Acid-base properties oxide surfaces

Acid-base properties of oxide surfaces are employed in many fields and their relationship with PZC has been often invoked. Adsorption and displacement of different organic molecules from gas phase was proposed as a tool to characterize acid-base properties of dry ZnO and MgO [341]. Hammet acidity functions were used as a measure of acid-base strength of oxides and some salts [342]. Acidity and basicity were determined by titration with 1-butylamine and trichloroacetic acid in benzene using indicators of different pAg. There is no simple correlation between these results and the PZC. Acid-base properties of surfaces have been derived from IR spectra of vapors of probe acids or bases, e.g. pyridine [343] adsorbed on these surfaces. The correlation between Gibbs energy of adsorption of organic solvents on oxides calculated from results obtained by means of inverse gas chromatography and the acceptor and donor ability of these solvents was too poor to use this method to characterize the donor-acceptor properties of the solids [344],... 

Acid-base reactivity is an important property of oxide catalysts, and its control is of interest in surface chemistry as well as being of importance in industrial applications. The exposed cations and anions on oxide surfaces have long been described as acid-base pairs. The polar planes of ZnO showed dissociative adsorption and subsequent decomposition of methanol and formic acid related with their surface acid-base properties[3]. Further examples related to the topic of acid-base properties have been accumulated to date[ 1,4-6]. 

Gas-phase methylation of catechol by methanol was studied on y -AI2O3 modified by the basic elements K, Li, Mg and Ca. Addition of 7.5 at.% Mg to y-AljOa was optimal and increased the 3-methyl catechol selectivity from 0.26 to 0.65. X-ray diffraction experiments showed the diffusion of Li and Mg cations into the y -AI2O3 bulk. This induces a change in the surface species (XPS data) and the surface acid-base properties (TPD experiments). Ca and K addition to y-alumina was ineffective due to formation of basic oxide layers on the sur ce. 

The field of surface-mediated synthesis of metal carbonyl clusters has developed briskly in recent years [4-6], although many organometallic chemists still seem to be unfamiliar with the methods or consider themselves ill-equipped to carry them out. In a typical synthesis, a metal salt or an organometallic precursor is brought from solution or the gas phase onto a high-area porous metal oxide, and then gas-phase reactants are brought in contact with the sample to cause conversion of the surface species into the desired products. In these syntheses, characteristics such as the acid-base properties of the support influence fhe chemisfry, much as a solvenf or coreactant influences fhe chemisfry in a convenfional synfhesis. An advanfage of... 

The acid-base oxides such as aluminas were used as catalysts, adsorbents or catalyst supports and it was interesting to know the surface acid-base properties of these catalysts. 

Relying on concepts such as hydrolysis, complexation, and acid-base properties, the approach embodied in this advanced mechanism is intriguing and demands further investigation in the context of electroless reactions, perhaps being co-opted into other mechanisms as the experimental conditions and results dictate. A possible drawback to the mechanism of surface incipient hydrous oxide mediators is their suggested low concentration, perhaps as low as 0.1% surface coverage [73], In practical electroless... 

The snrface acid-base properties of supported oxides can be conveniently investigated by studying the adsorption of suitably chosen basic-acidic probe molecules on the solid. As shown, acidic and basic sites are often present simultaneously on solid surfaces. The knowledge of the detailed amphoteric character of supported metal oxides is of extreme interest due to the possibility of using them as catalysts in different reactions in which acidity governs the reaction mechanism. 

When immersed in aqueous solutions, the surfaces of metal oxides are expected to be hydroxylated (see Section 3.1). However, metal oxides may also react with aqueous solutions leading to dissolution, which can effectively be thought of as mass transfer from the solid to aqueous phase. The rate and extent of dissolution reactions depend on a number of factors, including solution pH, acid-base properties of oxo groups on the metal oxide surface, types of ligands present in solution, metal... 

The surface area is a function of the temperature of preparation of the oxides [169, 486]. Thus, the apparent electrocatalytic activity decreases with increasing temperature of calcination (which is usually in the range 350°-500 °C) [227, 475]. However, if the calcination is carried out at too high temperature, the electrode surface is deactivated probably as a consequence of some dehydration, and the observed Tafel slope can be very high [487], The important relationship between the acid-base properties of an oxide surface in solution and its electrocatalytic properties has been pointed out by the present author [488]. 

Shen, J., Kobe, J. M., Chen, Y. and Dumesic, J. A. (1994). Synthesis and surface acid/base properties of magnesium-aluminium mixed oxides obtained from hydrotalcites. Langmuir 10, 3902. 

Shen, J. Y., Tu, M. and Hu, C. (1998). Structural and surface acid/base properties of hydrotalcite-derived MgAlO oxides calcined at varying temperatures. J. Solid State Chem. 137, 295. 

In order to try to clarify the different types of mechanism involving either redox cycles and/or acid-base properties, a study of the surface chemistry of single, doped and mixed oxides is of much interest. The calorimetric technique, by allowing heat transfer measurements, can provide very informative data on the thermodynamics of solid-gas interactions and for the study of the surface and reactivity of these metal oxides. 

The influence of the oxide support (i.e. AI2O3, Nb20s, Si02 and Ti02) on the surface properties, reduction and oxidation properties and acid-base properties of supported indium oxide catalysts has been investigated by temperature pro-... 

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