Chemisorption modifiers

Fig. 2.4 N, O, and F chemisorption modified valence DOS for a metal and a semiconductor with four excessive DOS features bonding lone pairs (< p), electron holes (< p), and dipoles...

The molecular chemisorption of CO on various alkali-modified metal surfaces has been studied extensively in the literature. It is well established that alkali modification of the metal surface enhances both the strength of molecular chemisorption and the tendency towards dissociative chemisorption. This effect can be attributed to the strongly electropositive character of the alkali, which results in donation of electron density from the alkali to the metal and then to the adsorbed CO, via increased backdonation into the... 

For alkali modified noble and sp-metals (e.g. Cu, Al, Ag and Au), where the CO adsorption bond is rather weak, due to negligible backdonation of electronic density from the metal, the presence of an alkali metal has a weaker effect on CO adsorption. A promotional effect in CO adsorption (increase in the initial sticking coefficient and strengthening of the chemisorptive CO bond) has been observed for K- or Cs-modified Cu surfaces as well as for the CO-K(or Na)/Al(100) system.6,43 In the latter system dissociative adsorption of CO is induced in the presence of alkali species.43... 

Solvent acido-basicity can also play a role. For instance, acidity of the solvent favours hydrogenolysis, while basicity of the solvent limits hydrogenolysis when hydrogenation competes with hydrogenolysis. A solvent can modify chemisorption, thus influencing selectivity. 

A typical adsorption process in electrocatalysis is chemisorption, characteristic primarily for solid metal electrodes. The chemisorbed substance is often chemically modified during the adsorption process. Then either the substance itself or some fragment of it is bonded chemically to the electrode. As electrodes mostly have physically heterogeneous surfaces (see Sections 4.3.3 and 5.5.5), the Temkin adsorption isotherm (Eq. 4.3.46) is suitable for characterizing the adsorption. 

If the activity of the catalyst is slowly modified by chemisorption of materials that are not easily removed, the deactivation process is termed poisoning. It is usually caused by preferential adsorption of small quantities of impurities (poisons) present in the feedstream. Adsorption of extremely small amounts of the poison (a small fraction of a monolayer) is often sufficient to cause very large losses in catalytic activity. The bonds linking the catalyst and poison are often abnormally strong and highly specific. Consequently, the process is often irreversible. If the process is reversible, a change in the temperature or the composition of the gas to which it is exposed may be sufficient to restore catalyst... 

The rather low coordination in the (100) and (110) surfaces will clearly lead to some instability and it is perhaps not surprising that the ideal surface structures shown in Figure 1.2 are frequently found in a rather modified form in which the structure changes to increase the coordination number. Thus, the (100) surfaces of Ir, Pt and Au all show a topmost layer that is close-packed and buckled, as shown in Figure 1.3, and the (110) surfaces of these metals show a remarkable reconstruction in which one or more alternate rows in the <001 > direction are removed and the atoms used to build up small facets of the more stable (111) surface, as shown in Figure 1.4, These reconstructions have primarily been characterised on bare surfaces under high-vacuum conditions and it is of considerable interest and importance to note that chemisorption on such reconstructed surfaces can cause them to snap back to the unreconstructed form even at room temperature. Recently, it has also been shown that reconstructions at the liquid-solid interface also... 

Poisoning is caused by chemisorption of compounds in the process stream these compounds block or modify active sites on the catalyst. The poison may cause changes in the surface morphology of the catalyst, either by surface reconstruction or surface relaxation, or may modify the bond between the metal catalyst and the support. The toxicity of a poison (P) depends upon the enthalpy of adsorption for the poison, and the free energy for the adsorption process, which controls the equilibrium constant for chemisorption of the poison (KP). The fraction of sites blocked by a reversibly adsorbed poison (0P) can be calculated using a Langmuir isotherm (equation 8.4-23a) ... 

Zn/AljOj catalysts, 31 249 -Zn/Cr Oj catalysts, 31 250 -ZnO/AljO, 31 276, 292-295 -ZnO binary catalyst, 31 257-287 activity patterns, 31 271-274 BET argon surface areas, 31 259 calcination, 31 261-262 catalytic testing, 31 272 chemisorption, 31 268-271 CO2 effects, selectivity, 31 284-285 color spectra, 31 259-261 component comparison, 31 258-259 methanol synthesis, 31 246-247 modifiers, weakening of adsorption energy, 31 283... 

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