Ammoximation reaction with titanium doped amorphous silica

The catalytic behavior and the role of the acidic sites and of the activated forms of molecular oxygen in the ammoximation reaction of cyclohexanone to cyclohexanone oxime were investigated on pure and titanium doped amorphous silicas. The samples were prepared by the sol-gel method under acidic and basic conditions. The introduction of low amounts of titanium on silicas, prepared under basic conditions, strongly increased the oxime yield and conversion. The sample containing 0.25% titanium resulted in a very active and selective catalyst. A further increase of the titanium content decreased the catalytic activity and also the catalyst deactivation, because of a decrease of the tars formation rate. The comparison of the catalytic data and the results of FT-IR and EPR analysis confirmed the bifunctional nature of the amorphous silica catalyst. On the first step of the reaction pathway, the imine formation, the paramount parameter is an intrinsic property of pure silica, related to its textural and structural features. The adsorption experiments showed that the silica prepared under basic conditions, the only active in ammoximation, was able to form surface imine on acidic sites. The nature and the role of the oxidizing sites seem more complex. EPR results showed the presence of radical species on titanium modified silica and also, in small amount, on silica itself; however, the oxime formation did not seem to be a property related only to the presence of activated oxygen species anchored to titanium sites. It has been proposed that the formation of oxime is due to a combined effect of the presence of tars and of the activated oxygen species due to the titanium, which are able to oxidize the imine to oxime.     

TiO_2薄膜超亲水性研究进展

简述了TiO2薄膜材料的超亲水性机理,概括了制备TiO2薄膜的基本方法有:静电自组装技术、微等离子体氧化法、液相沉积法、溶胶-凝胶法、化学气相沉积法、磁控溅射法等;并简要介绍了TiO2薄膜超亲水性材料在自清洁建材、防雾涂层、杀菌消毒等方面的应用现状与发展前景,并展望了今后的研究工作。     

纳米TiO2薄膜制备方法的研究进展

纳米二氧化钛以其优异的化学、物理性能受到关注。薄膜是纳米二氧化钛的重要形式,制备纳米二氧化钛薄膜具有重要意义和很好的应用前景。依据制备工艺中温度的要求,对制备纳米二氧化钛薄膜的方法进行了概述,高温制备的工艺主要有溶胶-凝胶法、水热法、气相沉积法,低温制备工艺主要有电泳沉积法、紫外光照射法、电化学制备法、模板自组装制备法。     

38DD350型电解槽阳极流场分布对钛板点蚀的影响

应用CFD软件建立38DD350型电解槽阳极流场的物理模型和数值模型,模拟出了电解槽阳极室中气液混合物液相和气相的整体分布。用涡街理论分析了钛板凸起部分气相的分布原因,认为钛板圆锥凸起部分出现的点蚀与Cl2在该部位的富集有关。     

纳米氧化锌的制备与应用研究

综述了纳米氧化锌的不同制备方法和各自的优缺点。纳米氧化锌的制备按原料的原始状态可分为：固相法、液相法和气相法。根据制备和合成过程不同,液相法可分为：水热合成法、溶胶-凝胶法、微乳液法和沉淀法等。具体介绍了纳米氧化锌在不同领域中的应用：制抗菌除臭、消毒、抗紫外线产品;用于催化剂和光催化剂;制备气体传感器及压电材料等。提出了纳米氧化锌应用研究中存在的一些问题,同时对未来的应用研究提出一些观点,指出了纳米氧化锌未来的发展方向。     

TiO_2纳米材料的制备方法与应用进展

介绍了纳米TiO2材料主要制备方法,包括液相法、气相法等。液相法主要有水热法,钛醇盐水解法,W/O微乳法等,气相法主要有四氯化钛气相法,钛醇盐气相水解法,低压气体蒸发法等。液相法中的几种方法由于工艺简单、条件温和,气相法反应速度快,过程易放大,容易实现连续生产。     

Catalytic behavior of vanadium substituted mesoporous molecular sieves

A series of V-MCM-41 samples with different pore sizes has been systematically investigated with both gas and liquid phase reactions. Methanol oxidation has been performed in the gas phase on these catalysts. Turnover frequencies are normalized by oxygen uptake measured under reaction conditions. A strong effect of pore size on the catalytic activity was observed in the form of a “volcano curve” and may be correlated with a variation in the local bond angle of Si–O–V. Considering this effect, the catalytic activity may be ‘tuned' to maximum by varying the pore size. As expected, the same effect was observed in the liquid phase oxidation of cyclohexene. In order to interpret the pore size effect, the reaction rates of both the gas phase and liquid phase oxidation were then correlated with the variation of edge energies of V K-edge XANES on these MCM-41 catalysts. Additional reactions were performed in the liquid phase to compare the activity of V-MCM-41 with that of crystalline vanadium and titanium silicalite zeolites. The possible causes of the difference in the catalytic behaviors of these materials is also discussed.     

The induction of chirality in sol-gel materials

We review the different approaches that lead to chiral sol-gel materials. These methods include the use of silanes bearing a chiral group for silylating the surface of the porous sol-gel (SG) material, the use of such silanes as monomers or co-monomers in SG polycondensations, the physical entrapment of chiral molecules by SG procedures, the imprinting of SG materials with chiral templates and the creation of chiral pores, and the induction of chirality in the matrix skeleton itself. Analytical methods for detecting chirality are reviewed, including fluorescence methods, electrochemical methods, NMR, and induced CD. Applications are reviewed as well, including sensing, catalysis, chromatography, and optics. While most of the examples are focused on silicas and derivatized silicas, the methods and the analytical tools are generally applicable to other oxides and to preparation procedures other than sol-gel processes.     

两步溶胶凝胶法制备TiO2/SiO2介孔复合材料及其光催化性能研究

制造TiO2/SiO2介孔复合物需要两步,首先是溶胶法,然后将其融入降解的甲基红中作为光催化剂.通过X射线、红外光谱和投射电镜对TiO2/SiO2介孔复合物进行研究,发现TiO2颗粒高度分散在SiO2的晶体中.TiO2在TiO2/SiO2介孔复合物中的基本结构和光催化反应之间的关系得到了特别的关注,这一关系为设计和应用光催化系统在降解有毒复合物的高效应用提供了重要信息.     

Titanium-based solid catalysts for transesterification of methyl-methacrylate by 1-butanol: the homogeneous catalysis contribution

Titanium-based solid catalysts were prepared according to two different procedures. In order to improve the stability of the SiOTi bond in the titanium grafted silica catalysts, the surface remaining hydroxyl groups were passivated to prevent the titanium leaching by SiOTi bond solvolysis. This was performed by grafting trimethoxy-silane groups on isolated silanols of silica, after or before metal grafting. The synthesised materials were characterised by FT-IR spectroscopy, and their catalytic properties evaluated in the reaction of transesterification of methyl-methacrylate (MMA) with 1-butanol (BuOH) in liquid phase to produce butyl-methacrylate (BuMA). An important titanium leaching (18–35%) was always detected with all the solid catalysts.

Investigation of the behaviour of Ti(OBu)₄ as homogeneous catalyst for very small concentrations of titanium was carried out in order to evaluate the catalytic contribution of the active dissolved species. We demonstrate here that the catalytic activity is mainly due to the homogeneous catalysis.     

Novel hybrid sol-gel coatings for corrosion protection of AZ31B magnesium alloy

This work aims to develop and study new anticorrosion films for AZ31B magnesium alloy based on the sol-gel coating approach.Hybrid organic-inorganic sols were synthesized by copolymerization of epoxy-siloxane and titanium or zirconium alkoxides. Tris(trimethylsilyl) phosphate was also used as additive to confer additional corrosion protection to magnesium-based alloy. A sol-gel coating, about 5-μm thick, shows good adhesion to the metal substrate and prevents corrosion attack in 0.005 M NaCl solution for 2 weeks. The sol-gel coating system doped with tris(trimethylsilyl)-phosphate revealed improved corrosion protection of the magnesium alloy due to formation of hydrolytically stable Mg-O-P chemical bonds.The structure and the thickness of the sol-gel film were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The corrosion behaviour of AZ31B substrates pre-treated with the sol-gel derived hybrid coatings was tested by electrochemical impedance spectroscopy (EIS). The chemical composition of the silylphosphate-containing sol-gel film at different depths was investigated by X-ray photoelectron spectroscopy (XPS) with depth profiling.     

New nanostructured sorbents for desulfurization of natural gas

Desulfurization of natural gas is achieved commercially by absorption with liquid amine solutions. Adsorption technology could potentially replace the solvent extraction process, particularly for the emerging shale gas wells with production rates that are generally lower than that from the large conventional reservoirs, if a superior adsorbent (sorbent) is developed. In this review, we focus our discussion on three types of sorbents: metal-oxide based sorbents, Cu/Ag-based and other commercial sorbents, and amine-grafted silicas. The advantages and disadvantages of each type are analyzed. Possible approaches for future developments to further improve these sorbents are suggested, particularly for the most promising amine-grafted silicas.     

直接甲醇燃料电池溶胶-凝胶流动相的制备与表征

对直接甲醇燃料电池溶胶-凝胶流动相的制备工艺进行了分析,采用溶胶-凝胶法以正硅酸甲酯为前驱体制备出了溶胶-凝胶流动相.分别以溶胶-凝胶流动相和液体流动相为燃料对比研究了直接甲醇燃料电池的放电性能,测定了溶胶-凝胶流动相在Nation117膜中的甲醇渗透率,研究了溶胶-凝胶流动相的质子电导率.实验结果表明,使用溶胶-凝胶...     

Gas‐ versus liquid‐phase α-pinene transformation over faujasite‐like zeolites and an amorphous silicoaluminate

The transformation of α-pinene was studied in both gas and liquid phase over a series of faujasite‐like zeolites having different framework composition. A comparison with an amorphous silicoaluminate having 13 wt% of Al₂O₃ (SA) was made. Camphene + limonene were the major products observed in liquid phase at 393 K at conversion levels lower than 90%. At 473 K, where the reaction in gas phase took place, limonene suffered an ulterior transformation mainly into terpinenes and terpinolenes and a faster deactivation of the zeolite catalysts as compared to the one in liquid phase was observed. This behaviour contrasts with the high stability shown by SA in gas phase. Over the wider pore system of SA undesired heavy products were formed in liquid phase at the expenses of the terpene isomers. However, in gas phase this ulterior transformation of monoterpenes was minimised. A maximum activity for the zeolite catalysts was observed when the number of Al^IV per unit cell reached about 17, a value where the population of Si(0Al) sites has been shown to reach the maximum. This revised version was published online in July 2006 with corrections to the Cover Date.     

I. Adsorption mechanism of chlorophenols on iron oxides, titanium oxide and aluminum oxide as detected by infrared spectroscopy

The adsorption of 2-chlorophenol, 2,3- and 2,4-dichlorophenols and 2,4,6-trichlorophenol in liquid and gas phase on iron, titanium and aluminum oxides seem to proceed in a similar way. Higher adsorption of chlorophenols either from gas phase or from aqueous solution was observed on -Fe₂O₃ than on -FeOOH. The low adsorption of chlorophenols from aqueous solution on oxide surfaces suggests that hydrophobic chlorophenols cannot effectively compete with water for the absorption on hydrophilic oxide surface sites. The adsorption of chlorophenols on iron, titanium and aluminum oxides was followed by the adsorption isotherm, HPLC and diffuse reflectance FT-IR (DRIFT) spectroscopy. The adsorption of the chlorophenols on the oxides under study is related to the amount of interfacial water content on the iron oxide. The alumina–chlorophenolate surface complex was found to be weak when compared with either the iron or titanium analogs as seen by the C---O stretching vibrations, leading to a lower adsorption on alumina than on iron and titanium oxides.     

Clustering behaviour in gas–liquid–solid circulating fluidized beds with low solid holdups of resin particles

The flow in a gas–liquid–solid circulating fluidized bed is self‐organised and manifests itself with clustering of particles and bubbles. The clustering behaviour in the fluidized bed at low solid holdups of resin particles was experimentally investigated with a high‐speed image measurement and treatment technique of complementary metal oxide semiconductor to enhance the fundamental understanding on such a flow. Several new physical quantities were suggested to characterise such ordered flow structures. The main findings are as follows. The clusters of solid particles largely exist as doublets and triplets, the mixed groups of particles and bubbles mostly exist as one bubble carrying two to four particles. Increasing superficial liquid velocity, particle diameter or density weakens the aggregation degrees of both particle and mixed clusters in the riser and downer, except that the increase of superficial liquid velocity enhances the mixed clustering behaviour in the riser. The climbing of the auxiliary liquid velocity or liquid phase viscosity intensifies the aggregation behaviour, except that the increase of liquid phase viscosity reduces the mixed clustering degree in the riser. The influences of superficial gas velocity and surface tension of liquid phase on the clustering behaviour seem to be a little complex and the trends are not simply increasing or decreasing. The life cycle of solid particle clusters in the GLS riser is not sensitive to the operation conditions, being around 0.07 s. The mixed clusters' life cycle is more sensitive to the conditions and physical properties of phases, changing from 0.02 to 0.07 s.     

Oxidation with no-redox oxides: ammoximation of cyclohexanone on amorphous silicas

The ammoximation in gas phase of cyclohexanone is a reaction with an oxidation step performed on an insulator oxide such as amorphous silica. Conventional mechanisms for such a kind of reaction are not useful. This paper reviews the efforts carried out to understand the catalytic behavior of the silica and highlights the particular catalytic features of the tars, the carbonaceous products formed during the ammoximation, in the oxidation step of the reaction. The catalytic behavior and the role of the acid sites, of the tars and of the activated forms of molecular oxygen were investigated on several commercial amorphous silicas and on pure and doped silicas prepared by sol-gel method. The silica catalyst shows a bifunctional behavior: acid sites are necessary for the formation of imine, the intermediate of the reaction, and oxidizing sites for the formation of oxime. For the first step the presence of silanols of the right acidity results is essential. For the oxidative step the carbonaceous products formed during the reaction seem to play an essential role. It has been suggested that the tars are formed by a polymerization reaction which occurs at the silica surface and involves, in the initiation stage, activated oxygen species generated by the silica surface. The reaction progression with time involves increasing amounts of the carbonaceous products, with a corresponding decline in access to the active sites by pore blockage and, as a consequence, with a corresponding decline in the catalytic activity.     

Gas mass transfer to AOT-based microemulsions

The present paper analyses the gas/liquid mass transfer process employing carbon dioxide as gas phase and ternary water in oil microemulsions as absorbent liquid phases. The liquid phases were obtained by a direct mixing of water, 2,2,4-trimethylpentane and sodium bis(2-ethylhexyl)sulfosuccinate (Aerosol OT). The characteristics of the microemulsions employed as liquid phase have been analysed to interpret the experimental results observed in the absorption process. More specifically, they have been analysed in relation to the percolation phenomenon and the effects produced by this phenomenon upon the different physical properties. Characteristic results have been observed for the gas/liquid mass transfer using microemulsions, because ternary microemulsions with high viscosity values in relation to pure water show a faster absorption process than the carbon dioxide/water system. This characteristic behaviour has been explained on the basis of the microemulsions internal dynamics.     

Mass transfer behaviour of gas-liquid jet loop reactors

A special type of jet loop reactor (JLR), designed for continuous operation and short residence times was investigated with regard to its mass transfer behaviour, described by the volumetric mass transfer coefficient k_La. The jet stream and superficial gas velocities are varied in two JLRs of different sizes, equipped with different nozzles. Fully desalinated water, 0.08 molar NaCI solution and solutions of different concentration of carboxymethyl cellulose (CMC) are used as the liquid phase. A steady-state physical method is employed to determine k_La: air oxygen is purged from the liquid phase by gaseous nitrogen. The measurements show that the reactor is characterized by high power density and high mass transfer performance. No limit of mass transfer capacity was observed in the chosen ranges of volumetric gas and liquid flow rates, i.e. at a given jet stream velocity, the relationship between k_La and the superficial gas velocity is nearly linear. The investigations show that the mass transfer contributed by the jet stream largely depends on liquid phase composition.     

Reactive distillation: Non-ideal flow behaviour of the liquid phase in structured catalytic packings

Reactive distillation, the combination of chemical reaction and multistage distillation, is one of the most important industrial applications of the multifunctional reactor concept. The most promising column internals for reactive distillation are the so-called structured catalytic packings that combine favourable characteristics of traditional structured packings and heterogeneous catalysts. The non-ideal flow behaviour of the gas and the liquid phase is a fundamental aspect in multiphase reactor design since it has a strong influence on the reactor performance. In this study, liquid phase residence time distributions for the catalytic structured packing MULTIPAK^® were measured by means of conductivity measurements under different liquid and gas flow rates and evaluated with differential models.