Catalysts catalytic reactions characterization, 75-96,

Both surface and bulk properties are relevant to catalytic reactivity. Although heterogeneous reactions by definition occur at the interface between a catalyst and reactant/product phase, the process of catalysis actually includes activation of an as-synthesized catalyst, catalytic reaction, and adverse processes leading to the deactivation of a working catalyst. Activation may involve chemical transformations of both the catalyst surface and bulk. For example, the iron oxide Fe Oj is chemically transformed into the active iron carbide during activation for the Fischer-Tropsch synthesis (FTS) from CO and [32, 33]. There are numerous other examples of reduction of a metal oxide to an active metal or oxidation of a metal to an active oxide, carbide, sulfide, or similar. Characterization of chemistry and structure of the surface and bulk of a catalyst nanoparticle using representative techniques are presented in Chapter 4. 

Catalyst films for electrochemical promotion studies should be thin and porous enough so that the catalytic reaction under study is not subject to internal mass-transfer limitations within the desired operating temperature. Thickness below 10 pm and porosity larger than 30% are usually sufficient to ensure the absence of internal mass-transfer limitations. Several SEM images of such catalyst films have been presented in this book. SEM characterization is very important in assessing the morphological suitability of catalyst films for electrochemical promotion studies and in optimizing the calcination procedure. 

This complex and structurally related molecules served as a functional homogeneous model system for commercially used heterogeneous catalysts based on chromium (e.g. Cp2Cr on silica - Union Carbide catalyst). The kinetics of the polymerization have been studied to elucidate mechanistic features of the catalysis and in order to characterize the potential energy surface of the catalytic reaction. 

In the following review we will focus on two classes of systems dispersed metal particles on oxide supports as used for a large variety of catalytic reactions and a model Ziegler-Natta catalyst for low pressure olefin polymerization. The discussion of the first system will focus on the characterization of the environment of deposited metal atoms. To this end, we will discuss the prospects of metal carbonyls, which may be formed during the reaction of metal deposits with a CO gas phase, as probes for mapping the environment of deposited metal atoms [15-19]. 

Effectiveness Factors for Hougen-Watson Rate Expressions. The discussion thus far and the vast majority of the literature dealing with effectiveness factors for porous catalysts are based on the assumption of an integer-power reaction rate expression (i.e., zero-, first-, or second-order kinetics). In Chapter 6, however, we stressed the fact that heterogeneous catalytic reactions are more often characterized by more complex rate expressions of the Hougen-Watson type. Over a narrow range of... 

This situation is termed pore-mouth poisoning. As poisoning proceeds the inactive shell thickens and, under extreme conditions, the rate of the catalytic reaction may become limited by the rate of diffusion past the poisoned pore mouths. The apparent activation energy of the reaction under these extreme conditions will be typical of the temperature dependence of diffusion coefficients. If the catalyst and reaction conditions in question are characterized by a low effectiveness factor, one may find that poisoning only a small fraction of the surface gives rise to a disproportionate drop in activity. In a sense one observes a form of selective poisoning. 

We will describe first the different methods of immobilization of catalysts, and highlight their advantages and disadvantages and their fields of application. We will then examine the properties of such supported complexes for the major classes of catalytic reactions. We will focus mainly on those studies where at least some characterization of the supported catalyst is given, unless the catalytic properties of the described system are outstanding the review is therefore far from being exhaustive. Finally, where possible, we will mention tests of recyclability, which are essential for the supported complex to be as a potential industrial catalyst. 

No evidence of ruthenium metal formation was found in catalytic reactions until temperatures above about 265°C (at 340 atm) were reached. The presence of Ru metal in such runs could be easily characterized by its visual appearance on glass liners and by the formation of hydrocarbon products (J/1J) The actual catalyst involved in methyl and glycol acetate formation is therefore almost certainly a soluble ruthenium species. In addition, the observation of predominantly a mononuclear complex under reaction conditions in combination with a first-order reaction rate dependence on ruthenium concentration (e.g., see reactions 1 and 3 in Table I) strongly suggests that the catalytically active species is mononuclear. 

Catalytic reactions in fluidized-bed reactors often involve the use of catalyst particles of different sizes, which may be characterized by a particle-size distribution. Consider the reaction A(g) -> products, for which the following data are available ... 

In this chapter I will cover only well-defined or well-characterized compounds. Results will be included that have appeared since reviews in 1991 on alkylidene and metalacyclobutane complexes [41] and in 1993 on ring-opening metathesis polymerization [30], but an overview of prior results that are especially relevant to olefin metathesis in particular will also be included. (An excellent and comprehensive text also has been published recently [1].) The terms well-defined or well-characterized originally were meant to imply that the alkylidene complex is isolable and is essentially identical to that in a catalytic reaction except for the identity of the alkylidene. These terms have been watered down from time to time in the literature, even to the point where they are used to describe a catalyst that is formed from a well-characterized transition metal precursor complex, but whose identity actually is not known. In this article I... 

In recent years, increasing use has been made of in situ methods in EM—as is true of other techniques of catalyst characterization such as IR, Raman, and NMR spectroscopy, or X-ray diffraction. Although the low mean-free path of electrons prevents EM from being used when model catalysts are exposed to pressures comparable to those prevailing in industrial processes, Gai and Boyes (4) reported early investigations of in situ EM with atomic resolution under controlled reaction conditions to probe the dynamics of catalytic reactions. Direct in situ investigation permits extrapolation to conditions under which practical catalysts operate, as described in Section VIII. 

Catalysis is a dynamic process, and deeper insights into its phenomenology are extractable from in situ measurements than from characterizations of catalysts before and after catalysis. A number of notable in situ experiments have relied on modifications of standard TEM operations under vacuum. The main functions of the EM depend on a high-vacuum environment, and the pressure in a TEM is usually of the order of 10-7-10-6 mbar. Because the influence of the reaction environment on the structure and activity of a catalyst is critical (3), the high-vacuum environment of a conventional EM is inappropriate for investigating a catalytic reaction, as are characterizations of catalysts in post-reaction environments (e.g., when the catalyst has been taken out of the reaction environment and cooled to room temperature). 

Catalyst characterization is a lively and highly relevant discipline in catalysis. A literature survey identified over 4000 scientific publications on catalyst characterization in a period of two years [14]. The desire to work with defined materials is undoubtedly present. No less than 78% of the 143 papers presented orally at the 1 llh International Congress on Catalysis [15] contained at least some results on the catalyst(s) obtained by characterization techniques, whereas about 20% of the papers dealt with catalytic reactions over uncharacterized catalysts. Another remarkable fact from these statistics is that about 10% of the papers contained results of theoretical calculations. The trend is clearly to approach catalysis from many different viewpoints with a combination of sophisticated experimental and theoretical tools. 

In situ characterization. Catalysts should preferably be investigated under the conditions under which they are active in the reaction. Various reasons exist why this may not be possible, however. For example, lattice vibrations often impede the use of EXAFS, XRD and Mossbauer spectroscopy at reaction temperatures the mean free path of electrons and ions dictates that XPS, SIMS and LEIS are carried out in vacuum, etc. Nevertheless, one should strive to choose the conditions as close as possible to those of the catalytic reaction. This means that the catalyst is kept under reaction gases or inert atmosphere at low temperature to be studied by EXAFS and Mossbauer spectroscopy or that it is transferred to the vacuum spectrometers under conditions preserving the chemical state of the surface. 

It has also been shown that the selectivity features of para-selective catalysts can be readily understood from an interplay of catalytic reaction with mass transfer. This interaction is described by classical diffusion-reaction equations. Two catalyst properties, diffusion time and intrinsic activity, are sufficient to characterize the shape selectivity of a catalyst, both its primary product distribution and products at higher degrees of conversion. In the correlative model, the diffusion time used is that for o-xylene adsorption at... 

Characterization is a central aspect of catalyst development [1,2], The elucidation of the structures, compositions, and chemical properties of both the solids used in heterogeneous catalysis and the adsorbates and intermediates present on the surfaces of the catalysts during reaction is vital for a better understanding of the relationship between catalyst properties and catalytic performance. This knowledge is essential to develop more active, selective, and durable catalysts, and also to optimize reaction conditions. 

Through such chemisorption studies, the values of >, have been determined not only by geometric accessibility, but also by the chemical heterogeneity of the surface. This can result in abnormal values of D, and demonstrates the scale effect on the kinetics and selectivity of catalytic reactions. For such studies, Farin and Anvir [213] derived the equations that can be applied for characterization of supported catalysts ... 

---