Oxidation mechanisms of carbon monoxide

We may distinguish four main types of mechanism (1) the reaction proceeds only on metallic gold particle, (2) it requires the simultaneous availability of metallic gold and cationic gold species, (3) it involves collaboration between metal and support, with the possible assistance of cationic species and (4) it proceeds solely via cationic species on the support. In the next section we examine mechanisms 1 and 2 then in Section 6.6.3, we look at mechanisms 3 and 4. 

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The Mechanism of Carbon Monoxide Oxidation on Solid Oxides.. 243... 

Seravalli, J., Kumar, M., Lu, W.-P., and Ragsdale, S. W., 1997, Mechanism of carbon monoxide oxidation by the carbon monoxide dehydrogenase/acetyl-CoA syndiase from Clostridium thermoaceticum Kinetic characterization of the intermediates, Biochem. 36 11241fi 11251. 

Hueso, J. L. Martinez-Martinez, D. Caballero, A. et al. Near-ambient X-ray photoemission spectroscopy and kinetic approach to the mechanism of carbon monoxide oxidation over lanthanum substituted cobaltites. Catal. Commun. 2009, 10, 1898-1902. 

Lai SCS, LehedevaNP, Housmans THM, Koper MTM. 2007. Mechanisms of carbon monoxide and methanol oxidation at single-crystal electrodes. Top Catalysis 46 320-333. 

A similar oxidation-reduction mechanism in the carbon monoxide oxidation reaction on oxide catalysts has been proposed by Benton (71), Bray (72), Frazer (73), and Schwab (74). In this reaction also, Mooi and Selwood (57) found that a decrease in the percentage of iron oxide, manganese oxide or copper oxide on the alumina support first increased the rate, and then at lower percentages decreased the rate, of carbon monoxide oxidation, indicating that valence stabilization is again operative in these cases. 

Almost all catalytic converters have to contend with the decay or poisoning of the catalyst In some form and the catalytic monolith Is no exception. Indeed this Is notorious In the automotive application where the catalytic converter must survive 50,000 miles of operation and still perform adequately. Although we shall use the kinetics of carbon monoxide oxidation over a platinum catalyst as an obvious and Important example, our main objective Is to develop a model which can handle any catalyst decay question and to point out the differences In two types of poisoning. Thus our study comes within the third main division of the subject as laid out by Butt (1 ) In 1972 not the mechanism or rate determination but the effect of deactivation on the operation of the reactor. 

Stampfl C and Scheffler M 1997 Mechanism of efficient carbon monoxide oxidation at Ru(OOOI) J. Vac. Sci. Technoi. A 15 1635... 

The mechanism of carbon elimination is similar to those of the earlier open-hearth processes, ie, oxidation of carbon to carbon monoxide and carbon dioxide. The chemical reactions and results are the same in both cases. The progress of the reaction is plotted in Figure 5. 

G. Fisher and co-workers, "Mechanism of the Nitric Oxide—Carbon Monoxide—Oxygen Reaction Over a Single Crystal Rhodium Catalyst," in M. 

Mechanisms of the Oxidation of Carbon Monoxide and Small Organic Molecules at Metal Electrodes... 

Gilman S. 1964. The mechanism of electrochemical oxidation of carbon monoxide and methanol on platinum. II. The reactant-pair mechanism for electrochemical oxidation of carbon monoxide and methanol. J Phys Chem 68 70-80. 

McCallum C, Pletcher D, 1978. An investigation of the mechanism of the oxidation of carbon monoxide adsorbed onto a smooth Pt electrode in aqueous acid. J Electroanal Chem 70 277. 

Anderson AB, Neshev NM. 2002. Mechanism for the electro-oxidation of carbon monoxide on platinum, including electrode potential dependence—Theoretical determination. J Electrochem Soc 149 E383-E388. 

It is true, however, that many catalytic reactions cannot be studied conveniently, under given conditions, with usual adsorption calorimeters of the isoperibol type, either because the catalyst is a poor heat-conducting material or because the reaction rate is too low. The use of heat-flow calorimeters, as has been shown in the previous sections of this article, does not present such limitations, and for this reason, these calorimeters are particularly suitable not only for the study of adsorption processes but also for more complete investigations of reaction mechanisms at the surface of oxides or oxide-supported metals. The aim of this section is therefore to present a comprehensive picture of the possibilities and limitations of heat-flow calorimetry in heterogeneous catalysis. The use of Calvet microcalorimeters in the study of a particular system (the oxidation of carbon monoxide at the surface of divided nickel oxides) has moreover been reviewed in a recent article of this series (19). 

The first scheme was ruled out by showing that, at room temperature, a surface formed by very brief exposure of the oxygen-saturated surface to carbon monoxide is stable after removal of the carbon monoxide from the reaction chamber. In other words, no further surface carbide formed by lateral reactions of adsorbed carbon monoxide with surface oxygen atoms. The second scheme was ruled out by showing that exposure of the surface formed in the latter experiment to oxygen had no effect. Consequently the third scheme is believed to represent the mechanism of oxidation of carbon monoxide at the step and kink sites of platinum. 

Two molecules of carbon monoxide were successively incorporated into an epoxide in the presence of a cobalt catalyst and a phase transfer agent [29]. When styrene oxide was treated with carbon monoxide (0.1 MPa), excess methyl iodide, NaOH (0.50 M), and catalytic amounts of Co2(CO)8 and hexadecyltrimethylammonium bromide in benzene, 3-hydroxy-4-phenyl-2(5H)-furanone was produced in 65% yield (Scheme 7). A possible reaction mechanism was proposed as shown in Scheme 8 Addition of an in situ... 

The Atomic Mechanism of a Catalytic Reaction Oxidation of Carbon Monoxide... 

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