磷钨酸／硅胶催化剂催化合成环己酮1，2-丙二醇缩酮

以溶胶-凝胶法制备的磷钨酸／硅胶为催化剂、通过环己酮和1，2-丙二醇反应合成了环己酮1，2-丙二醇缩酮，探讨磷钨酸／硅胶对缩酮反应的催化活性，较系统地研究了酮醇量比、催化剂用量、反应时间、带水剂用量对产品收率的影响。实验表明：磷钨酸／硅胶是合成环己酮1-2-丙二醇缩酮的良好催化剂，在门（酮）：门（醇）=1：1．5、催化剂用量为反应物料总质量的0．5％、环己烷为带水剂、反应时间45min的优化条件下，环己酮1，2-丙二醇缩酮的收率可达79．8％．     

Selectivities in methanol oxidation over silica supported molybdena

Selectivities in methanol oxidation over silica supported molybdenum oxide catalysts were investigated in relation with the phase distribution. The supported catalysts were prepared by impregnation with ammonium heptamolybdate. In addition to crystalline MoO₃, Mo containing cluster species of 1–2 nm size were observed by STEM even from a used catalyst with 13% catalyst loading. The percentage of Mo present as crystalline MoO₃ increases with the catalyst loading. An ESCA study indicates that part of surface Mo in the supported catalysts is reduced to Mo⁵⁺. The dimethyl ether selectivity increases with the catalyst loading and its formation occurs over the crystalline MoO₃ phase. The Selectivities to CO and methyl formate are greatly enhanced because of the presence of support, and are relatively independent of the catalyst loading and phase distribution. The dependence and independence of the Selectivities of different byproducts on the loading make the silica supported catalysts with high catalyst loadings less selective for the partial oxidation of methanol to formaldehyde.     

Silica-supported cobalt catalysts for the selective reduction of nitrogen monoxide with propene

Catalytic behavior of silica-supported transition metals for NO reduction with propene in the presence of oxygen was investigated. While both silica and cobalt oxides did not show any activity for the selective NO reduction, impregnated CoO/SiO₂ prepared from cobalt acetate showed good activity although the preparation conditions had significant effect on the activity. It was suggested that highly dispersed surface Co²⁺ ions on silica are responsible for the catalytic activity.     

Surface functionalized colloidal silica particles from an inverse microemulsion sol gel process

Colloidal silica particles are prepared via a sol gel technique carried out in an inverse microemulsion of water in a toluene solution of tetraethoxysilane (TEOS), stabilized by either an anionic surfactant AOT or isopropanol. Functionalized material was obtained using a functional coupling agent (RO)₃Si(CH₂)₃ X, X being a functional group such as methacryloyl, thiol, vinyl, amino group, or a chlorine atom. Functionalization can be carried out either directly via the direct copolycondensation of TEOS and the coupling agent, or in a two-step process involving a core-shell polycondensation of the coupling agent onto preformed silica particles. Kinetic studies of the copolycondensation are carried out using either²⁹Si NMR analysis or liquid chromatography. They show that the consumption of TEOS is more rapid than that of the coupling agent. The materials are characterized both chemically (elemental analysis, FTIR,¹³C and²⁹Si NMR CPMAS analysis), and by their particle size. The silica functionalized with a polymerizable methacryloyl group is encapsulated by a polymer layer in an inverse emulsion polymerization of acrylic acid. After inversion of the emulsion in water, the resulting material is covered with a layer of hydrophobic polymer in a conventional emulsion polymerization.     

Sodium Coordination Environments in Silica Films

The local structure centered on sodium after diffusion in silica (Na-SiO₂ samples) has been determined by means of extended X-ray absorption fine structure (EXAFS) studies. The Na-SiO₂ samples are of particular interest because (i) their sodium content can be varied over a wide range of concentration and (ii) their local structure is representative of that of soda–silica glass. EXAFS analyses reveal the existence of a well-defined local structure involving oxygen, sodium, and silicon neighbors. The Na-O, Na-Na, and Na-Si bonds lengths, which amount to 0.23, 0.30, and 0.38 nm, respectively, do not depend on sodium concentration. This environment closely resembles that found in soda–silica glass. Moreover, it is compatible with the "target site" and "the site memory effect" suggested by recent theories of the ionic conductivity in oxide glasses.     

含白炭黑胎面胶的混炼

以白炭黑作填充剂的轮胎具有滚动阻力低等优点。但是白炭黑在橡胶中不易分散。介绍了为提高含白炭黑的胎面胶的混炼质量，加速白炭黑在轮胎中的推广应用而采取的原材料、混炼工艺和混炼设备。     

Polymer nanocomposite powders and melt spun fibers filled with silica nanoparticles

Nanocomposite powders from polypropylene filled with surface modified and unmodified fumed silica have been prepared from polymer solution to achieve improved mixing and have been forwarded to fiber melt spinning. The surface of the fumed silica was modified with dodecyl alkoxy silanes. Crystallization velocity and viscosity of the PP nanocomposites thereof were determined to ensure good melt spinning processing conditions for all composite compositions. Upon addition of untreated filler particles, a shear thinning and an increased crystallization velocity of the polymer melt was found, while only minor changes were detected in the presence of surface modified fumed silica particles. The composites and the polymer fibers made from these powder composites by melt spinning were mainly characterized by optical microscopy (OM), scanning electron microscopy (SEM), mechanical measurements, differential scanning calorimetry (DSC), and solid‐state NMR. The unmodified fumed silica was found to have a strong influence on the mechanical fiber properties, while the surface modified silica only a small one. Fibers were additionally characterized with respect to the uniformity, the PP crystallinity, moisture absorption, and the water contact angle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 218–227, 2007     

溶胶-凝胶和碳热还原法制备碳化钛的研究

以钛酸四丁酯和酚醛树脂为原料，乙二醇甲醚为溶剂，冰乙酸为稳定剂，在硝酸的催化下制备出凝胶前驱体，再将制得的前驱体于流通的氩气环境中经高温碳热还原得到碳化钛。讨论了各因素对凝胶时间的影响，用TG，XRD和SEM对制得的前驱体和产品进行了表征。结果表明，控制溶液的pH在2～3，水与钛酸四丁酯的物质的量比为6：1，溶剂与钛酸四丁酯的体积比为4：1时，得到的凝胶红棕色透明，所需时间最短；且由XRD和SEM分析可知，碳热还原反应是由TiO2经历一系列的低价态氧化物转变完成的；前驱体在氩气环境中经1400℃反应1h后生成的产物为TiC，其表面光洁，粒径分布均匀，大小为0．1～0．5μm。     

Effects of the nanostructured SiO2 coating on the performance of LiNi0.5Mn1.5O4 cathode materials for high-voltage Li-ion batteries

LiNi_0.5Mn_1.5O₄ spinels coated with various amounts of fumed silica have been synthesized and investigated as cathode materials for high-voltage lithium-ion batteries at the elevated temperature (55 °C). The morphology and structure of the coated LiNi_0.5Mn_1.5O₄ samples were characterized by XRD, TEM and EDX. It was found that the surfaces of the coated LiNi_0.5Mn_1.5O₄ samples are covered with a porous, amorphous, nanostructured SiO₂ layer. The results of electrochemical experiments showed that the SiO₂-coated LiNi_0.5Mn_1.5O₄ samples display obviously improved capacity retention rate, and the improvement effect enhances with the increase of SiO₂ content. The XPS results revealed that the surfaces of the SiO₂-coated LiNi_0.5Mn_1.5O₄ cathode materials have relatively low content of LiF, and this is mainly responsible for their improved electrochemical cycling stability.     

Silica Nanoboxes as New Nano-structured Materials: Their Secondary Synthesis from Alumina-Rich Zeolites

Novel silica nanoboxes were prepared by controlled dealumination of Na-X and Ca-A type zeolites using ammonium hexafluorosilicate (AHFS). The silica-richer the parent zeolite, the smaller the average pore size produced and the narrower the pore size distribution obtained. This was due to the specific reactivity of the extracting agent with the zeolite framework aluminum atoms. High temperature calcination of the dealuminated X-zeolite (ammonium form) resulted in mesoporous materials exhibiting an ink-bottle shape, a quite high surface area (330 m²/g, no micropores), an average pore diameter of 4.5 nm with a quite narrow pore size distribution (± 1.0 nm) and finally, a pore opening diameter of 3.9 nm. The latter was determined by using the nitrogen sorption isotherms (BET technique) and related pore volume data. The sorption behavior also suggested the interconnecting character of the newly created nanoboxes. The periodicity of these nanoboxes throughout the mesoporous material was clearly shown by X-ray powder diffraction at very small angles. These materials, herein called monomodal nanoboxes because of the absence of micropores in the structure, were also thermally stable. Incorporation of orthosilicate into the obtained silica nanoboxes, in accordance with the recently developed technique for pore size engineering in zeolites, led to materials with smaller pore openings but having almost the same textural properties. Solid superacidic materials were prepared by incorporating a liquid superacid (triflic acid or trifluoromethanesulfonic acid) into the silica nanoboxes using the wet impregnation technique. The maximum triflic acid loading which did not significantly affect the mesoporous framework of the materials was 24 wt%. As a reference, the maximum loading of less acidic sulfuric acid was slightly lower. All this showed the high chemical stability of the silica nanoboxes for supporting very acidic species. Temperature-programmed desorption using a combined DTA/TGA system allowed the identification of the bound phases and some liquid phase of the loaded triflic acid.