溶胶-凝胶制备技术与新型催化材料Ⅲ.溶胶粒子表面修饰方法制备催化膜

提出用溶胶粒子表面修饰方法，结合溶胶凝胶技术制备无机催化膜．该方法的基本原理是利用合适的金属配合物在胶粒表面的吸附作用，经溶胶凝胶过程，将活性组分结合到无机膜中．实验测定结果表明：（ＮｉＥＤＴＡ）２－，ＶＯ－３，ＭｏＯ２－４，（Ｐｄ（ＮＨ３）４）２＋，ＰｄＣｌ２－４，ＰｔＣｌ２－６和ＲｈＣｌ３－６可用来修饰ＡｌＯＯＨ溶胶．以Ｐｄ／γＡｌ２Ｏ３催化膜的制备为例，经三次溶胶凝胶过程，可制得无裂缺的厚度为９μｍ的Ｐｄ／γＡｌ２Ｏ３催化膜，膜材料的平均孔直径为６ｎｍ，Ｐｄ被均匀地分布在膜的顶层，其平均粒径为２３ｎｍ．     

Linearization of column responses by correlation chromatography. Separation improvement and reduction of undesired adsorption effects

Summary Experiments and simulations prove that correlation chromatography can greatly reduce the disadvantage of a non-linear response of the chromatographic column. A factor that has been accepted as being an important source of error in correlation or multiplex chromatography, has been shown not to be. Separations affected, improve dramatically when correlation chromatography is used, and a substantial amount of correlation noise only arises when there is a large difference in separation between a conventional chromatogram and a correlogram.A model has been developed for simulating these nonlinearities. It is shown that, especially for correlation chromatography, the simulation results match the practical measurements very well.     

新生MnO2对酸性媒介黑T的吸附

以化学法合成的新生MnO2为吸附剂，对水中酸性媒介黑T（染料之一）进行了吸附脱色研究，并探讨了影响吸附的因素。结果表明，酸性媒介黑T的脱色率达95%。且PH是影响染料脱色的主要因素。     

Structure and electrochemical behaviour of 4,7-diazaheptyl-trimethoxy-silane and vinyl-trialkoxy-silane adsorbed at silver surface

Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li⁺ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods.     

Volumetric and infrared measurements on amorphous ice structure

We have simultaneously used adsorption isotherm volumetry and Fourier transform infrared spectroscopy in order to take the investigations on amorphous ice structure a step further, especially concerning porosity and annealing-induced modifications. We have studied surface reorganization during annealing and found that the number of surface sites decreases before crystallization, their relative ratios being different for amorphous and crystalline ice. We also present results confirming that ice can have a large specific surface area and nevertheless be non-microporous.     

On the influence of the surfactant''s polar group on the local and terminal velocities of bubbles

The local and the terminal velocities, the size and the degree of bubbles’ shape deformations were determined as a function of distance from the position of the bubble formation (capillary orifice) in solutions of n-octyltrimethylammonium bromide, n-octyldimethylphosphine oxide, n-octyl-β-D-glucopyranoside and n-octanoic acid.

These surface-active compounds have different polar groups but an identical hydrocarbon chain (C8) in the molecule. The motion of the bubbles was monitored and recorded using a stroboscopic illumination, a CCD camera, and a JVC professional video. The recorded bubble images were analyzed by the image analysis software. The bubbles accelerated rapidly and their shape was deformed immediately after detachment from the capillary. The extent of the bubbles’ shape deformation (ratio of horizontal and vertical diameters) was 1.5 in distilled water and dropped rapidly down to a level of ca. 1.05–1.03 with increasing surfactant concentration. After the acceleration period the bubbles either attained a constant value of the terminal velocity (distilled water and high concentrations of the solutions), or a maximum in the velocity profiles was observed (low concentrations). The values of the terminal velocity diminished drastically with increasing concentration, from the value of 35 cm/s in water down to about 15 cm/s, while the bubble diameter decreased by ca. 10% only. The surfactant adsorption at the surface of the bubbles was evaluated and the minimum adsorption coverages required to immobilize the bubbles’ surface were determined. It was found that this minimum adsorption coverage was ca. 4% for n-octyldimethylphosphine oxide, n-octyl-β-D-glucopyranoside, n-octanoic acid and 25% for n-octyltrimethylammonium bromide. The difference in the adsorption coverage together with the surfactants’ surface activities indicate that it is mainly the adsorption kinetics of the surfactants that governs the fluidity of interfaces of the rising bubbles.     

Microcalorimetric Adsorption of Alumina Oxide Catalysts for Combination of Ethylbenzene dehydrogenation and carbon Dioxide Shift-reaction

Styrene (STY) is now produced industrially in fairly large quantities by the dehydrogenation of ethylbenzene (EB) using promoted iron oxide catalyst with superheated steam.In this case, small amount of carbon dioxide formed as a by-product was known to inhibit the catalytic activity of commercial catalyst. Recently, there have been some reports which carbon dioxide showed positive effects to promote catalytic activities on the reaction over several catalysts.In this study, we attempted to combine the dehydrogenation of EB to STY with the carbon dioxide shift-reaction. The combine reaction (EB + CO2 → STY + H2O + CO) can be considered as one of the ways of using CO2 resources and can yield simultaneously STY and Carbon oxide.Alumina oxide catalysts such as Al2O3, Na2O/Al2O3 and K2O/Al2O3 were prepared by the usual impregnation method with an aqueous solution of NaNO3 and KNO3, and then calcined at 650℃ for 5 h in a stream of air. The reaction condition is 600℃, flow of CO2 38ml/mon and space velocity (EB) 1.28h-1.     

Classical, phenomenological analysis of the kinetics of reactions at the gas-exposed surface of mixed ionic electronic conductors

The kinetics of reactions occurring at the gas-exposed surfaces of charged mixed ionic electronic conductors (MIECs) are examined from theoretical first principles. Analysis based on the classical electrochemical potential-transition state theory model reveals that the nature of the reactions is electrochemical in general. However, the influence of the surface potential on the reaction rate is opposite for adsorption and incorporation reactions. Two-dimensional finite volume models of an MIEC as working electrode in a half-cell configuration are presented. The results for a simple, two-step reduction process show that the effect of the surface potential on the rate of reactions is minimal for incorporation-limited reactions but more influential for adsorption-limited reactions. An erratum to this article is available at .     

Interaction of indigo carmine dye with silica modified with humic acids at solid/liquid interface

Two distinct humic acids, one extracted from Brazilian peat soil, HA_PS, and another one obtained from commercial source, HA_FL, were attachment onto silica gel modified with aminopropyltrimethoxysilane, producing two material named SiHA_PS and SiHA_FL, respectively. The ability of these materials in removing indigo carmine dye from aqueous solution was followed through series of adsorption isotherms adjusted to modified Langmuir equation. The maximum number of moles adsorbed gave 6.82 ± 0.12 × 10⁻⁴ and 2.15 ± 0.17 × 10⁻⁴ mol g⁻¹ for SiHA_PS and SiHA_FL, respectively. Same interactions were calorimetrically followed and the thermodynamic data showed endothermic enthalpic values: 12.31 ± 0.55 and 24.69 ± 1.05 kJ mol⁻¹ for SiHA_PS and SiHA_FL surfaces, respectively. Gibbs free energies for two adsorption processes of indigo carmine dye presented negative values, reflecting dye/surface interactions must be accompanied by an increased in entropy values, which are 65 ± 3 and 98 ± 5 J mol⁻¹ K⁻¹ for SiHA_PS and SiHA_FL materials, respectively. The adsorption processes for both materials were spontaneous in nature although they presented an endothermic enthalpy for the interaction, resulting in an entropically favored process.