Oxygen reduction reaction catalysts catalytic effect

Many catalyst layer models have appeared in the literature during the last few years [15, 16, 17, 18, 19,20, 21]. This observation partly explains the complications associated with this topic. Still, much work remains to be completed since many effects have not yet been included, such as proton surface diffusion (outside the ionomer, [22,23]) and ionomer density (water content effect), which effectively and respectively increases/modifies the reactive surface area. The surface-sensitive nature of Pt catalysts on the oxygen reduction reaction rate [24] and electrochemical promotion (a catalytic effect, [25]) represent other examples which can also affect the reaction rate and surface area. All these effects are further compounded by the potential presence of hquid water which effectively modifies the reaction front, access to speeifie eatalyst particles and surface properties. 

The major challenge of non-precious metal electrocatalysis of oxygen reduction reaction continues to be the lack of knowledge of the active catalytic sites and reaction mechanisms. The difficulties in the identification of the active sites are augmented by the virtual absence of effective NPMC characterization tools for direct probing of the surface of heat-treated catalysts. Further progress in the development of NPMCs will likely depend on the ability to characterize and understand the source(s) of the activity of the catalysts that have been already developed and are under development today. 

Kondarides, D.I., Chafik, T. and Verykios, X.E. (2000) Catalytic reduction of NO by CO over rhodium catalysts. 2. effect of oxygen on the nature, population, and reactivity of surface species formed under reaction conditions, J. Catal., 191, 147. 

In these polymer-metal complexes of the Werner type, however, organometallic compounds are formed as reaction intermediates and/or activated complexes. As a result, the properties of polymer-metal catalysts in reductive reactions are different from those of polymer-metal catalysts in oxidative reactions. In the former, the catalytic reactions are very sensitive to moisture and air, and the complex catalysts often decompose in the presence of water and oxygen. Thus, reductive catalytic reactions are carried out under artificial conditions such as organic solvent, high pressure, and high temperature. Oxidative catalytic reactions, on the other hand, proceed under mild conditions aqueous solution, oxygen atmosphere, and room temperature. Therefore, it is to be expected that the catalytic effects of a polymer ligand will differ from the latter to the former. 

Here we shall briefly summarize the effects of individual poisons on various catalytic reactions taking place on automotive catalysts. There are three main catalytic processes oxidation of carbon monoxide and hydrocarbons and reduction of nitric oxide. Among secondary reactions there are undesirable ones which may produce small amounts of unregulated emissions, such as NH3, S03 (6), HCN (76, 77), or H2S under certain operating conditions. Among other secondary processes which are important for overall performance, in particular of three-way catalysts, there are water-gas shift, hydrocarbon-steam reforming, and oxygen transfer reactions. Specific information on the effect of poisons on these secondary processes is scarce. 

The SCR process consists of the reduction of NO (typically 95% NO and 5% NO2 v/v) with NH3. The reaction stoichiometry is usually represented as 4NO + 4NH3 + 02 4N2 + 6H2O. This reaction is selectively effected by the catalyst, since the direct oxidation of ammonia by oxygen is prevented In the case of the treatment of sulfur-containing gas streams, the DcNO reaction is accompanied by the catalytic oxidation of SO2 to SO3 Oxidation of SO2 is highly undesirable because SO3 is known to react with water and residual ammonia to form ammonium sulfates, which can damage the process equipment. 

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