Au@Pt纳米粒子单层膜对甲醇氧化的电催化性能及SERS研究

通过种子生长法合成Au@Pt核壳结构纳米粒子,采用两相成膜法制备单层粒子膜,并转移获得Au@Pt核壳纳米粒子单层膜电极,该电极表面纳米粒子分布均匀,具有较大的比表面,对甲醇的氧化具有较好的电催化活性.研究表明,利用内核Au的长程电磁场增强效应,该单层膜表现出均匀且优良的表面增强拉曼散射(SERS)活性,适合作为基底在分子水平上研究表面的吸附和反应.获得了Au@Pt核壳纳米粒子单层膜表面甲醇电催化氧化过程的SERS光谱,为深入分析表面反应机理提供了实验依据.     

多肽Langmuir膜控制下方解石晶体的生长

本文研究了聚β-苯甲基天门冬氨酸(PBA)Langmuir膜对碳酸钙成核和生长的诱导控制作用。在PBA Langmuir单分子膜作用下,我们得到形状规则、边缘清晰的花瓣状碳酸钙晶体。XRD分析表明所得碳酸钙晶体为沿(104)和(208)晶面取向生长的方解石晶型;AFM、TEM和SEM观察显示了方解石形貌的变化过程。结果表明多肽PBA Langmuir单分子膜对碳酸钙的结晶、生长取向和形貌具有良好的诱导和调控作用。     

硬脂酸单分子膜上电沉积Ag膜的研究

通过电沉积方法,以气/液界面上形成的硬脂酸单分子膜为模板诱导沉积金属银膜.考察了镀液pH值、单分子膜表面压及沉积电位对银膜形貌及结构的影响.实验发现,酸性镀液的气/液界面上形成的单分子膜不能诱导沉积银,而在中性和碱性镀液的气/液界面上可以诱导银膜的生长.当单分子膜处于液态或固态时,气/液界面有银膜形成;液态单分子膜上的银膜生长速度较快,且银膜的结构一致.随着电极电位的升高,银膜沉积的速度加快,呈环状向外生长的圆形银膜逐渐变得不规则.将不同实验条件下的银膜转移出来,采用扫描电镜(SEM)、透射电镜(TEM)对银膜的结构与形貌进行了表征.研究表明,银首先在单分子膜上异相成核,由八面体构型逐渐发展成星型,最终在气/液界面形成具有松枝状微观结构的光亮银膜.     

一种新型的铕络合物/TiO2发光薄膜

研究了Eu(DBM)3(DiBut-bpy)/TiO2/AA 单分子膜的表面压－分子面积(π－A)曲线和稳定性,单层膜中的TiO2纳米粒子是经TBT（tetrabutyloxyltitanium ,钛酸四丁酯）二维溶胶-凝胶法得到的.TiO2纳米粒子和铕络合物都被成功地转移到固体基片上，得到了具有良好的机械和热稳定性的新型发光薄膜.小角度X射线衍射结果证明这种复合膜具有层状有序的周期性结构.讨论了TiO2基质对复合膜发光机理的影响.     

纳米粒子的电容

纳米粒子的电容对由纳米点陈列所形成的单电子器件是一个十分重要的参数。基于少体理论,提出了计算纳米粒子量子点充电电容的理论模型,由此可以预测出室温下出现库仑台阶等单电子现象的最大纳米粒子粒径。采用简谐势模型计算模拟了CdS、PbS半导体纳米粒子的充电电容,发现CdS、PbS纳米粒子的尺寸上限为11与5 nm。理论计算结果与实验相吻合。     

Au-Ag三角纳米环单层膜的原位转化制备及 SERS效应

利用模板牺牲氧化还原反应将自组装在基片上的三角板银纳米粒子(边长约为79.2 nm)与氯金酸溶液作用进而原位转化形成三角纳米环. 通过紫外-可见(UV-Vis)光谱实时监测基片上银三角板纳米粒子在反应不同阶段的消光特性; 扫描电子显微镜(SEM)显示了银三角板纳米粒子转化过程的形貌变化; 利用X射线光电子能谱(XPS)对其成分进行分析. 表征结果表明, 三角纳米环的成分为Au-Ag合金或复合物; 随着基片与氯金酸溶液作用时间的增加, 自组装膜的表面等离子体共振峰逐渐红移; Au-Ag三角环状纳米粒子的平均壁厚度从29.3 nm缩小至16.2 nm. 以4-巯基苯胺(4-ATP)为探针分子研究了该Au-Ag三角环状纳米粒子单层膜的表面增强拉曼(SERS)活性. 自组装单层膜基底的SERS信号随着Au-Ag三角纳米环平均壁厚度的增加逐渐增强.     

功能化PbS量子点的水相合成及结构表征

在水溶液中以Pb(NO3)2和Na2S为原料,巯基乙酸为稳定剂,合成了水溶性PbS量子点.用透射电子显微镜、扫描电子显微镜、粒度分析仪和红外光谱对PbS量子点进行了表征,结果表明所合成的PbS量子点的平均粒径为25 nm左右,分散性好,且巯基乙酸成功修饰于PbS纳米粒子表面,使其具有进一步与生物分子偶联的作用.     

水溶性菁染料与类脂物混合单分子膜中J-聚集体形成的研究

报道了具有相同发色团,并有不同电荷的二种菁染料单分子膜中J-聚集体的形成。测定了单分子膜的π/A,△V/A曲线,反射光谱及吸收光谱。从实验结果得出:带正电荷的染料与花生酸混合形成单分子膜后,膜中染料的二聚体与J-聚集体随着表面压力改变存在着一个平衡。而带负电荷的染料与二十烷基胺成膜后,即使在很低的表面压下也有J-聚集体形成。同时染料分子在水面上的取向是各向异性。     

单分子层保护纳米 Au 粒子表面配位催化剂的制备及其应用

 贵金属纳米粒子由于其小尺寸效应而表现出特殊的催化性能. 综述了纳米 Au 粒子表面配位催化剂的制备方法及其在催化中的应用. 由于 Au 可与硫化物形成配位键, 所以硫化物可在 Au 表面形成有序单分子膜. 单分子膜保护的 Au 纳米粒子具有非常好的溶解性、分散性、稳定性, 以及由不同的表面功能团而导致的不同的催化性能. 该催化体系兼具均相催化剂和多相催化剂的特点, 这对开发新型催化剂具有重要的理论和实际意义.     

SnO2纳米粒子-花生酸LB膜有序组合体的研究

采用胶体化学法制备了稳定的SnO2纳米粒子（nanoparticleNP）水溶胶，用膜天平和原位布儒斯特角显微镜（BAM）考察了经典成膜材料花生酸（AA）在此水溶胶气-液界面的成膜性，并用LB膜技术在不同基底上制得了单层和多层AA-Sno2NP复合LB膜，通过TEM、小角X-ray、IR和UV-VIS光谱，进一步考察了该有序组装体的结构和周期性，以及组装作中Sno2纳米粒子的形貌、粒度分布和表面聚集状态.结果表明，用这种方法能够制得粒度分布均匀、农致密的Sno2纳米粒子复合LB膜，并且多层复合膜具有良好的周期性.     

Preparation of a vast CoFe2O4 magnetic monolayer by Langmuir-Blodgett technique

The preparation of ultrathin films of CoFe2O4 nanocrystallites is reported. TEM images of them showed 2-dimensional assembly of particles, demonstrating the uniformity of these nanocrystallites. The formation of a Langmuir monolayer of the surface coated CoFe2O4 nanocrystallites with oleate at the air/water interface and its stability were studied with pressure-area isotherm curves and Brewster Angle Microscope (BAM) images. Surface pressure vs surface area isotherms and TEM studies demonstrated that the increasing surface pressure resulted in a transition from a complex with well-separated domains of nanocrystallites to well-compressed, monoparticulate layers, and, ultimately, to multiparticulate layers.     

以无机硫为原料制备硫化铅量子点及其表征

根据高温下快速成核低温下慢速生长的量子点制备原理, 采用胶体化学的方法成功制备了不同粒径的硫化铅半导体量子点. 这种方法的特点是以无味和低毒的硫化钠作为制备硫化铅量子点硫的前驱物, 因此这是一种量子点的绿色化学合成方法. 油酸作为稳定剂控制硫化铅的粒径. 采用X射线衍射和高分辨透射电镜表征了量子点的晶体结构、形貌和粒径, 采用可见-近红外吸收光谱研究了硫化铅量子点的量子尺寸效应. 通过降低油酸的添加量可以促进量子点的生长, 得到较大粒径量子点. 并探讨了量子点的生长机理.     

Surfactant-assisted fabrication PbS nanorods, nanobelts, nanovelvet-flowers and dendritic nanostructures at lower temperature in aqueous solution

PbS nanostructures with different morphologies, such as rod-like, belt-like, downy-velvet-flower-like and dendrite-like, were fabricated successfully under varied reaction conditions in aqueous solution at lower temperature by the assistance of surfactant CTAB. Especially, among all the synthesis methods for PbS nanocrystals, this is the first report using basic acetate of lead, which was formed at initial reaction stage, as a precursor to control the crystal nucleation rate. This synthesis method is a promising one to metal sulfide for its easy control, low-cost and large-scale production. X-ray powder diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), field-emission scanning electron microscopy (FE-SEM) and UV-visible spectrophotometer (UV-vis) were used to characterize the products. A rational mechanism is proposed and three control factors to the crystal directional growth are also concluded.     

Orthogonal PbS nanowire arrays and networks and their Raman scattering behavior

Three-dimensional, orthogonal lead sulfide (PbS) nanowire arrays and networks have been prepared by using a simple, atmospheric pressure chemical vapor deposition (APCVD) method. These uniform nanowires (average diameter 30 nm) grow epitaxially from the surface of the initial PbS crystal seeds and form orthogonal arrays and networks in space. The growth mechanism has been explored, and the process was classified as homogeneous, epitaxial growth in the 200 directions. Furthermore, Raman spectra of PbS nanowires are reported here, and their characteristic Raman peak (190 cm(-1), no shoulder) could be used as a unique probe for the study of PbS nanomaterials.     

Synthesis of highly crystalline and monodisperse maghemite nanocrystallites without a size-selection process.

The synthesis of highly crystalline and monodisperse gamma-Fe(2)O(3) nanocrystallites is reported. High-temperature (300 degrees C) aging of iron-oleic acid metal complex, which was prepared by the thermal decomposition of iron pentacarbonyl in the presence of oleic acid at 100 degrees C, was found to generate monodisperse iron nanoparticles. The resulting iron nanoparticles were transformed to monodisperse gamma-Fe(2)O(3) nanocrystallites by controlled oxidation by using trimethylamine oxide as a mild oxidant. Particle size can be varied from 4 to 16 nm by controlling the experimental parameters. Transmission electron microscopic images of the particles showed 2-dimensional and 3-dimensional assembly of particles, demonstrating the uniformity of these nanoparticles. Electron diffraction, X-ray diffraction, and high-resolution transmission electron microscopic (TEM) images of the nanoparticles showed the highly crystalline nature of the gamma-Fe(2)O(3) structures. Monodisperse gamma-Fe(2)O(3) nanocrystallites with a particle size of 13 nm also can be generated from the direct oxidation of iron pentacarbonyl in the presence of oleic acid with trimethylamine oxide as an oxidant.     

用软刻蚀方法制备PbS纳米晶复合聚丙烯酸微图形

PbS microstructures have several applications such as Pb2+ion-selective sensors and IR detector.The method to prepare PbS nanocrystal embed in poly(acrylicacid) (PAA) microstructures produced by means of soft lithography and solid state polymerizatio n by γ-ray irradiation was described. PbS micro patterns were prepared by Micro molding in Capillaries (MIMIC) with aqueous solution of acrylic acid lead monomer, and then solid state polymerized by γ-ray irradiation. Finally, the sample was treated with aqueous solution of Na2 Stoconvert the Pb2+ to PbS in the matrix. High-resolution micro structures of PAA, which have PbS nanocrystals embedded in them, could be produced successfully in this way. The final products were characterized by TEM, XRD, and XPS. TEM image indicated that the PbS particles embedded in PAA had a diameter of smaller than 20nm. X-ray powder diffraction method was also used to characterize the PbS/PAA nanocomposite film. The XPS analysis showed the element Pb has been converted to PbS nanoparticles in the composite films.     

Quartz Crystal Microbalance Study of Q-State PbS Particle Formation in Lead Arachidate Langmuir-BIodgett Films

The formation of Q-state PbS particle in lead arachidate (PbAr) Langmuir-Blodgett films has been monitored using the quartz crystal microbalance (QCM) measurement. The study showed that the mass uptake of PbAr films with different thicknesses on exposure to hydrogen sulfide was consistent with that expected for the quantitative conversion of Pb²⁺ in the films to PbS and the corresponding conversion of PbAr to arachidic acid. Mass uptake measurement on PbAr films extensively exposed to H₂S gas showed the arachidic acid molecules left after Q-state particle formation could be quantitatively converted to PbAr by immersing the film in a stirred aqueous solution containing lead ions. Subsequent reexposure of the film to H₂S increases the mole fraction of PbS in the film.     

Mechanistic insight into domain formation and growth in a phase-separated Langmuir-Blodgett monolayer

The mechanism of the formation and growth of phase-separated domains in mixed arachidic acid (C19H39COOH) (AA) and perfluorotetradecanoic acid (C13F27COOH) (PA) monolayer films was investigated through a combination of surface pressure-area isotherm measurements and atomic force microscope (AFM) imaging. In the mixed AA-PA monolayer system, distinct discontinuous domains consisting primarily of AA form spontaneously in a surrounding continuous matrix enriched in PA. By varying the monolayer deposition conditions, including temperature, surface pressure, and the mechanical agitation of sample solutions, it was determined that phase-separated nuclei are formed initially in the bulk sample solution and further growth of domains proceeds on the subphase surface via an Ostwald ripening process involving the diffusion of AA from the matrix to the discontinuous domains. In addition, selective dissolution of the arachidic acid followed by in situ AFM imaging has allowed the visualization of the fusion of AA to the phase-separated domains and has highlighted some unusual pattern formation that occurs at low subphase temperatures.     

Morphological investigation of hybrid Langmuir-Blodgett films of arachidic acid with a hydrotalcite/dendrimer nanocomposite

A hydrotalcite clay/dendrimer nanocomposite prepared by the ionic exchange process was adsorbed from suspension of the nanocomposite on a Langmuir monolayer of arachidic acid at the air/water interface, followed by compressing and transferring onto an arachidic acid monolayer Langmuir-Blodgett (LB) film on mica. For comparison, the hydrotalcite-adsorbed hybrid film was also prepared. The morphology of hydrotalcite and the nanocomposite studied by transmission electron microscopy indicated the layered structures with respectively 1.2 +/- 0.3 and 3.2 +/- 0.5 nm repeating distances. The hybrid Langmuir films displayed the occupied surface area of 0.24 nm2 for both hydrotalcite and the nanocomposite. The formation of hybrid Langmuir films was confirmed by Brewster angle microscopy. Atomic force microscopic images of hybrid LB films revealed the formation of plateau domains with the height difference of 6 nm for hydrotalcite and 12 nm for the nanocomposite and the presence of dendrimers adsorbed on the clay surface of the nanocomposite.     

Fabrication of symmetric hierarchical hollow PbS microcrystals via a facile solvothermal process

Symmetric hierarchical hollow PbS structures consisting of nanowalls were successfully fabricated by a facile solvothermal process in ethylenediamine at 120 degrees C for 12 h, employing lead acetate trihydrate and dithizone as precursors; the thickness of the nanowalls is about 80 nm. No surfactants or other templates were used in the process. The synthesized product was characterized by X-ray powder diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), ultraviolet-visible spectrometer (UV-vis), near-infrared absorption spectroscopy (near-IR), and fluorescence spectrophotometer. The effect of the reaction conditions on the size and morphologies of PbS structures was investigated. The results show that the temperatures, solvent, and sulfur sources are crucial factors on the morphologies and sizes of the symmetric hierarchical hollow PbS microcrystals. A possible growth mechanism of hierarchical hollow PbS structures is presented. UV-vis absorption spectrum holds a weak peak at 253 nm; the near-infrared absorption spectrum of PbS microcrystals has the two absorption peaks centered at 9613 cm(-1) (1040 nm) and 6771 cm(-1) (1477 nm), showing a blue shift compared with the bulk PbS (approximately 3020 nm). And the fluorescence spectrum of PbS microcrystals consists of an emission peak with a maximum at 305 nm. These PbS microcrystals may have potential applications in the fundamental study of nanostructures as well as fabricating nanodevices.