Dissociative adsorption of carbon monoxide

Alternatively, an intermediate formation of an adsorbed methylene on the catalyst surface through the dissociative adsorption of carbon monoxide has been considered ... 

Non-dissociative, dissociative. If a molecule is adsorbed without fragmentation, the adsorption process is non-dissociative. Adsorption of carbon monoxide is frequently of this type. If a molecule is adsorbed with dissociation into two or more fragments both or all of which are bound to the surface of the adsorbent, the process is dissociative. Chemisorption of hydrogen is commonly of this type. 

When the carbon monoxide molecule dissociates upon adsorption, it is referred to as the dissociative adsorption of carbon monoxide. As in the case of molecular adsorption, the rate of adsorption here is proportional to the pressure of carbon monoxide in the system because this rate governs the number of gaseous collisions with the surface. For a molecule to dissociate as it adsorbs, however, two adjacent vacant active sites are required rather than the single site needed when a substance adsorbs in its molecular form. The probability of two vacant sites occurring adjacent to one another is proportional to the square of the concentration of vacant sites. These two observations mean that the rate of adsorption is proportional to the product of the carbon monoxide partial pressure and the square of the vacant-site concentration, Pco u-... 

The C-0 bond can be more easily activated when the CO molecule interacts with more than two metal atoms. Recently, the dissociative adsorption of carbon monoxide by polynuclear metal complexes, such as [(silox)2TaH2]2 (Eq. 57) [126, 127] and [(silox)2WCl]2 (Eq. 58) [126-129], and tetratungsten alkoxides [129] has been achieved. Hydrogenation of CO to give hydrocarbons promoted by metal clusters has been reviewed [130]. 

Experimental results on single crystals show that at temperatures below about 250 K, dissociative adsorption of carbon monoxide on the surface does not proceed. Molecular adsorption of carbon monoxide occurs on different sites, each showing different heats of adsorption. 

Adsorption of carbon monoxide (Eq.(5a)) is assumed to occur in parallel with the dissociative chemisorption of hydrogen (Eq. (5b)) (M is a catalyst site), hydrogen oxidation current is assumed to be generated by process (5c), and adsorbed carbon monoxide would oxidize electrochemically to CO2 according to Eq. (5d), reacting with a water-derived adsorbed oxygen species. 

After the brief introduction to the modem methods of ab initio quantum chemistry, we will discuss specific applications. First of all, we will discuss some general aspects of the adsorption of atoms and molecules on electrochemical surfaces, including a discussion of the two different types of geometrical models that may be used to study surfaces, i. e. clusters and slabs, and how to model the effect of the electrode potential in an ab initio calculation. As a first application, the adsorption of halogens and halides on metal surfaces, a problem very central to interfacial electrochemistry, will be dealt with, followed by a section on the ab initio quantum chemical description of the adsorption of a paradigmatic probe molecule in both interfacial electrochemistry and surface science, namely carbon monoxide. Next we will discuss in detail an issue uniquely specific to electrochemistry, namely the effect of the electric field, i. e. the variable electrode potential, on the adsorption energy and vibrational properties of chemisorbed atoms and molecules. The potential-dependent adsorption of carbon monoxide will be discussed in a separate section, as this is a much studied system both in experimental electrochemistry and ab initio quantum electrochemistry. The interaction of water and water dissociation products with metal surfaces will be the next topic of interest. Finally, as a last... 

To illustrate the difference between molecular adsorption and dissociative adsorption, we will postulate two models for the adsorption of carbon monoxide on metal surfaces. In one model. CO i.s adsorbed as molecules. CO,... 

Whereas determination of chemisorption isotherms, e.g., of hydrogen on metals, is a means for calculating the size of the metallic surface area, our results clearly demonstrate that IR studies on the adsorption of nitrogen and carbon monoxide can give valuable information about the structure of the metal surface. The adsorption of nitrogen enables us to determine the number of B5 sites per unit of metal surface area, not only on nickel, but also on palladium, platinum, and iridium. Once the number of B5 sites is known, it is possible to look for other phenomena that require the presence of these sites. One has already been found, viz, the dissociative chemisorption of carbon dioxide on nickel. 

A dissociative adsorption of methanol forming surface methoxy groups is suggested as the initial step. This is followed by the slow step, the formation of some form of adsorbed formaldehyde species. Evidence.for the bridged species is not available, experiments with °0 labeled methanol are expected to clarify this. Continued surface oxidation leads to a surface formate group and to carbon monoxide. All the byproducts can be obtained by combination of the appropriate surface species. 

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.

The change in the nature of the adsorption with increasing coverage (dissociative followed by associative) has been explained by a statistical consideration of the reaction mechanism shown above120). Associative adsorption is expected to occur at vacant sites for which all adjacent olefin binding sites are occupied by earlier dissociation products (or carbon monoxide, as shown by Fig. 6b), because dissociative adsorption (formation of vinyl and hydride species, followed by hydride migration to another alkene) requires two adjacent vacant sites. 

The fact that surface structure, in particular steps and coordinatively unsaturated sites, has an influence on the state and reactivity of carbon monoxide is entirely in keeping with the empirical correlation (Fig. 6) between heat of adsorption, electron binding energies, and molecular state. Elegant studies by Mason, Somorjai, and their colleagues (32, 33) have established that with Pt(lll) surfaces, dissociation occurs at the step sites only, and once these are filled carbon monoxide is adsorbed molecularly (Fig. 7). The implications of the facile dissociation of carbon monoxide by such metals as iron, molybdenum, and tungsten for the conversion of carbon monoxide into hydrocarbons (the Fischer-Tropsch process) have been emphasized and discussed by a number of people (32,34). 

Amorphous (rapidly quenched) metals and alloys have been investigated as catalysts (Schlogl, 1985). It has been found that adsorption characteristics of carbon monoxide on metallic glasses are different from those on crystalline materials. For example CO is found to dissociate readily on the surface of Ni76Bi2Si,2 metglass, but it is always molecularly adsorbed on metallic nickel (Prabhakaran Rao, 1985). 

The facile dissociative adsorption of CO on transition metals at low temperatures has been demonstrated by XPS or pulse techniques for Ti, V, Cr and Mn (96] and at elevated temperatures for Ni, Co and Ku with Fc as the borderline case [96, 97J. A more detailed study by Somorjai for Pt (111) surfaces showed that dissociation occurs at the step sites only, and once these are filled, carbon monoxide is absorbed moiccularly [98]. All of the XPS studies on chemisorption on iron, except at very low temperatures, are indicative of dissociative surpikm being the first step in Fischer-Tropsdi reactions (99 101). However, photoelectron spectroscopy has so far not delineated a logical sequence of precursors and intermediates 1102. ... 

Hydrogen goes as two protons to convert two oxide ions to hydroxide ions and the two electrons reduce two Cr + to Cr -. The behavior of carbon monoxide is equivalent. As written, there is no requirement of surface coordinative unsaturation. However, coordinative unsaturation in the oxide ions which are converted to hydroxide ions would favor reductive adsorption. Further, for reasons outlined in Section IV, Cr will be easier to reduce to Cr2+ when it is also coordinatively unsaturated. Further, where this is so, heterolytic dissociative adsorption in the sense of Eq. (7) might subsequently occur at Cr +fcus). 

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