Basicity, heterogeneous catalysis

A key feature of heterogeneous catalysis is that reactants from a gaseous or solution phase are adsorbed, or attached, to the surface of the catalyst. Not all surface atoms are equally effective for catalysis those that are effective are called active sites. Basically, heterogeneous catalysis involves (1) adsorption of reactants (2) diffusion of reactants along the surface (3) reaction at an active site to form adsorbed product and (4) desorption of the product. 

It would be difficult to over-estimate the extent to which the BET method has contributed to the development of those branches of physical chemistry such as heterogeneous catalysis, adsorption or particle size estimation, which involve finely divided or porous solids in all of these fields the BET surface area is a household phrase. But it is perhaps the very breadth of its scope which has led to a somewhat uncritical application of the method as a kind of infallible yardstick, and to a lack of appreciation of the nature of its basic assumptions or of the circumstances under which it may, or may not, be expected to yield a reliable result. This is particularly true of those solids which contain very fine pores and give rise to Langmuir-type isotherms, for the BET procedure may then give quite erroneous values for the surface area. If the pores are rather larger—tens to hundreds of Angstroms in width—the pore size distribution may be calculated from the adsorption isotherm of a vapour with the aid of the Kelvin equation, and within recent years a number of detailed procedures for carrying out the calculation have been put forward but all too often the limitations on the validity of the results, and the difficulty of interpretation in terms of the actual solid, tend to be insufficiently stressed or even entirely overlooked. And in the time-honoured method for the estimation of surface area from measurements of adsorption from solution, the complications introduced by... 

However, research into transition metal catalysis in ionic liquids should not focus only on the question of how to make some specific products more economical or ecological by use of a new solvent and, presumably, a new multiphasic process. Since it bridges the gap between homogeneous and heterogeneous catalysis, in a novel and highly attractive manner, the application of ionic liquids in transition metal catalysis gives access to some much more fundamental and conceptual questions for basic research. 

The reader must have already identified some of the basic concepts which play a key role in understanding the electrochemical activation of heterogeneous catalysis catalysis, electrocatalysis, promotion, electrochemical promotion, spillover, backspillover. It is therefore quite important to define these terms unambiguously so that their meaning is clearly determined throughout this book. 

Gas-surface interactions and reactions on surfaces play a crucial role in many technologically important areas such as corrosion, adhesion, synthesis of new materials, electrochemistry and heterogeneous catalysis. This chapter aims to describe the interaction of gases with metal surfaces in terms of chemical bonding. Molecular orbital and band structure theory are the basic tools for this. We limit ourselves to metals. 

Aluminas. Aluminas, porous AI2O3, are available in many forms. They constitute the most important carrier material in heterogeneous catalysis. Alumina is amphoteric and, as a con.sequence, soluble in both acidic and basic media. Precipitation can be performed from an acid solution by adding a base or from a basic solution by adding an acid, as schematically represented in Fig. 3.18. If, for example, at a pH of less than about 3 a base is added to an aqueous solution of aluminium sulphate, a precipitate is formed. If this material is filtered, dried and calcined, an amorphous porous AI2O3 is obtained. At other pH values different porous aluminas can be synthesized. 

The hydrogenation of p-unsaturated alcohols is a classical example of competing reaction processes in heterogeneous catalysis. In principle, either isomerization to an enol followed by tautomerization to the ketone can occur, or direct hydrogenation to the saturated alcohol is possible (1). It is fair to state that interest in this type of chemistry is derived from both basic scientific... 

In principle, sites a, IT, and c need not be association sites as depicted by Ogston but could be steric sites that form obstructions such that the adsorbed molecule is chirally directed. Only one active site is actually required providing the remaining two sites (protuberances or cavities) are different from each other and from the active site that catalyzes the reaction. They could be identical providing they are not symmetrically oriented with respect to the active site (not an isosceles triangle). These are the basic concepts for a chiral environment on a surface and they lead to the three basic methods for creating chiral surfaces in heterogeneous catalysis. 

The preceding list of examples, which is by no means exhaustive, confirms that the determination of heats of adsorption is of both fundamental and practical importance. However, in contrast with this basic importance which cannot be overemphasised (9), data on heats of adsorption, and particularly on calorimetric heats of irreversible adsorption processes, are relatively incomplete, as the careful perusal of any textbook on adsorption or heterogeneous catalysis will show. 

In this communication a study of the catalytic behavior of the immobilized Rhizomucor miehei lipase in the transesterification reaction to biodiesel production has been reported. The main drawbacks associated to the current biodiesel production by basic homogeneous catalysis could be overcome by using immobilized lipases. Immobilization by adsorption and entrapment have been used as methods to prepare the heterogeneous biocatalyst. Zeolites and related materials have been used as inorganic lipase supports. To promote the enzyme adsorption, the surface of the supports have been functionalized by synthesis procedures or by post-treatments. While, the enzyme entrapping procedure has been carried out by sol-gel method in order to obtain the biocatalyst protected by a mesoporous matrix and to reduce its leaching after several catalytic uses. 

Besides the practical application, the diversity of nanostructured carbon allotropes makes nanocarbon also an ideal model system for the investigation of structure-function correlations in heterogeneous catalysis. Nanocarbons can be tailored in terms of their hybridization state, curvature, and aspect ratio, i.e., dimensions of stacks of basic structural units (BSU), Chapters 1 and 2. The preferred exposition of two types of surfaces, which strongly differ in their physico-chemical behavior, i.e., the basal plane and prismatic edges, can be controlled. Such controlled diversity is seldom found for other materials giving carbon a unique role in this field of basic research. The focus of this chapter is set on the most prominent representatives of the... 

Nevertheless, the kinetic approach to heterogeneous catalysis can be rewarding if relative data for two or more structurally related reactants or catalysts are acquired and interpreted. Instead of applying several assumptions that simplify the reaction scheme and the model of the surface, which are necessary for absolute kinetic description, it is accepted that, under certain conditions, the same reaction scheme holds for all members of the series of reactants or catalysts and that all of the unknown but identical simplifications in the relative data cancel out. However, it is much safer to select a series of reactants in which the structural change from one member to another will be small enough to uphold the basic features of the mechanism than to assume the same for a set of catalysts that are not minor variations of a basic preparation. 

A major step towards applicability of multiphase catalysis in ionic liquids is the development of Supported Ionic Liquid Phase (SLIP) -catalysis by the Wasserscheid group [28,29]. The SLIP concept enables quasi-heterogeneous catalysis in ionic liquids and opens the door to the production of basic chemicals. 

The basic concept is the intuition that, whether homogeneous or heterogeneous, catalysis is primarily a process controlled by a molecular phenomenon since it implies the catalyzed transformation of molecules into other molecules. It follows that on the surface of metals or metal oxides, sulfides, carbides, nitrides usually involved as heterogeneous catalysts, the relevant surface species and the mechanism of their mutual reactions must be of molecular character, as occurs in homogeneous or enzymatic catalysis. 

This was the basic assumption developed in the early 1960s by Bond [1] and Ugo and Carra [2] in a rather preliminary way to support the so-called molecular approach to heterogeneous catalysis. ... 

The surface basicity of a solid catalyst can be defined in a way analogous to that applied to conventional bases. Thus, a surface Lewis base site is one that is able to donate an electron pair to an adsorbed molecule. If we take the definition of surface basicity in a more general way, it could be said that the active surface corresponds to sites with relatively high local electron densities. This general definition will include not only Lewis basicity but also single electron donor sites. We emphasize that the literature of heterogeneous catalysis often reports that both single-electron and electron-pair donor sites exist on basic catalysts. 

Microcalorimetry has gained importance as one of the most reliable method for the study of gas-solid interactions due to the development of commercial instrumentation able to measure small heat quantities and also the adsorbed amounts. There are basically three types of calorimeters sensitive enough (i.e., microcalorimeters) to measure differential heats of adsorption of simple gas molecules on powdered solids isoperibol calorimeters [131,132], constant temperature calorimeters [133], and heat-flow calorimeters [134,135]. During the early days of adsorption calorimetry, the most widely used calorimeters were of the isoperibol type [136-138] and their use in heterogeneous catalysis has been discussed in [134]. Many of these calorimeters consist of an inner vessel that is imperfectly insulated from its surroundings, the latter usually maintained at a constant temperature. These calorimeters usually do not have high resolution or accuracy. 

On solids, the amount and strength of acid or basic sites are quite independent parameters, so both of them must be analyzed independently for a complete characterization. Additionally, several different families of acid sites may occur in the same solid surface, so their distribution must be characterized. The key to the effective utilization of microcalorimetry in heterogeneous catalysis is the judicious choice of gas-phase molecules for study. 

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