Au@SiO2纳米核壳结构的制备及光学性质研究

采用一种新方法制备了Au@SiO2核壳结构的纳米颗粒,利用透射电镜和紫外-可见吸收光谱对产物的形貌和稳定性进行了表征。以对巯基苯甲酸(PMBA)作为探针分子,分析了Au@SiO2颗粒的SERS特性,结果表明Au@SiO2/PMBA具有稳定的SERS信号;通过控制SiO2前驱体(TEOS)的使用量,成功实现了对SiO2层厚度的调节;研究了Au@SiO2颗粒在碱性溶液中的稳定性,结果显示在pH 10的溶液中,SiO2壳层在24h内被明显腐蚀,96h后完全消失。此工作将为Au@SiO2的制备、存放和应用提供有益的参考。     

纳米TiO2薄膜的低温等离子体制备技术

以四氯化钛为源物质,氩气为载气,氧气为反应气体,利用低温等离子体增强化学气相沉积在硅基表面制备出了TiO2薄膜。使用场发射扫描电子显微镜、X射线衍射仪等检测分析表征TiO2薄膜的性能与性质,并探讨了工艺条件如基片材料、沉积时间和基片温度对薄膜性能的影响。结果表明：制备的薄膜表面光滑均匀,结构致密,最小晶粒尺寸约15 nm;薄膜的晶型主要依赖于沉积温度,低于300 ℃沉积的薄膜是无定形的,300 ℃之上沉积的薄膜是锐钛矿结构。     

中空TiO2纳米球的制备

报道了一种新的无机模板法合成中空的TiO₂纳米球,该法以TiCl₄为钛源,中空Sb₂S₃微球为模板,利用TiCl₄水解产生的TiO₂沉积在模板的表面,同时产生的HCl消蚀Sb₂S₃,一步制备中空纳米材料。     

不同壳层厚度的LaF3：Eu3+/LaF3核壳结构纳米颗粒制备及发光性质

表面缺陷会使纳米材料的发光中心产生严重的猝灭，而适当厚度的同质包覆层会减少其猝灭。本文利用共沉淀法合成了LaF₃：Eu³⁺纳米颗粒和LaF₃：Eu³⁺/LaF₃核壳结构纳米颗粒，研究了颗粒的晶体结构、形貌以及不同壳层厚度对发光性能的影响。研究发现：LaF₃：Eu³⁺核心和LaF₃：Eu³⁺/LaF₃核壳结构均为六方结构。包覆同质壳层可以提高稀土离子的发光性能，包覆厚度的不同导致LaF₃：Eu³⁺/LaF₃核壳结构的荧光强度与衰减时间均发生改变。其原因是未掺杂的LaF₃壳层可以将发光中心Eu³⁺离子与LaF₃：Eu³⁺核心的表面隔离，进而减少表面对发光中心的猝灭，提高材料的发光性能。这种修饰作用与壳层厚度相关。     

Fe2O3/Au/Ag磁性核壳纳米粒子的制备及其SERS研究

本文介绍了一种制备多功能磁性Fe2O3/Au/Ag纳米粒子的简捷方法, 制备的粒子直径大约在100 nm左右, 采用UV-vis和SEM对该结构进行了表征。并通过调节硝酸银的用量, 制备了一系列具有不同壳层厚度和表面结构的多重核壳纳米粒子。以苯硫酚(TP)为探针分子, 研究了不同银壳厚度的磁性纳米粒子的表面增强拉曼散射(SERS)活性。结果表明随Ag:Au比例的不断增加, 其SERS活性呈现先增大后减小的趋势, 这与表面结构的改变有关。     

自供能TiO2纳米管紫外探测器的制备与性能研究

采用液相沉积法在ITO衬底上以ZnO纳米棒阵列为模板合成了TiO₂纳米管阵列,并采用SEM、XRD对样品的形貌、结构等进行表征。在此基础上,以空白ITO导电玻璃为对电极制备了光电化学型紫外探测器,并对其光响应特性进行测试。实验结果表明,制得的TiO₂纳米管轻微弯曲,由单一稳定的锐钛矿相组成。制得的自供能TiO₂纳米管紫外探测器对300~400 nm紫外波段非常敏感而对可见光区无响应。在无外加偏压的条件下,TiO₂纳米管紫外探测器能够对紫外光实现探测,表现出自供能特性并且具有较高的光敏性。循环测试结果表明,制得的自供能TiO₂纳米管紫外探测器能够循环工作且性能稳定,上升时间和下降时间分别为0.33 s和0.38 s。     

磁控溅射技术制备TiO2薄膜的研究进展

介绍了磁控溅射法镀膜的基本原理,综述了近年来关于溅射功率、工作压强、氩氧比例、沉积温度和退火等工艺参数以及掺杂对T iO2薄膜结构、形貌和光学性质影响的研究进展,并对磁控溅射技术制备T iO2薄膜的发展方向进行了展望。     

核壳结构纳米颗粒Gd2O3:Tb3+/SiOx的制备及发光性能研究

以二甘醇为溶剂合成Gd2O3:Tb3+纳米颗粒,并在其表面包覆聚硅氧烷层,得到核壳结构纳米颗粒Gd2O3∶Tb3+/SiOx。为了研究Tb3+离子掺杂浓度对纳米颗粒发光性能的影响,采用几种不同Tb3+掺杂浓度进行纳米颗粒的合成,并对其发光性能进行了检测。结果表明:包裹聚硅氧烷层后的Gd2O3∶Tb3+纳米颗粒分散较好,聚硅氧烷层不会减弱Gd2O3∶Tb3+纳米颗粒的发光性能。Tb3+掺杂浓度对核壳结构纳米颗粒Gd2O3∶Tb3+/SiOx的发光存在浓度猝灭现象,猝灭摩尔分数为5%。这种具有发光特性的核壳结构纳米颗粒可作为生物传感器的探针用于生物分子的检测。     

Ag@SiO2纳米核壳结构对铒碲发光玻璃的发光增强机制

本研究首次把预先制备好的Ag@SiO₂纳米核壳结构成功地引进到碲化物发光玻璃70TeO₂-25ZnO-5La₂O₃-0.5Er₂O₃体内,发现(A)Ag(1.6×10^?6mol/L)@SiO₂(40 nm)@Er³⁺(0.5%):铒碲发光玻璃相对于样品(B)Er³⁺(0.5%):铒碲发光玻璃的可见光与红外光的激发光谱强度的最大增强依次为149.0%与161.5%,可见光与红外光的发光光谱强度则依次最大增强了155.2%与151.6%,同时还发现样品(A)相对于样品(B)的寿命显著变长。由于Ag@SiO₂的表面等离子体吸收峰恰好位于546.0 nm,它与铒离子的发光峰546.0 nm完全共振,因此,Ag@SiO₂对铒碲发光玻璃的发光共振增强作用显著。由于银的纳米核壳结构与玻璃的制作具有分步实现的优点,它既能成功控制Ag@SiO₂的尺寸,而且在Ag@SiO₂@Er:铒碲发光玻璃的制作过程中还具有可操作性强的优点,同时价格也更加便宜。在保证银不被氧化的前提下,还可控制稀土离子发光中心与银的表面等离子体之间的距离,因此能够成功地减少背向能量反传递。上述优点促成了Ag@SiO₂纳米核壳结构表面等离子体有效加强了Ag@SiO₂@Er³⁺:铒碲发光玻璃的常规光致发光强度。     

金纳米棒核／二氧化硅壳纳米复合结构的可控制备及细胞成像

采用模板合成以及溶胶凝胶方法制备了金纳米棒核／二氧化硅壳（GNR@SiO2）纳米复合粒子,探讨了这种新型纳米复合结构的可控制备、光谱性质、细胞毒性和细胞成像。通过紫外可见分光光度计、透射电镜、共聚焦显微镜对样品进行表征,结果表明：通过对反应时间的调控,获得的纳米复合粒子的二氧化硅壳层厚度可以控制在20～30nm。由于二氧化硅壳层的存在,大大提高了金纳米棒的稳定性,同时降低了金纳米棒的细胞毒性;此外,由于二氧化硅壳层具有良好的化学修饰作用,因此可以将荧光探针分子标记在二氧化硅壳层表面,修饰后的纳米复合粒子可以通过细胞内吞作用进入细胞,从而实现细胞内的光学成像。因此,该纳米粒子复合材料在生物传感、细胞成像以及光热治疗等方面有着良好的应用前景。     

刚性衬底上铜铟硒纳米棒阵列的合成与表征

在覆盖有钨电极的硅衬底上利用多孔阳极氧化铝模板为生长掩膜电沉积合成垂直排列的铜铟硒纳米棒阵列. 多孔阳极氧化铝模板由阳极氧化磁控溅射制备的铝膜制成. 扫描电子显微镜结果表明,该纳米棒阵列结构致密,直径约100 nm长度约1μm,纵横比为10. X射线衍射、微区拉曼光谱和高分辨透射电子显微镜结果表明,真空条件下450 oC退火处理的铜铟硒纳米棒是多晶纯相的黄铜矿结构的铜铟硒,在纳米棒轴向方向上有比较大的晶粒尺寸. 能量色散X射线光谱表明,铜铟硒纳米棒的化学组成接近InSe₂的化学计量比,由吸收光谱分析推算铜铟硒纳米棒带隙为0.96 eV.     

Applying the statistical experimental method to evaluate the process conditions of TiO2 nanotube arrays by anodization method

Vertically oriented TiO₂ nanotube arrays were successfully produced by the anodization technique in NH₄F/H₃PO₄ electrolyte. The structure and morphology were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). It is found that TiO₂ nanotube arrays annealed at 500 °C containing 100% anatase phase and entirely converted into rutile at 800 °C. The response surface methodology (RSM) and Box-Behnken design were applied to find the optimal factor conditions in production of TiO₂ nanotube arrays. Based on the results in preliminary experiments, we selected anodization time, anodization voltage and NH₄F concentration as the key factors to investigate their effects on responses. The regression models were built by fitting the experimental results with a second-order polynomial. By using the regression models, the optimal factor conditions were obtained as follows: anodization time of 300 min; anodization voltage of 15.39 V; NH₄F concentration of 0.50 M. Corresponding to the optimal factor conditions, the predicted average length and diameter of nanotube array were 1429 nm and 33 nm, respectively. Confirmation experiments using the optimized conditions were performed: TiO₂ nanotube arrays were obtained with an average tube length of 1420 nm and average tube diameter of 36 nm. The experimental results are in good agreement with the predicted results.     

Mesoporous nanotube aggregates obtained from hydrothermally treating TiO2 with NaOH

Nanotube aggregates with high porosity were prepared from hydrothermal treatment of TiO₂ particles in NaOH at 130 °C, followed by HCl rinsing to different pH values. Pore structure of the aggregates, which were mainly mesoporous, was characterized by analyzing the N₂ sorption isotherm with different methods including the t-plot and density function theory. The surface area, pore volume and mean pore size of the aggregates increased with the rinsing acidity to reach a maximum (e.g. 400 m²/g in surface area) at pH 1.6 and then decreased with further increase of the acidity. The crystalline phase and composition of the aggregates were, as well, significantly affected by the acidity of the post-treatment rinsing. Large-surface area aggregates were of loosely-attached nanotubes, composed of both anatase TiO₂ and H₂Ti₂O₅·H₂O, obtained under a mildly acidic rinsing condition, while basic or highly acidic conditions resulted in the formation of closely coagulated dense structures consisting of different crystalline phases.     

Synthesis and characterization of TiO2 nanotubes for humidity sensing

The highly ordered TiO₂ thin films are prepared by anodic oxidation and calcined at 300, 400, 500 and 600 °C, respectively. X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) are employed to analyze the structure and the morphology of the TiO₂ films. We design a novel sensor to investigate the humidity sensing behaviours of the samples. The samples calcined at 600 °C show high sensitivity with nearly two orders change in the resistance and short response and recovery time (<190 s) during the relative humidity variation from 11 to 95%.     

Passivation of TiO2 by ultra-thin Al-oxide

The passivation of sol–gel TiO₂ by ultra-thin layers of Al-oxide has been investigated using transient and spectral photovoltage (PV) techniques. The ultra-thin layers of Al-oxide were prepared by the ion-layer gas reaction (ILGAR) technique and modified by thermal treatments in air, vacuum or Ar/H₂S atmosphere. The samples where characterized by elastic recoil detection analysis (ERDA), X-ray photoelectron spectroscopy (XPS), and contact potential difference (CPD) technique. Without an Al-oxide surface layer, electronic states in the forbidden gap of TiO₂ are formed during thermal treatments in vacuum and Ar/H₂S. The trap density is strongly reduced at the TiO₂/Al-oxide interface. The formation of electronic defects is prevented by a closed ultra-thin layer of Al-oxide.     

Core/shell/shell spherical quantum dot with Kratzer confining potential: Impurity states and electrostatic multipoles

An exactly solvable problem of impurity states is considered in core/shell/shell spherical quantum dot. Kratzer molecular potential is taken for confinement potential. The analytical expressions are obtained for the energy spectrum and wave functions of the impurity electron. The dependencies of the total energy and the binding energy of the impurity on the parameters of the confining potential are investigated. The possibility of the impurity electron leakage is shown in the external environment, due to the specific form of the Kratzer potential. The character of the electrostatic field created by the impurity and the electron is observed on the basis of obtained results. The multipole corrections caused by the dipole and quadrupole moments of the electron are calculated. It is shown that the dipole moment is absent, and the problem reduces to the calculation of only z component for the average values of the diagonal elements of the quadrupole moment tensor. The dependencies of the average values of the quadrupole moment on the Kratzer potential parameters are studied.     

Photoluminescence of colloidal YVO4:Eu/SiO2 core/shell nanocrystals

YVO₄:Eu, and YVO₄:Eu/SiO₂ nanocrystals (NCs) were prepared by hydrothermal method with citrate as capping ligands. Their morphologies, structures, components, and photoluminescence properties were investigated and presented in this paper. A remarkable fluorescence enhancement up to 2.17 times was observed in colloidal YVO₄:Eu/SiO₂ NCs, compared to that of colloidal YVO₄:Eu NCs. This is mainly attributed to the formation of the outer protecting layers of biocompatible SiO₂ shells; which shield the Eu³⁺ ions effectively from water and thus reduces the deleterious effects of water on the luminescence. Meanwhile, on the basis of laser selective excitation, two kinds of luminescent centers were confirmed in the NCs, namely, inner Eu³⁺ ions and surface Eu³⁺ ions. The surface modifications for YVO₄:Eu NCs effectively reduced the surface defects and accordingly enhanced the luminescence. The core/shell NCs exhibited long fluorescence lifetime and high photostability under ultraviolet radiation.     

Preparation and characterization of upconversion luminescent LaF3:Yb,Er/LaF3 core/shell nanocrystals

LaF₃:Yb³⁺,Er³⁺/LaF₃ core/shell nanocrystals were successfully synthesized using solvothermal method. The crystal structure, morphology and photoluminescence properties of as-prepared nanocrystals were investigated in detail. XRD patterns show that the obtained LaF₃:Yb³⁺,Er³⁺ core and LaF₃:Yb³⁺,Er³⁺/LaF₃ core/shell nanocrystals exhibit hexagonal structure. The average particle size is about 9.3 nm and 11.4 nm for core and core/shell nanocrystals, respectively. Compared with LaF₃:Yb³⁺,Er³⁺ nanocrystals, both the upconversion emission intensity and the lifetime increase in LaF₃:Yb³⁺,Er³⁺/LaF₃ core/shell nanocrystals. The enhancement can be attributed to the LaF₃ shell which can eliminate the nonradiative centers on the surface of LaF₃:Yb³⁺,Er³⁺ nanocrystals.     

Studies of sol–gel TiO2 and Pt/TiO2 catalysts for NO reduction by CO in an oxygen-rich condition

The textural properties, morphological features, surface basicity and oxygen reduction behaviours of titania and Pt supported titania catalysts synthesized via a sol–gel method were studied by means of N₂ physisorption, SEM, TEM, CO₂-TPD and H₂-TPR techniques. Mesostructured TiO₂ shows a very narrow pore size distribution that uniformly centred at about 4 nm. High resolution TEM images confirmed that most of Pt particles on Pt/TiO₂-SG had a size smaller than 2 nm. Both the titania support and Pt loaded catalysts chiefly contained weak basic sites with small amount of strong basic sites. Loading Pt did not significantly alter the surface reduction characters of titania, indicating a weak interaction between Pt metals and titania support. Catalytic evaluation revealed that the selectivity of NO reduction over titania was insensitive to variation of textural property. On the bare titania, low NO conversion but high selectivity to N₂O was obtained. However, the Pt/TiO₂-SG catalysts exhibited high NO conversion and high selectivity to N₂, which is assumed to relate to NO dissociation catalysed by the metallic Pt clusters. In addition, when the reaction temperature was above 200 °C, 3–11% NO₂ was yielded over the Pt/TiO₂-SG catalysts, which was discussed on a basis of reaction competition, metal-support interaction and NO dissociation.     

Temperature-induced changes in morphology and structure of TiO2-Al2O3 fibers

Electrospinning of a sol-gel and polymer mixture is used to produce titania-alumina (TiO₂-Al₂O₃) fibers with diameters ranging from 200 to 800 nm. These composite metal-oxide fibers were calcined at various temperatures and their morphology is studied using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The decrease in the average diameter of the fibers with increasing temperature is observed. Powder X-ray diffraction (XRD) reveals that up to 800 °C the composite fibers have anatase titania structure whereas at 900 °C the fibers exhibit mixture of anatase and rutile phases. It is found that specific surface area decreases as a function of temperature in the 700-900 °C range. The change in phase (anatase-to-rutile) and the increase in crystallite size occur simultaneously. The presence of smaller amount of amorphous alumina in the primarily titania-based structure seems to play the role in stabilizing the anatase phase.