Physicochemical Characterization of Active Sites

Metals and/or metal oxides are required to dehydrogenate paraffinic reactants to olefins, which are dimerized or oligomerized via acid sites of the ZSM-5 to increase carbon number and then dehydrocycfized, first to napthenes and 

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It is now considered, by most groups working in this area, that vanadyl pyrophosphate (VO)2P207 is the central phase of the Vanadium Phosphate system for butane oxidation to maleic anhydride (7 ). However the local structure of the catalytic sites is still a subject of discussion since, up to now, it has not been possible to study the characteristics of the catalyst under reaction conditions. Correlations have been attempted between catalytic performances obtained at variable temperature (380-430 C) in steady state conditions and physicochemical characterization obtained at room temperature after the catalytic test, sometimes after some deactivation of the catalyst. As a consequence, this has led to some confusion as to the nature of the active phase and of the effective sites. (VO)2P207, V (IV) is mainly detected by X-Ray Diffraction. 

Physicochemical methods, i.e. adsorption of probe molecules followed by varied analytical techniques (gravimetry, chromatography, calorimetry, spectroscopic techniques, etc.) are currently used for estimating more precisely the concentration of the potential active sites.[34 36] However, very few methods are well adapted for this purpose most of the methods employed for the characterization of the acidity of solid catalysts lead to values of the total concentrations of the acid sites (Brpnsted + Lewis) and to relative data on their strength, whereas few of them discriminate between Lewis and Brpnsted acid sites. It is however the case for base adsorption (often pyridine) followed by IR spectroscopy, from which the concentrations of Brpnsted and Lewis sites can be estimated from the absorbance of IR bands specific for adsorbed molecules on Brpnsted or Lewis sites. 

The RF-GC methodology is technically very simple and it is combined with a mathematical analysis that gives the possibility for the estimation of various physicochemical parameters related to solid catalysts characterization in a simple experiment under conditions compatible with the operation of real catalysts. The experimentally determined kinetic quantities are not only consistent with the results of other techniques, but, moreover, they can give important information about the mechanism of the relevant processes, the nature of the active sites, and the topography of the heterogeneous surfaces. 

It is not proposed to review the properties of zeolites in general. Structural aspects related to catalysis are, however, discussed in detail. Accessibility of sites and other related factors basic to an understanding of zeolite catalytic behavior are also examined. Considerable emphasis is given to the chemistry of activation processes, the characterization of acid zeolite catalysts, and the physicochemical interactions of adsorbed molecules with zeolite surfaces. 

In this chapter, the dioxygen activation mechanism at the dinuclear copper-active sites of tyrosinase and catechol oxidase has been surveyed. In both enzymes, a (ji-rfirf -peToxo) dicopper(II) complex has been detected and characterized as a common reactive intermediate by several spectroscopic methods. In spite of longstanding efforts in the enzymological studies, mechanistic details of the enzymatic reactions (phenolase and catecholase activities) still remain ambiguous. On the other hand, recent developments in the model chemistry have provided a great deal of information about the structure and physicochemical properties as well as the reactivity of the peroxo intermediate and have advanced our understanding of the enzymatic reactions. 

RF-GC has been used to characterize solid catalysts under either steady- or non-steady-state conditions, compatible with the operation of real catalysts. RF-GC is not limited to chromatographic separation since RF-GC is accompanied by suitable mathematical analysis of the chromatographic data, the simultaneous determination of various physicochemical parameters related to the kinetics of the elementary steps (adsorption, desorption, surface reaction) and the nature of the active sites is possible. 

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