Aggregation and spectral properties of Mg(II) tetracarboxyphthalocyanine in aqueous solutions and solid xerogels

Based on spectroscopic studies of magnesium(II) tetracarboxyphthalocyanine molecules in liquid solutions, we have determined the role of the carboxyl groups and the aqueous medium during formation of associates. We have shown that the Q band of the associated form is split into two components of frequency separated by ∼250 cm⁻¹. The effect of the nature of the gel matrices on the spectral luminescence properties of magnesium(II) tetracarboxyphthalocyanine has been studied by incorporating the pigment into a series of xerogels differing in the chemical structure of the inorganic framework and the nanopore surface area. We discuss the reasons for the appearance of associated forms of the pigment in different xerogels. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 211–217, March–April, 2007.     

29Si MAS-NMR Study of Silica Gels and Xerogels: Influence of the Catalyst

Four silica gels were prepared by hydrolysis of tetraethoxysilane (TEOS) in ethanol, using different catalysts: HCl, NaOH, NH₃, and NBu₄F. Nitrogen adsorption-desorption isotherms indicated that the HCl-catalyzed xerogel was purely microporous, whereas the other samples exhibited a very broad distribution of mesopores and a variable amount of micropores. ²⁹Si MAS NMR spectroscopy of the wet gels (before drying) pointed to a low degree of condensation for the HCl-catalyzed gel, and to the presence of unhydrolyzed TEOS monomer in the NaOH-catalyzed gel. Comparison with the ²⁹Si MAS NMR spectra of the xerogels indicated a significant increase of the degree of condensation during the drying procedure (3 hrs at 120°C under vacuum) for the HCl-catalyzed gel.     

V-P-O／TiO2-SiO2催化剂的制备、表征及其在丙烷氧化制取丙烯酸反应中的应用研究

通过湿磨法,将钒-磷-氧(V-P-O)氧化物负载于钛硅干凝胶(TiO_2-SiO_2)上,制备了V-P-O/TiO_2-SiO_2氧化物催化剂,并运用BET,XRD,TEM及XPS等技术考察了润湿剂,V-P-O的含量及焙烧条件对催化剂结构的影响.由BET方法发现,以异丁醇为润湿剂对催化剂表面积影响较小.XRD和TEM考察结果表明,所制备的催化剂有较高的热稳定性.通过XPS分析,证实钒元素主要以V(Ⅳ)价态存在于催化剂的表面.V-P-O/TiO_2-SiO_2催化剂在丙烷氧化反应中显示了良好的催化性能.     

Preparation, thermal decomposition and lifetime of Eu(III)-phenanthroline complex doped xerogel

The main purpose of this work is proposing a new method of using non-isothermal formal kinetics analysis to predict the lifetime of luminescent complex materials. The Eu(III)-phenanthroline complex doped xerogel has been in situ synthesized by a catalyst-free sol-gel method. The photoluminescence spectra and TG curves of the xerogel verify the formation and decomposition of Eu(III)-phenanthroline complex in xerogel. The decomposition of the xerogel formally occurs in three steps. The Friedman and FWO isoconversional methods and multivariate non-linear regression method are used for formal kinetic analysis. The overall decomposition process below 800 °C is fitted by three-step consecutive reaction. The best fitted model for each step is F_n (n order reaction, the corresponding function f(α) is (1 − α)ⁿ). Correlation coefficient is 0.99956. The lifetime values of xerogel at different temperatures are predicted based on non-isothermal kinetic models by the 5% decomposition of europium organic complex.     

New polyfunctional silicon-containing amines C6[CH2CH2SiMe(OCH2CH2NR2)2]6 (R = H,Me) and their reactions with cobalt(ii) chloride and dicobalt octacarbonyl

Hexakis[bis(2-aminoethoxy)methylsilylethyl]benzene and hexakis[bis(N,N-dimethyl-2-aminoethoxy)methylsilylethyl]benzene C₆[(NR₂CH₂CH₂O)₂SiMeCH₂CH₂]₆ (4, R = H; 5, R = Me) were prepared from hexakis(methyldichlorosilylethyl)benzene C₆(Cl₂MeSiCH₂CH₂)₆ and 2-aminoethanol or N,N-dimethyl-2-aminoethanol, respectively. Compounds 4 and 5 react with anhydrous cobalt (ii) chloride to give poorly soluble dodecachloro{hexakis[bis(2-aminoethoxy)methylsilylethyl]benzene}hexacobalt and dodecachloro{hexakis[bis(N,N-dimethyl-2-aminoethoxy)methylsilylethyl]benzene}hexacobalt {Co₆[(NR₂CH₂CH₂O)₂SiMeCH₂CH₂]₆C₆}Cl₁₂ (R = H or Me), respectively. Polyfunctional amine 4 reacts with dicobalt octacarbonyl to produce hexakis[bis(2-aminoethoxy)methylsilylethyl]benzenedicobalt(ii) tetrakis(tetracarbonylcobaltate) {Co₂[(NH₂CH₂CH₂O)₂SiMeCH₂CH₂]₆C₆}[Co(CO)₄]₄. N,N-Dimethyl-substituted polyfunctional amine 5 is lowly reactive in the reaction with Co₂(CO)₈, whereas the simplest model of this compound, viz., bis(N,N-dimethyl-2-aminoethoxy)dimethylsilane (NMe₂CH₂CH₂O)₂SiMe₂, slowly reacts with Co₂(CO)₈ to give tris[bis(N,N-dimethyl-2-aminoethoxy)dimethylsilane]cobalt(ii) bis(tetracarbonylcobaltate) {Co[(NMe₂CH₂CH₂O)₂SiMe₂]₃}[Co(CO)₄]₂. Thermal decomposition and transformations of the resulting complexes under the action of oxygen and water were studied.     

高性能硫/碳凝胶复合正极材料的制备及应用

以碳凝胶作导电骨架,合成硫/碳凝胶复合物.XRD、SEM等表征显示,该复合材料完全保持了碳凝胶的形貌,颗粒大小在10μm以下,硫吸附在碳凝胶内部空隙中呈无定形态,表现出良好的电化学性能.以0.1C放电,该材料首圈放电容量达到1311mAh/g.0.2C循环充放,首圈放电容量为1107.1mAh/g,30周充放电后,放电容量仍不低于800mAh/g.     

介孔硅基干凝胶的降解性及其生物相容性研究

本研究利用改进的溶胶-凝胶工艺合成了介孔硅基干凝胶。通过差热-热重(DTA-TG)、X-射线衍射(XRD)、红外光谱(FTIR)和N₂等温吸附-脱附测试分析,以及扫描电镜(SEM)、透射电镜(TEM)观察,表征了硅基干凝胶的热效应、相态、结构、形貌特征,并对合成的硅基干凝胶进行了体外降解与细胞培养实验研究。测试结果表明：合成的硅基干凝胶为平均孔径3nm左右、最大比表面积901 m²·g^-1的介孔结构。体外模拟体液(Simulated body fluid,SBF)降解结果显示,低温处理的材料在42 d内完全降解,直线拟合符合一级反应动力学方程。通过添加钙磷成分或高温煅烧处理可以调控干凝胶的降解速率,使硅基干凝胶的降解呈现直线式匀速降解的特征。体外细胞培养表明：硅基干凝胶可促进C2C12细胞(C3H小鼠肌原细胞)的分化和繁殖,证明材料的生物相容性良好。     

二氧化锡/碳气凝胶的制备与电化学性能研究

应用真空浸渍法制备二氧化锡/碳气凝胶的复合材料. XRD、BET、SEM及TEM等测试结果显示,二氧化锡纳米颗粒（5~10 nm）均匀地填充在碳气凝胶的孔道内部. 在100 mA/g的电流密度下经过100周次充放电测试,该材料的容量保持率为首次循环的61.9%.     

Drying of alkoxide gels—Observation of an alternate phenomenology

The process of drying of a porous material as per the current phenomenological theory can be divided into two stages. At first the body shrinks by an amount equal to the volume of liquid that evaporates, and the liquid-vapor interface remains at the exterior surface of the body. The second stage begins when the body becomes too stiff to shrink and the liquid recedes into the interior, leaving air filled pores near the surface. We shall refer to this phenomenology as the drying front model. In our investigation of drying of alkoxide silica gels of less than 50 Angstroms pore radius, we have observed a different drying pattern, in which even after the gel body stops shrinking, drying continues to occur by evaporation on the exterior surface of the gel body, causing spontaneous nucleation of partially or fully dried opaque clusters, randomly distributed in the interior parts of the gel. These clusters than increase in number and size till they coalesce to form an opaque body. Upon further drying, the gel returns to its transparent form. We postulate that this is possible only if the rate of fluid flow in the pores by diffusion is faster than that by Darcy's flow, as well as the evaporation rate at the surface of the gel body. We shall refer to this as the cluster drying model. We shall present results of pin-hole drying experiments on cylindrical alkoxide gels showing that for identical gels the evaporation rate can be increased to change the phenomenology from cluster drying to one that exhibits both phenomenology simultaneously and finally to that of the drying front phenomenology. We shall also show the effect of gel pore size distribution on the phenomenology of drying under identical drying conditions. Finally, we will present evidence that for successful drying of large cylindrical alkoxide gels, drying conditions favoring cluster drying phenomenology is desirable.     

Organically modified xerogels as novel tailor-made supports for covalent immobilisation of enzymes (penicillin G acylase)

A novel application of organically modified silicates for covalent immobilisation of penicillin G acylase is reported. The immobilisation is efficient and the enzymatic preparation shows high specific activity and thermal stability. The technique opens new perspectives for the preparation of innovative tailor-made supports matching specific requirements of enzymatic processes.