Catalytic reaction steps dissociative adsorption

Reaction Steps 8.6 to 8.8 are also relevant to the catalytic reaction of methanol in a flow of CH3OH, although the steps 8.5 and 8.8 cannot be separated anymore. The net reaction for dissociative adsorption of methanol is expressed by ... 

In drafting a catalytic cycle as in Eqs. (132)-(135) we naturally have to ensure that the reaction steps are thermodynamically and stoichiometrically consistent. For instance, the number of sites consumed in the adsorption and dissociation steps must be equal to the number of sites liberated in the formation and desorption steps, to fulfill the criterion that a catalyst is unaltered by the catalytic cycle. 

Unraveling catalytic mechanisms in terms of elementary reactions and determining the kinetic parameters of such steps is at the heart of understanding catalytic reactions at the molecular level. As explained in Chapters 1 and 2, catalysis is a cyclic event that consists of elementary reaction steps. Hence, to determine the kinetics of a catalytic reaction mechanism, we need the kinetic parameters of these individual reaction steps. Unfortunately, these are rarely available. Here we discuss how sticking coefficients, activation energies and pre-exponential factors can be determined for elementary steps as adsorption, desorption, dissociation and recombination. 

Figure 1.1 Schematic representation of a well known catalytic reaction, the oxidation of carbon monoxide on noble metal catalysts CO + Vi 02 —> C02. The catalytic cycle begins with the associative adsorption of CO and the dissociative adsorption of 02 on the surface. As adsorption is always exothermic, the potential energy decreases. Next CO and O combine to form an adsorbed C02 molecule, which represents the rate-determining step in the catalytic sequence. The adsorbed C02 molecule desorbs almost instantaneously, thereby liberating adsorption sites that are available for the following reaction cycle. This regeneration of sites distinguishes catalytic from stoichiometric reactions.

Linear mechanisms are rather common for heterogeneous catalytic reactions. Examples are given and examined by Cornish-Bowden [43] and Ker-nevez [44]. Non-linear mechanisms, i.e. those including interactions of several molecules of the same or different surface substances, however, are more frequent. For example, a widely spread step of dissociative adsorption is non-linear. 

The oxide surface becomes reduced in this process if this were a step in a catalytic reaction, some other O-containing species would have to donate an O atom back to the substrate in order for the reaction to continue. Like the other types of reaction, 0-transfer adsorption can be either molecular or dissociative. 

In some cases, when the first (discharge) step is rate determining but the surface of the electrode is catalytically active for dissociation of the product of the overall reaction, for example, CI2 or H2 at active Pt, the 6 factor in the rate equation for the discharge step [Eq. (79)] can take appreciable values determined by the partial pressure, P, of the reaction product, for example, H2 in the HER, according to an adsorption isotherm of the form. 

These results have profound effects for the selective catalytic dehydrogenation of cyclohexane to benzene, a prototypical hydrocarbon conversion reaction. On Pt(lll), the intermediates, cyclohexene and a species, have been identified and the rate constants for some of the sequential reaction steps measured [56]. Adsorption and reaction studies of cyclohexane [39], cyclohexene [44], 1,3-cyclo-hexadiene [48], and benzene [39] on the two Sn/Pt(lll) alloys provide a rational basis for understanding the role of Sn in promoting higher selectivity for this reaction. One example of structure sensitivity is shown in Fig. 2.7, in which a monolayer of cyclohexyl (C H ) was prepared by electron-induced dissociation (EID) of physi-orbed cyclohexane to overcome the completely reversible adsorption of cyclohexane... 

Earlier we described the catalytic reaction as a series of consecutive steps at the surface, in which adsorbate and adsorbate-surface bonds are formed and/or broken on the reaction path towards the product molecule. The forces between surface atoms and adsorbate atoms responsible for rearrangement of the chemical bond are similar to those responsible for strong adsorption (E > 10 kcal/nx)l). The adsorption process dominated by such interaction is called chemisorption. Even on a single crystal metal surface, several adsorption modes are conceivable and for dissociation of a diatomic molecule many different reaction paths can be envisioned. However, usually only one particular surface atom configuration is preferred to lead to the idea of catalytic active site. If catalysis of a molecule is studied that has several reaction possibilities, some desirable and others not, a selective reaction usually requires a particular surface atom composition and rearrangement. 

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