Ho acetate nanofibers were calculated using the ImageJ software as 102 nm and 171 nm, respectively.     

Manufacture and Characterization of Poly (butylene terephthalate) Nanofibers by Electrospinning

Poly (butylene terephthalate) (PBT) nanofiber mats were prepared by electrospinning, being directly deposited in the form of a random fibers web. The effect of changing processing parameters such as solution concentration and electrospinning voltage on the morphology of the electrospun PBT nanofibers was investigated with scanning electron microscopy (SEM). The electrospun fibers diameter increased with rising concentration and decreased by increasing the electrospinning voltage, thermal and mechanical properties of electrospun fibers were characterized by DSC and tensile testing, respectively.     

Polymer nanofibers prepared by low-voltage near-field electrospinning

Electrospinning is a straightforward method to produce micro/nanoscale fibers from polymer solutions typically using an operating voltage of 10 kV–30 kV and spinning distance of 10 cm–20 cm. In this paper, polyvinyl pyrrolidone (PVP) non-woven nanofibers with diameters of 200 nm–900 nm were prepared by low-voltage near-field electrospinning with a working voltage of less than 2.8 kV and a spinning distance of less than 10 mm. Besides the uniform fibers, beaded-fibers were also fabricated and the formation mechanism was discussed. Particularly, a series of experiments were carried out to explore the influence of processing variables on the formation of near-field electrospun PVP nanofibers, including concentration, humidity, collecting position, and spinning distance.     

A simple and effective route for the preparation of poly(vinylalcohol) (PVA) nanofibers containing gold nanoparticles by electrospinning method

Poly(vinylalcohol) (PVA) nanofibers containing gold nanoparticles have been simply obtained by electrospinning a solution containing gold nanoparticles without the additional step of introducing other stabilizing agents. The optical property of gold nanoparticles in PVA aqueous solution was observed by UV-visible absorption spectra. Morphology of the Au/PVA nanofibers and distribution of the gold nanoparticles were characterized by transmission electron microscopy (TEM). The structure transformation was characterized from PVA to PVA/Au composite by Fourier transform infrared spectroscopy (FTIR).     

Synthesis and characterization of silver/lithium cobalt oxide (Ag/LiCoO2) nanofibers via sol–gel electrospinning

We report on the preparation and characterization of Ag/LiCoO₂ nanofibers (NFs) via the sol–gel electrospinning (ES) technique. Ag nanoparticles (NPs) were produced in an aqueous polyvinyl pyrrolidone (PVP) solution by using AgNO₃ precursor. A viscous lithium acetate/cobalt acetate/polyvinylalcohol/water (LiAc/(CoAc)₂/PVA/water) solution was prepared separately. A Ag NPs/PVP/water solution was prepared and added to this viscous solution and magnetically stirred to obtain the final homogeneous electrospinning solution. After establishing the proper electrospinning conditions, as-spun precursor Ag/LiAc/Co(Ac)₂/PVA/PVP NFs were formed and calcined in air at a temperature of 600 °C for 3 h to form well-crystallized porous Ag/LiCoO₂ NFs. Various analytical characterization techniques such as UV–vis, SEM, TEM, TGA, XRD, and XPS were performed to analyze Ag NPs, as-spun and calcined NFs. It was established that Ag NPs in the precursor Ag/LiAc/Co(Ac)₂/PVA/PVP NFs are highly self-aligned as a result of the behavior of Ag in the electric field of the electrospinning setup and the interaction of Ag ions with Li and Co ions in the NF. Ag/LiCoO₂ NFs exhibit a nanoporous structure compared with un-doped LiCoO₂ NFs because the atomic radius of Ag is larger than the radius of Co and Li ion; thus, no substitution between Ag and Li or Ag and Co atoms occurs, and Ag NPs are located at the interlayer of LiCoO₂ while some are left in the fiber.     

Electrospinning of Poly(Hydroxybutyrate-co-hydroxyvalerate) Fibrous Scaffolds for Tissue Engineering Applications: Effects of Electrospinning Parameters and Solution Properties

Electrospinning, a technology capable of fabricating ultrafine fibers (microfibers and nanofibers), has been investigated by various research groups for the production of fibrous biopolymer membranes for potential medical applications. In this study, poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV), a natural, biocompatible, and biodegradable polymer, was successfully electrospun to form nonwoven fibrous mats. The effects of different electrospinning parameters (solution feeding rate, applied voltage, working distance and needle size) and polymer solution properties (concentration, viscosity and conductivity) on fiber diameter and morphology were systematically studied and causes for these effects are discussed. The formation of beaded fibers was investigated and the mechanism presented. It was shown that by varying electrospinning parameters within the processing window that was determined in this study, the diameter of electrospun PHBV fibers could be adjusted from a few hundred nanometers to a few microns, which are in the desirable range for constructing “biomimicking” fibrous scaffolds for tissue engineering applications.     

新型镧配合物的合成与荧光性质

在氮气保护下,以无水乙醇为溶剂,制备了硝酸镧与4-氨基-1,2,4-三氮唑缩对二甲氨基苯甲醛(L)配合物,单晶结构分析确定其组成为LaL_3(NO_3)_3·(H_2O)_2·(C_2H_5OH)_2,配合物中La~(3+)分别与3个硝酸根、2个水分子和2个分子乙醇中的氧原子配位,配位数为10,并与4-氨基-1,2,4-三氮唑缩对二甲氨基苯甲醛以氢键形式结合形成立体结构分子.通过元素分析、红外光谱、固体荧光光谱等手段对合成的配体及配合物进行了表征.实验结果表明,4-氨基-1,2,4-三氮唑缩对二甲氨基苯甲醛是一种多晶粉末状的发光材料,固体荧光谱图显示荧光发射峰在451 nm处,为蓝色荧光,色纯度高,荧光量子效率高,而合成的配合物的荧光发射峰则红移至464 nm左右,同时荧光强度显著增强近一倍.     

熔融静电纺丝法制备单根聚合物微米纤维全可见光谱的放大自发发射特性研究

具有高能量转化效率的微纳尺度的激光光源的开发将极大地促进光电子系统的进一步集成。本文采用熔融静电纺丝方法成功制备了单根有机聚合物微米纤维，所制备的微米纤维表面光滑，成规范的圆柱形结构。我们通过在聚合物纤维中掺入不同的荧光染料，实现了在整个可见光范围内的光发射可调性。在光泵浦条件下，我们详细研究了单根聚合物微米纤维的放大自发发射特性，三种颜色的微米纤维均表现了较低的阈值和高增益的放大自发发射特性。采用时域有限差分法模拟微米纤维中的电场分布结果表明，纤维的柱状微结构有效地将光限制在圆柱体内，形成环形腔反馈，并沿着轴向传播，因而发射光表现了很好的方向性。这种可见光范围内可全色发射的单根的微米纤维的成功制备将为实现智能化、集成化、低成本和高可靠性的微纳激光光源器件提供可靠的技术支持。     

Nd:YAG激光透明陶瓷超细粉体的合成及其性能表征

以Al(NO3)3·9H2O和Y2O3为原料,按YAG化学计量比配成相应的硝酸盐混合液,并用一定量的Nd取代Y,加入尿素沉淀剂,利用无机体系均相沉淀法制备了YAG前驱体。对前驱体进行适当处理,并采用高温热解法在1200℃时制备出Nd∶YAG透明陶瓷超细粉体。通过对粉体样品进行XRD,TG DTA,SEM和红外光谱分析表明,所合成的YAG超细粉为立方晶系石榴石结构,晶格常数a=12.01nm。粉体样品颗粒度小、粒径均匀、流动性好,粒径在150～200nm之间。     

Preparation of LiCoO2 nanofibers by electrospinning technique

Using a sol-gel processing and electrospinning technique, extrathin fibers of PVA (polyvinyl alcohol)/lithium chloride/cobalt acetate composite were prepared. After calcinations of the above precursor fibers at 600°C, LiCoO₂ nanofibers with a diameter of 100-150 nm, were successfully obtained. Measurements of TG/DTA, IR, XRD, Raman, SEM, EDS, respectively, were performed to characterize the properties of the as-prepared materials. We observed a strong correlation between crystalline phase and morphology of the fibers and calcinations temperature.     

铈铕掺杂氯硅酸镁钙体系的相对光谱功率分布与色坐标定位

采用高温固相反应法合成铈铕掺杂氯硅酸镁钙系列粉体,利用X射线衍射(XRD)对晶体结构加以鉴定,并对其荧光光谱进行了测试和分析.通过光谱功率校准曲线,推演出样品的相对光谱功率分布,进而对粉体发光色坐标进行计算和表征.实验结果表明,合成粉体为面心立方晶体Ca8Mg(SiO4)4Cl2,铈铕单掺氯硅酸镁钙样品在紫外光激发下分...     

硝酸镁对GFAAS法测定微量铍的基体改进效应

以硝酸镁作为GFAAS法测量微量铍的基体改进剂,研究了硝酸镁对石墨炉灰化和原子化的影响,探讨了硝酸镁的作用机理.结果表明,硝酸镁能提高灰化温度,降低原子化活化能,并对吸收信号有延迟作用,从而有利于消除基体干扰,提高分析灵敏度.