Oxygen, chemisorption alcohols

A major problem in noble metal catalyzed liquid phase alcohol oxidations -which is principally an oxidative dehydrogenation- is poisoning of the catalyst by oxygen. The catalytic oxidation requires a proper mutual tuning of oxidation of the substrate, oxygen chemisorption and water formation and desorption. When the overall rate of dehydrogenation of the substrate is lower than the rate of oxidation of adsorbed hydrogen, noble metal surface oxidation and catalyst deactivation occurs. 

Eucken (88,89) and Wicke (90) have tried to explain the dehydrogenation and dehydration of isopropyl alcohol by an electron interchange between the alcohol and the zinc oxide alumina catalysts used for these conversions. We shall modify the mechanism proposed by Eucken and Wicke, following the theory of chemisorption. Contrary to these authors, we do not believe that the positions of the zinc and oxygen ions on the surface of the zinc oxide catalysts have any appreciable influence upon... 

Oxygen-containing compounds such as alcohols also undergo dissociative chemisorption, an example being the adsorption of gaseous methanol on molybdenum oxide catalysts (Eq. 5-28). Such metal oxides, and in particular mixed metal oxides, act as redox catalysts, as we shall see in Section 5.3.3. 

Like the reactions discussed above, this reaction involves an alcohol as the reactant. Probably, these reactions proceed through a common first step, namely the activation of the alcohol through chemisorption on the Lewis acid sites of alumina. This interaction takes place via one of the oxygen lone pairs of the alcohol, and is the first step of alcohol dissociation on Lewis acid-base pairs. 

Clean tungsten carbides, a-WC and a-W C, form essentially only hydrocarbons from CO—H2 reactions. At 673 K and atmospheric pressure, the main products on WC, W2C, and W are methane, CO2, and H2O (121). Ethane and propane are also formed at lower temperatures. WC was substantially more active than W2C and W. The nature of the products can be modified by oxide promoters, as for the case of Rh or Pt, or by the carbon vacancies at the surface (122). At 573 K and 5 MPa with 2H2/CO, turnover rates (based on sites titrated by CO chemisorption) of 0.25-0.85 s were reported for hydrocarbon synthesis over bulk and Ti02-supported tungsten carbides. In addition, WC and WC/Ti02 produced alcohols and other oxygenates with 20-50% selectivity. However, W2C of more metallic character did not produce any oxygenates. Coexistence of carbidic and oxidic components on the catalyst surface appeared to be responsible for alcohol formation. 

Oxygen produced by NO dissociation may react with propene activated by the metal surface either to form CO2 (redox decomposition mechanism) or to form an allyl alcoholate species. When the activity of the surface of the noble metal is inhibited by chemisorption of CO and/or other species the second pathway becomes the prevailing one and detectable by IR. Further, aUyl alcoholate quickly transforms to chemisorbed acrolein and then to acrylic acid. 

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