Mesoporous Titanium-containing Silicas. Synthesis and geometrical characteristics

Mesoporous titanium-containing silicas with TiO₂ contents from 1 up to 70 mol% were prepared. The obtained samples have been characterized by the powder X-ray diffraction data, the diffuse reflectance infrared Fourier transform method, and nitrogen adsorption at 77 K. Specific surface area, total pore volume, distribution pore volume on pore sizes were determined from nitrogen adsorption isotherm for synthesized titanosilicas. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ti-Si复氧化物载体对金催化剂上丙烯环氧化的影响

 以TiCl4和SiCl4为原料,采用水解和非水水解溶胶-凝胶两种方法制备了一系列不同Ti含量的Ti-Si复氧化物载体,继而用沉积-沉淀法制得载金催化剂. 采用X射线衍射、紫外-可见漫反射光谱、 N2吸附和高分辨透射电镜对催化剂进行了表征,并考察了催化剂在氢气和氧气存在下的丙烯气相环氧化催化性能. 研究表明,钛含量在6%～14%范围内时,两种方法制得的Ti-Si复氧化物均为无定形结构,但采用非水水解溶胶-凝胶法制得的载体比表面积较高. 以非水水解溶胶-凝胶法制备的钛含量10%的Ti-Si复氧化物为载体得到的载金催化剂表现出较高的活性和选择性,反应60 min时,丙烯转化率为5.7%, 240 min后降为3.3%, 环氧丙烷的选择性稳定于95%左右. 还考察了非水水解溶胶-凝胶的陈化时间和金沉积-沉淀溶液的pH值等对反应结果的影响.     

介孔Co3O4-CeO2复合氧化物的制备及在CO选择性氧化中的应用

以硝酸钴和硝酸铈为前驱物，SBA-15为硬模板，利用双溶剂法制备了Co3O4-CeO2介孔复合氧化物，通过X-射线衍射、N2吸脱附测试、程序升温还原和透射电子显微镜等技术对活性组分及载体进行了表征，并且与浸渍法和共沉淀法所制备的催化剂进行了对比分析。结果表明，相比于浸渍法和共沉淀法，采用双溶剂法制备的介孔Co3O4-CeO2复合氧化物具有均匀的介孔结构、较小的颗粒尺寸、较大的比表面积和较高的活性组分分散度。此外，CO氧化脱除评价显示与常规的共沉淀法和浸渍法所制备的催化剂相比该介孔复合氧化物具有较高的反应活性和选择性，其高活性主要归因于较高的比表面积和活性组分的高分散度。     

On Aging of Acid-Catalyzed Silica Sols—A Dynamic Light Scattering Study

Dynamic light scattering experiments in acid-catalyzed silica sols are discussed. It is shown that in spite of limited parameter accuracy and limited absolute knowledge of the particle sizes, the scattering data from various experiments are comparable with one another and give information about structural differences. Measurements at various angles indicate changes between non-spherical and nearly spherical particles and allow the estimation of gelling times before gelation.     

Adsorption Isotherm of Water Vapor and Its Large Hysteresis on Highly Ordered Mesoporous Silica

The first and second adsorption–desorption isotherms of water vapor on a new mesoporous material derived from kanemite have been measured. The isotherms show unusual type V isotherms and large hysteresis. The type V isotherms, which have never been observed for the other adsorbates, suggest that the mesoporous material has a hydrophobic surface, although the hydrophobicity decreased after treatment with water vapor because of rehydration of the surface. The significantly large hysteresis could be explained by the difference in contact angle between adsorption and desorption.     

Study of modified silicas by inverse gas chromatography. Influence of chain length on the conformation of n-alcohols grafted on a pyrogenic silica

Summary A fumed silica surface was systematically modified by the grafting of n-alkyl chains with increasing carbon numbers. The samples were characterized by the dispersive component of the surface energy, their specific interaction potential and enthalpies of adsorption of polar, in particular, alcohol probes. It is shown that the variation of the surface properties and adsorption capacities depend on the chain length of the graft. For instance, minimum values are recorded when the surface coverage by methylene groups corresponds either to one or two CH₂ surface layers. This behaviour is related to the mobility of the grafted alkyl chains, mobility which was examined by solid state NMR.     

Analysis of dinitrofluoranthenes by high resolution capillary gas chromatography/mass spectrometry

This paper reports the retention indices of eighteen of the possible twenty-five dinitrofluoranthene isomers.     

Fused silica capillary deactivation with D4 in the presence of oxygen

A new, simple procedure to deactivate fused silica capillaries without hydrothermal treatment is proposed. Based on high temperature reactions of octamethylcyclotetrasiloxane (D₄) in the presence of oxygen, this procedure results, upon coating with dimethylsilicone (SE-30), in columns which give almost symmetric peaks for as little as 150 pg of critical compounds, such as decylamine, thereby demonstrating very high inertness. A mechanism of the deactivation procedure, which, in contrast to previously developed procedures, is based on thermal reactions under aerobic conditions, is proposed.