Modern Applications of Electron Microscopy to Catalysis

The active sites of ultra-dispersed Pt/-Al₂O₃ catalysts are studied using high-resolution electron microscopy, Z-contrast and dark field. In addition we have calculated using a method based in density functional theory the electrostatic potential and charge distribution of the active sites. It is conclude that the most likely Pt clusters that are formed correspond to Pt₁₃ and Pt with icosahedral and decahedral structure. It is shown that this is consistent with the electron microscopy data.     

Preparation and properties of deep dye fibers from poly(ethylene terephthalate)/SiO2 nanocomposites by in situ polymerization

In this study, poly(ethylene terephthalate) (PET)/SiO₂ nanocomposites were synthesized by in situ polymerization and melt‐spun to fibers. The superfine structure and properties of PET/SiO₂ fibers were studied in detail by means of TEM, DSC, SEM, and a universal tensile machine. According to the TEM, SiO₂ nanoparticles were well dispersed in the PET matrix at a size level of 10–20 nm. The DSC results indicated that the SiO₂ nanoparticles might act as a marked nucleating agent promoting the crystallization of the PET matrix from melt but which inhibited the crystallization from the glassy state, owing to the “crosslink” interaction between the PET and SiO₂ nanoparticles. The tensile strength of 5.73 MPa was obtained for the fiber from PET/0.1 wt % SiO₂, which was 17% higher than that of the pure PET. The fibers were treated with aqueous NaOH. SEM photographs showed that more and deeper pits were introduced onto PET fibers, which provided shortcuts for disperse dye and diffused the reflection to a great extent. According to the K/S values, the color strength of the dyeing increased with increasing SiO₂ content. It is found that the deep dyeability of PET fibers was improved greatly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of the Silver Nanofluid by ASNSS Process

Arc Spray Nanoparticle Synthesis System (ASNSS) has been used to prepare the silver nanofluids in this study. The metal electrodes under the electrical discharge will melt and evaporate rapidly and condense to form the nanoparticles in the dielectric fluid at lower temperature and produce the suspended nanoparticle fluid. Thus, the mechanism of the ASNSS process is superheating the electrodes by plasma to form metallic nuclei and supercooling these nuclei by dielectric liquid to produce nanofluid. This study considers the different controlling parameters such as discharge current,discharge voltage, pulse-duration time, electrode diameter, and the temperature of dielectric liquid. The optimally operated parameters can be obtained to produce the finer particle size in nanofluid. The results indicate the silver electrodes in alcohol fluid will produce the spherical nanosilver particles. The mean particle size of silver in different dielectric liquid temperatures of-40, -20, 0, and 10℃ is about13.4, 15.8, 17.5, and 21.6 nm, respectively. This indicates that the well suspended fluid can be obtained by controlling the lower dielectric fluid temperature.     

Novel electrically conductive and ferromagnetic composites of poly(aniline‐co‐aminonaphthalenesulfonic acid) with iron oxide nanoparticles: Synthesis and characterization

Nanocomposites of iron oxide (Fe₃O₄) with a sulfonated polyaniline, poly(aniline‐co‐aminonaphthalenesulfonic acid) [SPAN(ANSA)], were synthesized through chemical oxidative copolymerization of aniline and 5‐amino‐2‐naphthalenesulfonic acid/1‐amino‐5‐naphthalenesulfonic acid in the presence of Fe₃O₄ nanoparticles. The nanocomposites [Fe₃O₄/SPAN(ANSA)‐NCs] were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, elemental analysis, UV–visible spectroscopy, thermogravimetric analysis (TGA), superconductor quantum interference device (SQUID), and electrical conductivity measurements. The TEM images reveal that nanocrystalline Fe₃O₄ particles were homogeneously incorporated within the polymer matrix with the sizes in the range of 10–15 nm. XRD pattern reveals that pure Fe₃O₄ particles are having spinel structure, and nanocomposites are more crystalline in comparison to pristine polymers. Differential thermogravimetric (DTG) curves obtained through TGA informs that polymer chains in the composites have better thermal stability than that of the pristine copolymers. FTIR spectra provide information on the structure of the composites. The conductivity of the nanocomposites (～ 0.5 S cm^?1) is higher than that of pristine PANI (～ 10^?3 S cm^?1). The charge transport behavior of the composites is explained through temperature difference of conductivity. The temperature dependence of conductivity fits with the quasi‐1D variable range hopping (quasi‐1D VRH) model. SQUID analysis reveals that the composites show ferromagnetic behavior at room temperature. The maximum saturation magnetization of the composite is 9.7 emu g^?1. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

基于金纳米-植酸胶束混合组装的过氧化氢传感器的电化学研究

采用混合组装技术,利用植酸胶束(IP6micelles)的磷酸酯键络合辣根过氧化物酶(HRP)和金纳米粒子(GNPs),形成了具有生物亲和性的纳米复合材料,保持了辣根过氧化物酶的生物活性,并利用金纳米粒子的高电子密度、介电特性和催化性能,实现了HRP与玻碳电极(GCE)表面的直接电子转移。Nafion膜的滴加能提高电极的选择性和稳定性。实验过程中借助紫外-可见吸收光谱和透射电子显微镜进行表征,实验结果证明:GNPs的高导电和高催化性能,结合植酸胶束的优良生物相容性和对酶的高负载量的特点,使得吸附在其上的HRP保持活性,制备的生物传感器能对H2O2进行电催化还原。Nafion/HRP-IP6micelles-GNPs/GCE对H2O2的线性浓度范围为5×10-7～1.15×10-5mol/L(线性相关系数r=0.993,n=9),最低检测限为0.1μmol/L(信噪比S/N=3),米氏常数为0.002 4 mmol/L。     

Using silica nanoparticles as curing reagents for epoxy resins to form epoxy–silica nanocomposites

Nanoscale colloidal silica showed high reactivity toward curing epoxy resins to form epoxy–silica nanocomposites under mild conditions. Adding a certain amount (5000 ppm) of magnesium chloride lowered the activation energy of the reaction from 71 to 46 kJ/mol. Less and more magnesium chloride both exhibited counter action on lowering the activation energy of the curing reaction. Tin chloride dihydrate and zinc acetylacetonate hydrate were also added into the curing compositions, however, showing no significant effect on promoting the curing reaction. Through this curing reaction, epoxy–silica nanocomposites containing high silica contents up to 70 wt % were obtained. Therefore, this reaction provided a novel and convenient route in preparation of epoxy–silica nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1237–1245, 2005     

银掺杂对二氧化钛晶型转变的影响

采用溶胶-凝胶法制备了银掺杂的TiO2粉末,用XRD分析了掺银TiO2胶体经不同温度热处理后的晶型转变。结果表明:与未掺银的TiO2粉末相比,掺银TiO2从锐钛矿相向金红石相转变的起始温度较高,而且锐钛矿-金红石相变的温区范围变窄,晶型转变过程较快。     

Preparation of three-dimensional ordered macroporous SiCN ceramic using sacrificing template method

Three-dimensional (3D) long range well ordered macroporous SiCN ceramics were prepared by infiltrating sacrificial colloidal silica templates with the low molecular weight preceramic polymer, polysilazane. This was followed by a thermal curing step, pyrolysis at 1250 °C in a N₂ atmosphere, and finally the removal of the templates by etching with dilute HF. The produced macroporous SiCN ceramics showed high BET surface areas (pore volume) in the range 455 m²/g (0.31 cm³/g)–250 m²/g (0.16 cm³/g) with the pore sizes of 98–578 nm, which could be tailored by controlling the sizes of the sacrificial silica spheres in the range 112–650 nm. The sphere-inversed macropores were interconnected by 50 ± 30 nm windows and 3–5 nm mesopores embedded in the porous SiCN ceramic frameworks, which resulted in a trimodal pore size distribution. The surface of the achieved porous SiCN ceramic was then modified by Pt–Ru nanoparticle depositing under mild chemical conditions.     

Effects of the reinforcement and toughening of acrylate resin/CaCO3 nanoparticles on rigid poly(vinyl chloride)

Novel composite particles based on nanoscale calcium carbonate (nano‐CaCO₃) as the core and polyacrylates as the shell were first synthesized by in situ encapsulating emulsion polymerization in the presence of the fresh slush pulp of calcium carbonate (CaCO₃) nanoparticles. Subsequently, these modified nanoparticles were compounded with rigid poly(vinyl chloride) (RPVC) to prepare RPVC/CaCO₃ nanocomposites. At the same time, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were investigated, and the synergistic effect of modified nanoparticles with chlorinated polyethylene (CPE) was also studied. The results showed that in the presence of nano‐CaCO₃ particles, the in situ emulsion polymerization of acrylates was carried out smoothly, and polyacrylates successfully encapsulated on the surface of nano‐CaCO₃ to prepare the modified nanoparticles, breaking down nano‐CaCO₃ particle agglomerates, improving their dispersion in the matrix, and also increasing the particle–matrix interfacial adhesion. Thus, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were very significant, and the cooperative effect of the nanoparticles with CPE occurred in the united modification system. Scanning electron microscopy analyses indicated that large‐fiber drawing and network morphologies coexisted in the system of joint modification of nanoparticles with CPE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3940–3949, 2007     

From Molecular Clusters to Metal Nanoparticles

Different methods to prepare supported metal nanoparticles of uniform size are discussed. (i) Supported ruthenium particles were generated from Ru and Ru-Fe bimetallic molecular metal carbonyl cluster precursors (MCC). (ii) Gold nanoparticle formation in the supercage of Y zeolite was studied on Au/NaY, Au/HY and Au-Fe/HY system. (iii) Palladium nanoparticles were grown in liquid phase then deposited on an SiO₂ support or they were grown on the support surface in a solid-liquid interfacial layer. The particle size control was more efficient in the latter two cases than in the preparation starting from MCC.