微乳液中球形及棒状SrTiO3纳米粒子的控制合成

以氢氧化锶和钛酸四丁酯为原料, 在水溶液/Triton X-100/环己烷/正己醇反相微乳液体系中制备了直径约为20～80 nm的钛酸锶球形纳米粒子和长约300～1200 nm、直径约为30～150 nm的钛酸锶纳米棒. 用XRD, ICP, TEM, SAED和SEM对样品的结构、成分和形貌进行了表征; 用DLS分析了样品的粒度分布. 结果显示, 水与表面活性剂的物质的量比(ω₀)、反应物浓度、陈化时间等因素都能影响钛酸锶纳米粒子的形貌和尺寸. 所得钛酸锶的锶钛物质的量比约为1.0, 粒度分布较窄, 为立方相单晶结构.     

(Ba, Sr)TiO3纳米棒的反相微乳法制备与表征

在氢氧化钡和氢氧化锶水溶液/Triton X-100/环己烷/正己醇四元W/O型反相微乳液中制备了钛酸锶钡纳米棒, 研究了ω₀值(水与表面活性剂Triton X-100的物质的量之比)、反应物浓度、陈化时间对产品形貌和尺寸的影响, 用TEM, SAED, SEM, EDS和XRD等技术对产品进行了表征. 结果表明, 所得Ba_0.7Sr_0.3TiO₃纳米棒长约500～1200 nm、直径约为50～120 nm; 具有立方相单晶结构. 产品中钡、锶、钛的物质的量之比约为0.7∶0.3∶1.     

(Ba, Sr)TiO3纳米棒的反相微乳法制备与表征

在氢氧化钡和氢氧化锶水溶液/Triton X-100/环己烷/正己醇四元W/O型反相微乳液中制备了钛酸锶钡纳米棒, 研究了ω₀值(水与表面活性剂Triton X-100的物质的量之比)、反应物浓度、陈化时间对产品形貌和尺寸的影响, 用TEM, SAED, SEM, EDS和XRD等技术对产品进行了表征. 结果表明, 所得Ba_0.7Sr_0.3TiO₃纳米棒长约500～1200 nm、直径约为50～120 nm; 具有立方相单晶结构. 产品中钡、锶、钛的物质的量之比约为0.7∶0.3∶1.     

反相微乳液法制备纳米Al2O3颗粒及其形成反应机理的研究

通过聚乙二醇辛基苯基醚(曲拉通X-100)/正丁醇/环己烷/水溶液形成的体系, 采用反相微乳液法合成了Al₂O₃纳米粒子. 对前驱体进行热分析(TG-DTG-DTA), 确定了合适的煅烧温度为1150 ℃. 采用X射线衍射(XRD)、透射电镜(TEM)、紫外可见分光光度法(UV-vis)分别对产物的结构、粒度和形貌进行了表征, 考察了微乳液中水与表面活性剂的物质的量之比(ω_o)、煅烧温度和煅烧时升温速率等关键因素对产物形貌和晶相的影响, 并通过分析进一步揭示了Al₂O₃纳米粒子的形成机理. 结果表明, 控制ω_o为10、煅烧温度为1150 ℃可得到分散性好、粒径分布均匀的Al₂O₃纳米粒子, 且2 ℃/min的升温速率更有利于产物向稳定的α晶相转变.     

单元和多元取代纳米氢氧化镍晶相及其结构稳定性研究

以硝酸镍为镍源,硫酸钴、硫酸铜、硫酸铝为掺杂原料,采用超声波辅助沉淀法分别制备了单元和多元取代纳米氢氧化镍。用X射线衍射（XRD）、傅里叶变换红外光谱（FTIR）、激光粒度仪（PSD）及电子显微镜（TEM、SEM）对样品晶相结构、形貌、粒度分布等进行了表征,研究了单元或多元取代对产物晶相及其结构稳定性的影响。结果表明,样品均为纳米级Ni（OH）₂,随着掺杂元素种类的增多,其一次粒子变得细小,团聚加重,二次粒子粒径增大。样品中α-Ni（OH）₂比例随取代元素增多而增大。相对于Co单元和Co/Cu双元取代,Co/Cu/Al三元取代的样品其晶相结构更稳定,在碱液中浸泡3周后仍为纯α-Ni（OH）₂。在相同掺杂比例下,Cu取代比Co取代更有利于α-Ni（OH）₂的生成,但Co取代的样品结构稳定性优于Cu取代的样品。     

新型反相微乳液制备纳米结构甲烷催化燃烧催化剂La0.95Ba0.05MnAl11O19-α的研究

提出一种由水, 异丙醇, 正丁醇组成的新型微乳液, 并以其为反应介质制备了甲烷高温燃烧La_0.95Ba_0.05MnAl₁₁O_19-a催化剂. 采用¹H NMR, FT-IR, 电导法及激光粒度散射法研究了新型微乳液中水的结构及相特性. 新型微乳液中水的体积分数小于一定值时, 电导率与水含量成非线性关系, k～φ曲线上存在一临界值(φ^P＝0.15). 水质子的化学位移随水含量的降低移向高场. 加入4% D₂O测定的O—D键的伸缩振动随水含量增加而向高波数方向移动. 异丙醇铝在新型微乳液中水解形成的Al(OH)₃ 胶体粒子的粒径范围为226～329 nm. 采用新型微乳液作为反应介质制备的Ba_0.05La_0.95MnAl₁₁O_19-α催化剂的粒径在30 nm, 明显小于纯水制备的样品(100 nm). BET 比表面积为65 m²/g, 比纯水制备样品高出约一倍. XRD结果显示, 1200 ℃焙烧10 h即可获得含单一β-Al₂O₃相的催化剂. Ba_0.05La_0.95MnAl₁₁O_19-α催化剂甲烷催化燃烧的T₁₀为420 ℃, 比纯水制备样品下降了90 ℃. 甲烷催化燃烧活性提高是由于含有较多Mnⁿ+纳米结构六铝酸盐的形成.     

CaCO3纳米微粒的层状液晶模板法制备及其生长过程中的形貌演变

在Triton X-100/n-C₁₀H₂₁OH/H₂O体系中，低角X射线衍射测试表明层状液晶的溶剂层厚度小于3 nm。利用层状液晶为模板制备了CaCO₃纳米微粒，并用透射电子显微镜(TEM)、X射线衍射(XRD)和选区电子衍射(SAED)进行了表征。TEM结果表明所得CaCO₃纳米粒子的形貌为球形，粒径在2～8 nm，分布较窄。XRD表明CaCO₃纳米微粒的物相为方解石型和球霰石型混合结构。在制备过程中，Ca(OH)₂的加入和CaCO₃纳米微粒的析出并未破坏层状液晶的对称性和长程有序性。此外，在Triton X-100/CH₃CH₂OH体系中，研究了CaCO₃纳米微粒的生长行为，发现小的纳米微粒先通过导向聚集生长成小的梭状物，然后小的梭状物继续生长，最后发生Ostwald陈化形成较为均一的两头尖的带状纳米结构，其宽度在50～200 nm，长度约为2 μm。     

等离子体修饰磁载TiO2光催化剂性能研究

以化学共沉法制备的CoFe₂O₄纳米粒子为磁核,采用TiCl₄水解包覆技术制备磁载二氧化钛纳米复合粒子CoFe₂O₄ /TiO_x(TCF),利用低温等离子体技术修饰TCF制备了CoFe₂O₄/TiO₂(PTCF)纳米复合光催化剂。运用VSM(振动样品磁强计)技术对样品磁性能进行研究,结果表明：等离子体修饰后的复合材料仍具有较高的饱和磁化强度,可在外加磁场作用下实现催化剂在水中的分离与回收;样品的XRD、TEM和UV-Vis分析测试结果表明：等离子体修饰后的复合材料有锐钛矿型TiO₂存在;TEM谱图显示磁核CoFe₂O₄的平均粒径约为20 nm,TCF复合粒子的粒径约为30~40 nm,TiO₂包覆层的厚度为10~20 nm。与纯TiO₂相比PTCF样品对光的吸收拓展到整个紫外-可见区,扩大了光谱响应范围;对甲基橙溶液降解的光催化活性评价研究表明：TCF复合粒子等离子体修饰后的PTCF纳米复合光催剂的光催化活性明显提高。     

高质量NaNdF4六方棱柱纳米棒的水热形貌控制合成及发光性质

采用水热法在温和的条件下合成了具有规则外形的六方棱柱状NaNdF₄纳米棒。X射线衍射（XRD）分析表明：产物为纯六方相NaNdF₄,场发射扫描电镜（SEM）分析表明产物形貌为棱柱状纳米棒,长约为550nm,棒的端部呈规则六边形,边长约为85nm。高分辨透射电子显微镜（HRTEM）和选区电子衍射（SD）显示所得样品为良好的单晶。NaNdF₄晶体的生长动力学过程表明：螯合剂（EDTA-Na₂）与稀土金属离子间的螯合作用受pH值影响,导致成核速度变化,进而影响NaNdF₄纳米晶的最终尺寸和形貌。室温下的NaNdF₄纳米棒的发光峰位于红外光范围（λ=892,1058,和1342nm）,其最强发射峰位于1058nm,对应于Nd³⁺的⁴F_3/2→⁴I_11/2f-f跃迁。     

室温固态反应制备纳米Ba1－xSrxTiO3固溶体及其结构与介电性能研究

采用室温固态反应合成了一系列Ba_1－xSr_xTiO₃固溶体纳米粉末(0≤x≤1.0). 经XRD物相分析和d-间距-组成图证明, 产品为立方晶系的完全互溶取代固溶体. TEM形貌观察, 粒子基本为球形, 平均粒径40 nm. 该方法具有产率高, 无需溶剂, 对环境无污染等优点. 通过制陶实验, 分别测定了该系列固溶体的室温介电常数、介电损失以及介电常数随温度的变化. 结果发现, 采用室温固态反应在BaTiO₃中掺入适量锶, 由于掺杂离子均匀进入母体晶格, 引起居里点降低, 室温介电常数达11000以上, 介电损耗由BaTiO₃纯相的0.03 (3%)降为0.008 (0.8%). 纳米粉体的烧结温度为1180 ℃, 比传统微米级粉体的烧结温度降低100～150 ℃.     

An Understanding of the Photocatalytic Properties and Pollutant Degradation Mechanism of SrTiO3 Nanoparticles

Strontium titanate nanoparticles have attracted much attention due to their physical and chemical properties, especially as photocatalysts under ultraviolet irradiation. In this paper, we analyze the effect of heating rate during the crystallization process of SrTiO₃ nanoparticles in the degradation of organic pollutants. The relationship between structural, morphological and photocatalytic properties of the SrTiO₃ nanoparticles was investigated using different techniques. Transmission electron microscopy and N₂ adsorption results show that particle size and surface properties are tuned by the heating rate of the SrTiO₃ crystallization process. The SrTiO₃ nanoparticles showed good photoactivity for the degradation of methylene blue, rhodamine B and methyl orange dyes, driven by a nonselective process. The SrTiO₃ sample with the largest particle size exhibited higher photoactivity per unit area, independent of the molecule to be degraded. The results pointed out that the photodegradation of methylene blue dye catalyzed by SrTiO₃ is caused by the action of valence band holes (direct pathway), and the indirect mechanism has a negligible effect, i.e. degradation by O₂^?? and ^?OH radicals attack.     

Nanosized SrTiO<Subscript>3</Subscript> powder from oxalate precursor microwave aided synthesis and thermal characterization

Nanosized strontium titanate (SrTiO₃) was synthesized from strontium titanyl oxalate hydrate, SrTiO(C₂0₄)₂4H₂0 (STO) precursor employing microwave heating technique. STO precursor was characterized by Thermogravimetry (TG) and differential thermal analysis (DTA) techniques prior to the heat treatment in conventional and microwave heating system. STO precursor heated in microwave heating system in air at 773 K for 30 min yielded pure cubic SrTiO₃. The product obtained by heating of STO precursor in the same system at 973 K for same duration was, however, much more crystalline. Experiments repeated in conventional furnace showed that SrTiO₃ was formed above 973 K. SrTiO₃ powder obtained was characterized by X-ray diffraction (XRD) and Transmission electron microscopy (TEM) techniques. TEM study shows that the particles of SrTiO₃ are nearly spherical in shape and the particle size of SrTiO₃ powder varies between 28 and 68 nm.     

激光CVD法合成SiC-Si3N4复合纳米颗粒

用激光化学蒸汽沉积(CVD)法合成了SiC-Si₃N₄复合纳米颗粒,并用X射线衍射(XRD),透射电子显微镜(TEM)和电子自旋共振磁力计(ESR)分析了试料的晶体结构,颗粒形状以及悬空键的状况。合成的试料粒度分布集中,平均粒径为32nm,颗粒由直径为5～30nm的单晶或多晶组成。试料纯度高,颗粒为近似球形,十分适合于粉体的加工和烧结。另外试料有很高的热稳定性,在加热的过程中的变化首先是悬空键减少,然后是相分解和颗粒长大。     

Comparable electrocatalytic performances of carbon- and Rh-loaded SrTiO3 nanoparticles

Both metallic Rh and nonmetallic carbon modifications can highly improve the electrocatalytic activity of SrTiO₃ nanoparticles. Carbon modifications was achieved by aerobic and anaerobic ethanol oxidation methods.     

Preparation of monodisperse nanoparticles containing poly(propylene imine)(NH2)32‐polystyrene

Polypropylenimine dendrimer (DAB‐Am‐32, generation 4.0) was converted into a macroinitiator DAB‐Am‐32‐Cl via reaction with 2‐chloropropionyl chloride. Monodisperse nanoparticles containing poly(propylene imine)(NH₂)₃₂‐polystyrene were prepared by emulsion atom transfer radical polymerization (ATRP) of styrene (St), using the DAB‐Am‐32‐Cl/CuCl/bpy as initiating system. The structure of macroinitiator was characterized by FTIR spectrum, ¹H NMR, and ¹³C NMR. The structure of poly(propylene imine)(NH₂)₃₂‐polystyrene was characterized by FT‐IR spectrum and ¹H NMR; the molecular weight and molecular weight distribution of poly(propylene imine)(NH₂)₃₂‐polystyrene were characterized by gel permeation chromatograph (GPC). The morphology, size and size distribution of the nanoparticles were characterized by photon correlation spectroscopy (PCS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The effects of monomer/macroinitiator ratio and surfactant concentration on the size and size distribution of the nanoparticles were investigated. It was found that the diameters of the nanoparticles were smaller than 100 nm (30–80 nm) and monodisperse; moreover, the particle size could be controlled by monomer/macroinitiator ratios and surfactant concentration. With the increasing of the ratio of St/DAB‐Am‐32‐Cl, the number‐average diameter (D_n), weight‐average diameter (D_w) were both increased gradually. With enhancing the surfactant concentration, the measured D_h of the nanoparticles decreased, while the polydispersity increased. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2892–2904, 2009     

Synthesis and electrophoretic deposition of high-dielectric-constant SrTiO3 nanoparticles

We have investigated on the synthesis of SrTiO₃ nanoparticles whose bulk exhibits dielectric constant of 300, and their colloidal dispersion. As a result, we successfully synthesized SrTiO₃ nanoparticles with an average diameter of 134–485 nm measured by a scanning electron microscopic observation. The SrTiO₃ nanoparticles with a negative charge (ζ = −25 to −31 mV) can be dispersed as colloidal nanoparticles in water, and the average diameter in the dispersion were 138–356 nm measured by a dynamic light scattering technique. The colloidal dispersion of SrTiO₃ nanoparticles is promising for fabrication of low-voltage organic field-effect transistors (FETs) by a wet-processing fabrication. We have also successfully prepared SrTiO₃ films with a thickness of 1–10 μm on n-doped silicon substrates by an electrophoretic deposition technique. The SrTiO₃ films on the silicon substrates are likely used as dielectric gate insulator to low-voltage organic FETs after a sintering treatment.     

Synthesize and Characterization of Ca2CuO3 Nanostructures via a Modified Sol–Gel Method Assisted by Hydrothermal Process

A sol–gel-hydrothermal method was used to prepare the highly homogeneous nanopowder of Ca₂CuO₃ ceramic with an average diameter of about 20–30?nm. In comparison with the conventional sol–gel process, this method caused the more purity product with smaller size of particle due to a high pressure and long reaction time. Photoluminescence measurement indicated that for Ca₂CuO₃ nanoparticles there are two emission peaks: one sharp band at about 400?nm and one broad visible emission band. The band gap energy of Ca₂CuO₃ nanoparticles has been estimated to be 3.09?eV that is far above the values reported earlier. The results showed that the morphology and particle size of the synthesized samples can be obviously affected by the reaction temperature and molar ratio (w) between citric acid and calcium nitrate. In this procedure, diethylene glycol monobutyl ether was used as both the solvent and the modest surfactant.     

Plasmon‐Induced Ammonia Synthesis through Nitrogen Photofixation with Visible Light Irradiation

We have successfully developed a plasmon‐induced technique for ammonia synthesis that responds to visible light through a strontium titanate (SrTiO₃) photoelectrode loaded with gold (Au) nanoparticles. The photoelectrochemical reaction cell was divided into two chambers to separate the oxidized (anodic side) and reduced (cathodic side) products. To promote NH₃ formation, a chemical bias was applied by regulating the pH value of these compartments, and ethanol was added to the anodic chamber as a sacrificial donor. The quantity of NH₃ formed at the ruthenium surface, which was used as a co‐catalyst for SrTiO₃, increases linearly as a function of time under irradiation with visible light at wavelengths longer than 550 nm. The NH₃ formation action spectrum approximately corresponds to the plasmon resonance spectrum. We deduced that plasmon‐induced charge separation at the Au/SrTiO₃ interface promotes oxidation at the anodic chamber and subsequent nitrogen reduction on the cathodic side.     

OTS自组装单层膜诱导定向生长SrTiO3功能陶瓷薄膜

采用自组装单层膜技术,以三氯十八烷基硅烷(octadecyl-trichioro-silane,OTS)为模版,在玻璃基片上成功制备了钛酸锶晶态薄膜.改性基板的亲水性测定与金相显微镜测试表明,紫外光照射使基板由疏水转变为亲水,OTS单分子膜对薄膜的沉积具有诱导作用:X射线衍射(XRD)与扫描电镜(SEM)表征显示,制备成功的钛酸锶薄膜结晶良好,样品表面均匀,在垂直基板表面方向上呈花状生长:EDS能谱测试为钛酸锶薄膜的化学组成提供了有力的证据;同时探讨了白组装单层膜和钛酸锶薄膜的形成机理.